JPH02138360A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in impact resistance, moldability, sliding properties, abrasion resistance, weathering resistance and molding appearance by mixing a thermoplastic resin such as a polyphenylene sulfide resin with a specified graft copolymer. CONSTITUTION:The title composition is obtained by mixing 10-90wt.% at least one thermoplastic resin (A) selected from among a polyphenylene sulfide resin, a polyamide resin, a polyester resin, a polycarbonate resin, a vinyl chloride resin, an olefin resin, a polyacetal resin, a polyarylate resin and a polyphenylene ether resin with 90-10wt.% graft copolymer (B) obtained by grafting 95-10wt.% total of an epoxy vinyl monomer (e.g., glycidyl methacrylate) and other vinyl monomers (e.g., styrene) onto 5-90wt.% polyorganosiloxane polymer (e.g., polymer of hexamethylcyclotrisiloxane) copolymerized with 0.1-50wt.% graft crosslinking agent (e.g., p-vinylphenylmethyldimethoxysilane).

Description

[Detailed description of the invention] [Industrial application field] The present invention improves the impact resistance, moldability, slidability, abrasion resistance, weather resistance, and molded appearance of thermoplastic resins such as polyphenylene sulfide resins. The present invention relates to an improved thermoplastic resin composition.

[Conventional technology]

Conventionally, high melting point thermoplastic resins such as polyphenylene sulfide resins have been known as high-performance engineering plastics with excellent heat resistance, chemical resistance, and flame retardancy. However, these thermoplastic resins, such as polyphenylene sulfide resins, have low elongation and are hard;
On the other hand, it has the disadvantage of being brittle.

Therefore, attempts have been made to improve the mechanical strength of this polyphenylene sulfide resin by blending it with other resins. for example,
Blend with epoxy resin (JP-A-51-11844), Blend with styrene resin (JP-A-51-6)
No. 2849), blends with engineering plastics and epoxy resins (Japanese Unexamined Patent Publication No. 59-16436)
Publication No. 0), etc. have been proposed. In addition, a method of adding silane compounds or silicone oil as an additive to improve electrical properties in the presence of moisture, improve mechanical strength when reinforcing glass fibers, and prevent solder adhesion (Japanese Patent Application Laid-Open No. 55-1989-1) 29!526, JP-A-52-52958, JP-A-54-135845), etc. have been proposed.

[Problem to be solved by the invention]

However, the improvement of mechanical strength is insufficient with these methods and good compatibilization techniques are needed to solve it with polymer blends.

In addition, improvements in physical properties by adding silane compounds or silicone oils show good results temporarily, but bleed-out occurs, so the improvements in physical properties cannot be maintained permanently. .

The present invention was made against the background of the problems of the prior art, and uses a specific modified polyorganosiloxane that can efficiently graft-polymerize a vinyl monomer to silicone rubber.
By graft polymerizing silicone rubber with a specific vinyl monomer that significantly improves compatibility with thermoplastic resins such as polyphenylene sulfide resins, the impact resistance, moldability, and sliding properties of thermoplastic resins such as polyphenylene sulfide resins can be improved. The purpose of the present invention is to provide a thermoplastic resin composition with improved mobility, abrasion resistance, molded appearance, etc.

[Means to solve the problem]

The present invention provides (A) polyphenylene sulfide resin;
10 to 90% by weight of at least one thermoplastic resin selected from polyamide resins, polyester resins, polycarbonate resins, vinyl chloride resins, olefin resins, polyacetal resins, polyarylate resins, and polyphenylene ether resins and (B) 5 to 90% by weight of a polyorganosiloxane polymer copolymerized with 0.1 to 50% by weight of a graft cross-agent, and 95 to 10% by weight of an epoxy-containing vinyl monomer and other vinyl monomers. 90 to 10% by weight of a graft copolymer obtained by graft polymerization, and a thermoplastic resin composition is provided.

In the present invention, the polyphenylene sulfide resin is suitably prepared by reacting the following repeating structural unit with sodium sulfide.

At this time, in order to control the degree of polymerization, it is preferable to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide.

A polymer having a degree of polymerization of 100 to 300 is preferable. The polyphenylene sulfide resin preferably contains 70 mol% or more of the repeating structural unit, and if it is less than 70 mol%, it is difficult to obtain a composition with excellent properties.

Methods for producing this polyphenylene sulfide resin include a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing p-dichlorobenzene in the presence of sodium sulfide in a polar solvent,
Examples include a method of self-condensing p-chlorothiophenol, but preferably p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfonic solvent such as sulfolane, where R is alkyl nitro group, phenyl group, alkoxy group, carboxylic acid group or metal base of carboxylic acid), etc., as long as it does not significantly affect the crystallinity of the polyphenylene sulfide resin. The proportion of the copolymer component used is preferably 10 mol% or less. In particular, trifunctional or higher functional phenyl, biphenyl,
When a naphthyl sulfide bond or the like is selected as a copolymerization component, it is preferably 3 mol% or less, more preferably 1 mol% or less.

