Color MasterBatch, also called color species. It is a new type of special colorant for polymer materials, also known as Pigment Preparation. Masterbatch is mainly used in plastics. Color masterbatch is composed of three basic elements: pigment or dye, carrier and additive. It is an aggregate made by evenly loading a super-normal amount of pigment into resin. It can be called pigment concentration (Pigment Concentration), so its The tinting power is higher than the pigment itself. During processing, a small amount of color masterbatch is mixed with uncolored resin to achieve a colored resin or product with a designed pigment concentration.

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Basic ingredients

Pigments or dyes

Pigments are divided into organic pigments and inorganic pigments.

Commonly used organic pigments include: phthalocyanine red, phthalocyanine blue, phthalocyanine green, light-fast red, macromolecular red, macromolecular yellow, permanent yellow, permanent violet, azo red, etc. Commonly used inorganic pigments include: cadmium red, cadmium yellow, titanium dioxide, carbon black, iron oxide red, iron oxide yellow, etc.

Carrier

It is the matrix of masterbatch. For special masterbatch, the same resin as the product resin is generally selected as the carrier. The two have the best compatibility, but the fluidity of the carrier must also be considered.

Dispersant

To promote the uniform dispersion of pigments and no longer agglomeration, the dispersant should have a lower melting point than the resin, good compatibility with the resin, and good affinity with the pigment. The most commonly used dispersants are: polyethylene low molecular weight wax and stearate.

Additives

Such as flame retardant, brightening, antibacterial, antistatic, antioxidant and other varieties. Unless the customer requests it, the above additives are generally not included in the masterbatch.

Development history

Masterbatch is a new product for coloring plastics and fibers developed in the s. It is a polymer composite made by loading a super-normal amount of pigment evenly into resin. Masterbatch is mainly composed of three parts: colorant, carrier and dispersant.

According to relevant information, the average annual growth rate of demand for color masterbatch in other countries in Asia is about 7%-9%, but the average annual growth rate of demand for color masterbatch in china is about 20%. China is expected to become the market with the fastest growing demand for masterbatch. Especially for colored and additive masterbatches, our country relies on imports. china has become the largest producer and consumer of masterbatch in Asia. There are 330 companies producing masterbatch in china, including 300 plastic-grade masterbatch factories and 30 fiber-grade masterbatch factories. These masterbatch manufacturers are mainly distributed in Fujian, Guangdong, Shandong, Zhejiang, Jiangsu, and Shanghai., Liaoning, Tianjin, Beijing, Hebei and other provinces and cities. There are nearly 50 companies with an annual production capacity of more than 1,000 tons of masterbatch in china. The national masterbatch production capacity is 300,000 tons per year. In , the demand for masterbatch in china was less than 120,000 tons. Serious excess production capacity has led to a general under-operation in the domestic color masterbatch industry. In addition to factors such as the rapid growth of new production equipment and insufficient product orders, an important factor is that the domestic color masterbatch product structure is single and the varieties are incomplete. General-purpose products account for a large proportion. The proportion of high-concentration, ultra-high-concentration, multi-functional color masterbatch and color masterbatch for fine fiber is smaller. In contrast, countries with higher masterbatch technology have a complete range of raw materials such as pigments and dispersants, and have formed a serialized and specialized product structure. In terms of variety development, china’s masterbatch manufacturers have developed masterbatch for fiber, masterbatch for film, masterbatch for wire and cable, polyolefin masterbatch, PVC masterbatch, and masterbatch for injection molding products. Relevant experts believe that in the future, color masterbatch will develop in the direction of multi-functionality, high color content and high technology content. The development of color masterbatch is accompanied by the improvement of production technology.

Advantages

1. Make the pigment have better dispersion in the product. During the production process of the color masterbatch, the pigment must be refined to improve the dispersion and tinting power of the pigment. The carrier of the special color masterbatch is the same as the plastic type of the product, and has good matching. After heating and melting, the pigment particles can be well dispersed in the plastic product.

2. It is helpful to maintain the chemical stability of the pigment. If the pigment is used directly, the pigment will absorb water, oxidize and other phenomena due to direct contact with air during storage and use. After making the color masterbatch, the resin carrier will separate the pigment and air, Moisture isolation can keep the quality of the pigment unchanged for a long time.

3. Ensure the stability of the color of the product. The masterbatch particles are similar to the resin particles, making it more convenient and accurate to measure. They will not stick to the container when mixing, and the mixture with the resin is also relatively uniform. Therefore, the added amount can be ensured to be stable, thereby ensuring Product color stability.

4. Protect the operator’s health. Pigments are generally in powder form and are easy to fly when added and mixed. If inhaled by the human body, it will affect the health of the operator.

5. Keep the environment clean.

6. Easy to use.

Heat resistance

The heat-resistant grade of the special color masterbatch is generally compatible with the plastic used for the product, and it can be used with confidence at normal temperatures. Different degrees of discoloration will only occur under the following circumstances: first, the temperature exceeds the normal range; second, the downtime is too long.

What is the difference between granulation coloring and masterbatch coloring?

Masterbatch coloring has the following advantages compared with granulation coloring:

1. Coloring and product processing are completed at one time, avoiding the heating process of plastics during granulation and coloring, which is beneficial to protecting the quality of plastic products.

2. Minimize the production process of plastic products.

3. Can save a lot of electricity

Will products colored with masterbatch not fade?

There is no absolutely non-fading product, and products colored with masterbatch may still fade, but the degree is different for different grades of products. Some are more obvious, while others are difficult to detect.

General color masterbatch and special color masterbatch

Special color masterbatch

It is a color masterbatch made according to the plastic type specified by the user and using the same plastic as the carrier. For example, PP masterbatch and ABS masterbatch use PP and ABS as carriers respectively.

Universal color masterbatch

It also uses a certain resin (often low melting point PE) as a carrier, but it can be applied to the coloring of other resins besides its carrier resin.

Universal color masterbatch is relatively simple and convenient, but it has many shortcomings. It is recommended that you choose special color masterbatch.

Why don’t many companies produce universal color masterbatch?

Most regular masterbatch companies in the world generally do not produce general-purpose masterbatch.

Universal color masterbatch has many shortcomings. In fact, the “universal” range of general masterbatch is very narrow, and the technical indicators and economic benefits are also poor. The specific manifestations are:

1. Poor predictability of coloring effects

Masterbatch is used for coloring. The pigments of general masterbatch will show different colors in different plastics, so the coloring effect is less predictable.

2. Affect other properties of plastic products

Especially affecting the strength, the product is easily deformed and twisted, which is more obvious for engineering plastics.

3.Higher cost

In order to be ‘universal’, general-purpose color masterbatches often use pigments with higher heat-resistant grades, resulting in waste.

In addition to coloring, can masterbatch also have functions such as flame retardant, brightening, antistatic, antioxidant, and UV resistance?

The color masterbatch can have some of these functions at the same time, if the factory requests this.

Sometimes, even though customers have not requested it, the color master company will also suggest users to add some additives according to the needs of the product, such as adding certain additives to the color masterbatch, such as brighteners. Of course, this will increase the cost of the product.

Things to note

1. How to use masterbatch?

The use of color masterbatch is very simple. You only need to mix it with resin particles according to the specified ratio and mix it by hand.

The following issues should be paid attention to during the operation of the equipment:

1.1. The mixing chamber of an injection molding machine or extruder generally has multiple temperature zones. The temperature of the section near the blanking port should be slightly higher. This is to make the color masterbatch melt quickly after entering the mixing chamber and mix with the plastic resin as quickly as possible. Mix evenly so that the masterbatch pigments are well dispersed in the product.

1.2. Appropriately apply back pressure to the injection molding machine, which can improve the mixing effect of the screw and facilitate the dispersion of pigments. The side effect of applying back pressure is to slow down the injection speed.

1.3. Appropriately increasing the die temperature of the extruder can increase the brightness of the product.

2. How to determine the proportion of color masterbatch used?

The basis for determining the proportion of color masterbatch used is to obtain a satisfactory coloring effect. As long as the surface tone of the product is uniform and there are no streaks or spots, it can be approved. The usage ratio of color masterbatch can be selected as follows:

1:100 Unless the mixing performance of the equipment is very good, uneven pigment dispersion may easily occur. It is generally not recommended for customers to use this ratio.

However, due to price pressure, some customers particularly hope to use this proportion of color masterbatch. For the sake of customers, more concentrated color masterbatch with such a low proportion is produced, and the dispersion of pigments can generally meet the requirements.

1:50 is used for plastic products with general coloring requirements. PE and PP color masterbatches mostly use this ratio.

1:33–1:25 is used for PO products with higher coloring requirements, and ABS products with lower or general coloring requirements.

1:20 is used for high-end plastic products, including PO and ABS, and can be widely used in injection molding, blow molding, spinning and other processes

1:20 or above is generally used for coloring high-end cosmetic containers, and is often used in small injection molding machines.

3. How to calculate the cost of using masterbatch?

When calculating the cost of masterbatch coloring, the weight of the masterbatch itself should be deducted.

For example: add 2 kilograms of color masterbatch to 100 kilograms of plastic resin. At this time, the total weight is already 102 kilograms. Assume that the resin price is 10 rmb/kg and the color masterbatch price is 20 rmb/kg.

Then the increased cost due to the use of color masterbatch in 102 kilograms of plastic products is:

2 kg × (20 rmb/kg-10 rmb/kg) = 20 rmb

Converted into the increased cost due to the use of color masterbatch per 100 kilograms of plastic products:

20 rmb/102 kg × 100 kg = 19.61 rmb

4. Will using masterbatch increase product cost?

In most cases this is the case. But in some cases, using masterbatch coloring is more economical than using toner coloring, because colorists can achieve the coloring effect of higher-priced pigments through a combination of several lower-priced pigments.

There are also two phenomena to consider:

1. In many cases, the pigments selected by plastic product manufacturers when using toners for color matching are not the most economical. Due to lack of familiarity with the pigments, repeated trials during color matching are very common, resulting in a waste of manpower and materials. This problem does not exist when using masterbatch.

2. The grades of products colored with color masterbatch are completely different from those colored with color powder, and their selling price is also higher. The higher selling price is often higher than the increased cost of using color masterbatch, so color On the contrary, the mother can create “profit”. From this perspective, in some cases, it is more “economical” to use masterbatch coloring than toner coloring.

5. Does the color masterbatch need to be dried before use?

Masterbatch generally does not need to be dried and can be used directly. However, except for ABS and NY masterbatch, they should be dried according to conventional processes.

What is the shelf life of masterbatch?

Masterbatch can be stored for a long time.

The pigments in the masterbatch are dispersed and fixed in the carrier resin and are in a closed state. Their quality will not change even if they are stored for a long time. But should be stored in a dry, cool environment

6. Can several different color masterbatch be used to prepare the color?

Generally, companies often use several color masterbatches to prepare specific colors for small-volume customers. However, without the guidance of the company’s technical personnel, customers are not allowed to use several color masterbatches together on their own initiative, let alone mixed use of color masterbatch produced by different companies, to avoid incompatibility and losses.

7. Will the use of masterbatch affect other properties of the product?

Some pigments have an impact on the flame retardant effect of products. When used in flame retardant products, please contact the masterbatch manufacturer.

8. Does the mold affect the use of masterbatch?

In order to fully display the coloring effect of the masterbatch, the mold must have corresponding quality, especially the surface must be very smooth.

Common defects

1. Under sunlight, there are striped pigment bands in the product.

This issue needs to be considered from two aspects: plastic physical and mechanical properties and plastic molding process:

1.1 The temperature of the injection molding equipment is not well controlled, and the masterbatch cannot be fully mixed with the resin after entering the mixing chamber.

1.2 The injection molding machine does not add a certain amount of back pressure, and the mixing effect of the screw is not good.

1.3 The dispersion of the color masterbatch is not good or the resin plasticization is not good.

In terms of process, the following adjustments can be made: 1. Slightly increase the temperature of the mixing cavity near the blanking port. 2. Apply a certain back pressure to the injection molding machine.

If it still does not improve after the above debugging, it may be a dispersion or matching problem with the masterbatch and resin, and you should contact the masterbatch manufacturer for resolution.

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2. After using a certain color masterbatch, the product appears to be more likely to break.

This may be due to poor diffusion and miscibility caused by the poor quality of the dispersants or additives selected by the manufacturer, which affects the physical and mechanical properties of the product.

3. After using the masterbatch according to the proportion in the instruction manual, the color is too dark (too light)

Although this question is simple, there are many possibilities, specifically:

3.1. The color masterbatch has not been carefully tested, and the pigment is too little or too much.

3.2. Inaccurate measurement during use, and a large number of some enterprises, especially small and medium-sized enterprises, use arbitrary measurement.

3.3. There is a problem with the matching of color masterbatch and resin. This may be due to improper selection of the color masterbatch carrier, or the manufacturer may change the resin variety at will.

3.4. The machine temperature is improper and the color masterbatch stays in the machine for too long.

Processing procedures: First check whether the resin type matches the masterbatch and whether the measurement is accurate. Secondly, adjust the machine temperature or speed. If there are still problems, please contact the masterbatch manufacturer.

4. With the same color masterbatch, resin and formula, why do the products injected by different injection molding machines have different colors?

This is often caused by the injection molding machine. Different injection molding machines have different mechanical conditions due to different manufacturing, usage time or maintenance conditions, especially the difference in the close contact between the heating element and the barrel, resulting in different dispersion states of the color masterbatch in the barrel. As mentioned above, phenomenon will appear.

5. After changing to another brand of resin, the color of the same masterbatch and formula has changed. Why is this?

The density and melt index of different grades of resin will be different, so the performance of the resin will be different, and the compatibility with the masterbatch will also be different, resulting in color changes. Generally speaking, as long as the density and melt index are the same If it is large, the color difference will not be too big. The color can be corrected by adjusting the amount of color masterbatch.

6. Will pigment migration of masterbatch during storage affect the quality of the product?

Some color masterbatches have a high pigment (or dye) content, in which case migration is normal. Especially when dye is added to the masterbatch, serious migration will occur. But this does not affect the quality of the product, because after the masterbatch is injected into the product, the pigment is at a normal color concentration in the product.

7. Why do some injection products have poor gloss?

There are many possibilities:

7.1. The nozzle temperature of the injection molding machine is too low

7.2. The mold finish of the injection molding machine is not good.

7.3. Product molding cycle is too long

7.4. The color masterbatch contains too much titanium dioxide.

7.5. The dispersion of color masterbatch is not good

8. After a period of time, some plastic products will fade.

The basic pigments used by the manufacturer are of poor quality and drift occurs.

9. Why is ABS masterbatch so prone to color differences?

Different brands of ABS produced in various countries have large color differences. Even for the same brand of ABS, there may be color differences in each batch. Of course, color differences will also occur after using masterbatch coloring. This is caused by the characteristics of ABS, and there is no complete solution internationally. However, this color difference is generally not serious.

Users must pay attention to this characteristic of ABS when using ABS masterbatch.

Production process

Requirements for colorants used in masterbatch

When using colorants for masterbatch, attention must be paid to the matching relationship between the colorants, plastic raw materials, and additives. The key points for selection are as follows.

(1) The pigment cannot react with resin and various additives, and has strong solvent resistance, low migration, and good heat resistance. In other words, masterbatch cannot participate in various chemical reactions. For example, carbon black can control the curing reaction of polyester plastic, so carbon black materials cannot be added to polyester.

Since the molding and processing temperature of plastic products is relatively high, the color material should not decompose and change color under the molding heating temperature. Generally, inorganic pigments have better heat resistance, while organic pigments and dyes have poorer heat resistance. This should be taken into consideration when selecting pigment types.

(2) The dispersion and tinting power of the colorant should be good. When the colorant is unevenly dispersed, it will affect the appearance and performance of the product; when the colorant has poor tinting strength, it will increase the amount of colorant and increase the material cost. The same colorant has different dispersibility and tinting power in different resins, so you should pay attention to this when selecting colorants.

The particle size of the colorant is also related to the dispersion. The smaller the particle size of the colorant, the better the dispersion and the stronger the tinting power.

(3) Other properties of colorants should be understood. For example, for plastic products used in food and children’s toys, colorants are required to be non-toxic; for plastic products used in electrical appliances, colorants with good electrical insulation should be selected; For plastic products used outdoors, colorants with good weather aging resistance should be selected.

Masterbatch production process flow

Masterbatch production process requirements are very strict, and wet processes are generally used. Masterbatch is made by water phase grinding, phase transfer, water washing, drying and granulation. Only in this way can product quality be guaranteed.

In addition, while the pigment is being ground, a series of tests should also be carried out, such as measuring the fineness of the sanding slurry, measuring the diffusion performance of the sanding slurry, measuring the solid content of the sanding slurry, and measuring the fineness of the color paste.

There are four methods in the process flow of color masterbatch production:

(1) Ink method: As the name suggests, it is a production method that uses ink paste in the production of masterbatch, that is, through three-roller grinding, a low-molecular protective layer is coated on the surface of the pigment. The ground fine color paste is mixed with the carrier resin, then plasticized through a two-roller mill (also called a two-roller open mill), and finally granulated through a single-screw or twin-screw extruder.

The process is as follows:

Ingredients are stirred for coarse color slurry, three-roller grinding for fine color slurry, two-roller plasticization, extrusion and granulation.

(2) Flushing method: The pigment, water and dispersant are sanded to make the pigment particles less than 1 μm, and the pigment is transferred into the oil phase through the phase transfer method, and then dried to obtain the color masterbatch. Organic solvents and corresponding solvent recovery devices are required for phase transfer. The process is as follows:

The fine color slurry is washed, evaporated, and the concentrated material is dried, added with a carrier, extruded and granulated.

(3) Kneading method: After mixing the pigment and the oily carrier, the pigment is washed from the water phase into the oil phase by kneading, taking advantage of the lipophilicity of the pigment. At the same time, the surface of the pigment is coated by an oily carrier to stabilize the pigment dispersion and prevent pigment aggregation.

