JPS6011549A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which give moldings having excellent surface gloss, coatability and resistance to solvents, heat and impact, containing a polyphenylene other and a specified thermoplastic resin obtd. by polymerizing a resin forming component contg. an arom. vinyl compd. and a vinyl cyanide compd. CONSTITUTION:A resin compsn. consists 5-90wt% polyphenylene ether, a thermoplastic resin obtd. by polymerizing a resin forming component contg. an arom. vinyl compd. and a vinyl cyanide compd. and 0-85wt% styrene resin, said thermoplastic resin containing 5-100wt% total free polymer which contains 1-50wt% polymer component (A) having a vinyl cyanide compd. content of 1-10wt%, 1-70wt% polymer component (B) having a vinyl cyanide compd. content of 10-20wt%, 5-90wt% polymer component (C) having a vinyl cyanide compd. content of 20-40wt% and 0-70wt% polymer component (D) having a vinyl cyanide compd. content of 40wt% or above, the quantity of the vinyl cyanide compd. accounting for 10-40wt% of the total free polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermoplastic resin composition that has excellent heat resistance, impact resistance, surface gloss of molded articles, paintability, and solvent resistance.

Polyphenylene ether is widely known as a resin with excellent heat resistance, mechanical properties, electrical properties, etc. However, this polyphenylene nitrate has disadvantages such as low impact resistance, poor processability and chemical resistance, and heat discoloration and dulling at high temperatures, so it is rarely used alone and is usually is used as a modified polyphenylene ether resin consisting of a composition of polystyrene and rubber-modified polystyrene. This modified polyphenylene ether resin has excellent heat resistance, mechanical properties, electrical properties, processability, etc., and is therefore widely used in automobile parts, office equipment, electrical appliance parts, and the like.

However, the rubber-modified tyristyrene is usually obtained by dissolving a rubbery polymer in a styrene monomer and then polymerizing it in a bulk form. It is necessary to limit the amount of the rubber-modified polystyrene, and it is usually used in an amount around 10% by weight or less of the rubber-modified polystyrene. A composition of rubber-modified polystyrene and polyphenylene ether with such a composition does not have sufficient impact resistance, and the corners and thin-walled parts may crack when the molded product is removed from the mold during molding. Ta. Therefore, in order to improve the impact resistance, rubber-like elastic bodies are mixed into the composition, but
In this case as well, impact resistance is not sufficient and it is easy to discolor due to heat.
It had drawbacks such as poor workability.

In addition, compositions of rubber-modified polystyrene and polyphenylene ether may cause phenomena such as poor surface gloss of molded products and cracks, crazes, and blow-outs (causing uneven color on the surface of the coating) to occur on the surface when painted. It has drawbacks such as easy coating, poor paintability, and poor solvent resistance.

On the other hand, styrene-acrylonitrile copolymer and hycomb polymer-styrene-acrylonitrile copolymer (AB
S resin) is widely used as a resin with excellent paintability, solvent resistance, impact resistance, and processability. However, these resins generally contain 20 to 30% by weight of acrylonitrile, and when mixed with polyphenylene ether, they generally have poor compatibility, resulting in poor appearance and poor impact resistance, heat resistance, and paintability. It has the disadvantage of being inferior.

Therefore, various means have been proposed to eliminate the drawbacks of the above-mentioned modified polyphenylene ether resins.

For example, Japanese Patent Publication No. 57-8139 reports a composition obtained by blending an ABS resin modified with methyl methacrylate and a polyphenylene ether resin. However, this composition has poor thermal stability, and since methyl methacrylate is expensive, the composition itself is expensive, which is industrially disadvantageous. In addition, special public service No. 48-40046
No. 1, No. 2003, reports a heat-resistant resin mixture made by mixing a styrene-acrylonitrile copolymer with a lower acrylonitrile content than ordinary products and polyphenylene ether. However, this mixture still had insufficient improvements in heat resistance and solvent resistance. Furthermore, the compositions and mixtures disclosed in these two publications were insufficient in terms of surface gloss and paintability of molded articles.

In addition, a composition has been proposed in which a specific amount of styrene resin containing a small amount of vinyl cyanide compound is added to styrene resin containing a large amount of vinyl cyanide compound, and these are mixed with polyphenylene ether. However, the paintability was not sufficient.

Therefore, the inventors of the present invention have conducted extensive studies on the composition of thermoplastic resin compositions that can be improved in all aspects, including heat resistance, impact resistance, surface gloss of molded products, solvent resistance, and paintability. We have discovered that the above improvements can be sufficiently achieved by blending an aromatic vinyl compound resin that has been polymerized so that the vinyl cyanide compound content has a specific compositional distribution with poly(5) phenylene ether. invention has been achieved.

The objects of the present invention are heat resistance, impact resistance, molded product surface gloss,
An object of the present invention is to provide a new thermoplastic resin composition that has excellent paintability and solvent resistance.

That is, the thermoplastic resin composition of the present invention contains polyphenylene ether of 5 to 90 weight is1. :='In the presence or absence of a mucilaginous IT polymer, a resinous component consisting of an aromatic vinyl compound, a vinyl cyanide compound, and if necessary, another vinyl monomer copolymerizable with these is polymerized. Thermoplastic resins 95-10% by weight and other styrenic resins 0-85%
% by weight, wherein the thermoplastic resin has a methyl ethyl ketone soluble content (total free polymer) of 5 to 100% by weight.
% by weight, and in the total free polymer, the content of (A) vinyl cyanide compound is 1 to 50% by weight, and the content of (A) vinyl cyanide compound is 1 to 50% by weight, and (B) vinyl cyanide compound. (6) (C) The content of vinyl cyanide compound is 20% by weight or more and 4.
5 to 90% by weight of a polymer component having a composition of less than 0% by weight; and 0 to 70% by weight of a polymer component having a composition of 40% or more of vinyl cyanide compounds; It is characterized in that the content of vinyl cyanide compound in the coalescence is 10 to 40% by weight.

