JPS60106857A - Modifier of affinity between organic high-molecular molding material and inorganic compounding agent - Google Patents

Abstract

PURPOSE:To provide the titled agent which improves the dispersibility of an inorg. compounding agent in an org. high-molecular molding material and imparts improved processability to the resulting molding material, consisting of a specified vinylsilane copolymer resin powder. CONSTITUTION:The titled modifier is composed of a vinylsilane copolymer resin powder obtd. by powdering an aq. emulsion contg. a copolymer obtd. by emulsion-polymerizing a vinylsilane (e.g. gamma-methacryloxypropyltrimethoxysilane) and vinyl acetate monomer and/or an acrylic monomer [e.g. butyl (meth)-acrylate] in the presence of an emulsifier (e.g. a polymerizable emulsifier such as an alkali metal saft of an alkyl sulfosuccinate). This modifier can improve the dispersibility of an inorg. compounding agent in an org. high-molecular molding material and has a characteristic of improving the processability of the resulting molding material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an affinity modifier for agents, and more particularly to an affinity modifier comprising a vinyl silane thread copolymer resin powder containing a silane group.

In recent years, there has been remarkable progress in 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 may contain various combinations such as vulcanizing agents, vulcanization accelerators, aging/oxidation inhibitors, adhesion agents, plasticizers, softeners, stabilizers, and blowing agents. #i drug is being used.

In particular, inorganic compounds 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 carbon black, zinc white, magnesium carbonate, silicic acid, silicate compound colloidal silica, etc., which are added to rubber to improve the physical properties of vulcanizates such as hardness, tensile strength, modulus, and anti-friction elasticity. A reinforcing agent is used.

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 organic molding material is poor, the physical properties of the resulting molding material will be significantly reduced, and practicality will be lost. Therefore, it has been desired to improve the dispersibility of inorganic compounded drugs.

In addition, there has been a desire for a chemical that can improve the processability of organic polymer molding materials containing inorganic compounds.

The present inventor investigated a drug that improves the dispersibility of an inorganic compound in an organic polymer molding material and improves the processability of the obtained molding material, and proposed that he As a result of extensive research into modifying the affinity, we discovered an affinity modifier for organic polymer molding materials and inorganic compounded chemicals, which consists of a vinyl silane copolymer resin powder containing silane groups. The invention has been completed.Since the affinity modifier of the present invention is made of a vinylsilane copolymer resin, it has an affinity with organic polymer molding materials such as rubber, thermosetting resin, and thermoplastic resin, and has excellent dispersibility. egoism,
Furthermore, since the vinyl silane copolymer resin contains silane groups, it has good affinity with inorganic compounded drugs and has excellent dispersibility of inorganic compounded drugs. Therefore, by adding the affinity modifier of the present invention during kneading of the organic polymer molding material and the inorganic compounded drug, the dispersibility of the inorganic compounded drug can be significantly improved. This effect is particularly noticeable when synthetic rubber is used as the organic polymer molding material.

Furthermore, since the affinity modifier of the present invention is a vinylsilane-based 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 creating molding materials that use a large amount of inorganic compounded chemicals.

A typical method for obtaining the vinyl silane copolymer resin powder containing silane groups, which is the affinity modifier of the present invention, is as follows:
It can be obtained by copolymerizing vinyl silane with a vinyl acetate monomer and/or an acrylic monomer using a known polymerization method, and then powdering the copolymer. The polymerization method may be any known method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. The powdering method may be spray drying, freeze drying, or evaporation to dryness if the film forming temperature is high. Particularly preferred is a powder obtained by spray drying an aqueous emulsion of a vinyl silane copolymer resin containing silane groups obtained by emulsion polymerization, which has good dispersibility of the inorganic compounded drug.

If you want to improve the dispersibility of the inorganic compounded drug, you can either disperse the inorganic compounded drug in a vinyl silane thread resin aqueous emulsion and pulverize it, or spray the aqueous emulsion and the inorganic compounded drug at the same time in a drying tower. It is best to powder it.