The polyamide resin used as component (A) is not particularly limited, and includes ethylene diamine, tetramethylene diamine, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2.2.4- and 2,4-
．． Aliphatics such as 4-trimethylhexamethylenediamine, 1,3- and 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexyl)methane, m-xylylenediamine, p-xylylenediamine, Polyamide derived from alicyclic or aromatic diamine and aliphatic, alicyclic or aromatic dicarboxylic acid such as adipic acid, speric acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid; ε- Polyamides obtained by ring-opening polymerization of lactams such as caprolactam and ω-dodecalactam; polyamides derived from 6-aminocaproic acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc., and copolymers thereof Nylon 6 (polycaproamide), nylon 6.6 (polyhexamethylene adipamide), nylon 12 (polydodecaamide), and nylon 6.6, which are polyamides or mixed polyamides and are produced industrially at low cost and in large quantities. 10 (polyhexamethylene diamine), nylon 4.6, and copolymers or mixtures thereof.

Furthermore, the degree of polymerization of the polyamide resin used here is not particularly limited, and usually has a relative viscosity (1 g of polymer is 98% by weight).
100mj of sulfuric acid! (measured at 25°C) is 1.8
Any polyamide resin in the range of ~6.0 can be used, but if one in the range of 2 to 5 is used,
A product with an excellent balance of impact resistance and moldability can be obtained.

There are no restrictions on the molecular structure of the polyamide resin, and it may be either linear polyamide or branched polyamide.

Further, the polyester resin used as component (A) is not particularly limited, but it is one obtained from a polycondensate of a dicarboxylic acid or a derivative such as an alkyl ester of a dicarboxylic acid and a diol.

Among the constituent components of the polyester resin, 70 to 100 mol% of the portion composed of dicarboxylic acid is introduced by terephthalic acid, and 30 to 0 mol% is comprised of isophthalic acid, terephthalenedicarboxylic acid, and adipic acid. , sebacic acid, etc. The moiety composed of glycol is introduced by ethanediol, propanediol, butanediol, penethanediol, and hexanediol, and may be composed of two or more of these.

Further, there may be a portion introduced by oxybenzoic acid or bisphenol A, and mixed polyester resins in which one or more of these polyester resins are mixed are also included in the scope of the present invention.

Such polyester resins include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and copolymers or mixtures thereof.

Furthermore, the polycarbonate resin used as component (A) is obtained by reacting bisphenols with a carbonate precursor such as phosgene or diaryl carbonate.

As the bisphenols, bis(hydroxyaryl)alkanes are preferred, such as 2,2'-bis(4-hydroxyphenyl)propane, 2'2'-bis(4-hydroxy-3,5-hydroxyphenyl) ) propane, 2
．． Examples include 2'-bis(4-hydroxy-3,5-dichlorophenyl)propane. These bisphenols are used alone or in combination.

There is no particular restriction on the degree of polymerization of the polycarbonate resin used here, and the intrinsic viscosity (solvent: methylene chloride, 20
(measured at °C) from 0.3 to 1. Od1/g can be used arbitrarily, and 0.35 to 0.7! Mi! /H, a product with a high level of balance between impact resistance and moldability can be obtained.

Furthermore, the vinyl chloride resin used as component (A) contains a vinyl chloride homopolymer and a double bond that can be copolymerized with vinyl chloride and at most 50% by weight (preferably 45% by weight or less) of vinyl chloride. It is a compound having at least one monomer, preferably a copolymer with another monomer.

Representative examples of compounds having at least one double bond include vinylidene chloride, ethylene, propylene, vinyl acetate, acrylic acid, methacrylic acid, and esters thereof, maleic acid and esters thereof, and acrylonitrile. These vinyl chloride resins are obtained by homopolymerizing or copolymerizing vinyl chloride alone or vinyl chloride and other vinyl monomers in the presence of a free radical catalyst.

The degree of polymerization of this vinyl chloride resin is usually 400 to 4,
500, particularly preferably 400 to 1,500.

Generally speaking, the olefin resin used as component (A) is typified by polyethylene and polypropylene, and each of these is a copolymer with a compound having at least one copolymerizable double bond. There may be,
Examples of such compounds include acrylic acid and methacrylic acid and their esters, maleic acid and its esters, maleic anhydride, and the like. These compounds are preferably copolymerized in a proportion of 10% by weight or less with respect to polyethylene or polypropylene.

The degree of polymerization of the above polyolefin resin is 300 to 6.
Preferably, it is 000.