The polyphenylene ether used in the present invention has the general formula: (wherein, X is hydrogen, chlorine, bromine or iodine, and R
Fi is a monovalent substituent selected from a hydrocarbon group, a hydrocarbon oxy group, a halodanized hydrocarbon group and a halodanized hydrocarbon oxy group having at least two carbon atoms between the halodan atom and the phenol nucleus, R1 is the same as R or is a halodane atom, and R2 and R3 are each the same as R1 or hydrogen. However, Fj p
Neither R1*R2 nor R3 has a tertiary carbon atom. ) is obtained by oxidative coupling polymerization of at least one phenol compound represented by () in the presence of a known catalyst.

Particularly preferred among the above phenol compounds are the general formula: (wherein R' and B11 are each monovalent substituents selected from hydrocarbon groups having 1 to 8 carbon atoms,
3' each represents a monovalent substituent selected from hydrocarbon groups having 1 to 8 carbon atoms or hydrogen. ), and specific examples of the most preferred phenol compounds include 2,6-dimethylphenol,
2,6-noethylphenol, 2-methyl-6-nitylphenol, 2-methyl-6-allylphenol, 2-
Methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-sibutylphenol, 2-methyl-6-frovirophenol, 2.3.6-dolimethylphenol, 2,3-dimethyl-6- Examples include nitylphenol.

Intrinsic viscosity [η
] (30°C in chloroform) is not particularly limited, but is preferably 0.2 to 1 dt/g, more preferably 0°3 to
It is 0°7 dt/9. The amount of polyphenylene ether blended in the thermoplastic resin composition of the present invention is 5 to 90% by weight, preferably 10 to 60% by weight. When the amount of polyphenylene ether is less than 5% by weight, no remarkable effect on improving heat resistance is observed, and when it exceeds 90% by weight, no effect on improving impact resistance and processability is observed.

The rubbery polymers used in the present invention include f-α-olefins such as polyethylene and polypropylene; Copolymers with ethylene α-olefin such as copolymers; copolymers of ethylene and unsaturated carenoic acid esters such as ethylene-methacrylate and ethylene-butyl acrylate; copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Polymers: Ethylene-zoropyrene-nonconjugated genter polymers such as ethylene-zolobylene-ethylidene nordernene copolymer and ethylene-zolopyrene-hexadiene copolymer; polybutadiene, styrene-butadiene random copolymers and block copolymers Diene rubbers such as acrylonitrile-butadiene copolymers and butanoene-isoprene copolymers; butylene-isoprene copolymers; and block copolymers of aromatic hydrocarbons such as styrene and aliphatic hydrocarbons such as butadiene and isoprene. Hydrogenated products of polymers; etc., and these can be used alone or in combination of two or more.

Preferably used rubbery polymers are ethylene-(10)zolopyrene-nonconjugated dientanipolymer and diene rubber. More preferred are polybutadiene and styrene-ptazoene copolymers, and the styrene content in this styrene-butadiene copolymer is preferably 50% by weight or less. Furthermore, when the rubbery polymer contains 10% by weight or more of toluene-insoluble parts, the surface gloss and solvent resistance of the molded product are good.

The aromatic vinyl compounds used in the present invention include styrene, α
-Methylstyrene, methylstyrene, vinylxylene,
Monochlorostyrene, dichlorostyrene, monobromustyrene, cybromustyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, etc.
These can be used alone or in combination of two or more. The aromatic vinyl compound preferably used is styrene, and even when two or more aromatic vinyl compounds are used together, it is preferable to use styrene in a proportion of 50% by weight or more.

The vinyl cyanide compound used in the present invention is acrylonitrile, methacrylaterile, etc., and acrylonitrile is preferred. In the thermoplastic resin used in the present invention, the content of vinyl cyanide compounds in the total free polymer is 10
-40%, preferably 15-35% by weight, more preferably 15-30% by weight, particularly preferably 20% by weight.
~28 weight-ffi%. If the vinyl cyanide compound content is less than 10% by weight, the surface gloss, impact resistance, paintability and solvent resistance of the molded product will be poor. If it exceeds 40% by weight, the surface gloss, impact resistance and heat resistance of the molded product will be poor.

The thermoplastic resin of the present invention is characterized in that the vinyl cyanide compound has a composition distribution in the total free polymer (methyl ethyl ketone soluble part), and the vinyl cyanide compound has a composition distribution in the total free polymer (methyl ethyl ketone soluble part). The composition is such that (A) a polymer component having a vinyl cyanide compound content of 1% by weight or more and less than 10% by weight is 1 to 50% by weight, preferably 5% by weight.
~30% by weight. If it is less than 1 weight, heat resistance, impact resistance, molded product surface gloss, and paintability will be poor. Moreover, if it exceeds 50% by weight, paintability and solvent resistance will be poor. (B) A polymer component having a composition in which the content of vinyl cyanide metal is 10% by weight or more and less than 20% by weight is 1 to 70% by weight, preferably 5 to 70% by weight.
% by weight, more preferably 10 to 50% by weight. If it is less than 1% by weight, heat resistance, impact resistance and paintability will be poor, and if it exceeds 70% by weight, paintability and solvent resistance will be poor. (C) A polymer component having a composition in which the vinyl cyanide compound content is 20% by weight or more and less than 40% by weight is 5 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 80% by weight.
It is. If the weight is less than 5, paintability and solvent resistance will be poor;
If the weight exceeds 0 weight, the heat resistance and impact resistance of the molded product will be poor in gloss coating. ■Content of vinyl cyanide compound is 40% by weight
The weight component of the above composition is 0 to 70% by weight, preferably 0 to 20% by weight, and more preferably free. If it exceeds 70% by weight, heat resistance, impact resistance, molded product surface gloss, and paintability will be poor.