(4) Metal soap method: The pigment is ground to a particle size of about 1 μm, and soap is added at a certain temperature so that the surface layer of each pigment particle is evenly moistened by the soap to form a layer of saponified liquid. When the metal After the salt solution is added, it chemically reacts with the saponification layer on the surface of the pigment to form a protective layer of metal soap (magnesium stearate). This prevents the ground pigment particles from causing flocculation and protects certain fine particles. Spend.

Precautions when using masterbatch

(1) Color masterbatch will absorb moisture after being stored for a period of time, especially PET, ABS, PA, PC, etc., so it must be dried according to the same process as natural color masterbatch and meet the moisture content requirements.

(2) You must be very careful when using color masterbatch to achieve the desired color, as color difference and changes in color and light often occur.

(3) Masterbatch will react with other additives, so be careful when using it.

(4) Attention should be paid to the selection of the dilution ratio of the color masterbatch. Choosing a high dilution ratio will result in lower production costs, but it will also be limited by processing equipment.

Masterbatch classification

The commonly used classification methods for color masterbatch are as follows:

Classified by carrier: such as PE masterbatch, PP masterbatch, ABS masterbatch, PVC masterbatch, EVA masterbatch, etc.

Classified by use: such as injection masterbatch, blow molding masterbatch, spinning masterbatch, etc. Each variety can be divided into different grades, such as:

1. Advanced injection masterbatch

Used in cosmetic packaging boxes, toys, electrical casings and other high-end products.

2. Ordinary injection masterbatch

Used for general daily plastic products, industrial containers, etc.

3. Advanced blown film masterbatch

Used for blow molding coloring of ultra-thin products.

4. Ordinary blown film masterbatch

Used for blow molding and coloring of general packaging bags and woven bags.

5. Spinning masterbatch

Used for spinning and coloring textile fibers. The masterbatch pigment has fine particles, high concentration, strong tinting power, and good heat resistance and light resistance.

6. Low-grade masterbatch

Used to manufacture low-level products that do not have high requirements on color quality, such as trash cans, low-level containers, etc.

Other

Color masterbatch: Jincheng masterbatch group produces black masterbatch, white masterbatch, red masterbatch, blue masterbatch, yellow masterbatch, green masterbatch, purple masterbatch, silver masterbatch, golden masterbatch

Titanium dioxide: General agent of Jincheng Masterbatch Group; Spain’s Meililian titanium dioxide R-CL69, R-CL595, Britain’s R-TC30, R-FC5, R-PP25, and the United States DuPont titanium dioxide R-902, R-900, R- 706, R-103, R-104, R-105, Japanese titanium dioxide R-930, Panzhihua Iron and Steel Co., Ltd. R-248, Panzhihua Iron and Steel Co., Ltd. R-258, Lomon R-996, etc. imported domestic titanium dioxide

General agent of Carbon Black Jincheng Masterbatch Group; Hualing brand N330, N220, N326, environmentally friendly high-pigment carbon black LT-1, LT-2, LT-3, LT-4, etc., and imported carbon black

Pigment additives: British Ultramarine , British Ultramarine , oily black, titanium blue, titanium green, fluorescent pigments, luminous powder, 2N blue, and other domestic pigments, imported pigments, antioxidants, anti-UV agents, foaming agents, defoaming agent, opening agent, antistatic agent, steel strengthening agent, whitening agent, toughening agent, fire retardant powder, Malaysian EBS, Japan EB-FF, diffusion oil, diffusion powder, filling, recycled materials and other domestic additives, Imported additives.

Application scope

It is widely used in polyethylene, polypropylene, polystyrene, ABS, nylon, PC, PMMA, PET and other resins to produce colorful fibers, clothing, daily plastics, wires and cables, household appliances, agricultural films, automobiles Accessories, health care equipment and other products.

Appendix: Performance of Pigments

1. Heat resistance: PVC and PE pigments have a temperature resistance of 160-180 degrees Celsius. ABS and PS pigments have a temperature resistance of 250-280 degrees Celsius. PP, PA and PET pigments have a temperature resistance of 280 degrees and above. Generally, the heat resistance time of the pigments is 4-10. minutes, generally, the higher the use temperature, the shorter the heat resistance time.

Phthalocyanine blue pigment has a temperature resistance of 325 degrees Celsius and changes color in 10 minutes.

2. The migration resistance of migratory pigments means that when colored plastic products are in long-term contact with other solid, liquid, gas, etc. substances or work in a specific environment, they may have physical and chemical interactions with the above substances, which is manifested as Pigments migrate from within the plastic onto the free surface of the article, or into adjacent plastics or solvents. Migration resistance rating standards: Level 1, Level 2, Level 3, Level 4, Level 5, Severe migration, Significant migration, Slight migration, No migration. 3. Most inorganic pigments have good light resistance.

4. Weather resistance refers to the color stability of pigments under natural conditions.

5. Titanium dioxide is divided into: anatase type (A) titanium dioxide rutile type (R) titanium dioxide. Titanium dioxide can improve hiding power, weather resistance, fading resistance, etc. ~~~ When the concentration of titanium dioxide is low, the whiteness of PP changes with the The increase rate of its content increases. When the concentration exceeds 1.5%, the whiteness no longer increases. From 1% to 8%, the whiteness increases by 2.8%. This shows that after exceeding a certain concentration range, increasing the dosage of titanium dioxide does not improve the whiteness. Spend. In order to further improve the whiteness, fluorescent whitening agents can be used. Only a small amount of fluorescent whitening agents can significantly improve the tinting power of titanium dioxide. Titanium dioxide, alias: titanium dioxide, titanium dioxide can effectively scatter visible light to plastics to impart whiteness, brightness, and opacity. The concentration of titanium dioxide in PP\ABS is 1%; in PVC it ​​is 4%; as the dosage of titanium dioxide increases, its hiding power gradually increases, and tends to balance when the concentration is greater than 8%. Generally speaking, the finer the titanium dioxide particles, the higher the tinting power and the stronger the hiding power.

6. Cadmium yellow has strong tinting power, excellent light resistance and weather resistance, and does not migrate or bleed (toxic pigments). This product can be used as a yellow colorant for plastics. It has bright color, excellent light resistance, heat resistance, solvent resistance, water resistance and alkali resistance, but it is not acid resistant, coloring and covering power is not very high.

7. Ultramarine blue has the function of whitening and toning. It can remove the yellow light in white products.

WOA1 - Masterbatch for elimination of moisture in plastics and method for producing masterbatch for elimination of moisture in plastics - Google Patents

Masterbatch for elimination of moisture in plastics and method for producing masterbatch for elimination of moisture in plastics Download PDF

Info

Publication number

WOA1

WOA1 PCT/JP/ JPW WOA1 WO A1 WO A1 WO A1 JP W JP W JP W WO A1 WO A1 WO A1

Authority

WO

WIPO (PCT)

Prior art keywords

inorganic compound

masterbatch

plastic material

plastic

moisture

Prior art date

-01-10

Application number

PCT/JP/

Other languages

French (fr)

Japanese (ja)

Inventor

Li Kong

Ying Zhang

Original Assignee

Chukyo Shoji. Co., Ltd.

Positive Force Investments Corporation

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

-01-10

Filing date

-01-10

Publication date

-07-19

-09-13 Priority claimed from JPA external-priority patent/JPB2/en

-01-10 Application filed by Chukyo Shoji. Co., Ltd., Positive Force Investments Corporation filed Critical Chukyo Shoji. Co., Ltd.

-07-19 Publication of WOA1 publication Critical patent/WOA1/en

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• Masterbatch (MB) Substances 0.000 title claims abstract description 124
• plastic Polymers 0.000 title claims abstract description 108
• plastic Substances 0.000 title claims abstract description 108
• manufacturing process Methods 0.000 title claims description 13
• elimination Effects 0.000 title abstract 3
• elimination reaction Methods 0.000 title abstract 3
• inorganic material Inorganic materials 0.000 claims abstract description 110
• inorganic compounds Chemical class 0.000 claims abstract description 108
• thermoplastic resin Polymers 0.000 claims abstract description 45
• chemical substances by application Substances 0.000 claims abstract description 44
• powder Substances 0.000 claims abstract description 20
• absorption reaction Methods 0.000 claims abstract description 15
• binding agent Substances 0.000 claims abstract description 7
• material Substances 0.000 claims description 85
• modifier Substances 0.000 claims description 39
• dehumidification Methods 0.000 claims description 22
• heat treatment Methods 0.000 claims description 22
• moulding Methods 0.000 claims description 20
• QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 17
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• adsorptive effect Effects 0.000 claims description 9
• BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
• Zeolite Inorganic materials 0.000 claims description 6
• HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
• zeolite Substances 0.000 claims description 6
• thermoplastic Polymers 0.000 claims description 5
• thermosoftening plastic Substances 0.000 claims description 5
• RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
• KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
• VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
• aluminates Chemical class 0.000 claims description 4
• QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
• cooling Methods 0.000 claims description 4
• KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
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• TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
• silica gel Substances 0.000 claims description 2
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• substance Substances 0.000 claims description 2
• particle Substances 0.000 abstract description 17
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• lubricant Substances 0.000 description 21
• defect Effects 0.000 description 18
• plasticizer Substances 0.000 description 16
• OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 14
• stearic acid Substances 0.000 description 14
• Polyethylene Substances 0.000 description 13
• polyethylene Polymers 0.000 description 13
• VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
• acrylonitrile butadiene styrene Polymers 0.000 description 12
• drying Methods 0.000 description 12
• heat stabilizer Substances 0.000 description 12
• HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 12
• XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
• antioxidant agent Substances 0.000 description 11
• method Methods 0.000 description 11
• hygroscopic agent Substances 0.000 description 9
• mixing Methods 0.000 description 8
• mixture Substances 0.000 description 8
• wax Substances 0.000 description 8
• KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
• PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
• antioxidant effect Effects 0.000 description 6
• calcium carbonate Inorganic materials 0.000 description 6
• change Effects 0.000 description 6
• magnesium stearate Nutrition 0.000 description 6
• additive Substances 0.000 description 5
• effects Effects 0.000 description 5
• polyethylene resin Polymers 0.000 description 5
• resin Polymers 0.000 description 5
• resin Substances 0.000 description 5
• storage Methods 0.000 description 5
• OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
• acid Substances 0.000 description 4
• PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
• calcium Substances 0.000 description 4
• calcium Inorganic materials 0.000 description 4
• CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
• JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 4
• paraffin wax Substances 0.000 description 4
• Epoxy Substances 0.000 description 3
• Nylon Substances 0.000 description 3
• XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
• aluminium Inorganic materials 0.000 description 3
• XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
• BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
• calcium stearate Substances 0.000 description 3
• calcium stearate Nutrition 0.000 description 3
• constituent Substances 0.000 description 3
• injection moulding Methods 0.000 description 3
• moulding (plastic) Methods 0.000 description 3
• nylon Polymers 0.000 description 3
• physical effect Effects 0.000 description 3
• poly(methyl methacrylate) Polymers 0.000 description 3
• polymethyl methacrylate Substances 0.000 description 3
• process Effects 0.000 description 3
• XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
• ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
• OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 2
• IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
• ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 2
• NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
• Di-2ethylhexylphthalate Substances 0.000 description 2
• ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
• TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
• CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
• QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
• Tris buffer Substances 0.000 description 2
• UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 2
• aliphatic group Chemical group 0.000 description 2
• SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
• carboxylates Chemical class 0.000 description 2
• coating agent Substances 0.000 description 2
• coating method Methods 0.000 description 2
• colorant Substances 0.000 description 2
• compounds Chemical class 0.000 description 2
• copolymer Polymers 0.000 description 2
• AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
• PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 2
• VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
• discoloration Methods 0.000 description 2
• extrusion Methods 0.000 description 2
• impaired effect Effects 0.000 description 2
• impurity Substances 0.000 description 2
• VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
• oil Substances 0.000 description 2
• oils Nutrition 0.000 description 2
• NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
• pellet Substances 0.000 description 2
• OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
• polybutylene terephthalate Polymers 0.000 description 2
• polyethylene terephthalate Substances 0.000 description 2
• polyethylene terephthalate Polymers 0.000 description 2
• polyvinyl chloride Polymers 0.000 description 2
• polyvinyl chloride Substances 0.000 description 2
• sorption measurement Methods 0.000 description 2
• IMYZYCNQZDBZBQ-UHFFFAOYSA-N (+-)-8-(cis-3-octyl-oxiranyl)-octanoic acid Natural products CCCCCCCCC1OC1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-UHFFFAOYSA-N 0.000 description 1
• ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
• VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
• IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
• YXGOYRIWPLGGKN-UHFFFAOYSA-N 2,3-ditert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=C(O)C=CC(O)=C1C(C)(C)C YXGOYRIWPLGGKN-UHFFFAOYSA-N 0.000 description 1
• MLJRLEGXZUNRLY-UHFFFAOYSA-N 2,4-ditert-butylphenol;phosphorous acid Chemical compound OP(O)O.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 MLJRLEGXZUNRLY-UHFFFAOYSA-N 0.000 description 1
• XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
• LMIQZMJKGJNJLY-UHFFFAOYSA-N 2-tert-butyl-6-methylbenzene-1,4-diol Chemical compound CC1=CC(O)=CC(C(C)(C)C)=C1O LMIQZMJKGJNJLY-UHFFFAOYSA-N 0.000 description 1
• Actinopterygii Species 0.000 description 1
• BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
• LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
• SRORDPCXIPXEAX-UHFFFAOYSA-N CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC Chemical compound CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC SRORDPCXIPXEAX-UHFFFAOYSA-N 0.000 description 1
• UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
• ROZZMLUWBPPEMU-GRVYQHKQSA-L Calcium linoleate Chemical compound [Ca+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O ROZZMLUWBPPEMU-GRVYQHKQSA-L 0.000 description 1
• LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
• FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
• RZUHBLGLDSYPOM-UHFFFAOYSA-N OP(O)(=O)OP(=O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC Chemical class OP(O)(=O)OP(=O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC RZUHBLGLDSYPOM-UHFFFAOYSA-N 0.000 description 1
• PO4 Inorganic materials 0.000 description 1
• Poly (ethylene oxide) Polymers 0.000 description 1
• Polypropylene Substances 0.000 description 1
• Polystyrene Substances 0.000 description 1
• Silane Coupling Agent Substances 0.000 description 1
• VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
• YLFRJROMPGNJRP-UHFFFAOYSA-L [dibutyl(3-sulfanylpropanoyloxy)stannyl] 3-sulfanylpropanoate Chemical compound [O-]C(=O)CCS.[O-]C(=O)CCS.CCCC[Sn+2]CCCC YLFRJROMPGNJRP-UHFFFAOYSA-L 0.000 description 1
• UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
• XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
• UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 1
• action Effects 0.000 description 1
• WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
• SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
• JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
• LDPRTCCYTJALQN-UHFFFAOYSA-K aluminum ethyl acetate triacetate Chemical compound C(C)(=O)[O-].[Al+3].C(C)(=O)OCC.C(C)(=O)[O-].C(C)(=O)[O-] LDPRTCCYTJALQN-UHFFFAOYSA-K 0.000 description 1
• anti-wrinkle effect Effects 0.000 description 1
• RAKMKCZMVZBODU-PIQLPZBWSA-L barium(2+);(z)-12-hydroxyoctadec-9-enoate Chemical compound [Ba+2].CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O.CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O RAKMKCZMVZBODU-PIQLPZBWSA-L 0.000 description 1
• AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
• biosynthetic process Effects 0.000 description 1
• calcium chloride Substances 0.000 description 1
• calcium chloride Inorganic materials 0.000 description 1
• HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
• YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
• coloring Methods 0.000 description 1
• conventional method Methods 0.000 description 1
• deterioration Effects 0.000 description 1
• deteriorative effect Effects 0.000 description 1
• dibutyltin dilaurate Substances 0.000 description 1
• dietary fatty acids Nutrition 0.000 description 1
• HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
• dispersing agent Substances 0.000 description 1
• esters Chemical class 0.000 description 1
• ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
• evaporation Methods 0.000 description 1
• evaporation Effects 0.000 description 1
• exhibiting effect Effects 0.000 description 1
• fatty acid Substances 0.000 description 1
• fatty acid Natural products 0.000 description 1
• fatty acids Chemical class 0.000 description 1
• filler Substances 0.000 description 1
• filling Methods 0.000 description 1
• fluid Substances 0.000 description 1
• inhibitory effect Effects 0.000 description 1
• injection Methods 0.000 description 1
• injection Substances 0.000 description 1
• isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
• liquid paraffin Drugs 0.000 description 1
• HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
• magnesium Inorganic materials 0.000 description 1
• magnesium Substances 0.000 description 1
• magnesium chloride Inorganic materials 0.000 description 1
• magnesium sulfate Inorganic materials 0.000 description 1
• magnesium sulphate Nutrition 0.000 description 1
• VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
• maleic acid derivatives Chemical class 0.000 description 1
• metal Inorganic materials 0.000 description 1
• metal Substances 0.000 description 1
• molding material Substances 0.000 description 1
• oxidative effect Effects 0.000 description 1
• phenolic antioxidant Substances 0.000 description 1
• NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
• phosphate Substances 0.000 description 1
• XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
• XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
• polycarbonate Substances 0.000 description 1
• polycarbonate Polymers 0.000 description 1
• polypropylene Polymers 0.000 description 1
• polystyrene Polymers 0.000 description 1
• preparation method Methods 0.000 description 1
• raw material Substances 0.000 description 1
• APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
• soybean oil Nutrition 0.000 description 1
• soybean oil Substances 0.000 description 1
• sulfur Substances 0.000 description 1
• sulfur Inorganic materials 0.000 description 1
• suppression Effects 0.000 description 1
• tendon Anatomy 0.000 description 1
• VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
• ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
• whitening effect Effects 0.000 description 1
• zinc laurate Drugs 0.000 description 1
• GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
• zinc ricinoleate Drugs 0.000 description 1
• GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1

Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques

Definitions

• the present invention relates to a plastic dehumidification master batch and a method for producing a plastic dehumidification master batch.
• pre-drying is not required when molding highly hygroscopic plastic materials such as ABS resin (acrylonitrile 'butadiene' styrene copolymer), nylon, polymethyl methacrylate, and poly vinyl chloride. Don't help, become things!
• ABS resin acrylonitrile 'butadiene' styrene copolymer
• nylon polymethyl methacrylate
• poly vinyl chloride
• JP - A discloses a master notch containing a hygroscopic agent.
• This master batch is a master notch used for adding a hygroscopic agent to a plastic material when producing a plastic molded product that exhibits hygroscopicity with an internally added hygroscopic agent.
• this master batch is formed by coating the center part of the thermoplastic resin and the hygroscopic agent with the outer layer of the thermoplastic resin so that the hygroscopic agent in the central part is produced during the production and storage of the master batch. It has a structure that prevents moisture absorption.
• JP-A-10- discloses a masterbatch containing alumina.
• This master batch contains alumina, a silane coupling agent, etc., in addition to the force colorant, which is a coloring masterbatch that is used to add a colorant to a plastic material when producing colored molded articles.
• Alumina is generally hygroscopic although it is contained in this master batch to improve the physical properties of the molded product.
• the present invention makes it possible to dehumidify a plastic material in a short time and with low energy without heating for the purpose of drying, and it is possible to form a plastic material without preliminary drying by a dryer. It was an object to provide a master batch for plastic dehumidification. Means for solving the problem
• One invention is a masterbatch that is mixed when a plastic material is molded, heated together with the plastic material, and melts with the plastic material, and includes a dehumidifying agent and a thermoplastic resin as a binder. And the dehumidifying agent improves the compatibility between the inorganic compound powder and the thermoplastic resin by covering the surface of the inorganic compound with a hygroscopic powder and the inorganic compound at room temperature.
• a surface modifying agent that suppresses the moisture absorption function of the inorganic compound when heated, and a plastic dehumidification masterbatch that absorbs moisture contained in the plastic material when it is molded, which is also effective.
• Another invention is a method for producing a masterbatch comprising a dehumidifying agent and a thermoplastic resin as a binder, mixed when molding a plastic material, heated together with the plastic material, and melted with the plastic material.
• a powder of a hygroscopic inorganic compound, The dehumidifying agent is prepared by heating while contacting with a surface modifier, and after cooling the obtained dehumidifying agent, the cooled dehumidifying agent and the thermoplastic resin are mixed. It is a manufacturing method of a masterbatch.
• the plastic dehumidification masterbatch of the present invention (hereinafter sometimes simply referred to as "masterbatch”) has the following effects.
• the dehumidifying agent since it contains a dehumidifying agent, it can be easily dehumidified by dispersing the dehumidifying agent in the plastic material simply by mixing it when molding the plastic material.
• thermoplastic resin is formed by covering the inorganic compound with a surface modifier that improves the compatibility with the thermoplastic resin and forming a dehumidifier. It is easy to disperse the dehumidifier in the cocoon. Therefore, a dehumidifying agent can be uniformly contained in the masterbatch, and by mixing the masterbatch quantitatively with the plastic material, the dehumidifying agent can be reliably mixed with the plastic material and dehumidified. .
• the surface modifier that constitutes the dehumidifying agent coats an hygroscopic inorganic compound, thereby suppressing the hygroscopic function of the inorganic compound at room temperature and exerting the hygroscopic function of the inorganic compound during heating.
• the dehumidifier When the dehumidifier is stored at room temperature before use, it easily absorbs moisture when heated together with the plastic material during use. Therefore, this masterbatch preserves the hygroscopic function of the inorganic compound before use, and when used, the hygroscopic function of the inorganic compound is reliably exerted to dehumidify the plastic material.
• the dehumidifying agent is difficult to absorb moisture at room temperature, the dehumidifying function of the dehumidifying agent is unlikely to be impaired even if the master batch is exposed to a normal humidity environment during storage or preparation for use.
• the plastic material can be easily dehumidified by mixing with the plastic material when molding the plastic material.
• the step of pre-drying the material can be omitted. Therefore, the molding process of the plastic material can be shortened, and the plastic material can be molded in a shorter time and with lower energy than before.
• it is not necessary to heat the plastic material only for pre-drying it is possible to prevent the plastic material from being overheated and deteriorated.
• the inorganic compound powder and the surface modifier are heated while being brought into contact with each other, compared with the case of non-heating.
• the entire surface of the inorganic compound can be more reliably coated with the surface modifier. Therefore, it is possible to efficiently prepare a dehumidifying agent and efficiently obtain a master batch for plastic dehumidification.
• the plastic dehumidification masterbatch of the present invention is a masterbatch that is used when molding a plastic material and dehumidifies the plastic material.
• This master batch contains at least a dehumidifying agent and a thermoplastic resin as a binder as basic components.
• this master notch is mixed with the plastic material when molding the plastic material, the thermoplastic resin and the plastic material are melted by the heating during molding, and the dehumidifying agent is dispersed in the plastic material to absorb the moisture in the plastic material. can do.
• the dehumidifying agent constituting the masterbatch is composed of an inorganic compound powder having hygroscopicity and a surface modifier for coating the surface of the inorganic compound.
• the surface modifier constituting the dehumidifying agent coats the surface of each particle of the inorganic compound to improve the compatibility between the inorganic compound and the thermoplastic resin, and at the same time has a function of absorbing moisture of the inorganic compound. It is a substance that suppresses and exhibits the hygroscopic function of inorganic compounds during heating.
• “suppressing the hygroscopic function of an inorganic compound” means inhibiting the hygroscopic function of the inorganic compound
• “exhibiting the hygroscopic function of an inorganic compound” means the hygroscopic function of the inorganic compound. It means not disturbing.
• Examples of such surface modifiers that can be used include titanate coupling agents, aluminum coupling agents, R ⁇ raffin, and stearic acids. These surface modifiers have an affinity for both inorganic compounds and thermoplastic resins and bind chemically or physically to the surface of the inorganic compound powder. This can improve the compatibility between the inorganic compound and the thermoplastic rosin. In addition, by heating in contact with the inorganic compound and covering the entire surface of the inorganic compound, the hygroscopic function of the inorganic compound can be suppressed at room temperature, and the hygroscopic function of the inorganic compound can be reliably exerted during heating.
• titanate coupling agent conventionally known ones can be used.
• use isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate Can do.
• a conventionally well-known thing can be used as said aluminum type coupling agent.
• aluminum isopropylate, aluminum ethylate, aluminum tris (ethyl acetate acetate), ethyl acetate acetate aluminum diisopropylate and the like can be used.
• paraffin A conventionally well-known thing can be used as said paraffin.
• fluid paraffin polyethylene ⁇ raffin wax, polyethylene wax and the like can be used.
• stearic acid in addition to stearic acid, stearic acid salts such as calcium stearate and magnesium stearate can be used.
• the ratio of the surface modifier contained in the dehumidifier is preferably a ratio sufficient to cover at least the entire surface of the powder of the inorganic compound in order to suppress the hygroscopic function of the inorganic compound at room temperature. . Therefore, the proportion of the surface modifier can be appropriately set depending on the surface area of the inorganic compound, but in general, the proportion of the surface modifier relative to 100 parts by weight of the inorganic compound is 1 part by weight or more and 40 parts by weight or less, preferably 1 part by weight. Part to 10 parts by weight, more preferably 1 part to 5 parts by weight.
• the amount of the surface modifier exceeds 40 parts by weight relative to 100 parts by weight of the inorganic compound, the compatibility between the inorganic compound and the thermoplastic resin does not improve much with respect to the amount of surface modifier added, and in the master notch. This is not preferable because the dehumidifying agent may aggregate. 1 to 5 parts by weight more efficient The dehumidifying agent can be uniformly dispersed in the master batch.
• the inorganic compound constituting the dehumidifying agent is a powdery inorganic compound having hygroscopicity, and is a chemically hygroscopic inorganic compound that absorbs moisture by a chemical reaction with moisture, or an adsorption that absorbs moisture by adsorbing moisture.
• Functional inorganic compounds can be used. Only one inorganic compound may be used alone, or two or more inorganic compounds may be used in combination. Preferably, at least one chemically hygroscopic inorganic compound is used. If a chemically hygroscopic inorganic compound is used, moisture can be more reliably absorbed under heating conditions.
• the chemically hygroscopic inorganic compound and the adsorptive inorganic compound are used in combination.
• Inorganic compounds although moisture absorption is suppressed by the surface modifier at room temperature, actually absorb completely and are not completely inhibited.
• the combined use of the chemically hygroscopic inorganic compound and the adsorptive inorganic compound can more reliably suppress the moisture absorption of the chemically hygroscopic inorganic compound at room temperature, and the master batch can be stored for a long time. Become. The theoretical basis for this is not necessarily clear, but it is considered that the adsorptive inorganic compound absorbs moisture preferentially over the chemically hygroscopic inorganic compound at room temperature.
• Examples of the chemically hygroscopic inorganic compound include calcium carbonate, barium oxide, and aluminum oxide. These inorganic compounds are suitable for use because they are highly reactive with moisture and absorb moisture quickly, and among them, calcium carbonate is highly safe and can be most preferably used.
• the chemically hygroscopic inorganic compound used in the present invention is not limited to these as long as it is an inorganic compound that absorbs moisture by a chemical reaction with moisture, but also calcium chloride, magnesium chloride, magnesium sulfate, sulfuric acid. Calcium or the like can also be used.
• Examples of the adsorptive inorganic compound include zeolite, silica gel, diatomaceous earth, and the like. Since these are porous and excellent in hygroscopicity, they can be suitably used.
• the adsorptive inorganic compound used in the present invention is not limited to these as long as it is an inorganic compound that absorbs moisture by adsorbing moisture.
• the powder of the inorganic compound preferably has a particle size of 20 ⁇ m or less. If the particle size is 20 ⁇ m or less, even if it is added to a plastic material that has a large surface area per unit weight and good dehumidification efficiency, the moldability will be impaired, and the physical properties and appearance of the resulting molded product will deteriorate. evil It will not be made. More preferably, the particle diameter is 3 / zm or more and 10 / zm or less. Note that the particle size of 20 m or less does not necessarily mean that the particle size of all inorganic compound powders must be 20 m or less, for example, the particle size of 97% or more of powders is 20 ⁇ m or less. If so, an effect can be obtained. The particle diameter can be measured with a laser particle diameter measuring instrument, and the major axis of the measured particle can be used as the particle diameter.
• the proportion of the dehumidifying agent contained in the masterbatch is preferably 5 wt% or more and 90 wt% or less. If it is less than 5% by weight, it is not preferable because a large amount of master batch must be prepared in order to remove moisture contained in the plastic material. On the other hand, if it exceeds 90% by weight, the moldability of the master batch deteriorates, which is not preferable. More preferably, it is 20 to 80% by weight, and most preferably 40 to 60% by weight.
• the masterbatch of the present invention contains thermoplastic rosin.
• This thermoplastic resin functions as a binder that binds the dehumidifying agent and other constituents contained in the masterbatch to each other, and is sometimes referred to as a carrier resin.
• the thermoplastic resin used in the present invention include ABS resin (acrylonitrile 'butadiene' styrene), polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, SBS (styrene 'butadiene' styrene copolymer), Examples include EVA (polybutyl alcohol), polyoxyethylene, nylon, polystyrene, and polybutylene terephthalate.
• the thermoplastic resin used in the present invention is not limited to these, and other types of thermoplastic resin can be used.
• thermoplastic resin having good compatibility with the plastic material to which the masterbatch is added. More preferably, the same type of thermoplastic resin as the plastic material to which the masterbatch is added is used.
• the plastic material to which the masterbatch is added is ABS resin
• ABS resin it is most preferable to use the same type of ABS resin as the thermoplastic resin used in the masterbatch. SBS, EVA, etc., which are compatible with these, can also be suitably used. Only one type of thermoplastic resin may be used alone, or two or more types may be used in combination.
• the ratio of the thermoplastic resin contained in the masterbatch of the present invention is 90% by weight or less. preferable. More preferably, it is 40 wt% or more and 60 wt% or less. When the ratio of the thermoplastic resin is within this range, the moldability when producing the master batch is improved.
• the plastic dehumidification masterbatch of the present invention may contain additives such as a lubricant, a plasticizer, a heat stabilizer, an antioxidant and the like in addition to the dehumidifier and the thermoplastic resin. wear.
• additives such as a lubricant, a plasticizer, a heat stabilizer, an antioxidant and the like in addition to the dehumidifier and the thermoplastic resin. wear.
• a lubricant can be added to the masterbatch of the present invention. Thereby, in the master notch manufacturing process, the moldability of the master batch can be stabilized, and friction with the plastic material when the master notch is added to the plastic material can be reduced.
• a conventionally well-known thing can be used as a lubricant. Only one type of lubricant may be used alone, or two or more types may be used in combination. Specific examples of the lubricant used in the present invention include, but are not limited to, the following.
• Examples of the lubricant include hydrogen carbonate lubricants such as liquid paraffin, paraffin wax, and polyethylene wax, fatty acid lubricants such as stearic acid, metal stearates such as calcium stearate, zinc stearate, magnesium stearate, and zinc stearate. Examples include tendon-based lubricants. Among these, stearic acid is excellent in compatibility with various thermoplastic rosins, and therefore can be suitably used.
• the ratio of the lubricant contained in the master batch is preferably 15% by weight or less. This is because if the lubricant is contained in an amount of more than 15% by weight, the molding material is lost due to slippage of the constituent materials of the master batch when the master batch is molded.
• the ratio of the lubricant is more preferably 3% by weight or more and 6% by weight or less. When the ratio of the lubricant is within this range, the lubricity between the constituent materials can be improved and the moldability can be kept good when the master batch is molded. In addition, when the masterbatch is added to the plastic material, friction between the masterbatch and the plastic material can be moderately moderated.
• a plasticizer can be added to the master batch of the present invention, whereby the moldability of the master batch can be further improved.
• the plasticizer may be used for plastic molding as long as it is compatible with the thermoplastic resin contained in the masterbatch.
• Various plasticizers can be used. Only one type of plasticizer may be used alone, or two or more types may be used in combination. Specific examples of the plasticizer include, but are not limited to, the following.
• plasticizer examples include phthalate esters such as diheptyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), diisanol phthalate (DINP), and diisodecyl phthalate (DIDP).
• DHP diheptyl phthalate
• DOP di-2-ethylhexyl phthalate
• DINP diisanol phthalate
• IDDP diisodecyl phthalate
• Plasticizers aliphatic dibasic esters such as di-2-ethylhexyl adipate (DOA), disononyl adipate (DINA), di-2-ethylhexyl sebacate (DOS), epoxy soy bean oil, epoxy dihydro oil, Examples thereof include epoxy plasticizers such as epoxy stearic acid puchinole, epoxyhydrophthalate dioctyl, bisphenol A diglycidyl ether, and the like. Among these, phthalate ester plasticizers can be suitably used because they are excellent in compatibility with various thermoplastic resins and have good heat resistance and cold resistance.
• the proportion of plasticizer contained in the masterbatch is preferably 50% by weight or less. More preferably, it is 3 to 8% by weight.
• a heat stabilizer can be added to the masterbatch of the present invention, thereby preventing discoloration of the thermoplastic resin due to heating during molding of the master notch.
• various heat stabilizers used in plastic molding cases can be used. Only one type of heat stabilizer may be used alone, or two or more types may be used in combination. Specific examples of heat stabilizers include, but are not limited to, the following.
• heat stabilizer examples include aliphatic carboxylate lithium stearate, magnesium stearate, calcium laurate, calcium linoleate, calcium stearate, barium ricinoleate, barium stearate, zinc laurate, and zinc ricinoleate.
• Aliphatic carboxylate heat stabilizers such as zinc stearate, dimethyltin bis 2-ethylhexylthioglycolate, organic Zmercapands such as mono-Z dimethyltin stearoxychetyl mercaptide, dibutyltin maleate, dibutyltin Organotin maleates such as bisbutyl maleate, dibutyltin dilaurate, dibutyltin bis-2-ethylhexylthioglycolate, dibutyltin ⁇ -mercaptopropionate, and dioctyltin dilaurate, dioctyl Tin bis 2-ethylhexyl thioglycolate, etc.
• organotin heat stabilizers such as organotin carboxylates can be exemplified.
• the proportion of the heat stabilizer contained in the master batch is preferably 10% by weight or less. More preferably, it is 1% by weight or more and 3% by weight or less.
• An antioxidant can be added to the masterbatch of the present invention, whereby the thermoplastic resin can be prevented from acidifying by heating during the production of the masterbatch, thereby preventing the quality from deteriorating.
• the anti-oxidation agent various types of anti-oxidation agents generally used for plastic forming force are used as long as they are compatible with the thermoplastic resin contained in the masterbatch. be able to. Only one type of anti-oxidation agent may be used alone, or two or more types may be used in combination. Specific examples of the anti-oxidation agent include the following, but are not limited thereto.
• antioxidants examples include 2, 6 tert-butyl-4 methylphenol, n-otadecyl-3- (3 ', 5, -di-tert-butyl-4, hydroxyphenol) propionate, tetrakis [Methylene-3- (3 ', 5, di-tert-butyl 4-hydroxyphenol) propionate] Methane, tris (3,5-di-tert-butyl 4-hydroxybenzyl) isocyanurate, tri Ethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenol) propionate], 2,2, -methylenebis (4-methyl-6t-butylphenol), 4,4'-thiobis (3-methyl-) 6-t butylphenol), 4, 4'-butylidenebis (3-methyl-6-t butylphenol) and other phenolic antioxidants, dilauryl 3, 3, monothiodipropionate, dimyristyl 3, 3 -Sulfur antioxidants such as
• the proportion of the antioxidant contained in the master batch is preferably 15% by weight or less.
• the blending ratio standard of the dehumidifying agent, the thermoplastic rosin, and various additives is shown, it goes without saying that they should be prepared within a range that adds them all to 100% by weight.
• the inorganic compound powder and the surface modifier are mixed while heating to coat the surface of the inorganic compound with the surface modifier to obtain a dehumidifying agent.
• the heating temperature at this time is preferably 90 ° C or higher and 130 ° C or lower.
• agitators having a heating function can be used for mixing. For example, using a Nauter mixer, a ribbon mixer, a Henschel mixer, a super mixer, etc. with a jacket, it is possible to mix while heating by passing heated oil through the jacket.
• the dehumidifying agent obtained in the first step is cooled to 40 ° C. or lower.
• the cooling may be active cooling such as flowing cold water through the jacket of the stirrer, or may be allowed to cool.
• the cooled dehumidifying agent is mixed with the thermoplastic resin and, if necessary, various additives (such as a lubricant, a plasticizer, a heat stabilizer, and an antioxidant).
• various additives such as a lubricant, a plasticizer, a heat stabilizer, and an antioxidant.
• Various agitators can be used for mixing, as in the first step.
• the mixture obtained in the second step is heated to 90 ° C or higher and 220 ° C or lower to form a predetermined shape such as a dice, cylinder, sphere, or flat sphere. And get master notch.
• various extruders capable of being heated and kneaded can be used.
• the use of a twin-screw extruder is preferred because a master batch can be obtained with a good appearance in which inorganic compound powder is uniformly dispersed. If it is a twin-screw extruder with a vacuum function, the volatile components generated by heating the mixture can be removed, and a master batch having a better appearance can be obtained.
• the plastic dehumidification masterbatch of the present invention can be used by mixing with various plastic materials.
• plastic materials for example, ABS resin, nylon, polymethyl methacrylate, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc. are added to thermoplastic resin that requires special pre-drying in the conventional method. Can also be used. In addition, it can be used by adding to a thermoplastic resin moistened by improper storage. In addition, after use, recycle resin It is also possible to use it by adding it to (regenerated resin).
• the master batch of the present invention is added to a plastic material. It is preferable to use a master batch in which the thermoplastic resin contained in the master batch is compatible with the plastic material to which the master batch is added. It is more preferable if the thermoplastic resin contained in the masterbatch is the same type as the plastic material to be added to the masterbatch.
• the proportion of the masterbatch added to the plastic material can be determined as appropriate depending on the moisture content of the plastic material, but it is usually 6% by weight or less.
• various additives such as a plasticizer, a heat stabilizer, and an antioxidant can be added to the plastic material as necessary.
• the plastic material to which the master batch has been added is molded by various known molding methods such as an extrusion molding method, an injection molding method, and a T-die method.
• the plastic material is heated and melted.
• the plastic material and the master batch are melted together, and the dehumidifying agent contained in the master batch is dispersed in the plastic material.
• the dehumidifier since the inorganic compound powder is covered with the surface modifier, the dehumidifier has an affinity for the plastic material and is uniformly dispersed in the plastic material.
• the dehumidifying agent spreads quickly to every corner of the plastic material, and the moisture in the plastic material can be absorbed and removed efficiently. Therefore, if the master batch of the present invention is used, the plastic material can be molded without pre-drying.
• the molded body thus obtained does not have a defect in appearance due to the evaporation of moisture, although the plastic material as a raw material is not preliminarily dried.
• heating for pre-drying is not required, discoloration of plastic materials and deterioration of physical properties due to over-drying are not caused. Since it does not require long-time heating for pre-drying, the plastic material can be molded in a short time and with less energy! The As a result, it is possible to realize a molded body of a plastic material that is low in cost and is environmentally friendly.
• Example 1 acid calcium carbonate powder having a particle diameter of 10 ⁇ m is prepared as an inorganic compound, stearic acid is used as a surface modifier, polyethylene is used as a thermoplastic resin, and polyethylene wax is used as a lubricant.
• No. 1 master batch was created. Table 1 shows the composition ratio. Polyethylene wax not only functions as a lubricant, but also functions as a dispersant for dispersing calcium oxide powder in a thermoplastic resin, and also functions as a plasticizer.
• the prepared master notch (No. 1) was added to a pre-dried polyethylene resin pellet containing 1% by weight of water, and a film was formed by the T-die method. As a result, it was possible to obtain a polyethylene film having no defects in appearance.
• the master batch (No. 1) was added to recycled polyethylene resin pellets containing 0.5 wt % / 0 moisture which had not been pre-dried, and a film was formed by the T-die method. As a result, it was possible to obtain a recycled polyethylene film having no defects in appearance.
• Example 2 acid calcium carbonate powder having a particle size of 8 ⁇ m as an inorganic compound, stearic acid as a surface modifier, ABS resin and SBS as a thermoplastic resin, magnesium stearate as a lubricant, and EBS (ethylene bis-stearic acid amide) and DO P (di-2-ethylhexyl phthalate) as a plasticizer were prepared, and a master batch No. 2 was prepared through the above first to third steps. The composition ratio is shown in Table 2.
• the prepared master notch (No. 2) was added in the range of 1 wt% to 2 wt% with respect to the ABS resin that had not been pre-dried, and molded by an injection molding method. As a result, it was possible to obtain a molded body of ABS resin with no defects in appearance.
• Example 3 a calcium oxide powder having a particle size of 8 ⁇ m as an inorganic compound, stearic acid as a surface modifier, SBS as a thermoplastic resin, magnesium stearate and polyethylene wax as a lubricant, filling Calcium carbonate was prepared as an agent and blended in the proportions shown in Table 3 to prepare No. 3 and No. 4 master batches. Note that No. 3 creates a master batch through the above first to third steps, and No. 4 omits the first step in the first to third steps, and the second step A master batch was prepared by adding calcium. Next, each master batch was allowed to stand in a natural environment for 24 hours and then visually observed to examine changes in size and color.
• ABS fat 94% by weight was mixed with 6% by weight of a masterbatch that was allowed to stand for 24 hours in a natural environment and injection molded to obtain a container. The obtained container was visually observed to check for defects in appearance. The results are shown in Table 3.
• No. 3 masterbatch and No. 4 masterbatch differ in the form of the inorganic compounds contained. That is, in No. 3, the inorganic compound is covered with the surface modifier, whereas in No. 4, the inorganic compound is not covered with the surface modifier and is contained as it is. ing.
• the surface of the container of No. 3 is smooth and free of defects. There was a water-like pattern on the surface. This is because the No. 3 masterbatch sufficiently dehydrated the water in the ABS resin, while the No. 4 masterbatch cannot completely dehumidify the water in the ABS resin.
• Example 4 first, calcium oxide powder having a particle size of 10 ⁇ m and zeolite having a particle size of 10 ⁇ m were used as the inorganic compound, stearic acid was used as the surface modifier, polyethylene was used as the thermoplastic resin, and polyethylene wax was used as the lubricant.
• the master batches No. 5 and No. 6 were prepared through the first and third steps. The composition ratio is shown in Table 4. Next, after leaving the obtained master patches No. 5 and No. 6 in a natural environment for 36 hours, each of the master batches was pre-dried and regenerated containing 0.5% by weight of water. A film was formed by mixing with polyethylene resin. At this time, the masterbatch was added to the recycled polyethylene resin so that the masterbatch force was 3% by weight.
• the No. 5 masterbatch and No. 6 masterbatch differ in the inorganic compounds that make up the dehumidifier.
• No. 5 contains only one kind of acid-hypercalcium which is a chemically hygroscopic inorganic compound
• No. 6 contains zeolite, which is an additional inorganic compound in addition to calcium oxide. It differs in that it contains. None of the films formed using a masterbatch that was allowed to stand for 36 hours before use produced water-like defects. For this reason, the moisture absorption function of each masterbatch was suppressed before use, and a certain dehumidification function was ensured. It turns out that it got wet. However, particulate defects occurred only in the No. 5 film.
• Example 5 first, a titanate coupling agent, an aluminate coupling agent, and raffine were prepared as surface modifiers, and the stearic acid of master patch No. 5 prepared in Example 4 above was prepared. Instead, No. 7-9 master batches were prepared using the prepared surface modifiers. The composition is shown in Table 5.
• Example 6 first, the master batch No. 9 prepared in Example 5 above was changed to 40% by weight of calcium oxide and 10% by weight of zeolite in the master compound No. 10, and a master batch of No. 10 was prepared. . Next, the obtained master batch No. 10 was left in a natural environment in the same manner as in Example 5 above, and after 36 hours, the appearance of the master batch was visually observed to check for changes in appearance. As a result, it was confirmed that there was no change in appearance after 36 hours.
• the master batch of No. 10 is different from the master batch of No. 9 only in that it contains a dehumidifier composed of zeolite, which is only a dehumidifier having a calcium oxide power as a dehumidifier.
• the appearance of the masterbatch after standing for 36 hours was whitened for No. 9, whereas no change was observed for No. 10. From this, it can be seen that in the No. 10 master batch, the moisture absorption of the oxidizing power Lucium is more reliably inhibited.
• the combined use of a chemically hygroscopic inorganic compound and an adsorptive inorganic compound inhibits the moisture absorption of the chemically hygroscopic inorganic compound for a longer period of time than the adsorption of the chemically hygroscopic inorganic compound only by the surface modifier. It was revealed that the master batch can be stored for a long time.