Furthermore, the polyacetal resin used as component (A) is a stabilized polyoxymethylene resin having polyether bonds, and is a homopolymer type having only oxymethylene groups in the main chain, or a homopolymer type having only oxymethylene groups in the main chain, or oxymethylene groups and oxyethylene groups. There are copolymer types with groups.

Furthermore, the polyarylate resin used as component (A) is a polymer synthesized from aromatic dicarboxylic acid and dihydric phenol, and the main raw materials are terephthalic acid chloride or isophthalic acid chloride and bisphenol A. As a reaction solvent, methylene chloride or the like is used.

The repeating structural units of the polyarylate resin when terephthalic acid chloride and bisphenol A are used are as follows.

Furthermore, the polyphenylene ether resin used as component (D) has the formula -i (wherein, X is a hydrogen atom, or a chlorine atom, a bromine atom, or an iodine atom; and a monovalent substituent selected from halogenated hydrocarbon groups and halogenated hydrocarbon oxy groups having at least two carbon atoms between the halogen atom and the phenol nucleus, R cloud is the same as R1, or halogen atom, R3
and R4 are each the same as R1 or a hydrogen atom. However, none of R1 to R4 has a tertiary carbon atom. ) are obtained by oxidative coupling polymerization of one or more phenolic compounds represented by the following in the presence of a known catalyst, and those obtained by further modifying this with maleic anhydride.

Among the above phenol compounds, particularly preferred ones are those of the general formula A monovalent substituent selected from hydrocarbon groups of numbers 1 to 8 or a hydrogen atom. 2,6-diethylphenol, 2-methyl-6
-Ethylphenol, 2-methyl-6-allylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-sibutylphenol, 2
-Methyl-6-buapyrphenol, 2,3.6-)limethylphenol, 2,3-dimethyl-6-ethylphenol, 2,3.6-triethylphenol, 2.3.
6-) Liprovirphenol, 2,6-cymethyl-3-
Examples include ethylphenol, 2,6-dimethyl-3-propylphenol, and the like.

Specific examples of the most preferred polyphenylene ether resin include polyphenylene ether obtained from 2,6-dimethylphenol and polyphenylene obtained by copolymerization of 2,6-dimethylphenol and 2.3.6-)limethylphenol. It is ether. Especially 2,3
．． Copolymerized polyphenylene ether obtained from 6-trimethylphenol and 2,6-dimethylphenol has good heat resistance, impact resistance, surface gloss of molded products, moldability, solvent resistance, and thermal stability.

The intrinsic viscosity [η] (measured in chloroform at 30°C) of the polyphenylene ether used in the present invention is not particularly limited, but is preferably 0.2 to 1 d.
ft/g, more preferably 0.25-0.7d
It is 1/g.

Among these components (A), polyphenylene sulfide resins, polyamide resins, HoIJ ester resins, and polyphenylene ether resins are preferred, and polyphenylene sulfide resins are more preferred.

These (A) components are used alone or in a mixture, and their proportions in the composition are 10 to 90% by weight,
Preferably it is 20 to 80% by weight.

Next, the polyorganosiloxane polymer used in the graft copolymer (B) of the present invention is obtained by co-condensing organosiloxane (1) and graft cross-agent (II).

Here, as the organosiloxane (1), for example, general 2R', SiO<a-*>/l (in the formula,
R' is a substituted or unsubstituted monovalent hydrocarbon group, and n
represents an integer of O to 3), and has a linear, branched or cyclic structure,
Preferred is an organosiloxane having a cyclic structure.

The substituted or unsubstituted monovalent hydrocarbon group present in this organosiloxane (I) includes, for example, a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, and substituted groups thereof with a halogen atom or a cyano group. Examples include hydrocarbon groups.

Further, in the average compositional formula, the value of n is an integer of 0 to 3.

Specific examples of organosiloxane (I) include cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trinotyltriphenylcyclotrisiloxane;
Mention may be made of linear or branched organosiloxanes.

Note that this organosiloxane (1) has been condensed in advance and has a weight average molecular weight of 500 to 10. It may be a polyorganosiloxane of about '000.

In addition, when the organosiloxane (1) is a polyorganosiloxane, the molecular chain terminal thereof is, for example, a hydroxyl group,
It may be blocked with an alkoxy group, trimethylsilyl group, dimethylvinylsilyl group, methylphenylvinylsilyl group, methyldiphenylsilyl group, or the like.

Further, examples of the graft cross-agent ([) used in the present invention include the following.

(In the formula, RS represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and an alkoxysilyl group.

(b) R' p S i O, s-p,, t (In the formula, R- represents a vinyl group or an allyl group, and p represents an integer of O to 2.) Specific examples: Vinylmethyldimethoxysilane, tetravinyl Tetramethylcyclosiloxane, allylmethyldimethoxysilane.