The content of all the free polymers in the thermoplastic resin is usually 5 to 100% by weight, preferably 10 to 100% by weight, and more preferably 15 to 100(13)% by weight.

The intrinsic viscosity (in toluene at 30 DEG C.) of all free polymers is 0.1 to 1.5, preferably 0.3 to 1 DEG, and more preferably 0.4 to 0.8.

Other vinyl monomers copolymerizable with the aromatic vinyl compound and vinyl cyanide compound used in the present invention include methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate,
Alkyl esters of acrylic acid such as hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate,
Ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, (14) Methacrylic acid alkyl esters such as phenyl methacrylate, benzyl methacrylate, anhydrous Examples include unsaturated acid anhydrides such as maleic acid, itaconic anhydride and citraconic anhydride, unsaturated acids such as acrylic acid and methacrylic acid, and these may be used alone or in combination of two or more.

The other copolymerizable vinyl monomer is preferably 50% by weight or less, more preferably 3% by weight in the copper lipid component.
It is blended in a proportion of 0% by weight or less.

The styrenic resin used in the present invention is a polymer of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and other copolymerizable monomers, and these aromatic vinyl compounds and copolymers As possible other monomers, all of the specific compounds exemplified as aromatic vinyl compounds and vinyl cyanide compounds and other copolymerizable vinyl monomers in the resinous constituent components can be used. Furthermore, the styrenic resin can also contain rubbery polymers such as those exemplified above, if necessary.

Preferred styrene resins include polystyrene, &'
J Chlorstyrene, polyα-methylstyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-α-methylstyrene copolymer, styrene-
α-Methylstyrene-methyl methacrylate copolymer, styrene-α-methylstyrene-acrylonitrile-methyl methacrylate copolymer, etc., and rubber modified products thereof.These may be used alone or in combination of two or more. Can be used. The acrylonitrile content in the styrene resin is 40% by weight or less, and the methyl methacrylate content is 80%.
It is preferable that the styrene content is 20% by weight or more. 1. The amount of the styrene resin added to the thermoplastic resin composition of the present invention is 0 to 85% by weight. If it exceeds %, paintability, heat resistance, impact resistance, and molded product surface gloss will be poor.

When the thermoplastic resin or styrenic resin used in the present invention contains a rubbery polymer, the preferable content of the rubbery polymer in these resins depends on the polymerization method of the resinous constituent components, or the resulting thermoplastic resin or styrene resin. It varies depending on the size of the rubbery polymer particles dispersed in the styrene resin. For example, resinous constituents can be subjected to bulk polymerization, solution polymerization,
When polymerizing by suspension polymerization, bulk-solution polymerization, bulk-suspension polymerization, etc., the particle size of the rubbery polymer is preferably 0.5 to 5 μm from the viewpoint of impact resistance, and from the viewpoint of surface gloss of the molded product. 0.5-2μ is preferable. In this case, the content of the rubbery polymer is preferably 3 to 20% by weight. On the other hand, when the resinous constituent components are polymerized by emulsion polymerization, emulsion-suspension polymerization, etc., the particle size of the rubbery polymer is preferably 0.05 to 1μ, and in this case, the content of the rubbery polymer is 10 to 70μ. weight%
, and more preferably 20 to 60 weight. especially,
From the viewpoint of impact resistance, the content is preferably 30 to 50% by weight.

In order to obtain a thermoplastic resin composition that has improved heat resistance, impact resistance, molded product surface gloss, paintability, and solvent resistance in a well-balanced manner, which is the objective of the present invention, the thermoplastic resin used in the present invention must be emulsified. Preferably, (17) is obtained by polymerization.

When a rubbery polymer is used in the thermoplastic resin and styrene resin used in the present invention, the characteristics of the resinous polymer grafted to the rubbery polymer, that is, the grafting ratio (solvent methyl ethyl ketone), impact resistance, moldability, etc. Product surface gloss,
From the viewpoint of improving solvent resistance and paintability, 10 parts by weight or more, more preferably 300 parts by weight, per 100 parts by weight of the rubbery polymer.
The amount is preferably 200 parts by weight, and the thickness of the resinous polymer grafted onto the surface of the rubbery polymer is 100 to 200 parts by weight.
The thickness is preferably in the range of 200 angstroms from the viewpoint of surface gloss of the molded product. The thickness of this resinous polymer can be measured using electron micrographs using common methods for observing externally grafted resinous polymers.

In the present invention, when a thermoplastic resin or styrene resin is obtained by graft polymerizing a resinous component onto a rubbery polymer by emulsion polymerization, the rubbery polymer used is in a latex state. Ru. As this latex, a rubbery polymer latex obtained by an emulsion polymerization method (18) can be used, or a solid rubbery polymer obtained by another method can be used as a monomer and/or a rubbery polymer latex obtained by another method. : It is also possible to use a rubbery polymer latex which is made into an emulsion after being dissolved in an organic solvent.