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Abstract

Disclosed is a masterbatch for elimination of moisture in plastics, which contains a dehumidifying agent and a thermoplastic resin as a binder. The dehumidifying agent is composed of an inorganic compound powder having moisture absorption properties and a surface modifying agent for covering the surfaces of inorganic compound particles. The surface modifying agent improves compatibility between the inorganic compound and the thermoplastic resin, and suppresses the moisture absorption function of the inorganic compound at room temperature, while allowing the inorganic compound to perform the moisture absorption function when heated.

Description

明 細 書  Specification プラスチック除湿用マスターバッチ及びプラスチック除湿用マスター バッチの製造方法  Plastic dehumidification masterbatch and method for producing plastic dehumidification masterbatch 技術分野  Technical field [] 本発明は、プラスチック除湿用マスターバッチおよびプラスチック除湿用マスターバ ツチの製造方法に関する。  [] The present invention relates to a plastic dehumidification master batch and a method for producing a plastic dehumidification master batch. 背景技術  Background art [] 射出成形法、押出成形法、 Tダイ法等の各種プラスチック成形法にぉ 、ては、水分 を含んで!/、るプラスチック材料を加熱溶融して成形すると、加熱により水分が気化す ることによって、成形品の表面にふくれや曇りが生じたり、水紋状、あるいは魚の目の ような形状の外観上の不具合が生じやすくなる。このような成形品の外観上の不具合 は、プラスチック材料が 0. 5重量％程度の水分を含んでいるだけでも発生することが ある。そこで、プラスチック材料を成形する際には、一般に、プラスチック材料を熱風 乾燥機等により予め乾燥 (いわゆる予備乾燥)させて力も使用している。特に、 ABS 榭脂（アクリロニトリル 'ブタジエン 'スチレン共重合ィ匕合物）、ナイロン、ポリメタクリル 酸メチル、ポリ塩ィ匕ビニル等の吸湿性の高 、プラスチック材料を成形する際には予備 乾燥は欠力せな 、ものとなって!/、る。  [] In the case of various plastic molding methods such as injection molding, extrusion molding, T-die method, etc., moisture is vaporized by heating when plastic material containing water! / Is heated and melted. As a result, the surface of the molded product is likely to be blistered or cloudy, or a defect in appearance such as a water pattern or a fish eye is likely to occur. Such defects in the appearance of the molded product may occur even if the plastic material contains only about 0.5% by weight of water. Therefore, when molding a plastic material, generally, the plastic material is preliminarily dried (so-called pre-drying) with a hot air dryer or the like, and force is also used. In particular, pre-drying is not required when molding highly hygroscopic plastic materials such as ABS resin (acrylonitrile 'butadiene' styrene copolymer), nylon, polymethyl methacrylate, and poly vinyl chloride. Don't help, become things! [] ところで、プラスチックの成形に際しては従来多種多様なマスターバッチが用いられ ており、吸湿剤ある 、は吸湿性を有する添加剤を含有したマスターバッチは既に開 示されている。例えば、特開 — 号公報には、吸湿剤を含有するマスター ノ ツチが開示されている。このマスターバッチは、内添された吸湿剤により吸湿性を 発揮するプラスチックの成形品を製造する際に、プラスチック材料に吸湿剤を添加す るために用いるマスターノツチである。マスターバッチを製造する際あるいはマスター ノ ツチを保存する際に吸湿剤が吸湿すると、成形品の吸湿性が低下し、又、プラスチ ック材料を成形する際に吸湿剤がプラスチック材料中に分散し難くなる。そこでこの マスターバッチは、熱可塑性榭脂と吸湿剤カゝらなる中心部を、熱可塑性榭脂の外層 により被覆することにより、マスターバッチの製造中および保存中に中心部の吸湿剤 が吸湿するのを防ぐ構造となっている。 [] By the way, various types of master batches are conventionally used for molding plastics, and master batches containing hygroscopic agents or additives having hygroscopic properties have already been disclosed. For example, JP - A discloses a master notch containing a hygroscopic agent. This master batch is a master notch used for adding a hygroscopic agent to a plastic material when producing a plastic molded product that exhibits hygroscopicity with an internally added hygroscopic agent. If the hygroscopic agent absorbs moisture when manufacturing the masterbatch or storing the master notch, the hygroscopicity of the molded product will be reduced, and the hygroscopic agent will be dispersed in the plastic material when molding the plastic material. It becomes difficult. Therefore, this master batch is formed by coating the center part of the thermoplastic resin and the hygroscopic agent with the outer layer of the thermoplastic resin so that the hygroscopic agent in the central part is produced during the production and storage of the master batch. It has a structure that prevents moisture absorption. [] また、特開平 10— 号公報にはアルミナを含有するマスターバッチが開示さ れている。このマスターバッチは、着色された成形品を製造する際にプラスチック材 料に着色剤を添加するために用いられる着色用マスターバッチである力 着色剤の 他、アルミナ、シランカップリング剤等を含有している。アルミナは、このマスターバッ チにおいては成形品の物性改良のために含有されているものの、一般に吸湿性を有 する。  [] Also, JP-A-10- discloses a masterbatch containing alumina. This master batch contains alumina, a silane coupling agent, etc., in addition to the force colorant, which is a coloring masterbatch that is used to add a colorant to a plastic material when producing colored molded articles. ing. Alumina is generally hygroscopic although it is contained in this master batch to improve the physical properties of the molded product. 発明の開示  Disclosure of the invention 発明が解決しょうとする課題  Problems to be solved by the invention [] 従来吸湿剤や吸湿可能なアルミナを含有するマスターバッチはあるものの、プラス チック材料の成形時に除湿作用を発揮させるものではない。だから、乾燥機による予 備乾燥に代えてプラスチック材料の成形時にプラスチック材料を除湿するためのマス ターバッチとして使えるものではな力つた。 [] Although there are conventional masterbatches containing a hygroscopic agent and hygroscopic alumina, they do not exert a dehumidifying action when molding plastic materials. Therefore, it could not be used as a master batch to dehumidify plastic materials when molding plastic materials instead of pre-drying with a dryer. [] 本発明は、乾燥を目的して加熱することなぐ短時間且つ低エネルギーでプラスチ ック材料の除湿が可能であり、乾燥機による予備乾燥を経ずにプラスチック材料の成 形を可能とするプラスチック除湿用マスターバッチを提供することを課題とした。 課題を解決するための手段  [] The present invention makes it possible to dehumidify a plastic material in a short time and with low energy without heating for the purpose of drying, and it is possible to form a plastic material without preliminary drying by a dryer. It was an object to provide a master batch for plastic dehumidification. Means for solving the problem [] 一つの発明は、プラスチック材料を成形する際に混合しプラスチック材料とともに加 熱されて該プラスチック材料と溶け合うマスターバッチであって、除湿剤と、バインダ 一としての熱可塑性榭脂と、を含有し、前記除湿剤は、吸湿性を有する無機化合物 の粉末と、前記無機化合物の表面を被覆して前記無機化合物と前記熱可塑性榭脂 との相溶性を向上させるとともに、常温では前記無機化合物の吸湿機能を抑制し、 加熱時には前記無機化合物の吸湿機能を発揮させる表面修飾剤と、力もなる、前記 プラスチック材料に含まれる水分をプラスチック材料の成形時に吸収するプラスチッ ク除湿用マスターバッチである。  [] One invention is a masterbatch that is mixed when a plastic material is molded, heated together with the plastic material, and melts with the plastic material, and includes a dehumidifying agent and a thermoplastic resin as a binder. And the dehumidifying agent improves the compatibility between the inorganic compound powder and the thermoplastic resin by covering the surface of the inorganic compound with a hygroscopic powder and the inorganic compound at room temperature. A surface modifying agent that suppresses the moisture absorption function of the inorganic compound when heated, and a plastic dehumidification masterbatch that absorbs moisture contained in the plastic material when it is molded, which is also effective. [] 別の発明は、除湿剤と、バインダーとしての熱可塑性榭脂とを含有し、プラスチック 材料を成形する際に混合しプラスチック材料とともに加熱されて該プラスチック材料と 溶け合うマスターバッチの製造方法であって、吸湿性を有する無機化合物の粉末と、 表面修飾剤と、を接触させながら加熱することにより前記除湿剤を調製し、得られた 除湿剤を冷却した後に、該冷却した除湿剤と前記熱可塑性榭脂とを混合する、ブラ スチック除湿用マスターバッチの製造方法である。 [] Another invention is a method for producing a masterbatch comprising a dehumidifying agent and a thermoplastic resin as a binder, mixed when molding a plastic material, heated together with the plastic material, and melted with the plastic material. A powder of a hygroscopic inorganic compound, The dehumidifying agent is prepared by heating while contacting with a surface modifier, and after cooling the obtained dehumidifying agent, the cooled dehumidifying agent and the thermoplastic resin are mixed. It is a manufacturing method of a masterbatch. 発明の効果  The invention's effect [] 本発明のプラスチック除湿用マスターバッチ（以下、単に「マスターバッチ」と記載す ることがある。）によれば、以下の作用効果を奏する。  [] The plastic dehumidification masterbatch of the present invention (hereinafter sometimes simply referred to as "masterbatch") has the following effects. 第 1に、除湿剤を含有しているため、プラスチック材料を成形する際に混合するだけ で、除湿剤をプラスチック材料中に分散させてプラスチック材料を容易に除湿するこ とがでさる。  First, since it contains a dehumidifying agent, it can be easily dehumidified by dispersing the dehumidifying agent in the plastic material simply by mixing it when molding the plastic material. [] 第 2に、熱可塑性榭脂との相溶性を向上させる表面修飾剤により無機化合物が被 覆されて除湿剤が構成されていることにより、マスターバッチを製造する際に、熱可塑 性榭脂中に除湿剤を分散させるのが容易である。したがって、マスターバッチ中に均 等に除湿剤を含有させることができ、プラスチック材料にこのマスターバッチを定量混 合することにより，プラスチック材料に定量の除湿剤を確実に混合して除湿することが できる。  [] Second, when a masterbatch is produced, a thermoplastic resin is formed by covering the inorganic compound with a surface modifier that improves the compatibility with the thermoplastic resin and forming a dehumidifier. It is easy to disperse the dehumidifier in the cocoon. Therefore, a dehumidifying agent can be uniformly contained in the masterbatch, and by mixing the masterbatch quantitatively with the plastic material, the dehumidifying agent can be reliably mixed with the plastic material and dehumidified. . [] 第 3に、除湿剤を構成する表面修飾剤は、吸湿性を有する無機化合物を被覆する ことにより常温では無機化合物の吸湿機能を抑制し、加熱時には無機化合物の吸湿 機能を発揮させるため、除湿剤は、使用前に常温で保存されているときには吸湿し にくぐ使用時にプラスチック材料とともに加熱されると吸湿しやすくなる。したがって 、このマスターバッチは、使用前には無機化合物の吸湿機能が温存され、使用時に は無機化合物の吸湿機能が確実に発揮されてプラスチック材料を除湿することがで きる。  [] Thirdly, the surface modifier that constitutes the dehumidifying agent coats an hygroscopic inorganic compound, thereby suppressing the hygroscopic function of the inorganic compound at room temperature and exerting the hygroscopic function of the inorganic compound during heating. When the dehumidifier is stored at room temperature before use, it easily absorbs moisture when heated together with the plastic material during use. Therefore, this masterbatch preserves the hygroscopic function of the inorganic compound before use, and when used, the hygroscopic function of the inorganic compound is reliably exerted to dehumidify the plastic material. [] 第 4に、除湿剤が常温では吸湿しにくいため、保存時や使用準備時にマスターバッ チが通常の湿度環境下に暴露されたとしても、除湿剤の除湿機能が損なわれにくい  [] Fourth, since the dehumidifying agent is difficult to absorb moisture at room temperature, the dehumidifying function of the dehumidifying agent is unlikely to be impaired even if the master batch is exposed to a normal humidity environment during storage or preparation for use. [] 上記の作用効果を奏することにより、この発明のマスターバッチによれば、プラスチ ック材料を成形する際にプラスチック材料と混合することによりプラスチック材料を容 易に除湿することができ、従来のプラスチック材料の成形工程にぉ ヽてプラスチック 材料を予備乾燥する工程を省略することができる。したがって、プラスチック材料の成 形工程を短縮することができ、従来よりも短時間且つ低エネルギーでプラスチック材 料を成形することができる。また、予備乾燥のみを目的としてプラスチック材料を加熱 する必要がな 、ため、プラスチック材料が過熱されて劣化するのを防ぐこともできる。 [] By exerting the above-described effects, according to the master batch of the present invention, the plastic material can be easily dehumidified by mixing with the plastic material when molding the plastic material. In the plastic material molding process The step of pre-drying the material can be omitted. Therefore, the molding process of the plastic material can be shortened, and the plastic material can be molded in a shorter time and with lower energy than before. In addition, since it is not necessary to heat the plastic material only for pre-drying, it is possible to prevent the plastic material from being overheated and deteriorated. [] 次に、他の発明のプラスチック除湿用マスターバッチの製造方法によれば、無機化 合物の粉末と、表面修飾剤とを接触させながら加熱することにより、非加熱の場合に 比べ、より確実に表面修飾剤で無機化合物の表面全体を被覆することができる。した がって、除湿剤を効率よく調製し、プラスチック除湿用マスターバッチを効率よく得る ことができる。  [] Next, according to the method for producing a plastic dehumidification masterbatch of another invention, the inorganic compound powder and the surface modifier are heated while being brought into contact with each other, compared with the case of non-heating. The entire surface of the inorganic compound can be more reliably coated with the surface modifier. Therefore, it is possible to efficiently prepare a dehumidifying agent and efficiently obtain a master batch for plastic dehumidification. 発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION [] 本発明のプラスチック除湿用マスターバッチは、プラスチック材料を成形する際に 使用してプラスチック材料を除湿するマスターバッチである。このマスターバッチは、 基本成分として、少なくとも除湿剤と、バインダーとしての熱可塑性榭脂とを含有して V、る。プラスチック材料を成形する際にこのマスターノツチをプラスチック材料に混合 すると、成形時の加熱によって熱可塑性榭脂とプラスチック材料とが溶け合い、除湿 剤がプラスチック材料中に分散してプラスチック材料中の水分を吸収することができ る。 [] The plastic dehumidification masterbatch of the present invention is a masterbatch that is used when molding a plastic material and dehumidifies the plastic material. This master batch contains at least a dehumidifying agent and a thermoplastic resin as a binder as basic components. When this master notch is mixed with the plastic material when molding the plastic material, the thermoplastic resin and the plastic material are melted by the heating during molding, and the dehumidifying agent is dispersed in the plastic material to absorb the moisture in the plastic material. can do. [] マスターバッチを構成する除湿剤は、吸湿性を有する無機化合物の粉末と、無機 化合物の表面を被覆する表面修飾剤とにより構成されている。  [] The dehumidifying agent constituting the masterbatch is composed of an inorganic compound powder having hygroscopicity and a surface modifier for coating the surface of the inorganic compound. [] 除湿剤を構成する表面修飾剤は、無機化合物の各粒子の表面を被覆して、無機 化合物と熱可塑性榭脂との相溶性を向上させるとともに、常温では無機化合物の吸 湿機能を抑制し、加熱時には無機化合物の吸湿機能を発揮させる物質である。なお 、ここで言う「無機化合物の吸湿機能を抑制」とは、無機化合物の吸湿を阻害すること を意味し、「無機化合物の吸湿機能を発揮させる」とは、無機化合物の吸湿機能をほ とんど阻害しないことを意味する。このような表面修飾剤として、例えば、チタネート系 カップリング剤、アルミニウム系カップリング剤、ノ《ラフィン、ステアリン酸類等を用いる ことができる。これらの表面修飾剤は、無機化合物と熱可塑性榭脂との双方に対して 親和性を有しており、無機化合物の粉末の表面に化学的あるいは物理的に結合す ることにより無機化合物と熱可塑性榭脂との相溶性を向上させることができる。また、 無機化合物と接触させて加熱し、無機化合物の表面全体を被覆することにより、常温 では無機化合物の吸湿機能を抑制し、加熱時には無機化合物の吸湿機能を確実に 発揮させることができる。その理論的な根拠は必ずしも明らかではないが、これらの表 面修飾剤は、常温ではその組織が水分子を通過させにくい状態であり、加熱により 水分子が通過可能に組織が緩んだ状態に変化するものと考えられる。表面修飾剤 は、これらに限定されるものではなぐまた、一種類だけを単独で使用してもよぐ 2種 類以上を組み合わせて使用してもょ 、。 [] The surface modifier constituting the dehumidifying agent coats the surface of each particle of the inorganic compound to improve the compatibility between the inorganic compound and the thermoplastic resin, and at the same time has a function of absorbing moisture of the inorganic compound. It is a substance that suppresses and exhibits the hygroscopic function of inorganic compounds during heating. As used herein, “suppressing the hygroscopic function of an inorganic compound” means inhibiting the hygroscopic function of the inorganic compound, and “exhibiting the hygroscopic function of an inorganic compound” means the hygroscopic function of the inorganic compound. It means not disturbing. Examples of such surface modifiers that can be used include titanate coupling agents, aluminum coupling agents, R << raffin, and stearic acids. These surface modifiers have an affinity for both inorganic compounds and thermoplastic resins and bind chemically or physically to the surface of the inorganic compound powder. This can improve the compatibility between the inorganic compound and the thermoplastic rosin. In addition, by heating in contact with the inorganic compound and covering the entire surface of the inorganic compound, the hygroscopic function of the inorganic compound can be suppressed at room temperature, and the hygroscopic function of the inorganic compound can be reliably exerted during heating. The theoretical basis for this is not always clear, but these surface modifiers are in a state where the tissue is difficult for water molecules to pass through at room temperature, and the tissue changes into a relaxed state that allows water molecules to pass through heating. It is thought to do. Surface modifiers are not limited to these, and only one type may be used alone, or two or more types may be used in combination. [] 上記チタネート系カップリング剤としては、従来公知のものを使用できる。