JPS5855184B2 - Compatibility modifier between organic polymer molding materials and inorganic compounded chemicals - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an affinity modifier for an organic polymer molding material and an inorganic compounded chemical, and more specifically, the present invention relates to an affinity modifier for an organic polymer molding material and an inorganic compounded chemical, and more specifically, it relates to an affinity modifier made of a vinyl copolymer resin powder containing carboxyl groups. Regarding modifiers.

In recent years, there has been remarkable development in organic polymer molding materials such as rubber, vinyl chloride resin, polyester resin, polyurethane resin, and silicone resin.

Depending on the purpose of use, organic polymer molding materials contain various compounded chemicals such as vulcanizing agents, vulcanization accelerators, aging/oxidation inhibitors, tackifiers, plasticizers, softeners, stabilizers, and blowing agents. It is used.

In particular, inorganic compounded chemicals include fillers such as calcium carbonate, clay, talc, diatomaceous earth, etc. whose primary purpose is to increase the volume of products and reduce costs, or they are compounded with rubber and vulcanized. Reinforcing agents such as carbon black, zinc white, magnesium carbonate, silicic acid, and silicic acid compounds are used to improve the physical properties of objects, such as hardness, tensile strength, modulus, and anti-fracture elasticity.

The properties required when blending inorganic compounds such as fillers and reinforcing agents into organic polymer molding materials are: (1) They must be easily and uniformly dispersed during kneading (2)
(3) It does not impair processability; (3) It does not impair water resistance, chemical resistance, heat resistance, and light resistance; (4) It can be blended in large quantities; and (5) it does not inhibit vulcanization.

In particular, it is well known that if the dispersibility of the inorganic compounded chemical in the natural molding material is poor, the physical properties of the resulting molding material will be significantly reduced, and practicality will be lost.

Therefore, there has been a need to improve the dispersibility of inorganic compounded chemicals.

Additionally, there has been a demand for a blending method that improves processability.

The present inventor has investigated methods for improving the dispersibility of inorganic compounded chemicals in organic polymeric molding materials and improving the processability of the obtained molding materials. As a result of intensive research into improving the affinity, we discovered an affinity modifier for organic polymer molding materials and inorganic compounded chemicals, which consists of a vinyl copolymer resin powder containing carboxyl groups, and the present invention. completed.

Since the affinity modifier of the present invention is made of vinyl copolymer resin, it has good affinity with organic polymer molding materials such as rubber, thermosetting resin, and thermoplastic resin, and has good dispersibility. Since the system copolymer resin contains carboxyl groups, it has good affinity with inorganic compounded chemicals and has excellent dispersibility of inorganic compounded chemicals.

Therefore, by adding the affinity modifier of the present invention during kneading of an organic polymer molding material and an inorganic compounded chemical, the dispersibility of the inorganic compounded chemical can be significantly improved.

Especially when synthetic rubber is used as an organic polymer molding material,
Such effects are noticeable.

Furthermore, since the affinity modifier of the present invention is a vinyl copolymer resin, it has a thermoplasticizing effect and has the effect of improving the processability of molding materials using the affinity modifier of the present invention. have

Furthermore, since the affinity modifier of the present invention is a polymer compound,
Since it does not reduce the physical properties of the molding material and can be used in large amounts, it is useful when obtaining a molding material that uses a large amount of inorganic compounded chemicals.

A typical method for obtaining carboxyl group-containing vinyl copolymer resin powder, which is the affinity modifier of the present invention, is as follows:
It is obtained by copolymerizing an unsaturated carboxylic acid and a vinyl monomer using a known polymerization method, and then pulverizing the resultant mixture.

The polymerization method may be any known method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

Particularly preferred is a powder obtained by spray drying an aqueous emulsion of a vinyl copolymer resin containing carboxyl groups obtained by emulsion polymerization, which has good dispersibility of the inorganic compounded chemicals.

If it is desired to further improve the dispersibility of the inorganic compounded chemical, the inorganic compounded chemical is dispersed in an aqueous vinyl resin emulsion and then spray-dried to form a powder.

Examples of unsaturated carboxylic acids used in the present invention include crotonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, monoalkylmaleic acid, monoalkylfumaric acid, monoalkylfumaric acid, etc. Any monomer having a carboxyl group can be used.

The amount of unsaturated carboxylic acid used is 1 to 30% of the total monomers.
Preferably, it is % by weight.

The vinyl monomer used in the present invention may be any monomer that copolymerizes with an unsaturated carboxylic acid.

For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl esters of alpha-branched carboxylic acids having 10 carbon atoms (Beoba: a trade name of Shell Chemical Co., Ltd.); methyl acrylate, ethyl acrylate, acrylic Acrylic esters such as butyl methacrylate; methacrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate; dibutyl maleate,
Unsaturated acid esters such as dibutyl fumarate; ethylene, styrene, acrylonitrile, vinyl chloride, vinylidene chloride, and the like.

In addition to these vinyl monomers, vinyl monomers, divinyl monomers, diallyl monomers, etc. having functional groups such as glycidyl groups, amide groups, N-methylol groups, and hydroxyl groups may be used in combination. You can also do it.

Suitable monomeric silk combinations include vinyl acetate/crotonic acid, vinyl acetate/veova/crotonic acid, vinyl acetate/acrylic acid ester/acrylic acid, vinyl acetate/ethylene/crotonic acid, vinyl acetate/ethylene/nuccrylic acid, acetic acid. Vinyl/ethylene/vinyl chloride/ichonic acid, etc.