The preferred rubbery polymer latex used is: (1) 70% by weight or more of particles with a particle size of 500X to 1730X are present;
and has a dull (toluene insoluble part, the same hereinafter) content of 50% by weight or more, (2) has a particle size of 1730X to 4400X of 70% by weight or more, and has a glue content of 60% by weight.
or more; (i) particle size is 4400X or more and 50% by weight or more is present, and the glue content is 70 to 20% by weight; (ii) the polymer latex ■/■ = 5 to 50/95
-50% by weight mixture, ■The polymer latex ■/■=95-515-95% by weight, or ■The polymer latex ■/■/■=
It is a mixture of 0 to 50/95 to 4015 to 60% by weight.

When the rubbery polymer latex of (1) or (2) is used, the molded product has particularly good surface gloss, workability, and stress crack resistance. ■When using the rubbery polymer latex,
Particularly good impact resistance.

Furthermore, when the polymer latex of (1), (2), or (2) is used, the molded product has particularly good surface gloss, stress crack resistance, impact resistance, and processability.

The thermoplastic resin of the present invention is preferably obtained in the presence of a rubbery polymer in terms of impact resistance.

As mentioned above, the thermoplastic resins used in the present invention have different vinyl cyanide compound contents in the total free polymer.
It contains the polymer component b), which can be obtained by polymerizing while varying the monomer composition of the resinous component used.

In order to carry out polymerization by varying the monomer composition, first polymerize a resinous component with a low vinyl cyanide compound content,
Next, a resinous component having a higher vinyl cyanide compound content is polymerized, and the content of the vinyl cyanide compound in the resinous component is increased stepwise in this way and the vinyl cyanide compound is repeatedly polymerized. A method of polymerizing while continuously increasing the cyanide compound content. First, a resinous component with a high vinyl cyanide compound content is polymerized, and then a resinous component with a lower vinyl cyanide compound content is polymerized. A method in which the vinyl cyanide compound content in the resinous constituent components is lowered stepwise and polymerized repeatedly;
A method may be used in which the content of the vinyl cyanide compound in the resinous component is continuously lowered during polymerization, or a combination of these methods may be used. The relationship between the monomer composition in the resinous constituent components and the resinous polymer composition to be produced can be determined using commonly used copolymer composition formulas (e.g., by Takayuki Otsu [
It is described in Revised Polymer Synthesis no Kagaku J, pages 108-109, Kagaku Dojin Co., Ltd. (1979), etc. ), the thermoplastic resin of the present invention can be easily obtained by appropriately controlling the polymerization conditions including the monomer composition.

For example, when polymerizing in the presence of a rubbery polymer,
Methods of adding each monomer to this rubbery polymer include (21) ■ A method of adding a monomer mixture, ■ A method of adding each monomer individually without mixing them, ■ ■ and ■ A method that combines the above methods, ■ Divide into two or more doses and add in stages,
Methods of ■ or ■, ■ Continuous addition, methods of ■, ■, or ■ above, or ■ A method of combining [F] to ■ above, etc. can be used. The same can be applied to the case where polymerization is carried out in the absence of a polymer.

The following can be used as various chemicals used when polymerizing the resinous constituents using the emulsion polymerization method.

Preferred polymerization initiators include organic hydrocarbons such as cumene hydroperoxide, zoisopropylpenzene hydrochloride, para-menthane hydrochloride, and monooxide. - A redox initiator in combination with an oxide and a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, (22) a mixed formulation of a sugar-containing pyrophosphate formulation/sulfoxylate formulation, etc. , persulfates such as potassium persulfate and ammonium persulfate, azobisisobutyronitrile, benzoylnon-oxide, lauroyl 9-oxide, and the like can be optionally used. Particularly preferably, an oxidizing agent of organic-hydrono-4-,'-oxides such as cumene hydroperoxide, diisoprobylpenzene hydro-oxide, para-menthane hydrono-oxide, and monooxides, and a sugar-containing oxidizing agent are preferably used. It is a redox initiator in combination with a reducing agent, which is represented by birophosphoric acid formulation, sulfoxylate formulation, sugar-containing birophosphoric acid formulation/sulfoxylate mixture formulation, etc.

As the molecular weight regulator, preferably used are mercaptans such as normal octyl mercaptan, normal dodecyl mercaptan, tertiary dodecyl mercaptan, and mercazotoethanol, various terpenes, and rhodanized hydrocarbons such as chloroform and carbon tetrachloride. can do.

Preferred emulsifiers include rosinate salts such as potassium rosinate and sodium rosinate, sodium and potassium salts of fatty acids such as potassium oleate, sodium oleate, potassium laurate, sodium laurate, sodium stearate, and potassium stearate; Sulfuric ester salts of aliphatic alcohols such as sodium lauryl sulfate, alkylaryl sulfonic acids such as sodium dodecylbenzenesulfonate, and the like can all be used.

As a method for measuring the composition distribution in the total free polymer of the present invention, for example, Polymer Journal Vol. 6
rA L532-536 (1974) (described later in Examples).

As long as the thermoplastic resin of the present invention does not exceed the scope of the present invention,
More than one species may be used in combination.

Methods for preparing the thermoplastic resin composition of the present invention include: (1) A method in which each component is dissolved in an organic solvent, swollen, and mixed.

■ A method in which each component is mixed in a lamixer or the like, then melt-mixed using an extruder and then pelletized.

■ A method in which a powder mixture recovered using a non-solvent is melt-mixed using an extruder and then turned into pellets.

■ A method in which a thermoplastic resin, styrene resin, polyphenylene ether, etc. are further added to the pellets of (■), mixed in a mixer, etc., and then melted and mixed using an extruder and then pelletized.