(c) HS R＠QOLs-q>it
(In the formula, R1 is a divalent or trivalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms, R11 is a monovalent hydrocarbon group containing no aliphatic unsaturated group having 1 to 6 carbon atoms, q is 0~
Indicates an integer of 2. ) Specific example: γ-mercaptopropylmethyldimethoxysilane.

CH.

(d) CHt -6-COO-(cHz) F S
i R'S (wherein R9 is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group, r is an integer of 1 to 6, and S is an integer of O to 2) Specific example: T-methacrylate Roxypropylmethyldimethoxysilane.

Among these graft cross-agents (II), particularly preferred are compounds having both the unsaturated group represented by (a) above and an alkoxysilyl group.

To explain this graft cross-agent (a) in more detail, the above-mentioned -catalytic R5 is a hydrogen atom or a carbon number 1
~6 alkyl group, but hydrogen atom or carbon number 1~
2 is preferably an alkyl group, and more preferably a hydrogen atom or a methyl group.

These (a) graft cross-agents include p
-vinylphenylmethyldimethoxysilane, 1-(m-
vinylphenyl) methyldimethyliso0 (s-m+i
x propoxysilane, 2-(p-vinylphenyl)ethylenemethyldimethoxysilane, 3-(p-vinylphenoxy)propylmethyljethoxysilane, 3-(p-vinylbenzoyloxy)propylmethyldimethoxysilane,
1 (o-vinylphenyl)-1,1,2-trimethyl-2,2-dimethoxydisilane, 1-(p-vinylphenyl)-1,1-diphenyl-3-ethyl-3,3
-jethoxydisiloxane, m-vinylphenyl- [3
In addition to -(triethoxysilyl)propyl]diphenylsilane, (3-(p-isopropenylbenzoylamino)probylcophenyldibroboxysilane), mixtures thereof can be mentioned. (a) As the graft cross-agent, , preferably P-vinylphenylmethyldimethoxysilane, 2-(P-vinylphenyl)ethylmethyldimethoxysilane, 3-(P-vinylbenzoyloxy)
Propylmethyldimethoxysilane, more preferably p-vinylphenylmethyldimethoxysilane. When this (a) graft crossover agent is used, a product with a high grafting rate can be obtained, and therefore a composition that is the object of the present invention is even more excellent.

The proportion of the above-mentioned graft cross-agent (n) used is 0.1 to 50% by weight, preferably 0.5 to 10% by weight, more preferably 0. .5~
5% by weight, and if it is less than 0.1% by weight, a high grafting rate cannot be obtained in the graft polymerization of the obtained polyorganosiloxane-based polymer and the monomer, and as a result,
The interfacial adhesion between the polyorganosiloxane polymer and the vinyl polymer decreases, delamination occurs, and the graft copolymer does not have sufficient impact strength.

On the other hand, when the proportion of the graft cross-agent (II) exceeds 50% by weight, the grafting rate increases, but the polymerization of the grafted vinyl polymer decreases as the graft cross-agent (If) increases, and this vinyl polymer As a result, sufficient impact strength cannot be obtained.

The polyorganosiloxane polymer is produced by shear-mixing the organosiloxane (I) and the grafting agent (n) using a homomixer in the presence of an emulsifier such as alkylbenzenesulfonic acid, and condensing the mixture. can do. This emulsifier becomes a condensation initiator that acts as an emulsifier for organosiloxane (1).

The amount of this emulsifier used is usually about 0.1 to 5% by weight, preferably about 0.3 to 3% by weight, based on the total amount of components (1) and (11).

In addition, the amount of water used at this time is (1) component and (n)
The amount is usually 100 to 500 parts by weight, preferably 200 to 400 parts by weight, per 100 parts by weight of the components.

Further, the condensation temperature is usually 5 to 100''C.

In addition, when producing the polyorganosiloxane polymer,
A crosslinking agent can also be added as a third component to improve the impact resistance of the resulting resin. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. The amount of this crosslinking agent added is usually about 10% by weight or less, preferably about 5% by weight or less, based on the total amount of organosiloxane (1) and grafting agent (II).

The polystyrene equivalent weight average molecular weight of the polyorganosiloxane polymer obtained in this way is usually
10,000 to 1,000,000, preferably 50,
It is about 000 to 500,000.

The graft copolymer used in the present invention is a copolymer obtained by graft polymerizing an epoxy group-containing vinyl monomer and another vinyl monomer in the presence of the polyorganosiloxane polymer thus obtained. be.

Here, as the epoxy group-containing vinyl monomer,
Examples include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, and glycidyl itaconate.