例えば、ィ ソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジォクチルパイロホスフ エート)チタネート、テトラオクチルビス (ジトリデシルホスフアイト)チタネート、ビス (ジォ クチルパイロホスフェート)ォキシアセテートチタネート等を使用することができる。上 記アルミニウム系カップリング剤としては、従来公知のものを使用できる。例えば、ァ ルミ-ゥムイソプロピレート、アルミニウムェチレート、アルミニウムトリス（ェチルァセト アセテート）、ェチルァセトアセテートアルミニウムジイソプロピレート等を使用すること ができる。上記パラフィンとしては、従来公知のものを使用できる。例えば、流動パラ フィン、ノ《ラフィンワックス、ポリエチレンワックス等を使用することができる。上記ステ アリン酸類としては、ステアリン酸の他、ステアリン酸カルシウム、ステアリン酸マグネ シゥム等のステアリン酸の塩類を使用することができる。 [] As the titanate coupling agent, conventionally known ones can be used. For example, use isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate Can do. A conventionally well-known thing can be used as said aluminum type coupling agent. For example, aluminum isopropylate, aluminum ethylate, aluminum tris (ethyl acetate acetate), ethyl acetate acetate aluminum diisopropylate and the like can be used. A conventionally well-known thing can be used as said paraffin. For example, fluid paraffin, polyethylene << raffin wax, polyethylene wax and the like can be used. As the stearic acid, in addition to stearic acid, stearic acid salts such as calcium stearate and magnesium stearate can be used. [] 除湿剤に含有される表面修飾剤の割合は、常温時に無機化合物の吸湿機能を抑 制するために、少なくとも無機化合物の粉末の表面全体を被覆するに足る割合とす るのが好ましい。したがって、表面修飾剤の割合は無機化合物の表面積により適宜 設定することができるが、一般には、無機化合物 100重量部に対する表面修飾剤の 割合は、 1重量部以上 40重量部以下、好ましくは 1重量部以上 10重量部以下、更に 好ましくは 1重量部以上 5重量部以下である。無機化合物 100重量部に対して表面 修飾剤を 40重量部より多くすると、無機化合物と熱可塑性榭脂との相溶性は表面修 飾剤の添加量に対してあまり向上しないうえに、マスターノツチ中で除湿剤が凝集す る可能性があるため好ましくない。 1重量部以上 5重量部以下とすれば、より効率よく 除湿剤をマスターバッチ中に均一〖こ分散させることができる。 [] The ratio of the surface modifier contained in the dehumidifier is preferably a ratio sufficient to cover at least the entire surface of the powder of the inorganic compound in order to suppress the hygroscopic function of the inorganic compound at room temperature. . Therefore, the proportion of the surface modifier can be appropriately set depending on the surface area of the inorganic compound, but in general, the proportion of the surface modifier relative to 100 parts by weight of the inorganic compound is 1 part by weight or more and 40 parts by weight or less, preferably 1 part by weight. Part to 10 parts by weight, more preferably 1 part to 5 parts by weight. If the amount of the surface modifier exceeds 40 parts by weight relative to 100 parts by weight of the inorganic compound, the compatibility between the inorganic compound and the thermoplastic resin does not improve much with respect to the amount of surface modifier added, and in the master notch. This is not preferable because the dehumidifying agent may aggregate. 1 to 5 parts by weight more efficient The dehumidifying agent can be uniformly dispersed in the master batch. [] 除湿剤を構成する無機化合物は、吸湿性を有する粉末状の無機化合物であり、水 分との化学反応により吸湿する化学吸湿性無機化合物、あるいは水分を吸着するこ とにより吸湿する吸着性無機化合物を用いることができる。無機化合物は、 1種類だ けを単独で使用してもよぐ 2種類以上を併用してもよい。好ましくは、化学吸湿性無 機化合物を少なくとも 1種類使用する。化学吸湿性無機化合物を用いれば、加熱条 件下でより確実に吸湿することができる。より好ましくは、化学吸湿性無機化合物と、 吸着性無機化合物とを併用する。無機化合物は、常温で表面修飾剤により吸湿が抑 制されているものの、実際には完全に阻害できているわけではなく徐々に吸湿する。 しかしながら、化学吸湿性無機化合物と吸着性無機化合物とを併用することにより、 常温時に化学吸湿性無機化合物が吸湿するのをより確実に抑制することができ、マ スターバッチの長時間保存が可能となる。その理論的な根拠は必ずしも明らかでは な 、が、常温では吸着性無機化合物が化学吸湿性無機化合物よりも優先して吸湿 するためであると考えられる。  [] The inorganic compound constituting the dehumidifying agent is a powdery inorganic compound having hygroscopicity, and is a chemically hygroscopic inorganic compound that absorbs moisture by a chemical reaction with moisture, or an adsorption that absorbs moisture by adsorbing moisture. Functional inorganic compounds can be used. Only one inorganic compound may be used alone, or two or more inorganic compounds may be used in combination. Preferably, at least one chemically hygroscopic inorganic compound is used. If a chemically hygroscopic inorganic compound is used, moisture can be more reliably absorbed under heating conditions. More preferably, the chemically hygroscopic inorganic compound and the adsorptive inorganic compound are used in combination. Inorganic compounds, although moisture absorption is suppressed by the surface modifier at room temperature, actually absorb completely and are not completely inhibited. However, the combined use of the chemically hygroscopic inorganic compound and the adsorptive inorganic compound can more reliably suppress the moisture absorption of the chemically hygroscopic inorganic compound at room temperature, and the master batch can be stored for a long time. Become. The theoretical basis for this is not necessarily clear, but it is considered that the adsorptive inorganic compound absorbs moisture preferentially over the chemically hygroscopic inorganic compound at room temperature. [] 上記化学吸湿性無機化合物としては、例えば、酸ィ匕カルシウム、酸化バリウム、及 び酸ィ匕アルミニウムを挙げることができる。これらの無機化合物は、水分との反応性が 高く速やかに吸湿するため好適に使用することができ、中でも酸ィ匕カルシウムは安全 性が高く最も好適に使用することができる。尚、本発明に使用する化学吸湿性無機 化合物は、水分との化学反応により吸湿する無機化合物であればこれらに限定され るものではなぐ他に、塩ィ匕カルシウム、塩化マグネシウム、硫酸マグネシウム、硫酸 カルシウム等を使用することもできる。  [] Examples of the chemically hygroscopic inorganic compound include calcium carbonate, barium oxide, and aluminum oxide. These inorganic compounds are suitable for use because they are highly reactive with moisture and absorb moisture quickly, and among them, calcium carbonate is highly safe and can be most preferably used. The chemically hygroscopic inorganic compound used in the present invention is not limited to these as long as it is an inorganic compound that absorbs moisture by a chemical reaction with moisture, but also calcium chloride, magnesium chloride, magnesium sulfate, sulfuric acid. Calcium or the like can also be used. [] 上記吸着性無機化合物としては、例えば、ゼォライト、シリカゲル、珪藻土等が挙げ られる。これらは多孔質であり、吸湿性に優れるため好適に使用することができる。尚 、本発明に使用する吸着性無機化合物は、水分を吸着することにより吸湿する無機 化合物であればこれらに限定されるものではない。  [] Examples of the adsorptive inorganic compound include zeolite, silica gel, diatomaceous earth, and the like. Since these are porous and excellent in hygroscopicity, they can be suitably used. The adsorptive inorganic compound used in the present invention is not limited to these as long as it is an inorganic compound that absorbs moisture by adsorbing moisture. [] 無機化合物の粉末は、粒子径が 20 μ m以下であることが好まし 、。粒子径が 20 μ m以下であれば、単位重量あたりの表面積が大きぐ除湿効率が良いだけでなぐプ ラスチック材料に添加しても、成形性を損ねたり、得られる成形体の物性や外観を悪 化させることがない。さらに好ましくは、粒子径が 3 /z m以上 10 /z m以下である。尚、 粒子径が 20 m以下とは、必ずしも全ての無機化合物の粉末の粒子径が 20 m以 下でなければならないのではなぐ大部分、例えば 97%以上の粉末の粒子径が 20 μ m以下であれば、効果を得ることができる。また、粒子径はレーザー粒子径測定器 により測定することができ、測定した粒子の長径を粒子径とすることができる。 [] The powder of the inorganic compound preferably has a particle size of 20 µm or less. If the particle size is 20 μm or less, even if it is added to a plastic material that has a large surface area per unit weight and good dehumidification efficiency, the moldability will be impaired, and the physical properties and appearance of the resulting molded product will deteriorate. evil It will not be made. More preferably, the particle diameter is 3 / zm or more and 10 / zm or less. Note that the particle size of 20 m or less does not necessarily mean that the particle size of all inorganic compound powders must be 20 m or less, for example, the particle size of 97% or more of powders is 20 μm or less. If so, an effect can be obtained. The particle diameter can be measured with a laser particle diameter measuring instrument, and the major axis of the measured particle can be used as the particle diameter. [] マスターバッチに含まれる除湿剤の割合は、 5重量％以上 90重量％以下が好まし い。 5重量％より少ない場合、プラスチック材料に含まれる水分を除去するために多 量のマスターバッチをカ卩えなければならないため、好ましくない。また、 90重量％を 超えると、マスターバッチの成形性が悪ィ匕するので、好ましくない。より好ましくは、 20 重量％以上 80%以下、最も好ましくは、 40重量％以上 60重量％以下である。  [] The proportion of the dehumidifying agent contained in the masterbatch is preferably 5 wt% or more and 90 wt% or less. If it is less than 5% by weight, it is not preferable because a large amount of master batch must be prepared in order to remove moisture contained in the plastic material. On the other hand, if it exceeds 90% by weight, the moldability of the master batch deteriorates, which is not preferable. More preferably, it is 20 to 80% by weight, and most preferably 40 to 60% by weight. [] 本発明のマスターバッチには、熱可塑性榭脂が含有される。この熱可塑性榭脂は、 マスターバッチ中に含有される除湿剤や他の構成成分を互 、に結合するバインダー として機能するものであって、キャリアレジンなどと称される場合もある。本発明におい て使用する熱可塑性榭脂は、例えば、 ABS榭脂（アクリロニトリル 'ブタジエン'スチレ ン）、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリメタクリル酸メチル 、 SBS (スチレン 'ブタジエン 'スチレン共重合体）、 EVA (ポリビュルアルコール）、ポ リオキシエチレン、ナイロン、ポリスチレン、ポリブチレンテレフタレート等が挙げられる 。本発明において使用する熱可塑性榭脂は、これらに限定されるものではなぐ他の 種類の熱可塑性榭脂を使用することもできる。  [] The masterbatch of the present invention contains thermoplastic rosin. This thermoplastic resin functions as a binder that binds the dehumidifying agent and other constituents contained in the masterbatch to each other, and is sometimes referred to as a carrier resin. Examples of the thermoplastic resin used in the present invention include ABS resin (acrylonitrile 'butadiene' styrene), polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, SBS (styrene 'butadiene' styrene copolymer), Examples include EVA (polybutyl alcohol), polyoxyethylene, nylon, polystyrene, and polybutylene terephthalate. The thermoplastic resin used in the present invention is not limited to these, and other types of thermoplastic resin can be used. [] 熱可塑性榭脂は、マスターバッチを添加する対象となるプラスチック材料との相溶 性が良好なものを使用するのが好ましい。さらに好ましくは、マスターバッチを添加す る対象となるプラスチック材料と同種の熱可塑性榭脂を使用するのがよ 、。例えば、 マスターバッチを添加する対象となるプラスチック材料が ABS榭脂であるときは、マス ターバッチに使用する熱可塑性樹脂としては、同じ種類の ABS榭脂を用いるのが最 も好ましぐ ABS榭脂と相溶性を有する SBSあるいは EVAなども好適に使用すること ができる。熱可塑性榭脂は、 1種類のみを単独で使用してもよぐ 2種類以上を併用し てもよい。  [] It is preferable to use a thermoplastic resin having good compatibility with the plastic material to which the masterbatch is added. More preferably, the same type of thermoplastic resin as the plastic material to which the masterbatch is added is used. For example, when the plastic material to which the masterbatch is added is ABS resin, it is most preferable to use the same type of ABS resin as the thermoplastic resin used in the masterbatch. SBS, EVA, etc., which are compatible with these, can also be suitably used. Only one type of thermoplastic resin may be used alone, or two or more types may be used in combination. [] 本発明のマスターバッチ中に含まれる熱可塑性榭脂の割合は、 90重量％以下が 好ましい。より好ましくは、 40重量％以上 60重量％以下である。熱可塑性榭脂の割 合がこの範囲であれば、マスターバッチを製造する際の成形性が良好になる。 [] The ratio of the thermoplastic resin contained in the masterbatch of the present invention is 90% by weight or less. preferable. More preferably, it is 40 wt% or more and 60 wt% or less. When the ratio of the thermoplastic resin is within this range, the moldability when producing the master batch is improved. [] 本発明のプラスチック除湿用マスターバッチには、除湿剤及び熱可塑性榭脂の他 に、例えば、滑剤、可塑剤、熱安定剤、酸化防止剤、等の添加剤を含有することがで きる。 [] The plastic dehumidification masterbatch of the present invention may contain additives such as a lubricant, a plasticizer, a heat stabilizer, an antioxidant and the like in addition to the dehumidifier and the thermoplastic resin. wear. [] 本発明のマスターバッチには、滑剤を添加することができる。それにより、マスター ノ ツチの製造工程において、マスターバッチの成形性を安定させるとともに、マスター ノ ツチをプラスチック材料に添加した際における当該プラスチック材料との摩擦を低 減することができる。滑剤としては従来公知のものを使用することができる。滑剤は、 1 種類のみを単独で使用してもよぐ 2種類以上を併用してもよい。本発明に使用する 滑剤としては、具体的には以下のものが挙げられる力 これらに限定されるものでは ない。  [] A lubricant can be added to the masterbatch of the present invention. Thereby, in the master notch manufacturing process, the moldability of the master batch can be stabilized, and friction with the plastic material when the master notch is added to the plastic material can be reduced. A conventionally well-known thing can be used as a lubricant. Only one type of lubricant may be used alone, or two or more types may be used in combination. Specific examples of the lubricant used in the present invention include, but are not limited to, the following. [] 上記滑剤としては、流動パラフィン、パラフィンワックス、ポリエチレンワックス等の炭 化水素系滑剤、ステアリン酸等の脂肪酸系滑剤、ステアリン酸カルシウム、ステアリン 酸亜鉛、ステアリン酸マグネシウム、ステアリン酸亜鉛等の金属せつけん系滑剤等を 例示することができる。中でも、ステアリン酸は、各種の熱可塑性榭脂との相溶性に 優れるため、好適に用いることができる。  [] Examples of the lubricant include hydrogen carbonate lubricants such as liquid paraffin, paraffin wax, and polyethylene wax, fatty acid lubricants such as stearic acid, metal stearates such as calcium stearate, zinc stearate, magnesium stearate, and zinc stearate. Examples include tendon-based lubricants. Among these, stearic acid is excellent in compatibility with various thermoplastic rosins, and therefore can be suitably used. [] マスターバッチ中に含有される滑剤の割合は、 15重量％以下が好ましい。滑剤を 1 5重量％より多く含有させると、マスターバッチを成形する際に、マスターバッチの構 成材料が互いにスリップすることにより、力えって成形性が損なわれるためである。滑 剤の割合は、さらに好ましくは、 3重量％以上 6重量％以下である。滑剤の割合がこ の範囲であれば、マスターバッチを成形する際に構成材料同士の潤滑性を向上させ 、成形性を良好に保つことができる。また、マスターバッチをプラスチック材料に添カロ した際は、マスターバッチとプラスチック材料との摩擦を適度に緩和することができる  [] The ratio of the lubricant contained in the master batch is preferably 15% by weight or less. This is because if the lubricant is contained in an amount of more than 15% by weight, the molding material is lost due to slippage of the constituent materials of the master batch when the master batch is molded. The ratio of the lubricant is more preferably 3% by weight or more and 6% by weight or less. When the ratio of the lubricant is within this range, the lubricity between the constituent materials can be improved and the moldability can be kept good when the master batch is molded. In addition, when the masterbatch is added to the plastic material, friction between the masterbatch and the plastic material can be moderately moderated. [] 本発明のマスターバッチには、可塑剤を添加することができ、それによりマスターバ ツチの成形性をさらに向上させることができる。可塑剤は、マスターバッチ中に含有さ れる熱可塑性榭脂と相溶性を有するものであればよぐプラスチック成形用に用いら れる種々の可塑剤を使用することができる。可塑剤は、 1種類のみを単独で使用して もよぐ 2種類以上を併用してもよい。可塑剤としては、具体的には以下のものが挙げ られる力 これらに限定されるものではない。 [] A plasticizer can be added to the master batch of the present invention, whereby the moldability of the master batch can be further improved. The plasticizer may be used for plastic molding as long as it is compatible with the thermoplastic resin contained in the masterbatch. Various plasticizers can be used. Only one type of plasticizer may be used alone, or two or more types may be used in combination. Specific examples of the plasticizer include, but are not limited to, the following. [] 上記可塑剤としては、例えば、フタル酸ジヘプチル（DHP)、フタル酸ジ 2ェチルへ キシル (DOP)、フタル酸ジイソノ-ル（DINP)、フタル酸ジイソデシル (DIDP)等の フタル酸エステル系可塑剤、アジピン酸ジ 2ェチルへキシル（DOA)、アジピン酸ジィ ソノニル (DINA)、セバシン酸ジ 2ェチルへキシル (DOS)等の脂肪族二塩基酸エス テノレ、エポキシィヒ大豆油、エポキシィヒアマ二油、エポキシステアリン酸プチノレ、ェポキ シヒドロフタル酸ジォクチル、ビスフエノール Aジグリシジルエーテル等のエポキシ系 可塑剤等を例示することができる。