There are methods for obtaining molded products by using the pellets or powders (1) and (2) to (2) alone or by mixing them, or by adding each component to the mixture and then using an injection molding machine.

Further, it is also possible to use known mixing equipment such as a Banbury or a kneader in each of the above methods. A composition may also be obtained by further adding and mixing a thermoplastic resin, styrene resin 1, IJ phenylene ether, or other polymers to the above pellets and melt-mixing them using an extruder.

The thermoplastic resin composition of the present invention can be used for injection molding, sheet extrusion,
It can be used as various molded products by vacuum forming, irregular shaping, foam molding, etc.(25).

When using the thermoplastic resin composition of the present invention, commonly used antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, foaming agents, glass fibers, etc. can be added.

The following group of compounds can be used as flame retardants useful in the present invention. Generally speaking, the more multi-walled flame retardants are compounds containing elements that help impart flame retardancy, such as halogens such as bromine and chlorine, antimony, phosphorus and nitrogen.

The halodane-containing compound has the general formula A, where n represents an integer of 1 to 10, and R represents an alkylene, alkylidene, or alicyclic bond group, such as methylene, ethylene, zolopyrene, isozolopyrene, isozolobylidene, butylene, and represents groups such as butylene, amidino, cyclohexylene, cyclopentylidene, etc., or ni(26) thyl, carbunyl, amine or sulfur-containing linking groups such as sulfide, sulfoxide or sulfone, car? Represents a bonding group such as a nate or phosphorus-containing bond. In addition, R is a bond composed of two or more alkylenes or alkylidenes interconnected via each group such as aromatic, amino, ether, ester, carbunyl, sulfide, sulfoxide, sulfone, or phosphorus-containing bond. It can also be a group. In addition, R is dihydric phenol,
Alternatively, it may be a bisphenol A1 carbonate bond. Ar and Ar' are mono- or polycarbocyclic aromatic groups, such as phenylene, biphenylene, terphenylene, naphthylene, and the like. Ar and Abi may be the same or different.

X is a monovalent carbon group, examples of which are methyl, ethyl,
Alkyl groups such as propyl, isopropyl, butyl and decyl; aryl groups such as phenyl, naphthyl, biphenyl, xylyl and tolyl; aralkyl groups such as benzyl and phenethyl; alicyclic hydrocarbon groups and inert substituents such as cyclopentyl and cyclohexyl includes monovalent hydrocarbon groups having the following. If more than one X is present, they may be the same or different from each other. Y is a group selected from organic and organometallic groups. The group represented by Y is (1)
halogen, such as chlorine, bromine, iodine or fluorine; (2) an ether group represented by the general formula E (E is the same monovalent hydrocarbon group as X); a hydrocarbon group and (4) an aryl nucleus of a carbocyclic aromatic group represented by Ar or Ar', such as a phenyl nucleus 1
Other substituents which are substantially inert are included, provided that each substituent has at least one, preferably two, halogen atoms, such as nitro, cyano, and the like. The symbol d represents an integer ranging from 1 to the maximum number of substitutable hydrogen atoms in the aromatic ring constituting Ar or Ar'. The symbol e is an integer ranging from O up to the number of substitutable hydrogen atoms that R has. Symbols a, b and C are O
Represents an integer containing . If b is not 0, neither a nor C is O, and if b is O, then a or C
Either one may be 0.

When b is O, the aromatic groups of Ar and Ar' are connected by direct carbon-carbon bonds. The hydroxyl substituents and Y substituents on the aromatic groups Ar and Ar' can be located at any of the ortho, meta or nocra positions on the aromatic ring. Furthermore, these substituents can have any arbitrary geometrical arrangement with respect to each other. Representative examples of diaromatic compounds included within the scope of the above formula are as follows.

2.2-bis-(3,5-dichlorophenyl) solon, bis-(2-chlorophenyl)methane, bis-(2
,6-cybromphenyl)methane, 1,1-bis-(4
-iodophenyl)ethane, 1,2-his-(2,6-
dichlorophenyl)ethane, 1,1-pis-(2-chloro-4-iodophenyl)ethane, 1,1-bis-(2
-chloro-4-methylphenyl)ethane, ■, 1-bis-(3,5-dichlorophenyl)ethane, 2,2-bis-(3-phenyl-4-bromphenyl)ethane, 2,
3-bis-(4,6-dichlornaphthyl)zolopane, 2
, 2-bis-(2,6-dichlorophenyl)pentane,
2.2-bis-(3,5-(29)cybromphenyl)hexane, bis-(4-chlorophenyl)phenylmethane, bis-(3,5-dichlorophenyl)cyclohexylmethane, bis-(3- Nitro-4
-bromophenyl)methane, bis-(4-hydroxy-
2,6-zochloro-3-methoxyphenyl)methane, 2
,2-bis-(3,5--,>chloro-4-hydroxyphenyl)propane, 2,2-bis-(3-bromo-4
-Hydroxyphenyl)fronogun.

In the specific compounds exemplified above, the divalent aliphatic group corresponding to R may be substituted with a sulfide group, a sulfoxide group, or the like. Examples of substituted benzenes included in the above general formula are tetrabromobenzene, hexachlorobenzene, hexabromobenzene, and hihyphenyls, such as 2,2
'-cyclobiphenyl, 2,4'-dibromobiphenyl, 214'-cyclobiphenyl, hexabromobiphenyl, octabromobiphenyl, decabromobiphenyl and halodanated diphenyl ethers containing 2 to 10 halogen atoms. do. Preferred halogen-containing compounds that can be used in the present invention are aromatic halodane-containing compounds, such as chlorinated benzene, brominated benzene,
Chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, brominated terphenyl or having two phenyl nuclei linked by divalent alkylene groups and phenyl nucleus 1
A compound having at least two chlorine or bromine atoms per chlorine or bromine atom, or a mixture of two or more of these.