In addition, other vinyl monomers include styrene, α-methylstyrene, vinylxylene, monochlorostyrene,
Dichlorostyrene, monobromstyrene, dibromstyrene, p-butylstyrene, ethylstyrene, vinylnaphthalene, 0-methylstyrene, p-methylstyrene,
Aromatic alkenyl compounds such as dimethylstyrene and sodium styrene sulfonate; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, butyl methacrylate, allyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate , acrylic acid esters such as dimethylaminoethyl methacrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; ethylene,
Olefins such as propylene; conjugated diolefins such as butadiene, isoprene, and chlorobrene; and vinyl acetate, vinyl chloride, vinylidene chloride, triallylisocyanurate, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-o -Maleimides such as chlorphenylmaleimide and N-dichlorohexylmaleimide may be mentioned, and these may be used alone or in combination.

When graft polymerizing a polyorganosiloxane-based polymer with an epoxy group-containing vinyl monomer and other vinyl monomers, the charging composition should be such that the polyorganosiloxane-based polymer is 5 to 90% by weight or 10% by weight. -70% by weight, more preferably 20-60% by weight, and the total amount of vinyl monomers is 95-10% by weight, preferably 90-3% by weight.
0% by weight, more preferably 80 to 40% by weight.

If the polyorganosiloxane polymer content is less than 5% by weight, sufficient impact strength cannot be obtained, while if it exceeds 90% by weight, a good powder cannot be obtained as a graft copolymer and it will not be dispersed during blending.

The content of the polyorganosiloxane polymer in the entire composition is preferably 5 to 30% by weight, 5% by weight.
If it is less than 30% by weight, sufficient impact strength may not be obtained, while if it exceeds 30% by weight, heat resistance may decrease.

Further, the content of the epoxy group-containing vinyl monomer in the graft copolymer is preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, and if it is less than 0.05% by weight, for example, polyphenylene The compatibilization effect between the sulfide resin and the graft copolymer decreased, while 3
If it exceeds 0% by weight, the degree of gelation will increase and extrusion moldability may become difficult. Other vinyl monomers are not essential, but from the relationship between the amounts of the polyorganosiloxane polymer and the epoxy group-containing vinyl monomer in the graft polymer, the proportion of the epoxy group-containing vinyl monomer in the graft polymer is determined as described above. It is preferable to use an amount of Particularly preferably epoxy group-containing vinyl monomer/
The ratio of other vinyl monomers is 0.5-95/99.5-
5 (wt%), more preferably 1 to 90/99
~10 (wt%).

Furthermore, the content of the epoxy group-containing vinyl monomer in the entire composition is preferably 0.01 to 5% by weight, more preferably 0.02 to 4% by weight, and if it is less than 0.01% by weight, for example, polyphenylene sulfide The compatibilization effect between the system resin and the graft copolymer decreased, while at 5% by weight
If it exceeds 100%, the degree of gelation becomes high and extrusion moldability may become difficult.

Furthermore, the grafting ratio to the polyorganosiloxane polymer in the graft copolymer is preferably 10% by weight or more, and if it is less than 10% by weight, the molded appearance may deteriorate and may be undesirable.

The proportion of the above graft copolymer (B) in the composition of the present invention is 10 to 90% by weight, preferably 7 to 15% by weight.
OW amount%, more preferably 20 to 50% by weight,
If it is less than 10% by weight, the impact resistance of the resulting composition will decrease, while if it exceeds 90% by weight, the heat resistance and chemical resistance will decrease.

When producing the graft copolymer (B) used in the present invention, an epoxy-containing vinyl monomer or other vinyl monomer (hereinafter collectively referred to as "vinyl monomer") is added to the polyorganosiloxane polymer.
is graft-polymerized by ordinary radical polymerization to obtain a composition containing the graft copolymer (B).

Here, depending on the type of radical polymerization initiator, as mentioned above, the latex of polyorganosiloxane polymer made acidic by alkylbenzenesulfonic acid may be
Needs to be neutralized with alkali. Examples of this alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine,
Triethylamine and the like are used.

In addition, as a radical polymerization initiator, for example, an oxidizing agent consisting of an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide, a sugar-containing iron birophosphate formulation, or a sulfoxylate formulation. Redox system initiators in combination with reducing agents such as sugar-containing iron birophosphate formulation 7/mixed formulation of sulfoxylate formulation - persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, dimethyl -2,2'
-Azo compounds such as azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide, and preferably the redox-based initiator. .

The amount of these radical polymerization initiators used is usually 0.05 to 5 parts by weight per 100 parts by weight of the nil monomer.
Parts by weight, preferably 0.1 to 3 parts by weight.

As the radical polymerization method at this time, it is preferable to carry out emulsion polymerization or solution polymerization.