The vinylsilane used in the present invention is preferably a hydrolyzed type, such as vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris(2-methoxy-ethoxy)silane, vinyltriacetoxysilane, γ-methacrylooxyprobyltrimethoxysilane, vinyltrichlorosilane, γ-methacrylooxyprobyltris(methoxy-ethoxy) ) silane, but γ-methacrylooxybrobyltrimethoxysilane is most preferred from the viewpoint of copolymerizability.

The vinyl acetate monomer used in the present invention is a mixture of vinyl acetate alone and a copolymerized 11tF monomer.

Copolymerizable υ monomers include acrylic ester, methacrylic ester, ethylene, hinyl chloride, vinyl ester of saturated carboxylic acid branched at the α position, acrylic acid,
Examples of the acrylic monomer used in the present invention include methacrylic acid, itaconic acid, crotonic acid, acrylamide, acrylonitrile, N-methylolacrylamide, and dimethylaminoethyl methacrylate. Acrylic acid alkyl esters and methacrylic acid alkyl esters in which the alkyl group has 1 to 12 carbon atoms. Styrene is a monomer copolymerized with these. Other monomers include small amounts of N-methylolacrylamide, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, acrylamide, acrylonitrile, vinyl acetate, and vinyl esters of saturated carboxylic acids branched in the α-position. 0 Suitable copolymer combinations include vinyltrimethoxysilane/vinyl acetate; vinyltrimethoxysilane/vinyl acetate/ethylene; vinyltriethoxysilane/vinyl acetate...ethylene/vinyl chloride; vinyltris(2-methoxy- ethoxy)silane, vinyl acetate, crotonic acid; vinyltriacetoxysilane, vinyl acetate, vinyl ester of saturated carboxylic acid branched at the alpha position; vinyltrimethoxysilane, butyl acrylate, methyl methacrylate; vinyltriethoxysilane・2-ethylhexyl acrylate ・methyl methacrylate ・acrylic acid; vinyltrimethoxysilane ・butyl acrylate ・styrene; vinyltriacetoxysilane ・butyl acrylate ・
Methyl methacrylate; Vinyltris(2-methoxyethoxy)silane・2-ethylhexyl acrylate・
Styrene; γ-methacrylic secondary xypropyltrimethoxysilane/acrylic iSe ocdyl/medyl methacrylate; vinyltrimethoxysilane/vinyl acetate/acrylic f'+'p-butyl; vinyltriethoxysilane/self-i
'IF Bicol Ethylene.

Edyl acrylate; Vinyltriacetoxysilane・l
Ii'rf! The composition ratio of i-vinyl, methyl methacrylate, and acrylic acid is required.

The proportion of vinyl silane is preferably 0.5 to 15% by weight, particularly 1 to 10% by weight, based on the total weight of the vehicle used.

As the emulsifier, any general emulsifier that can be used in emulsion polymerization can be used.

However, in order to further improve the dispersibility, the following polymerizable emulsifiers are used. That is, (1) alkaline salt of alkylaryl sulfosuccinate Na03SOH-0000H20H'' OH2R20-
000RI (wherein R1 is an alkyl group having 8 to 20 carbon atoms) (2)
Sodium (glycerin n-alkenylsuccinoylglycerin)borate (3) Alkaline salt of sulfopropyl maleic acid monoalkyl ester HG -COOR3 1 HO-000, (OH2)3so3Na (4) Polyoxyethylene alkyl ester of acrylic acid or methacrylic acid 4! OH2=O-coo (0H20H20)nR5 (wherein R4 is H or OH3, R5 is an alkyl group having 8 to 20 carbon atoms, and n is an integer of 1 to 20).

These polymerizable emulsifiers copolymerize with monomers and do not remain as emulsifiers, so they greatly contribute to improving water resistance.

Anionic emulsifiers are also used for the same purposes as polymeric emulsifiers.