Also, a mixture of the above-mentioned halodane-containing compound and antimony oxide is particularly preferred as a flame retardant.

Generally preferred phosphorus-containing compounds include elemental phosphorus, organic phosphonic acids, phosphonates, phosphinates, phosphonites,
selected from phosphinites, phosphine oxytos, phosphines, phosphites and hypophosphates. A typical example is triphenylphosphine oxyto. These may be used alone or in combination with the halodane-containing compound and optionally antimony oxide. Typical phosphorus-containing compounds preferably used in the present invention have the general formula QO-P-()Q (wherein Q may be the same or different, each being a hydrocarbon group, such as alkyl, cycloalkyl, aryl, (alkyl-substituted aryl or aryl-substituted alkyl group; halodane; hydrogen; or a combination thereof, where at least one Q represents an aryl group) and its nitrogen homologues.

Specific examples of suitable naphosphates include phenylbisdodecyl phosphate, phenylbisneopentyl phosphate,
Phenylethylene hydroxyphosphate, phenylbis-(a+s,s'-trimethylhexylphosphate), ethyldiphenylphosphate, 2-ethylhexyldi(p-tolyl)phosphate, diphenylhydroxyphosphate, bis(2-ethylhexyl)P- IJ /l/ * Sulphate, tritolyl phosphate, bis-(2-ethylhexyl)-phenylphosphate), IJ (nonylphenyl)bosphate, phenylmethylhydroxyphosphate, di(dodecyl)? - tolyl phosphate, tricresyl phosphate, triphenyl phosphate, herodanated triphenyl phosphate, dibutylphenyl phosphate,
Includes 2-chloroethyl diphenyl phosphate, P-tolylbis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. Preferred phosphates are those in which each Q is an aryl group. The most preferred phosphate is triphenyl phosphate. Furthermore, it is preferred to use triphenyl phosphate in combination with hexabromobenzene and phosphate with hexabromobenzene and optionally antimony monoxide.

Particularly preferred compositions have one or more isopropyl substituents 1! : Contains a mixture of triaryl phosphates on one or more aryl groups.

(33) (A and A' are the same or different, each methyl,
It represents a phenyl, benzyl or mono-, dimethyl or trimethylpencyl group. ) are also used.

(XI is hydrogen, hydroxyl, amino group, alkyl group having 1 to io carbon atoms, alkoxy group having 1 to 1 o carbon atoms, or aryloxy group having 6 to 1 o carbon atoms, k, Yl, and Y
A phosphorus compound in which 2 represents an alkyl group, aryl group, or alkoxy group each having 1 to 8 carbon atoms, 2 digits oxygen or sulfur, and m and p each represent an integer of 0 to 4 may also be used.

(34) Also, phosphonitrile chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, tris(
Phosphorous-nitrogen containing compounds such as aziridinyl)phosphine oxide or tetrakis(hydroxymethyl)phosphonium chloride can also be used. Generally preferred nitrogen-containing compounds include S-triazine compounds, and specific preferred compounds include melamine, formoguanamine, acetoguanamine, benzoguanamine, 1,6-bis-(4,
6-Diami2-1,3.5-triazine-2)hexane, 1,6-bis-(4,6-diami2-1,3.5-
triazine-2)-3-hexanenitrile,
)-3-hexa/cal d gnic acid, 1,6-bis-(4,
6--)amino-1,3,5-triazine-2)-3-
Hexaneamide, 1,6-bis-(4,6-diami-1-,3,.5-triazone-2)-3-(aminomethyl)hexane, I,4-bis-(4,6-zoamino-113 ,5- ) riazine-2)butane, ■,2-bis-(4,6-zoamino-1..3,5-triazine-2)ethane, 1,6-bis(4,6-&amino-1.
,3.5-triazone-2)-:4. -hexaneaminomethylcardanil, 1,6-bis(46-diamitsu-1.3.5-triazone-2)-3-hexane-(
2-penzimidazole), isocyanuric acid, trimethyl isocyanurate, triphenyl isocyanurate,
Tris (2-hydroxyethyl) isocyanurate, cyanuric acid, methyl cyanurate, phenyl cyanurate, diphenyl cyanurate, triphenyl cyanurate, trimethyl cyanurate, tris (2-hydroxyethyl) cyanurate, melamine cyanurate, formoguanamine cyanurate nurate, acetoguanamine cyanurate, benzoguanamine cyanurate, melamine trimethyl isocyanurate, melamine tris(2-hydroxyethyl) isocyanurate, melamine trimethyl cyanurate, adipoguanamine diisocyanurate, ■, 3.
5-triguanamine hexane diisocyanurate and the like. These may be used alone or in combination of two or more, or may be used in combination with the halodane-containing compound, antimony oxide, phosphorus compound, etc. In addition, the thermoplastic resin composition of the present invention further comprises: Depending on the required performance, other known polymers such as ABS resin, A
S resin, polystyrene, rubber-modified polystyrene, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, ysv butadiene, butadiene-styrene copolymer, polyphenylene ether, acrylic rubber, ethylene-propylene polymer, EPDM , styrene-
Butadiene block polymer, styrene-butadiene-styrene block polymer e, styrene-butadiene-styrene radial teleblock polymer, polypropylene, butadiene-acrylonitrile copolymer, polyvinyl chloride,
Polycarbonate, PET, PBT.