The affinity modifier of the present invention is used with inorganic compounded chemicals,
It is used by kneading it with an organic polymer molding material.

The affinity modifier improves the dispersibility of the inorganic compounded drug in the organic polymeric molding material, allowing easy and uniform dispersion.

The tear resistance, setting properties, abrasion resistance, etc. of the resulting molding material are improved, the modulus and hardness are also significantly increased, and the processability is improved.

The usage ratio of the affinity modifier of the present invention is not particularly limited, but it is preferable to use 1 to 100 parts by weight per 100 parts by weight of the inorganic compounded chemical.

Examples, comparative examples, and test examples will be explained below.

Example 1 95 parts by weight of vinyl acetate, 5 parts by weight of crotonic acid, polyvinyl alcohol as a protective colloid, and sodium persulfate as a polymerization catalyst, were emulsion copolymerized in water to produce an aqueous emulsion of a vinyl copolymer resin containing carboxyl groups. I got it.

An affinity modifier made of a vinyl copolymer resin powder containing 5% by weight of carboxyl groups (calculated as unsaturated carboxylic acid) by drying and powdering this carboxyl group-containing vinyl copolymer resin aqueous emulsion by spray drying. I got it.

Example 2 In Example 1, instead of 95 parts by weight of vinyl acetate and 5 parts by weight of crotonic acid, 50 parts by weight of methyl methacrylate,
An affinity modifier made of a carboxyl group-containing vinyl copolymer resin powder was obtained in the same manner as in Example 1, except that 45 parts by weight of butyl acrylate and 5 parts by weight of methacrylic acid were used.

Example 3 95 parts by weight of vinyl acetate and 5 parts by weight of crotonic acid were dissolved in methanol and copolymerized using butyl peroxide as a polymerization catalyst to obtain a methanol solution of a vinyl copolymer resin containing carboxyl groups.

An affinity modifier consisting of a vinyl copolymer resin powder containing 5% by weight of carboxyl groups (in terms of unsaturated carboxylic acid) by removing methanol by evaporation and pulverizing the methanol solution of the vinyl copolymer resin containing carboxyl groups. I got it.

Comparative Example 1 Carboxyl group-free vinyl polymerization was carried out in the same manner as in Example 1, except that 100 parts by weight of vinyl acetate was used instead of 95 parts by weight of vinyl acetate and 5 parts by weight of crotonic acid. A resin powder was obtained.

Test Example 1 The difference between using SBR rubber as the organic polymer molding material, using white carbon as the inorganic compounded chemical, and using and not using the affinity modifier obtained in Example 1 is as follows. I tested it.

Compounding recipe Blend A Blend B SBR rubber 100 1000 Tubusil N3 5o 5゜ (Note 1) Zinc white No. 3 33 Stearic acid 11 Sulfur 2
2 Accelerator 22 A c t ing S L 1.51.
5 (Note 2) Example 1 Affinity.

Modifier (Note 1) White carbon manufactured by Nihon Silikani Gyo Co., Ltd. (Note 2) Activator manufactured by Yoshitomi Pharmaceutical Co., Ltd. First, the above formulation excluding sulfur and accelerator was mixed at a rotation ratio of 1:1.2. After kneading using a roll with a front roll of 17 rpm and a roll temperature of 30 to 40'C, heat treatment is performed for 3 minutes with a roll at a temperature of 105C.

Sulfur and an accelerator were added to the grains, and the mixture was vulcanized at a temperature of 150°C in a three-stage steam heating press.

The unvulcanized Mooney viscosity, vulcanization rate, vulcanization time, and the vulcanizate were tested for tensile strength, modulus, hardness, and bow tear strength.

The test results are shown in Table 1.

Test Example 2 The affinity modifier obtained in Example 2 was used and tested in the same manner as in Test Example 1.

The test results were similar to Example 1.

Test Example 3 The affinity modifier obtained in Example 3 was used and tested in the same manner as in Test Example 1.

The test results were similar to Example 1.

Test example 4 Using polyvinyl chloride resin as an organic polymer molding material,
Calcium carbonate was used as the inorganic compound chemical, and the difference between the case of using the affinity modifier obtained in Example 1 and the case of using the vinyl polymer resin powder obtained in Comparative Example 1 was tested as follows.

(Blend recipe) Blend C Blend D 100 100 10 10 3 Polyvinyl chloride resin Calcium carbonate stabilizer Affinity modifier obtained in Example 1 Vinyl polymer resin powder obtained in Comparative Example 1 The above compound was mixed using a roll kneader. Kneaded at 160'C for 5 minutes, then kneaded at 180°C for 210 minutes, 100kg/m
A sheet was created under the following press sheet conditions.

This sheet was tested for tensile strength, tensile elongation, bending strength, and bending modulus.

The test results are shown in Table 2.

Claims (1)

[Scope of Claims] 1. An affinity modifier for an organic polymer molding material made of a vinyl copolymer resin powder containing a carboxyl group and an inorganic compounded chemical. 2. The affinity modifier according to claim 1, wherein the vinyl copolymer resin powder has a carboxyl group content of 1 to 30% by weight in terms of unsaturated carboxylic acid. 3. The affinity modifier according to claim 1 or 2, wherein the vinyl copolymer resin powder is a powder obtained by spray drying an aqueous vinyl copolymer resin emulsion.