Examples of anionic emulsifiers include sodium alkylbenzenesulfonate, sodium α-olefinsulfonate,
Polyoxyethylene alkyl or dialkyl phenyl ether (ii) sodium acid ester, sodium dialkyl sulfohydride, sodium polyoxyethylene alkyl ether sulfosuccinate, sodium polyoxyethylene alkyl ether mono- or diester phosphate, sodium alkyldiphenyl disulfonate, etc. One or more of these may be used together with an anionic surfactant.

Cationic emulsifiers are also used for the same purpose as polymerizable emulsifiers and anionic emulsifiers. Examples of cationic emulsifiers include quaternary ammonium salts, alkylamine salts, alkyl bimparides, alkylpicolium no-1 rides, Benzalkonium chloride, alkylamidomethylpyridium chloride, alkyloxymethylpyridium chloride, boronoxyethylenealkylamine, polyoxyethylenealkylamide, salts of quaternary ammonium group-containing botanicals, sulfonium group-containing polymers 1) Salts of polymers, salts of phosphonium group-containing polymers, etc. are preferred. Particularly useful are quaternary ammonium salts such as methylammonium chloride and stearylammonium chloride.The above emulsifiers may be used alone or in combination with a nonionic surfactant.

The affinity modifier of the present invention is used together with an inorganic compound drug,
It is used by kneading kudzu with organic polymer molding materials.

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

The resulting molding material has improved tensile strength, bending strength, modulus, etc., as well as improved workability.

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 compound drug.

The present invention will be explained below with reference to Examples, ratio R 6'l+, and test examples.

Example 1 A monomer mixture consisting of 90 parts by weight of vinyl acetate and 10 parts by weight of vinyltrimethoxysilane was emulsion polymerized in the presence of a double layer of polyoxyethylene nonyl phenyl ether) to a glass transition temperature of 52. 8°0, copolymer-containing 40
An aqueous emulsion with a viscosity of 500 centipoly was obtained.

The aqueous emulsion of a vinyl silane thread copolymer resin containing silane groups is dried by spray drying to form a powder, and the affinity modifier is made of a vinyl silane copolymer resin powder containing 10% by weight (in terms of vinyl methoxysilane) of silane groups. Example 2 Emulsion polymerization of a mixed monomer consisting of 75 parts by weight of butyl acrylate, 20 parts by weight of methyl methacrylate, and 5 parts by weight of vinyltriethoxysilane in the presence of 2 parts by weight of sodium lauryl sulfonate. The glass transition temperature is 45.2°.
An aqueous emulsion containing a C copolymer of 140% by weight and a viscosity of 100 centipoise was obtained.

This vinyl silane thread copolymer resin aqueous emulsion was spray-dried to obtain an affinity modifier consisting of a vinyl silane copolymer resin powder containing 5% by weight of silane groups (in terms of vinyltriethoxysilane).

Example 3 100 parts by weight of water and 1 part of 2Mff of lauryltrimethylammonium chloride were charged into an autoclave, the m element in the autoclave was removed, and then 1.6 parts by weight of vinyltriacetoxysilane and 56 parts of vinyl acetate were added. Add 6 parts by weight of the monomer mixture with thorough stirring, raise the internal temperature to 60°C, add 1 part by weight of a 10% aqueous solution of ammonium persulfate, and raise the internal temperature to 80°C. 20 atmospheres of ethylene was added. Then, the remaining monomer mixture was added dropwise over a period of 5 hours together with a single portion of a 10% ammonium persulfate aqueous solution, and 1'1' of the mixture was added dropwise over a period of 5 hours. was raised to 85°C to carry out late polymerization for 1.5 cycles, and the copolymer-containing f with a glass transition temperature of -2.3°0
An aqueous emulsion having a weight of 40 g% and a viscosity of 250 centimeters was obtained.