Polyacetal, polyamide, epoxy resin, I-lip vinylidene, ? May be used by appropriately blending with lysulfone, ethylene-vinyl acetate copolymer, yJe isoprene, natural comb, chlorinated dithyl rubber, chlorinated polyethylene, PPS resin, polyether, ether ketone, etc.〇(37) Next The present invention will be explained in more detail with reference to production examples and examples, but these are merely illustrative and do not limit the content of the present invention. In addition, in each side below, parts and q indicate parts by weight and weight q6't-, respectively.

Production Examples Polyphenylene ether used in Examples and Comparative Examples was obtained by the following method.

After thoroughly purging the inside of the stainless steel reaction vessel equipped with an oxygen blower, a cooling coil, and a stirrer at the bottom of the reactor with nitrogen, 53.6 g of cupric bromide and 11 g of di-n-butylamine were added.
10.9 seconds Further, 8.75 kg of 2,6-xylenol was dissolved in 40 tons of toluene and added. After stirring to obtain a homogeneous solution, polymerization was carried out for 120 minutes while rapidly blowing oxygen into the reaction vessel. During polymerization, water was circulated through a cooling coil to maintain the internal temperature at 30°C. After the polymerization was completed, 301 g of toluene was added, and a 20 g aqueous solution of 430 g of disodium ethylenediaminetetraacetate dissolved in water was added to stop the reaction (38).

The polymer solution phase was removed by centrifugation. While vigorously stirring the polymer solution phase, methanol was gradually added to form a slurry. After being separated from each other, the polymer was thoroughly washed with methanol, and after being separated from each other, it was dried to obtain Polymer-A.

A polybutadiene rubber polymer latex shown in Table 1 used for the production of thermoplastic resins and styrenic resins was obtained by emulsion polymerization.

Table 1 The latex particle diameters in the table were measured by the cre-ong method using sodium alginate (the M amount indicates the particle diameter content). Dull content refers to the percentage by weight of undissolved matter after coagulating and drying the latex, dissolving it in toluene at room temperature (20° C.) for 20 hours, and separating the latex with a 100-mesh wire mesh.

Next, thermoplastic resins and styrene resins (polymer B) used in Examples and Comparative Examples were prepared using the rubbery polymer latex shown in Table 1, as well as styrene and acrylonitrile.
It was manufactured by emulsion polymerization using the recipe 2.

Polymerization was carried out in three stages, the first stage was carried out in batch polymerization, and the second stage was carried out in batch polymerization.
In the second and third stages, monomers were continuously added and combined, and the polymerization was finally carried out to a polymerization conversion of nearly 100 units.

Polymer B-1 was polymerized according to the recipe shown in the following table, and other polymers were polymerized in accordance with the same method.
I got the result.

Rice The acrylonyl-IJ content in the total free polymer was determined by nitrogen analysis.

The compositional distribution of acrylonitrile in the future free polymer is determined by adding cyclohexane little by little to a homogeneous solution in which a certain amount of the soluble portion is dissolved in methyl ethyl ketone, and measuring the weight of the precipitated polymer and the acrylonitrile content by nitrogen analysis. I lost it by something.

Thermoplastic resin styrenic resin used in Examples and Comparative Examples (
Polymer B) was converted into polybutadiene (TS
Produced by solution polymerization using RBR-OZL), styrene, and acrylonitrile.

(42) (43) Examples and Comparative Examples The various polymers described above were mixed according to the composition ratios shown in Table 4, extruded into pellets using a twin-screw kneading extruder at a temperature of 260°C to 300°C, and then sufficiently dried. 24 using injection molding machine
Impact resistance, heat resistance, molded product surface gloss at 0°C to 280°C,
Test pieces for measuring paintability and solvent resistance were molded and measured according to the test method below. The results are shown in Table 4.

Evaluation method: After annealing the heat-resistant molded product at 110°C for 2 hours, ASTMD6
The heat distortion temperature was measured at 264 psi in the thickness range according to No. 48.

■Impact resistance Measured according to ASTM D 256 with a thickness of 1 and a notch.

The surface gloss of the molded product was visually evaluated according to the following evaluation criteria.

0: Very good O: Good Δ: Slightly poor (44) ×: Poor (■) Paintability A molded article (plate-like) was painted using the following Orinon Denki paint and thinner.

Paint: Silanet A) I (trade name) Thinner: Zolanetna 201 (trade name) After painting, the occurrence of cracks, crazes, and blow-in on the surface of the coating film, and the appearance were visually evaluated according to the following evaluation criteria.

◎; Very good ◎; Good △; Slightly poor ×; Bad ■ Chemical resistance A test piece for measuring heat deformation temperature was immersed in gasoline for 5 hours, and then the cracking state and swelling ratio were measured.

The appearance of cracks was visually evaluated according to the following evaluation criteria.

◎; Very good O; Good △; Slightly - ×; Bad (45) Gasoline swelling rate [Article] Weight before soaking in gasoline x 100 (46) (48) -351- Procedural amendment Showa 058 8 May 10th, Kazuo Wakasugi, Commissioner of the Japan Patent Office, 1, Indication of the case, Patent Application No. 118158/1982, 2, Name of the invention, Thermoplastic resin composition 3, Person making the amendment, Relationship with the case, Name of the applicant for the patent (417) Japan Synthetic Rubber Co., Ltd. 4, Agent Address: 40 Toranomon, 5-13-1, Toranomon, Minato-ku, Tokyo Mori Building Column 6: Detailed explanation of the invention in the specification: Amount of amendment: In the top table of page 41 of the specification: "1st stage styrene/acrylonide 11 parts [parts] 1 is r33.5/22.4J vr 33.5/22.9 J, 72nd stage styrene/acrylonide 110 nitrile [parts]" is r 19.010 .9
4 J toaroker 19. O/1.34J, "3rd stage styrene/ac 110 nitrile [parts]" is r22.51
0.75'' is r22.510.76J.