During emulsion polymerization, known emulsifiers, the aforementioned radical initiators, chain transfer agents, and the like are used.

Here, as the emulsifier, anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenyl ether disulfonate, sodium dialkali succinate sulfonate, polyoxyethylene alkyl ester, polyoxyethylene alkyl allyl ether, etc. One or more nonionic emulsifiers may be used.

The amount of emulsifier used is usually 0 to the vinyl monomer.
．． It is about 5 to 5% by weight.

As a chain transfer agent, t-dodecylmercaptan, octylmercaptan, n-tetradecylmercaptan, n
-Mercaptans such as hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide are usually used in an amount of 0.02 to 1% by weight based on the vinyl monomer.

During emulsion polymerization, in addition to radical polymerization initiators, emulsifiers, chain transfer agents, etc., various electrolytes and pH
1! Generally, 100 to 500 parts by weight of water and the radical polymerization initiator, emulsifier, chain transfer agent, etc. are used in the above ranges, based on 100 parts by weight of the monomer, in combination with a conditioning agent, etc. Polymerization temperature 5-100°C, preferably 5
Emulsion polymerization is carried out under conditions of 0 to 90°C and polymerization time of 0.1 to 10 hours.

In the case of emulsion polymerization, it is carried out by adding a vinyl monomer and a radical initiator to a latex containing a polyorganosiloxane polymer obtained by condensation of organosiloxane (1) and a graft cross-agent (IN). You can also.

On the other hand, in the case of solution polymerization, a polyorganosiloxane polymer and a vinyl monomer are dissolved in an organic solvent, and a radical initiator, a chain transfer agent if necessary, and various additives are added thereto, and radical polymerization is performed.

Examples of the organic solvent used in this solution polymerization include toluene, n-hexane, cyclohexane, chloroform, and tetrahydrofuran.

During solution polymerization, a radical polymerization initiator and, if necessary, a chain transfer agent, etc. are used in combination, and 80 to 500 parts by weight of an organic solvent are usually added to 100 parts by weight of the vinyl monomer, and the radical polymerization initiator, Solution polymerization is carried out using a chain transfer agent and the like in an amount within the above range, and at a polymerization temperature of 5 to 150°C, preferably 50 to 130'C, and a polymerization time of 1 to 10 hours.

In the case of this solution polymerization, impurities can be reduced more significantly than in the case of emulsion polymerization.

When the graft copolymer (B) used in the present invention is produced by emulsion polymerization, it is purified by coagulating it by a conventional salt coagulation method, washing the obtained powder with water, and then drying it.

In the case of solution polymerization, unreacted monomers and solvent are distilled off by steam distillation, and the resulting resin mass is crushed and dried to refine the resin.

In order to obtain the composition of the present invention, the components (A) and (B) are mixed, for example, in a mixer, and then melt-kneaded in an extruder at 280 to 320'C to form pellets. Furthermore, each component can be easily melted and kneaded directly in a molding machine to be molded.

The compositions of the invention include antioxidants such as 2.6-di-butyl-4-medylphenol, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2.
2-methylene-bis-(4-ethyl-6-tert-butylphenol), tris(di-nonylphenyl)phosphite; UV absorbers such as pt-butylphenyl salicylate, 2,2'-dihydroxy-4- Methoxybenzophenone, 2-(2'-hydroxy-4-m-octoxyphenyl)benzotriazole; Lubricants such as paraffin wax, stearic acid, hydrogenated oils, stearamide, methylene bisstearamide, n-butyl stearate, Ketone wax, octyl alcohol, hydroxystearic acid triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris(dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane,
Hexabromobenzene, tetrabromobisphenol A
; Antistatic agents, such as stearamidopropyldimethyl-β-hydroxyethyl, ammonium drate; Color inhibitors, such as titanium oxide, carbon black; Fillers, such as calcium carbonate, clay, silica, glass fibers, glass spheres, carbon fibers ;Pigments etc. can be added as necessary.

The thermoplastic resin composition pelletized in this way is processed and processed by conventional means such as compression molding and injection molding.
molded.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and % in the examples are parts by weight and % by weight unless otherwise specified.

In addition, various measurement items in the examples were as follows.

The grafting rate was determined by the following method. Namely.

Accurately weigh and collect 1 g of material, add 20 cc of acetone to it, let it rise for 10 hours, and then rotate at a rotation speed of 20.00 O.
Separate the soluble and insoluble components using a rpm centrifuge,
The insoluble matter was dried in a vacuum dryer to obtain an insoluble matter (X). On the other hand, the amount of rubber (R) in the insoluble matter (X) was calculated from the polymerization composition and the polymerization conversion rate, and the grafting rate was determined using the following formula.

Izot impact strength is ASTM-D256.1/4'
Measurements were taken at 23°C with a notch and -30°C with a 1/4# notch.