This aqueous vinyl silane copolymer resin emulsion was spray-dried, containing 2% by weight of silane groups (in terms of vinyltriacetoxysilane), 15% by weight of ethylene, and 83% by weight of vinyl acetate.
Example 4: Compatibility modifier consisting of vinylsilane copolymer resin powder containing % by weight According to Example 3, vinyltriethoxysilane and vinyl acetate were mixed under ethylene pressure using alkylaryl sulfosuccinate as an emulsifier. After emulsion copolymerizing and vinyl chloride, the product is spray-dried to obtain a vinyl silane system containing 5% silane groups (in terms of vinyltriethoxysilane), 10% by weight of ethylene, 30% by weight of vinyl chloride, and 55% by weight of vinyl acetate. An affinity modifier made of copolymer resin powder was obtained.

The glass transition temperature of this copolymer resin was 21.5°C.

Example 5 A mixed monomer consisting of 60 parts by weight of butyl acrylate, 25 parts by weight of methyl methacrylate, 5 parts by weight of acrylic acid, and 10 parts by weight of vinyltrimethoxysilane was prepared in the presence of 2 parts by weight of alkylallyl succinate. Copolymer content of 40% by weight with glass transition temperature -15.4°0 through emulsion polymerization,
An aqueous emulsion with a viscosity of 150 centipoise was obtained.

This vinyl silane yarn copolymer tree 11i, f water WJs emulsion was spray-dried, silane group 10% (in terms of vinyl trimethoxysilane) butyl acrylate 60%
An affinity modifier consisting of a vinylsilane copolymer resin powder containing 30 iLt% of methyl methacrylate was obtained.

Example 6 In the presence of 2 parts by weight of lauryl sulfone 11'9 soda,
Acrylic bacteria Butyl 75i1 [Okibe and Styrene 20i-
1-<Ill: 111 parts were emulsified in a mixture consisting of 5 parts by weight of vinyltriethoxysilane, and glass transition humidity 1': U-5o, co-i, I (including the combined I obtained an aqueous emulsion with an amount of 40 weight and a viscosity of 1-1% and a viscosity of 200 cm.
(Vinyltriethoxysilane 4% fil) An affinity modifier consisting of a vinylsilane copolymer resin powder containing 75% by weight of butyl acrylate and 20% by weight of styrene was obtained.

Comparative Example 1 The mixed monomer used in Example 5 was changed to a mixed monomer consisting of 5 parts by weight of butyl acrylate, 90 parts by weight of methyl methacrylate, and 5 parts by weight of vinyltrimethoxysilane. In the same manner as in Example 5 except for this, a vinyl silane copolymer resin powder containing 1% by weight of silane groups (in terms of vinyltrimethoxysilane), 5% by weight of butyl acrylate, and 90% by weight of methyl methacrylate was obtained.

The glass transition temperature of this copolymer resin was 91.6°C.

Comparative Example 2 The mixed monomers used in Example B were mixed monomer fH consisting of 5 parts by weight of butyl acrylate, 90 parts of styrene, and 5 parts of i'tlXs vinyltriethoxysilane.
The silane group 5 was prepared in the same manner as in Example 6 except that the f-isomer was used.
A vinyl silane copolymer resin powder containing 1% (in terms of vinyltriethoxysilane), 5% by weight of butyl acrylate, and 90% by weight of styrene was obtained. The glass transition temperature of this copolymer resin was 87.3°. It was C.

Comparative Example 3 A silane group was produced in the same manner as in Example 5 except that the mixed monomer used in Example 5 was changed to a mixed monomer consisting of 65 parts by weight of butyl acrylate and 35 parts by weight of methyl methacrylate. A copolymer resin powder containing no copolymer resin was obtained.

The glass transition temperature of this copolymer resin was -19.8°0.

Test Example 1 Using SBR rubber as the organic polymer molding material and white carbon as the inorganic compounded chemical, the affinity modification obtained in Examples 1 to 6 and the case in which all the resin powder obtained in Comparative Examples 1 to 2 were used. , and the case where it was not used was tested as follows.