中でも、フタル酸エステル系可塑剤は、各種の熱 可塑性榭脂との相溶性に優れ、耐熱性、耐寒性が良好であるため、好適に用いるこ とができる。マスターバッチ中に含有される可塑剤の割合は、 50重量％以下が好まし い。さらに好ましくは、 3重量％以上 8重量％以下である。  [] Examples of the plasticizer include phthalate esters such as diheptyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), diisanol phthalate (DINP), and diisodecyl phthalate (DIDP). Plasticizers, aliphatic dibasic esters such as di-2-ethylhexyl adipate (DOA), disononyl adipate (DINA), di-2-ethylhexyl sebacate (DOS), epoxy soy bean oil, epoxy dihydro oil, Examples thereof include epoxy plasticizers such as epoxy stearic acid puchinole, epoxyhydrophthalate dioctyl, bisphenol A diglycidyl ether, and the like. Among these, phthalate ester plasticizers can be suitably used because they are excellent in compatibility with various thermoplastic resins and have good heat resistance and cold resistance. The proportion of plasticizer contained in the masterbatch is preferably 50% by weight or less. More preferably, it is 3 to 8% by weight. [] 本発明のマスターバッチには、熱安定剤を添加することができ、それによりマスター ノ ツチ成形時の加熱による熱可塑性榭脂の変色を防ぐことができる。熱安定剤として は、プラスチックの成形カ卩ェにおいて用いられる種々の熱安定剤を使用することがで きる。熱安定剤は、 1種類のみを単独で使用してもよぐ 2種類以上を併用してもよい 。熱安定剤としては、具体的には以下のものが挙げられる力 これらに限定されるも のではない。  [] A heat stabilizer can be added to the masterbatch of the present invention, thereby preventing discoloration of the thermoplastic resin due to heating during molding of the master notch. As the heat stabilizer, various heat stabilizers used in plastic molding cases can be used. Only one type of heat stabilizer may be used alone, or two or more types may be used in combination. Specific examples of heat stabilizers include, but are not limited to, the following. [] 上記熱安定剤としては、脂肪族カルボン酸塩ステアリン酸リチウム、ステアリン酸マ グネシゥム、ラウリン酸カルシウム、リノール酸カルシウム、ステアリン酸カルシウム、リ シノール酸バリウム、ステアリン酸バリウム、ラウリン酸亜鉛、リシノール酸亜鉛、ステア リン酸亜鉛等の脂肪族カルボン酸塩熱安定剤、ジメチルスズビス 2—ェチルへキシ ルチオグリコレート、モノ Zジメチルスズステアロキシェチルメルカプタイド等の有機ス ズメルカプタイド類、ジブチルスズマレエート、ジブチルスズビスブチルマレエート、ジ ブチルスズジラウレート、ジブチルスズビス 2—ェチルへキシルチオグリコレート、ジ プチルスズ β メルカプトプロピオネート等の有機スズマレエート類、およびジォクチ ルスズジラウレート、ジォクチルスズビス 2—ェチルへキシルチオグリコレート等の 有機スズカルボキシレート類等の各種有機スズ系熱安定剤を例示することができる。 マスターバッチ中に含有される熱安定剤の割合は、 10重量％以下が好ましい。より 好ましくは、 1重量％以上 3重量％以下である。 [] Examples of the heat stabilizer include aliphatic carboxylate lithium stearate, magnesium stearate, calcium laurate, calcium linoleate, calcium stearate, barium ricinoleate, barium stearate, zinc laurate, and zinc ricinoleate. , Aliphatic carboxylate heat stabilizers such as zinc stearate, dimethyltin bis 2-ethylhexylthioglycolate, organic Zmercapands such as mono-Z dimethyltin stearoxychetyl mercaptide, dibutyltin maleate, dibutyltin Organotin maleates such as bisbutyl maleate, dibutyltin dilaurate, dibutyltin bis-2-ethylhexylthioglycolate, dibutyltin β-mercaptopropionate, and dioctyltin dilaurate, dioctyl Tin bis 2-ethylhexyl thioglycolate, etc. Various organotin heat stabilizers such as organotin carboxylates can be exemplified. The proportion of the heat stabilizer contained in the master batch is preferably 10% by weight or less. More preferably, it is 1% by weight or more and 3% by weight or less. [] 本発明のマスターバッチには、酸化防止剤を添加することができ、それによりマスタ 一バッチ製造時に熱可塑性榭脂が加熱により酸ィ匕して品質が劣化するのを防ぐこと ができる。酸ィ匕防止剤としては、マスターバッチに含まれる熱可塑性榭脂と相溶性を 有するものであればよぐプラスチックの成形力卩ェに一般的に用いられる種々の酸ィ匕 防止剤を使用することができる。酸ィ匕防止剤は、 1種類のみを単独で使用してもよぐ 2種類以上を併用してもよい。酸ィ匕防止剤としては、具体的には以下のものが挙げら れるが、これらに限定されるものはない。  [] An antioxidant can be added to the masterbatch of the present invention, whereby the thermoplastic resin can be prevented from acidifying by heating during the production of the masterbatch, thereby preventing the quality from deteriorating. . As the anti-oxidation agent, various types of anti-oxidation agents generally used for plastic forming force are used as long as they are compatible with the thermoplastic resin contained in the masterbatch. be able to. Only one type of anti-oxidation agent may be used alone, or two or more types may be used in combination. Specific examples of the anti-oxidation agent include the following, but are not limited thereto. [] 上記酸化防止剤としては、 2, 6 ジー tーブチルー 4 メチルフエノール、 n オタ タデシルー 3— (3' , 5，—ジ— t—ブチル—4，ヒドロキシフエ-ル）プロピオネート、テ トラキス一 [メチレン一 3— (3' , 5，一ジ一 t—ブチル 4—ヒドロキシフエ-ル）プロピ ォネート]メタン、トリス（3, 5—ジ一 t—ブチル 4—ヒドロキシベンジル)イソシァヌレ ート、トリエチレングリコール ビス [3— (3— t—ブチルー 4ーヒドロキシー5—メチ ルフエ-ル）プロピオネート]、 2, 2，ーメチレンビス一（4ーメチルー 6 t—ブチルフエ ノール）、 4, 4'ーチォビス一（3—メチルー 6— t ブチルフエノール）、 4, 4'ーブチリ デンビスー（3—メチルー 6— t ブチルフエノール）等のフエノール系酸化防止剤、ジ ラウリル 3, 3，一チォジプロピオネート、ジミリスチルー 3, 3，ーチオシプロピオネー ト、ジステアリル—3, 3，一チォジプロピオネート、ペンタエリスリトールテトラキス（3— ラウリルチオプロピオネート）等の硫黄系酸化防止剤、トリスノユルフェ-ルホスフアイ ト、ジステアリルペンタエリスリトールジホスフアイト、トリス（2, 4 ジ一 t—ブチルフエ -ル）ホスファイト、テトラキス（2, 4 ジ一 t—ブチルフエ-ル） 4, 4'—ビフエ-レン ージーホスファイト等のリン酸系酸ィ匕防止剤等を例示することができる。マスターバッ チ中に含有される酸化防止剤の割合は、 15重量％以下が好ましい。なお、除湿剤、 熱可塑性榭脂および各種添加剤の配合割合基準を示したが、それらをすベて加算 して 100重量％になるような範囲内で調製すべきことはいうまでもない。  [] Examples of the antioxidant include 2, 6 tert-butyl-4 methylphenol, n-otadecyl-3- (3 ', 5, -di-tert-butyl-4, hydroxyphenol) propionate, tetrakis [Methylene-3- (3 ', 5, di-tert-butyl 4-hydroxyphenol) propionate] Methane, tris (3,5-di-tert-butyl 4-hydroxybenzyl) isocyanurate, tri Ethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenol) propionate], 2,2, -methylenebis (4-methyl-6t-butylphenol), 4,4'-thiobis (3-methyl-) 6-t butylphenol), 4, 4'-butylidenebis (3-methyl-6-t butylphenol) and other phenolic antioxidants, dilauryl 3, 3, monothiodipropionate, dimyristyl 3, 3 -Sulfur antioxidants such as thiocypropionate, distearyl-3,3, monothiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), trisnoyl ferrule phosphate, distearyl pentaerythritol di Phosphate acids such as phosphite, tris (2,4 di-t-butylphenol) phosphite, tetrakis (2,4 di-tert-butylphenol) 4,4'-biphenyl-enzyme phosphite An anti-wrinkle agent and the like can be exemplified. The proportion of the antioxidant contained in the master batch is preferably 15% by weight or less. In addition, although the blending ratio standard of the dehumidifying agent, the thermoplastic rosin, and various additives is shown, it goes without saying that they should be prepared within a range that adds them all to 100% by weight. [] 以下、本発明のマスターバッチの製造方法について説明する。本発明のマスター ノ ツチは、以下の第 1〜3の工程を経て製造することができる。 [] Hereinafter, a method for producing a master batch of the present invention will be described. Master of the present invention The notch can be manufactured through the following first to third steps. [] [第 1の工程] [] [First step] まず、第 1の工程において、無機化合物の粉末と、表面修飾剤とを加熱しながら混 合することにより、無機化合物の表面を表面修飾剤で被覆して除湿剤を得る。このと きの加熱温度は 90°C以上 130°C以下が好ましい。混合には、加熱機能を有する各 種攪拌機を用いることができる。例えば、ジャケット付きの、ナウターミキサー、リボンミ キサ一、ヘンシェルミキサー、スーパーミキサー、などを用い、ジャケットに加熱された オイル等を通すことにより加熱しながら混合することができる。  First, in the first step, the inorganic compound powder and the surface modifier are mixed while heating to coat the surface of the inorganic compound with the surface modifier to obtain a dehumidifying agent. The heating temperature at this time is preferably 90 ° C or higher and 130 ° C or lower. Various agitators having a heating function can be used for mixing. For example, using a Nauter mixer, a ribbon mixer, a Henschel mixer, a super mixer, etc. with a jacket, it is possible to mix while heating by passing heated oil through the jacket. [] [第 2の工程]  [] [Second step] 次に、第 2の工程においては、まず、第 1の工程で得られた除湿剤を 40°C以下にな るまで冷却する。ここで、冷却とは、攪拌機のジャケットに冷水を流すなど積極的な冷 却でもよいし、あるいは放冷でもよい。次に、冷却した除湿剤と、熱可塑性榭脂、およ び必要に応じて各種の添加剤 (滑剤、可塑剤、熱安定剤、酸化防止剤等)とを混合 する。混合には、第 1の工程と同様に、各種の攪拌機を用いることができる。  Next, in the second step, first, the dehumidifying agent obtained in the first step is cooled to 40 ° C. or lower. Here, the cooling may be active cooling such as flowing cold water through the jacket of the stirrer, or may be allowed to cool. Next, the cooled dehumidifying agent is mixed with the thermoplastic resin and, if necessary, various additives (such as a lubricant, a plasticizer, a heat stabilizer, and an antioxidant). Various agitators can be used for mixing, as in the first step. [] [第 3の工程]  [] [Third step] 次に、第 3の工程においては、第 2の工程で得られた混合物を 90°C以上 220°C以 下に加熱してサイコロ状、円柱状、球状、扁平な球状等、所定形状に成形しマスター ノ ツチを得る。第 3の工程においては、加熱混練可能な各種の押出成形機を使用す ることができる。特に、二軸押出成形機を用いると、無機化合物の粉末が均一に分散 した外観の良 、マスターバッチを得ることができるため好ま Uヽ。真空機能を備えた 二軸押出成形機であれば、混合物を加熱することによって発生する揮発成分を取り 除くことができ、より外観の良いマスターバッチを得ることができる。  Next, in the third step, the mixture obtained in the second step is heated to 90 ° C or higher and 220 ° C or lower to form a predetermined shape such as a dice, cylinder, sphere, or flat sphere. And get master notch. In the third step, various extruders capable of being heated and kneaded can be used. In particular, the use of a twin-screw extruder is preferred because a master batch can be obtained with a good appearance in which inorganic compound powder is uniformly dispersed. If it is a twin-screw extruder with a vacuum function, the volatile components generated by heating the mixture can be removed, and a master batch having a better appearance can be obtained. [] 本発明のプラスチック除湿用マスターバッチは、各種のプラスチック材料に混合し て使用することができる。例えば、 ABS榭脂、ナイロン、ポリメタクリル酸メチル、ポリ塩 ィ匕ビニル、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート 等の、従来の方法では特に念入りな予備乾燥を必要とする熱可塑性榭脂に添加して も使用することができる。また、不適切な保存等によって湿気を帯びた熱可塑性榭脂 に添加して使用することができる。また、使用後のペットボトル等によるリサイクル榭脂 (再生榭脂）に添加して使用することも可能である。 [] The plastic dehumidification masterbatch of the present invention can be used by mixing with various plastic materials. For example, ABS resin, nylon, polymethyl methacrylate, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc. are added to thermoplastic resin that requires special pre-drying in the conventional method. Can also be used. In addition, it can be used by adding to a thermoplastic resin moistened by improper storage. In addition, after use, recycle resin It is also possible to use it by adding it to (regenerated resin). [] 以下、本発明のプラスチック除湿用マスターバッチを使用したプラスチック材料の成 形方法について説明する。まず、プラスチック材料に、本発明のマスターバッチを添 加する。マスターバッチは、そのマスターバッチに含有される熱可塑性榭脂が、マス ターバッチを添加する対象となるプラスチック材料と相溶性を有するものを使用する のが好ましい。マスターバッチに含有される熱可塑性榭脂が、マスターバッチを添カロ する対象となるプラスチック材料と同種のものであれば、より好ましい。プラスチック材 料に添加するマスターバッチの割合は、プラスチック材料の含水分量によって適宜決 定することができるが、通常は 6重量％以下でよい。プラスチック材料には、マスター ノ ツチの他に、必要に応じて、可塑剤、熱安定剤、酸化防止剤等の各種の添加剤を 添カロすることができる。  [] Hereinafter, a method for forming a plastic material using the plastic dehumidification masterbatch of the present invention will be described. First, the master batch of the present invention is added to a plastic material. It is preferable to use a master batch in which the thermoplastic resin contained in the master batch is compatible with the plastic material to which the master batch is added. It is more preferable if the thermoplastic resin contained in the masterbatch is the same type as the plastic material to be added to the masterbatch. The proportion of the masterbatch added to the plastic material can be determined as appropriate depending on the moisture content of the plastic material, but it is usually 6% by weight or less. In addition to the master notch, various additives such as a plasticizer, a heat stabilizer, and an antioxidant can be added to the plastic material as necessary. [] 次に、マスターバッチを添加したプラスチック材料を、押出成形法、射出成形法、 T ダイ法等、各種公知の成形法にて成形する。一般にプラスチック材料を成形する際 には、そのプラスチック材料を加熱して溶融させる。プラスチック材料が加熱されると 、プラスチック材料とマスターバッチが互いに溶け合い、マスターバッチに含有される 除湿剤がプラスチック材料中に分散する。このとき、除湿剤は、無機化合物の粉末が 表面修飾剤によって覆われているため、プラスチック材料との親和性を有し、プラス チック材料中に均一に分散する。また、それとともに加熱されることにより、表面修飾 剤による無機化合物の吸湿機能の抑制が解除され、無機化合物の吸湿機能が発揮 される。その結果、除湿剤がプラスチック材料の隅々まで速やかに広がり、プラスチッ ク材料中の水分を効率的に吸収して除去することができる。したがって、本発明のマ スターバッチを用いれば、プラスチック材料を予備乾燥することなく成形することが可 能となる。  Next, the plastic material to which the master batch has been added is molded by various known molding methods such as an extrusion molding method, an injection molding method, and a T-die method. Generally, when molding a plastic material, the plastic material is heated and melted. When the plastic material is heated, the plastic material and the master batch are melted together, and the dehumidifying agent contained in the master batch is dispersed in the plastic material. At this time, since the inorganic compound powder is covered with the surface modifier, the dehumidifier has an affinity for the plastic material and is uniformly dispersed in the plastic material. Further, when heated together with this, the suppression of the hygroscopic function of the inorganic compound by the surface modifier is released, and the hygroscopic function of the inorganic compound is exhibited. As a result, the dehumidifying agent spreads quickly to every corner of the plastic material, and the moisture in the plastic material can be absorbed and removed efficiently. Therefore, if the master batch of the present invention is used, the plastic material can be molded without pre-drying. [] このようにして得られた成形体は、原料であるプラスチック材料を予備乾燥して 、な いにもかかわらず、水分の蒸発に起因する外観上の欠陥等がない。また、予備乾燥 のための加熱が不要なので、過乾燥によるプラスチック材料の変色や物性の劣化等 を引き起こすことがない。し力も、予備乾燥のための長時間の加熱等が不要であるた めに、短時間で且つより少な!/、エネルギーでプラスチック材料を成形することができ る。その結果、低コストでし力も環境に優しいプラスチック材料の成形体を実現するこ とがでさる。 [] The molded body thus obtained does not have a defect in appearance due to the evaporation of moisture, although the plastic material as a raw material is not preliminarily dried. In addition, since heating for pre-drying is not required, discoloration of plastic materials and deterioration of physical properties due to over-drying are not caused. Since it does not require long-time heating for pre-drying, the plastic material can be molded in a short time and with less energy! The As a result, it is possible to realize a molded body of a plastic material that is low in cost and is environmentally friendly. 実施例 1  Example 1 [] 実施例 1では、無機化合物として粒径 10 μ mの酸ィ匕カルシウム粉末、表面修飾剤 としてステアリン酸、熱可塑性榭脂としてポリエチレン、滑剤としてポリエチレンワックス を用意し、第 1〜3の工程を経て No. 1のマスターバッチを作成した。その組成割合 を表 1に示す。尚、ポリエチレンワックスは、滑剤として機能するのみならず、酸化カル シゥム粉末を熱可塑性榭脂中に分散させるための分散剤として機能するとともに、さ らに、可塑剤としても機能する。  [] In Example 1, acid calcium carbonate powder having a particle diameter of 10 μm is prepared as an inorganic compound, stearic acid is used as a surface modifier, polyethylene is used as a thermoplastic resin, and polyethylene wax is used as a lubricant. Through the process, No. 1 master batch was created. Table 1 shows the composition ratio. Polyethylene wax not only functions as a lubricant, but also functions as a dispersant for dispersing calcium oxide powder in a thermoplastic resin, and also functions as a plasticizer. [] [表 1]  [] [Table 1] [] 作成したマスターノ ツチ (No. 1)を、 1重量％の水分を含有する予備乾燥していな いポリエチレン榭脂ペレットに添加し、 Tダイ法にて製膜した。