Melt flow rate (MFR) is JIS K7
210, at the temperatures shown in Table 3, using 10 kg.

Heat distortion temperature is based on ASTM D648, load 1
Measured at 8.6 kg/cd without annealing.

Chemical resistance was determined by applying constant strain at a strain rate of 1% to a test piece (1/8'xi/2" x 5"), applying dioctyl phthalate (DOP) and brake fluid to the deflected part, and The time taken to break after being left at 23°C was measured and used as an index of chemical resistance.

O indicates no breakage or cracking for 100 hours or more.

Glossiness was measured at 45°C according to ASTM D523.

The weld strength retention rate was determined by measuring the tensile strength (Tw) of a test piece molded using a mold with a weld line in the center of an ASTMI dumbbell, and then measuring the tensile strength (Tw) of a test piece molded with a mold without a weld line. The tensile strength (To) was measured using the same method, and the weld strength retention rate was determined using Tw/ToX100%.

The sliding properties were determined as follows.

That is, in the friction and wear test, a lead dust type sliding tester was used, and the same material or steel (345C) was used as the mating material. The test piece has an outer diameter of 25.6cm and an inner diameter of 20°OIl!
No. 11 hollow cylindrical material was used, and a counterpart material of the same shape was also used.

The measurement conditions for the coefficient of dynamic friction were a load of 5 kg and a running speed of 3.75 C1/sec in an atmosphere with a room temperature of 23° C. and a humidity of 50%.

The coefficient of dynamic friction is calculated using the following formula.

(In the formula, μ is the specific wear amount, F is the force applied to the load cell, P
is the load, R is the arm length to the load cell, rl is the inner diameter, and rl is the outer diameter.) The measurement conditions for the specific wear amount are a load of 5 for the same material in an atmosphere of room temperature 23°C and humidity 50%. kg, running speed 3.7
5C11/sec, 12.600 rotations (running speed 0.241
G*), and in the case of steel (345C), it was measured at a load of 10 kg, a running speed of 15 C1/sec, and 80,000 rotations (running speed of 6 h).

The specific wear amount is calculated using the following formula.

PXβ×α (where A is the specific wear amount, ΔW is the change in sample weight, P
is the load, l is the traveling distance, and α is the density of the sample.) The weather resistance test was conducted using a Sunshine Weather Meter (manufactured by Toyo Rika, model WE-USN-HC) and exposed for 200 hours (63°C5 rain). After that, the Izot impact strength was measured.

Molding processability was determined by whether gelation or molded product cracking occurred during the process of granulating with an extruder and obtaining a molded product with a molding machine.

The appearance of the molded product was determined based on whether flow marks such as silver were generated on the surface of the molded product.

Reference Example 1 [Polyorganosiloxane polymer (R-1~
3) Production] p-vinylphenylmethyldimethoxysilane and octamethylcyclotetrasiloxane were mixed in the proportions shown in Table 1, and this was added to 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved. , by homomixer 3
Stir for a minute to emulsify and disperse.

This liquid mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet, and a stirrer, heated at 90°C for 6 hours while stirring and mixing, and cooled at 5°C for 24 hours to complete condensation.

The condensation rate of octamethylcyclotetrasiloxane in the obtained polyorganosiloxane polymer was 92.8%.

This polyorganosiloxane polymer latex was neutralized to pH 1 with an aqueous sodium carbonate solution.

Table 1 Reference Example 2 (Production of Graft Copolymers G-1 to 8) Internal volume 7I equipped with a stirrer! Into a glass flask of
Batch polymerization components consisting of the polyorganosiloxane polymer latex and various monomers shown in the table were added, and the temperature was raised while stirring. When the temperature reaches 45°C, an active solution consisting of 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of formaldehyde sodium sulfoxylate trihydrate and 15 parts of ion-exchanged water is added. An aqueous solution of the agent and 0.1 part of diisopropylbenzene hydroperoxide were added, and the reaction was continued for 1 hour.

After that, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.02 part of potassium hydroxide, t
- 0.1 part of dodecyl mercaptan, 0.1 part of diisopropylbenzene hydroperoxide. A mixture of incremental polymerization components consisting of 2 parts and various monomers in the proportions shown in Table 2 was added continuously over a period of 3 hours to continue the reaction.

After the addition was completed, the reaction was continued for 1 hour with further stirring, and then 2,2-methylene-bis-(4-ethylene-6-t
-butylphenol) was added, and the reaction product was taken out from the flask.

The product is then coagulated using 2 parts of potassium chloride,
A powdered polymer was recovered by dehydration, water washing, and drying.

Table 2 shows the monomer polymerization conversion rate, as well as the grafting rate and intrinsic viscosity [η] measured by the method described above.