(2) In the table on page 48 of the specification, in "Mixing ratio C part)" of "Comparative Example 7", does the "Amount!" of "Polymer-Human" say "5"? "2", "rB of polymer J" of "styrenic resin"
-18J's "Ibuki" is "7.5") 2r26.5J
, '2r where the quantity 1 of rB-19J is r 7.5 J
It is assumed to be 26.5J.

Procedural amendment dated September 14, 1980, Manabu Shiga, Commissioner of the Patent Office, Indication Patent No. 87358-1181582, Title of invention: Thermoplastic resin composition 4, Address of agent: 5-13 Toranomon, Minato-ku, Tokyo No. 1 Toranomon 40 Mori Building 5, Detailed explanation of the invention column 6 of the specification subject to amendment, Contents of amendment (1) Page 10 of the specification, 3 lines from the bottom, next to "Hydrogen additive:" Insert "acrylic rubber" into.

(2) On page 10 of the same page, the second line from the bottom says, “...can be done.”
Insert the following sentence after .

“The acrylic rubber preferably has 2 to 1 carbon atoms.
It is a polymer obtained by polymerizing a monomer whose main component is one or more monomers selected from (meth)acrylic acid alkyl esters having two alkyl groups. Specifically, the (meth)acrylic acid alkyl ester is (
Examples include ethyl, butyl, hexyl, octyl, 2-ethylhexyl, and lauryl esters of meth)acrylic acid. Furthermore, if necessary, a monomer copolymerizable with the acrylic acid alkyl ester can be copolymerized. Examples of such monomers include ethylenically unsaturated monomers such as acrylonitrile, vinyltoluene, styrene, and α-
Examples of conjugated diene monomers include butadiene, isoprene, 2,3-dimethylbutadiene, perylene, chloroprene, etc.; as dicyclopentadiene, ethylidenenorgyrunene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1.
Examples include 4-cyclointadiene and 1.5-cyclooctanoene.

These monomers can be used alone or in combination of two or more. The proportion of the monomer copolymerizable with the alkyl ester of (meth)acrylic acid is preferably 0 to 50% by weight, more preferably 0 to 30% by weight based on the total monomers. (3) On page 20, lines 11-12, after "this", insert "(4) to (b) each polymer may be blended, but preferably".

(4) On page 21, line 9, insert the following sentence next to "I can do...".

"Among these, a method in which polymerization is carried out while continuously changing the vinyl cyanide compound content in the resinous constituents is preferred." (5) "Obtained by..." on page 39, line 10 of the same. Next, insert the following text.

"The rubbery polymer-4 was produced as follows.

That is, in a stainless steel reaction vessel equipped with four-stage paddle blades,
-Butyl acrylate-185 parts, 1,3-butadiene 15
0.2 parts of potassium stearate, 1.5 parts of potassium laurate, 0.1 part of sodium alkylnaphthalene sulfonate, 0.1 part of potassium hydroxide, 1 part of potassium chloride.
Add 5 parts of ion-exchanged water and 90 parts of ion-exchanged water, raise the temperature while stirring at 90 r-p, m, and when it reaches 45°C, add 0.25 parts of potassium persulfate. From then on, keep the temperature constant at 45°C. The polymerization reaction was carried out in a controlled manner, and when the polymerization conversion rate reached 90%, the reaction was stopped by adding 1 part of diethylhydroxyamine O-1, and the unreacted monomer was substantially distilled off by steam distillation. Thus, IS polymer latex 4 was obtained.

89.2% of the particles had a particle size of 1,730 to 4,400X, and the ruel content was 78%. (6) 40th page 16
Insert the following sentence after "I got..." in the line.

"As a result of examining the composition distribution of acrylonitrile in the total free polymer for the obtained polymer B-1, it was found that the acrylonitrile content was continuously changing." (7) Same page 41, In the column for polymer rB-16J in Table 2, "85" in the "20 or more to less than 40" column was changed to "35".
”.

(8) Insert the following column under the rB-17J column in Table 2 on page 41.

(5)

Claims (1)

[Claims] A resin composition consisting of 5 to 90% by weight of polyphenylene ether, an aromatic vinyl compound, a vinyl cyanide compound, and, if necessary, other vinyl monomers copolymerizable with these in the presence or absence of a rubbery polymer. A composition comprising 95 to 10% by weight of a thermoplastic resin obtained by polymerizing components and 0 to 85% by weight of another styrenic resin, wherein the thermoplastic resin has a methyl ethyl ketone soluble content (total free polymer). 5
~100% by weight, and in the total free polymer (6)
The content of vinyl cyanide compound is 1 weight or more and 10 weight
The polymer component having a composition of less than 1 to 50 weight 1 (B) The polymer component having a composition of 10 wt % or more and less than 20 wt % of the vinyl cyan compound 1 to 70 i Amount 1 (C) of the vinyl cyan compound Contains 5-90% by weight of a polymer component having a composition of 20% by weight or more and less than 40% by weight, and 0-70% by weight of a polymer component having a composition of 40% by weight or more of a vinyl cyanide compound. A thermoplastic resin composition characterized in that the content of vinyl cyanide compound in the total free polymer is 10 to 40% by weight.