その結果、外観に不具 合のないポリエチレンフィルムを得ることができた。また、マスターバッチ (No. 1)を、 0 . 5重量0 /0の水分を含有する予備乾燥していない再生ポリエチレン樹脂ペレットに添 加し、 Tダイ法にて製膜した。その結果、外観に不具合のない再生ポリエチレンフィル ムを得ることができた。 [] The prepared master notch (No. 1) was added to a pre-dried polyethylene resin pellet containing 1% by weight of water, and a film was formed by the T-die method. As a result, it was possible to obtain a polyethylene film having no defects in appearance. In addition, the master batch (No. 1) was added to recycled polyethylene resin pellets containing 0.5 wt % / 0 moisture which had not been pre-dried, and a film was formed by the T-die method. As a result, it was possible to obtain a recycled polyethylene film having no defects in appearance. 実施例 2  Example 2 [] 実施例 2では、無機化合物としてとして粒径 8 μ mの酸ィ匕カルシウム粉末、表面修 飾剤としてステアリン酸、熱可塑性榭脂として ABS榭脂および SBS、滑剤としてステ アリン酸マグネシウムおよび EBS (エチレンビスステアリン酸アミド）、可塑剤として DO P (フタル酸ジ 2ェチルへキシル）を用意し、上記第 1〜3の工程を経て No. 2のマスタ 一バッチを作成した。その組成割合を表 2に示す。  [] In Example 2, acid calcium carbonate powder having a particle size of 8 μm as an inorganic compound, stearic acid as a surface modifier, ABS resin and SBS as a thermoplastic resin, magnesium stearate as a lubricant, and EBS (ethylene bis-stearic acid amide) and DO P (di-2-ethylhexyl phthalate) as a plasticizer were prepared, and a master batch No. 2 was prepared through the above first to third steps. The composition ratio is shown in Table 2. [] [表 2] N o . 2 [] [Table 2] N o. 2 組成物  Composition 含有量 （重量％) 無機化合物 酸化カルシウム 50  Content (wt%) Inorganic compounds Calcium oxide 50 表面修飾剤 ステアリン酸 1- 5  Surface modifier Stearic acid 1-5 A B S樹脂 12  A B S resin 12 熱可塑性樹脂  Thermoplastic resin S B S 30  S B S 30 ステアリン酸マグネシウム 1. 5  Magnesium stearate 1.5 滑剤  Lubricant E B S 1. 5  E B S 1.5 可塑剤 D O P 3. 5  Plasticizer D O P 3.5 [] 作成したマスターノツチ (No. 2)を、予備乾燥していない ABS榭脂に対して 1重量 %以上 2重量％以下の範囲内で添加し、射出成形法にて成形した。その結果、外観 に不具合のない ABS樹脂の成形体を得ることができた。 [] The prepared master notch (No. 2) was added in the range of 1 wt% to 2 wt% with respect to the ABS resin that had not been pre-dried, and molded by an injection molding method. As a result, it was possible to obtain a molded body of ABS resin with no defects in appearance. 実施例 3  Example 3 [] 実施例 3では、無機化合物として粒径 8 μ mの酸ィ匕カルシウム粉末、表面修飾剤と してステアリン酸、熱可塑性榭脂として SBS、滑剤としてステアリン酸マグネシウムお よびポリエチレンワックス、充填剤として炭酸カルシウムを用意し、表 3に示す割合で 配合して No. 3および No. 4のマスターバッチを作成した。なお、 No. 3は、上記第 1 〜3の工程を経てマスターバッチを作成し、 No. 4は、上記第 1〜3の工程において 第 1の工程を省略し、第 2の工程において酸ィ匕カルシウムを添カ卩してマスターバッチ を作成した。次に、各マスターバッチを 24時間自然環境下で放置した後、 目視にて 観察し、大きさ及び色の変化を調べた。さらに、 ABS榭脂 94重量％に対し、自然環 境下で 24時間放置したマスターバッチ 6重量％を混合し、射出成形して容器を得た 。得られた容器の目視で観察し、外観上の不具合の有無を調べた。その結果を表 3 に示す。  [] In Example 3, a calcium oxide powder having a particle size of 8 μm as an inorganic compound, stearic acid as a surface modifier, SBS as a thermoplastic resin, magnesium stearate and polyethylene wax as a lubricant, filling Calcium carbonate was prepared as an agent and blended in the proportions shown in Table 3 to prepare No. 3 and No. 4 master batches. Note that No. 3 creates a master batch through the above first to third steps, and No. 4 omits the first step in the first to third steps, and the second step A master batch was prepared by adding calcium. Next, each master batch was allowed to stand in a natural environment for 24 hours and then visually observed to examine changes in size and color. Furthermore, 94% by weight of ABS fat was mixed with 6% by weight of a masterbatch that was allowed to stand for 24 hours in a natural environment and injection molded to obtain a container. The obtained container was visually observed to check for defects in appearance. The results are shown in Table 3. [] [表 3] N o . 3 N o . 4 無機化合物 酸化カルシウム BO 50 表面修飾剤 ステアリン酸 1. 5 一 [] [Table 3] No. 3 No. 4 Inorganic compound Calcium oxide BO 50 Surface modifier Stearic acid 1.5 熟可塑性  Ripe plasticity S B S 30 30 樹脂  S B S 30 30 Resin 組成  Composition ステアリン酸  stearic acid 1. 5 1. 5 マグネシウム  1. 5 1. 5 Magnesium 滑剤  Lubricant ポリエチレン  Polyethylene 4 4 ワックス  4 4 Wax 充填剤 炭酸カルシウム 13 14. 5 Filler Calcium carbonate 13 14. 5 24時間放置後のマスタ 大きさ 変化なし 膨張 Master after standing for 24 hours Size No change Expansion —バッチの外観 色 変化なし 白化  —Batch appearance Color No change Whitening 有り 容器の外観 （不具合の有無） 無し  Yes Appearance of container (existence of defects) No (水紋状）  (Water pattern) No. 3のマスターバッチと No. 4のマスターバッチとでは、含有される無機化合物の 態様が異なっている。すなわち、 No. 3では無機化合物が表面修飾剤で覆われてい るのに対し、 No. 4では、無機化合物が表面修飾剤で覆われておらず、裸のまま含 有されている点で異なっている。まず、自然環境下に 24時間放置したマスターバッ チを添加して作成した容器の外観を比較すると、 No. 3の容器の表面は滑らかで不 具合が無いのに対し、 No. 4の容器は表面に水の跡のような (水紋状の)模様がみら れた。これは、 No. 3のマスターバッチは ABS榭脂中の水分を十分に除湿したのに 対し、 No. 4のマスターバッチは ABS榭脂中の水分を完全には除湿できず、 ABS榭 脂中に残った水分が気化して容器の表面に水紋状の模様を生じたものと推察される 。次に、 24時間放置した後のマスターバッチの外観を比較すると、 No. 3は変化がな いのに対し、 No. 4は膨張し、又、白化している。これにより、 No. 3のマスターバッチ に含まれる無機化合物（酸化カルシウム）はほとんど吸湿していないが、 No. 4のマス ターパツチに含まれる無機化合物は空気中の水分を多量に吸収したものと推察され る。以上のことから、無機化合物が表面修飾剤で覆われていない場合 (No. 4)は、保 存時に空気中の水分を吸収して吸湿機能が著しく低下し、使用時に ABS榭脂中の 水分を十分に吸収することができないことが明ら力となった。また、これに対し、無機 化合物が表面修飾剤で覆われている場合 (No. 3)は、通常の自然環境下では無機 化合物の吸湿機能が温存されるため、使用時に吸湿機能が確実に発揮されて ABS 榭脂を十分に除湿可能であることが明らかとなった。 実施例 4 No. 3 masterbatch and No. 4 masterbatch differ in the form of the inorganic compounds contained. That is, in No. 3, the inorganic compound is covered with the surface modifier, whereas in No. 4, the inorganic compound is not covered with the surface modifier and is contained as it is. ing. First, when comparing the appearance of a container made by adding a master batch left in a natural environment for 24 hours, the surface of the container of No. 3 is smooth and free of defects. There was a water-like pattern on the surface. This is because the No. 3 masterbatch sufficiently dehydrated the water in the ABS resin, while the No. 4 masterbatch cannot completely dehumidify the water in the ABS resin. It is inferred that the water remaining in the container evaporated and a water-striped pattern was formed on the surface of the container. Next, comparing the appearance of the masterbatch after standing for 24 hours, No. 3 is unchanged, while No. 4 is expanded and whitened. As a result, the inorganic compound (calcium oxide) contained in the No. 3 master batch hardly absorbs moisture, but the inorganic compound contained in the No. 4 master patch is presumed to have absorbed a large amount of moisture in the air. It is done. Based on the above, when the inorganic compound is not covered with a surface modifier (No. 4), moisture content in the air is absorbed during storage and the moisture absorption function is significantly reduced. It became clear that they could not absorb enough. On the other hand, when the inorganic compound is covered with a surface modifier (No. 3), the moisture absorption function of the inorganic compound is preserved in a normal natural environment. As a result, it has become clear that ABS can be sufficiently dehumidified. Example 4 [] 実施例 4では、まず、無機化合物として粒径 10 μ mの酸化カルシウム粉末および 粒径 10 μ mのゼオライト、表面修飾剤としてステアリン酸、熱可塑性樹脂としてポリェ チレン、滑剤としてポリエチレンワックスを用意し、上記第 1 3の工程を経て No . 5お よび No . 6のマスターバッチを作成した。その組成割合を表 4に示す。次に、得られ たマスターパッチ No . 5および No . 6を自然環境下で 36時間放置した後、それらの マスターバッチをそれぞれ予備乾燥して ヽな 、0. 5重量％の水分を含有する再生ポ リエチレン榭脂に対して、混合してフィルムを成形した。なお、このときマスターバッチ 力 3重量％となるように再生ポリエチレン榭脂に対してマスターバッチを添加した。得 られたフィルムを目視で観察し、外観上の不良の有無を調査した。この調査では、水 紋状の外観不良等、成形時の水分の揮発により生じた外観不良を「水紋状の不良」 とし、粒子状の不純物の発生による外観の不良を「粒子状の不良」として、それぞれ について有無を確認した。その結果を表 4に示す。  In Example 4, first, calcium oxide powder having a particle size of 10 μm and zeolite having a particle size of 10 μm were used as the inorganic compound, stearic acid was used as the surface modifier, polyethylene was used as the thermoplastic resin, and polyethylene wax was used as the lubricant. The master batches No. 5 and No. 6 were prepared through the first and third steps. The composition ratio is shown in Table 4. Next, after leaving the obtained master patches No. 5 and No. 6 in a natural environment for 36 hours, each of the master batches was pre-dried and regenerated containing 0.5% by weight of water. A film was formed by mixing with polyethylene resin. At this time, the masterbatch was added to the recycled polyethylene resin so that the masterbatch force was 3% by weight. The obtained film was visually observed to investigate the appearance of defects. In this survey, the appearance defect caused by moisture volatilization during molding, such as a water-pattern appearance defect, is referred to as “water-pattern defect”, and the appearance defect due to the generation of particulate impurities is referred to as “particulate defect”. The presence or absence of each was confirmed. The results are shown in Table 4. [] [表 4]  [] [Table 4] No . 5のマスターバッチと No . 6のマスターバッチとでは、除湿剤を構成する無機 化合物が異なっている。すなわち、 No . 5は化学吸湿性無機化合物である酸ィ匕カル シゥムの 1種のみを含有しているのに対し、 No. 6は酸化カルシウムに加えて更に吸 着性無機化合物であるゼォライトを含有している点で異なっている。使用前に 36時 間放置したマスターバッチを用いて成形したフィルムは、いずれも水紋状の不良が生 じなかった。このことから、いずれのマスターバッチも使用前には吸湿機能が抑制さ れ、一定の除湿機能が担保されていたため、使用時にポリエチレン榭脂を十分に除 湿したことがわかる。ところが、粒子状の不良が No. 5のフィルムにのみ生じた。これ は、 No. 5のマスターパッチに含有される酸ィ匕カルシウム力 使用前に徐々に吸湿し 、経時によりその表面が固くなつたため、フィルム成形時にポリエチレン樹脂と相溶せ ずにその一部が不純物としてフィルム表面に出現したものと推察される。一方、 No. 6は粒子状の不良は生じておらず、使用前に酸ィ匕カルシウムの表面が硬化するほど 吸湿しな力 たことが分かる。以上のことから、化学吸湿性無機ィ匕合物に加えて更に 吸着性無機化合物を含有することにより、保存時の化学吸湿性無機化合物の吸湿を より確実に抑制可能であることが明ら力となった。 The No. 5 masterbatch and No. 6 masterbatch differ in the inorganic compounds that make up the dehumidifier. In other words, No. 5 contains only one kind of acid-hypercalcium which is a chemically hygroscopic inorganic compound, whereas No. 6 contains zeolite, which is an additional inorganic compound in addition to calcium oxide. It differs in that it contains. None of the films formed using a masterbatch that was allowed to stand for 36 hours before use produced water-like defects. For this reason, the moisture absorption function of each masterbatch was suppressed before use, and a certain dehumidification function was ensured. It turns out that it got wet. However, particulate defects occurred only in the No. 5 film. This is because the acid and calcium strength contained in the No. 5 master patch gradually absorbs moisture before use, and the surface became harder over time, so that part of it was not compatible with polyethylene resin during film formation. It is assumed that it appeared on the film surface as an impurity. On the other hand, No. 6 has no particulate defects, and it can be seen that the surface of the calcium oxide was hardened before use, so that it absorbed moisture. From the above, it is clear that the moisture absorption of the chemically hygroscopic inorganic compound during storage can be more reliably suppressed by further containing the adsorptive inorganic compound in addition to the chemically hygroscopic inorganic compound. It became. 実施例 5  Example 5 [] 実施例 5では、まず、表面修飾剤としてチタネート系カップリング剤、アルミネート系 カップリング剤、ノ《ラフィンを用意し、上記実施例 4で作成したマスターパッチ No. 5 のステアリン酸に替え、用意した各表面修飾剤を用いて No. 7〜9のマスターバッチ を作成した。その組成を表 5に示す。  In Example 5, first, a titanate coupling agent, an aluminate coupling agent, and raffine were prepared as surface modifiers, and the stearic acid of master patch No. 5 prepared in Example 4 above was prepared. Instead, No. 7-9 master batches were prepared using the prepared surface modifiers. The composition is shown in Table 5. 次に、 No. 5および No. 7〜9のマスターバッチについて自然環境下で放置し、 24 時間後と、 36時間後にマスターバッチの外観を目視にて観察し、外観変化の有無を 調べた。その結果を表 5に示す。  Next, the master batches of No. 5 and Nos. 7 to 9 were left in a natural environment, and the appearance of the master batch was visually observed after 24 hours and after 36 hours to check for changes in appearance. The results are shown in Table 5. [] [表 5]  [] [Table 5] 24時間放置後にはレ、ずれのマスターパッチも外観変化して ヽな 、ことから、ステア リン酸の他、チタネート系カップリング剤、アルミネート系カップリング剤及びパラフィン の!、ずれも常温では無機化合物（酸ィ匕カルシウム）の吸湿を抑制することが確認され た。更に長時間マスターバッチを放置すると 36時間後には、 No. 9のみが白化し、そ の他の No. 5、 7及び 8は変化しなかった。このことから、ステアリン酸、チタネート系力 ップリング剤及びアルミネート系カップリング剤は、ノ ラフィンに比べて、常温で無機 化合物の吸湿機能を抑制する効果がより大きいことが明らかとなった。 After standing for 24 hours, the appearance of the misaligned master patch will change, so that in addition to stearic acid, titanate coupling agents, aluminate coupling agents and paraffin! It was confirmed that the moisture absorption of the compound (acid calcium) was suppressed. If the master batch is left for a long time, only No. 9 will turn white after 36 hours. The other Nos. 5, 7 and 8 did not change. This indicates that stearic acid, titanate-based coupling agents, and aluminate-based coupling agents have a greater effect of suppressing the hygroscopic function of inorganic compounds at room temperature than norafine. 実施例 6  Example 6 [] 実施例 6では、まず、上記実施例 5で作成したマスターバッチ No. 9において無機 化合物を酸化カルシウム 40重量％とゼォライト 10重量％に変更し、 No. 10のマスタ 一バッチを作成した。次に、得られた No. 10のマスターバッチについて、上記実施 例 5と同様に自然環境下で放置し、 36時間後にマスターバッチの外観を目視にて観 察し、外観変化の有無を調べた。その結果、 36時間後に外観変化の無いことを確認 した。  [] In Example 6, first, the master batch No. 9 prepared in Example 5 above was changed to 40% by weight of calcium oxide and 10% by weight of zeolite in the master compound No. 10, and a master batch of No. 10 was prepared. . Next, the obtained master batch No. 10 was left in a natural environment in the same manner as in Example 5 above, and after 36 hours, the appearance of the master batch was visually observed to check for changes in appearance. As a result, it was confirmed that there was no change in appearance after 36 hours. [] No.10のマスターバッチは、除湿剤として、酸化カルシウム力もなる除湿剤だけで なぐゼォライトからなる除湿剤を含有している点でのみ No.9のマスターバッチとは 異なっている。 36時間放置後のマスターバッチの外観は、 No.9が白化したのに対し 、 No.10は変化が無かった。このことから、 No.10のマスターバッチ中では、酸化力 ルシゥムの吸湿はより確実に阻害されていることがわかる。これにより、化学吸湿性無 機化合物と吸着性無機化合物とを併用することにより、表面修飾剤のみで化学吸湿 性無機化合物の吸着を阻害するよりも更に長時間化学吸湿性無機化合物の吸湿を 阻害し、マスターバッチを長時間保存可能にできることが明らかとなった。  [] The master batch of No. 10 is different from the master batch of No. 9 only in that it contains a dehumidifier composed of zeolite, which is only a dehumidifier having a calcium oxide power as a dehumidifier. The appearance of the masterbatch after standing for 36 hours was whitened for No. 9, whereas no change was observed for No. 10. From this, it can be seen that in the No. 10 master batch, the moisture absorption of the oxidizing power Lucium is more reliably inhibited. As a result, the combined use of a chemically hygroscopic inorganic compound and an adsorptive inorganic compound inhibits the moisture absorption of the chemically hygroscopic inorganic compound for a longer period of time than the adsorption of the chemically hygroscopic inorganic compound only by the surface modifier. It was revealed that the master batch can be stored for a long time.