(Composition) SBR rubber 100 Nipsil VN3 (Note 1) 50 Zinc white 3 3 Stearic acid 1 Sulfur 2 Accelerator 2 Acting SL (Note 2) i, 5 Affinity modifier or resin powder 3 (Note 1 ) White carbon (Note 2) Activator First, use the above formulation excluding the sulfur and accelerator using a roll with a rotation ratio of 1:1:2, a roll temperature of 30 to 40°C, and a rotation ratio of 1:1:2. After kneading, the mixture was vulcanized using rolls at a temperature of 105°C for 3 minutes and a stage steam heating press at a humidity of 150°C.

The unvulcanized Mooney viscosity, vulcanization rate, vulcanization time, and the tensile strength, modulus, hardness, and σ1 crack strength of the vulcanized product were tested. The test results are shown in Table 1.

Test Example 2 Examples 1 to 6 using polyvinyl chloride A/resin as the organic polymer molding material and calcium carbonate as the inorganic compound
Tests were conducted as follows: when the affinity modifier was used, when all the vinyl polymer resin powders obtained in Comparative Examples 1 and 2 were used, and when they were not used.

(Mixture recipe) Polyvinyl chloride resin 100 Calcium carbonate 10 Stabilizer 3 Affinity modifier or resin powder 3 The above mixture was kneaded using a roll kneader at a temperature of 16o0° for 5 minutes, and further kneaded at 180°a, io for 5 minutes. , 100kg/m
A sheet was created under the press sheet conditions of 2.

This sheet was tested for tensile strength, tensile elongation/flexural strength, and flexural modulus. The test results are as shown in Table 1 ○ Table 1 Procedural City Official Book (Voluntary) 1! jAugust 14, 1980 1 Case description 1981 Application No. 215747 2 Name of the invention Aritsuki Polymer molding agent and nothing Relationship with Oriru Personnel I'1 Patent Applicant's Office 4-10-33 Akasaka, Minato-ku, Tokyo Name 4th generation Hoechst Synthesis Co., Ltd. Person 〒540 (1) Mei 101 ``Invention'' Contents of amendment in column 6 of "Detailed Description" (1) "Ester" on page 8, line 12 of the specification is amended to read "1 Nisder, dimethylaminoethyl methacrylate."

(2) 3 lines from the bottom of page 10 [(3) Sulfopropyl]
Before that, break a line and add "(In the formula, R2 is an alkyl group having 12 to 20 carbon atoms)"
Join.

(3) Add a line break next to the blank page on page 10 and add [(wherein R3 is an alkyl group having 8 to 20 carbon atoms).

(4) In lines 12 and 19 of page 16, line 13 of page 11, and line 8 of page 19, the words "transition temperature" are corrected to "transition temperature."

(5) "Drug" on page 19, line 12 has been changed to "drug."

(6) "Inorganic combination drug" on page 20, line 19 is amended to "inorganic combination drug."

that's all

Claims (1)

[Scope of Claims] An affinity modifier between an organic polymer molding agent and an inorganic compounded drug, which is made of a vinylsilane copolymer LIT' IJt7 powder obtained by powdering an aqueous emulsion containing a copolymer. . 2. The affinity modifier according to claim IJII, item 1, wherein the aqueous emulsicon uses a polymerizable fL agent. 3. The affinity modifier according to claim 1, wherein the aqueous emulsion uses an anionic emulsifier. 4. The affinity modifier according to claim 1, wherein the aqueous emulsion uses a cationic emulsifier. 5. An aqueous emulsion containing a copolymer obtained by emulsion polymerization of (a) vinyl silane and (b) a vinyl acetate monomer and/or an acrylic monomer is blended with an inorganic compound and powdered. An affinity modifier for organic polymer molding materials and inorganic compounded chemicals, which is made from the obtained vinyl silane thread copolymer resin powder. 6. The affinity modifier according to claim 5, wherein the inorganic compounded drug is colloidal silica.