Examples 1 to 16, Comparative Examples 1 to 6 Each component shown in Table 3 was heated at a temperature of 2
The mixture was melt-kneaded at a temperature of 80 to 320''C to produce a pellet.

This pellet was molded into a 5o injection molding machine (manufactured by Toshiba ■, l5-8).
A test piece was prepared by molding at a molding temperature of 280 to 320° C., and its physical properties were evaluated. 3rd result
Shown in the table.

In addition, in the Examples and Comparative Examples, the following was used as the (A) component.

PPS (polyphenylene sulfide resin); manufactured by Tobren ■, Tobren T-4 Nylon 6; manufactured by Toshi ■, Amilan CM1.017 nylon 4.6s manufactured by DSM, 5tanyl PBT (polybutylene terephthalate); manufactured by Polyplastic ■, Duranex XD499PC (Polycarbonate); manufactured by Idemitsu Petrochemical ■, A-2200 pvc (polyvinyl chloride); manufactured by Toagosei Chemical ■, Aron TS700 MPP (maleic anhydride modified polypropylene); manufactured by Mitsubishi Yuka ■, MODICP-10B POM (polyoxy methylene); made by polyplastic ■, Duracon M90 Polyarylate; made by Unitika ■, U polymer PPE (
Polyphenylene ether) was obtained by the following method.

A polymerization reaction of 2,6-xylenol of PPE Bo1 enylene ale was carried out in a toluene solution at 30° C. while blowing oxygen using cupric bromide and di-n-butylene amine as catalysts.

After the polymerization was completed, an aqueous solution of disodium ethylenediaminetetraacetate was added to remove the catalyst.

The polymer solution phase was removed from the resulting product mixture by centrifugation. While vigorously stirring this polymer solution, methanol was gradually added to form a slurry.

After separating the solid content, it was thoroughly washed with methanol and dried to obtain a polymer (PPEI). [η] of the polymer PPEI measured at 30°C using chloroform as a solvent was 0.40a/g.

After tri-blending 100 parts by weight of the polymer PPEI with 2 parts of maleic anhydride and 71 parts of 2,5-dimethyl-2,5-di(t-butylene peroxy) hexa at room temperature, Using a two-wheel extruder with a directional rotation vent, the polymer was melt-kneaded at a cylinder temperature of 300°C and a screw rotation speed of 15 Orpm to pelletize the polymer to obtain maleic anhydride-modified polyphenylene ether (PPE2). Ta. As is clear from Table 3,
According to Examples 1 to 16, thermoplastic resin compositions targeted by the present invention were obtained.

On the other hand, in Comparative Examples 1 to 7, the desired effects of the present invention cannot be obtained.

That is, in Comparative Examples 1 and 2, the amount of grafting agent in the polyorganosiloxane polymer was outside the range, and the Izot impact strength was poor. Comparative Example 3 is an example of a composition outside the scope of the present invention that uses a graft copolymer that does not use an epoxy group-containing monomer. Poor appearance. Comparative Example 4 is an example in which the graft copolymer is below the range of the present invention, and the impact resistance and weld strength retention are poor. Comparative example 5
is an example in which the graft copolymer exceeds the scope of the present invention and has an inferior heat distortion temperature. Comparative Example 6 shows the physical properties of PP5 (polyphenylene sulfide resin).

〔Effect of the invention〕

The thermoplastic resin composition of the present invention has highly balanced impact resistance, moldability, and chemical resistance. In addition, the composition of the present invention eliminates the drawbacks of conventional polyphenylene sulfide resins and polyarylate resins, and further improves the weather resistance, cold resistance, and sliding properties that are the characteristics of silicone rubber.
We succeeded in imparting properties such as abrasion resistance, resulting in a new thermoplastic resin with excellent characteristics not found in conventional thermoplastic resins. Therefore, the thermoplastic resin composition of the present invention is a molding material that satisfies the requirements of the molding processing industry, and can be applied to new fields of use such as sliding parts, outdoor parts, heat-resistant parts, and chemical resistance. The industrial significance is extremely large.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent attorney Takashi Shirai

Claims (1)

[Claims] (1) (A) At least one selected from polyphenylene sulfide resin, polyamide resin, polyester resin, polycarbonate resin, vinyl chloride resin, olefin resin, polyacetal resin, polyarylate resin, and polyphenylene ether resin. 10 to 90% by weight of one type of thermoplastic resin and 5 to 90% by weight of a polyorganosiloxane polymer copolymerized with (B) 0.1 to 50% by weight of a grafting agent, an epoxy-containing vinyl monomer, and other vinyl. A thermoplastic resin composition comprising: 90 to 10% by weight of a graft copolymer obtained by graft polymerizing 95 to 10% by weight of a total of monomers.