Claims

請求の範囲 The scope of the claims [1] プラスチック材料を成形する際に混合しプラスチック材料とともに加熱されて該プラ スチック材料と溶け合うマスターバッチであって、  [1] A masterbatch that is mixed when molding a plastic material, heated together with the plastic material, and melts into the plastic material, 除湿剤と、バインダーとしての熱可塑性榭脂と、を含有し、  Containing a dehumidifying agent and thermoplastic rosin as a binder, 前記除湿剤は、吸湿性を有する無機化合物の粉末と、前記無機化合物の表面を 被覆して前記無機化合物と前記熱可塑性榭脂との相溶性を向上させるとともに、常 温では前記無機化合物の吸湿機能を抑制し、加熱時には前記無機化合物の吸湿 機能を発揮させる表面修飾剤と、からなる、前記プラスチック材料に含まれる水分を プラスチック材料の成形時に吸収するプラスチック除湿用マスターバッチ。  The dehumidifying agent coats the surface of the inorganic compound having a hygroscopic property and the surface of the inorganic compound to improve the compatibility between the inorganic compound and the thermoplastic resin, and at a normal temperature, absorbs moisture of the inorganic compound. A plastic dehumidification masterbatch that absorbs moisture contained in the plastic material when the plastic material is molded, and a surface modifier that suppresses the function and exhibits a moisture absorption function of the inorganic compound during heating. [2] 前記表面修飾剤は、前記無機化合物の表面を被覆する際に加熱された表面修飾 剤であり、該表面修飾剤は、チタネート系カップリング剤、アルミネート系カップリング 剤、ノラフィン類、及びステアリン酸類力もなる群より選ばれた少なくとも 1種である、 請求項 1に記載のプラスチック除湿用マスターバッチ。  [2] The surface modifier is a surface modifier heated when the surface of the inorganic compound is coated, and the surface modifier includes a titanate coupling agent, an aluminate coupling agent, norafines, 2. The plastic dehumidification masterbatch according to claim 1, wherein the masterbatch is at least one selected from the group consisting of stearic acids. [3] 前記無機化合物は、水分との化学反応により吸湿する化学吸湿性無機化合物であ る、請求項 1または請求項 2に記載のプラスチック除湿用マスターバッチ。  [3] The plastic dehumidification masterbatch according to claim 1 or 2, wherein the inorganic compound is a chemically hygroscopic inorganic compound that absorbs moisture by a chemical reaction with moisture. [4] 前記化学吸湿性無機化合物は、酸化カルシウム、酸化バリウム、及び酸化アルミ- ゥムカもなる群より選ばれる少なくとも 1種である、請求項 3に記載のプラスチック除湿 用マスターバッチ。  [4] The plastic dehumidification masterbatch according to claim 3, wherein the chemically hygroscopic inorganic compound is at least one selected from the group consisting of calcium oxide, barium oxide, and aluminum oxide. [5] 前記化学吸湿性無機化合物で構成された除湿剤に加え、更に、水分を吸着するこ とにより吸湿する吸着性無機化合物で構成された除湿剤をも含有する、請求項 3また は請求項 4に記載のプラスチック除湿用マスターバッチ。  [5] In addition to the dehumidifying agent composed of the chemical hygroscopic inorganic compound, it further contains a dehumidifying agent composed of an adsorptive inorganic compound that absorbs moisture by adsorbing moisture. Item 5. A master batch for plastic dehumidification according to Item 4. [6] 前記吸着性無機化合物は、シリカゲル、ゼォライト及び珪藻土力 なる群より選ば れる少なくとも 1種である、請求項 5に記載のプラスチック除湿用マスターバッチ。 6. The plastic dehumidification masterbatch according to claim 5, wherein the adsorptive inorganic compound is at least one selected from the group consisting of silica gel, zeolite and diatomaceous earth. [7] 除湿剤と、バインダーとしての熱可塑性榭脂とを含有し、プラスチック材料を成形す る際に混合しプラスチック材料とともに加熱されて該プラスチック材料と溶け合うマス ターバッチの製造方法であって、 [7] A method for producing a master batch comprising a dehumidifying agent and a thermoplastic resin as a binder, mixed when molding a plastic material, heated together with the plastic material, and melted with the plastic material, 吸湿性を有する無機化合物の粉末と、表面修飾剤と、を接触させながら加熱するこ とにより前記除湿剤を調製し、得られた除湿剤を冷却した後に、該冷却した除湿剤と 前記熱可塑性榭脂とを混合する、プラスチック除湿用マスターバッチの製造方法。 The dehumidifying agent is prepared by heating while bringing a powder of an inorganic compound having hygroscopicity into contact with a surface modifier, and after cooling the obtained dehumidifying agent, the cooled dehumidifying agent and The manufacturing method of the masterbatch for plastic dehumidification which mixes the said thermoplastic resin. PCT/JP/ -01-10 -01-10 Masterbatch for elimination of moisture in plastics and method for producing masterbatch for elimination of moisture in plastics WOA1 (en)

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* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title WOA1 (en) * -10-26 -05-05 日本クラウンコルク株式会社 Moisture-absorbing resin composition and molded products thereof

Citations (5)

* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title JPSA (en) * -04-12 -07-10 Kenrich Petrochemicals Manufacture of inorganic matter dispersed body in polymer medium JPHA (en) * -06-27 -01-14 Kanebo Nsc Ltd Preparation of one component modified silicone resin composition JPA (en) * -10-25 -05-20 Toppan Printing Co Ltd Resin composition having drying ability, and laminate and package using the same JPA (en) * -01-12 -07-29 オムヤ・アー・ゲー Method for treating inorganic fillers with polydialkylsiloxanes and fatty acids to obtain hydrophobic fillers and their use in polymers for breathable films JPA (en) * -06-23 -01-13 Fuji Seal Inc Moisture absorbent-containing pellet, its production method, and method for manufacturing hygroscopic molded article

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Patent Citations (5)

* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title JPSA (en) * -04-12 -07-10 Kenrich Petrochemicals Manufacture of inorganic matter dispersed body in polymer medium JPHA (en) * -06-27 -01-14 Kanebo Nsc Ltd Preparation of one component modified silicone resin composition JPA (en) * -01-12 -07-29 オムヤ・アー・ゲー Method for treating inorganic fillers with polydialkylsiloxanes and fatty acids to obtain hydrophobic fillers and their use in polymers for breathable films JPA (en) * -10-25 -05-20 Toppan Printing Co Ltd Resin composition having drying ability, and laminate and package using the same JPA (en) * -06-23 -01-13 Fuji Seal Inc Moisture absorbent-containing pellet, its production method, and method for manufacturing hygroscopic molded article

Cited By (2)

* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title WOA1 (en) * -10-26 -05-05 日本クラウンコルク株式会社 Moisture-absorbing resin composition and molded products thereof USB2 (en) -10-26 -12-08 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Moisture-absorbing resin composition and molded product thereof

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