JPH09255863A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having improved impact resistance and resistance to organic solvents and manifesting excellent balance in physical properties by formulating a specific graft-modified ethylene-vinyl acetate copolymer to a polycarbonate resin. SOLUTION: This resin composition comprises (A) 99-50wt.% of a polycarbonate resin and (B) 1-50wt.% of a graft-modified ethylene-vinyl acetate prepared by graft-polymerizing (ii) 0.1-50 pts.wt. of a compound bearing glycidyl groups and/or an unsaturated glycidyl ester of the formula (Ar is a 6-23 aromatic hydrocarbon bearing at least one of glycidyloxy group; R is H, methyl) and (iii) 0-500 pts.wt. of vinyl monomers onto (i) 100 pts.wt. of an ethylene-vinyl acetate polymer in the presence of (iv) 0.001-10 pts.wt. of a radial initiator based on 100 pts.wt. of the total of the components (ii) and (iii). The component (i) is composed of 50-99% of ethylene and 50-1wt.% of vinyl acetate and preferably has a melt flow rate of 0.1-500g/10 minutes according to JIS K6730.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition comprising a polycarbonate resin and a graft-modified ethylene-vinyl acetate copolymer, which has a good balance of impact strength, organic solvent resistance, rigidity, heat resistance, moldability and the like. Regarding things.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in transparency, heat resistance, mechanical strength, etc.
It is used for OA equipment, housings for automobile parts, etc., interior materials for vehicles, airplanes, etc. However, the impact strength of a polycarbonate resin is excellent in a thin-walled molded product, but is greatly reduced in the case of thick-walled molding, and the impact strength at low temperature is also insufficient, and improvement is required. Further, the polycarbonate resin has low chemical resistance to organic solvents and the like, and its use as an engineering resin is limited, so that the excellent properties inherent to the polycarbonate resin cannot often be utilized.

As a method of solving such a problem, a method of blending a polycarbonate resin and a polyolefin resin such as polypropylene has been attempted. But,
Since the polycarbonate resin and the polyolefin resin originally have poor compatibility with each other, they cannot be uniformly dispersed even if they are simply mixed, and the surface layer peels off, resulting in only those having poor surface gloss and mechanical strength.

Therefore, as a method for improving the compatibility between the polycarbonate resin and the polyolefin resin, Japanese Patent Laid-Open No. 5 (1999) -53242 has been proposed.
JP-A-295221 discloses a method of blending a polycarbonate resin with a modified propylene-based polymer resin obtained by melt-kneading and polymerizing an aromatic vinyl monomer and an epoxy group-containing vinyl monomer with respect to a propylene-based polymer. Kaihei 27
Japanese Patent No. 1422 discloses a method of blending an epoxy group-containing olefin polymer with a polycarbonate resin. However, although the compatibility between the polycarbonate resin and the polyolefin resin is improved by these methods, the effect of improving the mechanical properties is not always sufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the problems of conventional compositions, improves the low temperature impact strength of polycarbonate resins, the impact strength of thick molded products, and the resistance to organic solvents, and further improves heat resistance. Provided is a thermoplastic resin composition having an excellent balance of physical properties such as properties and rigidity.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that for a polycarbonate resin, a compound having a specific glycidyl group in an ethylene-vinyl acetate copolymer and a vinyl-based compound. It was found that the above object can be achieved by blending a graft-modified ethylene-vinyl acetate copolymer obtained by reacting a monomer in the presence of a radical initiator, and reached the present invention.

That is, the present invention relates to (A) a polycarbonate resin in an amount of 99 to 50% by weight and (B) (b1) 100 parts by weight of an ethylene-vinyl acetate copolymer, (b2) the following general formula (I): :

[0008]

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A glycidyl group represented by the formula (wherein Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). With a compound (b2-1) and / or unsaturated glycidyl ester (b2-2) 0.1
To 50 parts by weight, and (b3) vinyl-based monomer 0 to 50
0 parts by weight of the total of the components (b2) and (b3) is 100
A resin composition comprising 0.001 to 10 parts by weight of (b4) 1 to 50% by weight of a graft-modified ethylene-vinyl acetate copolymer polymerized in the presence of a radical initiator with respect to 1 part by weight. Is.

The (A) polycarbonate resin used in the present invention is not particularly limited as long as it is used for molding, but specific examples thereof include aromatic polycarbonate resins, aliphatic polycarbonate resins and aliphatic-aromatic resins. Examples thereof include group polycarbonate resins, and among these, aromatic polycarbonate resins are preferably used. Aromatic polycarbonate resins are generally produced by reacting an aromatic dihydroxy compound with a carbonate precursor.

As the aromatic dihydroxy compound,
For example, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,2-
(4-Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-)
Bisphenols such as 3-methylphenyl) propane,
Bis (4-hydroxyphenyl) ether, bis (3,3
Dihydric phenol ethers such as 5-dichloro-4-hydroxyphenyl) ether, dihydroxydiphenyls such as p, p′-dihydroxydiphenyl and 3,3′-dichloro-4,4′-dihydroxydiphenyl, bis (4
-Hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and other dihydroxyarylsulfones, resorcinol, hydroquinone and other dihydroxybenzenes, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-
Dihydroxybenzenes substituted with a halogen or an alkyl group such as 3-methylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (3,5-dibromo-4-)
Examples thereof include compounds such as dihydroxydiphenyl sulfides such as hydroxyphenyl) sulfoxide and dihydroxydiphenyl sulfoxides, and these may be used alone or in combination of two or more kinds. Among these, 2,2-bis (4-hydroxyphenyl) propane is preferably used.

Examples of the carbonate precursor include carbonyl halides represented by phosgene and the like, carbonyl esters represented by diphenyl carbonate and the like, halofolates and the like. These may be used alone or in combination of two or more kinds. Used. Further, the polycarbonate resin used in the present invention may be partially branched, for example, a thermoplastic random branched polycarbonate resin obtained by reacting a polyfunctional aromatic compound with a divalent phenol and a carbonate precursor,
Further, it may be a mixture of linear polycarbonate and branched polycarbonate.

Examples of the polyfunctional aromatic compound include 1,1,1-tri (4-hydroxyphenyl) ethane, trimellitic anhydride, trimellitic acid, trimellitoyl trichloride, and 4-chloroformylphthalic anhydride. Substance, pyromellitic acid, pyromellitic dianhydride, mellitic acid,
Mellitic acid anhydride, trimesic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic acid anhydride and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The (B) graft-modified ethylene-vinyl acetate copolymer used in the present invention is an ethylene-vinyl acetate copolymer which is the component (b1), and a general formula (I) which is the component (b2):

[0015]

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(In the formula, Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) Compound (b2-1) and / or unsaturated glycidyl ester (b2-2) and vinyl monomer as component (b3) are polymerized in the presence of a radical initiator as component (b4). It is manufactured by As the component (b1), ethylene 50 to 9
An ethylene-vinyl acetate copolymer having 9% by weight and 50 to 1% by weight of vinyl acetate and having a melt flow rate according to JIS K6730 of 0.1 to 500 g / 10 min is preferably used. If the amount is out of the above range, the balance of thermal decomposition resistance, fluidity and mechanical properties tends to deteriorate. The general formula (I) which is one of the components (b2) for modifying the ethylene-vinyl acetate copolymer (b1):

[0017]

[Chemical 6]

(Wherein Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms and at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). The compound (b2-1) is derived from a modifier having at least one acrylamide group and at least one glycidyl group in the molecule. The acrylamide group includes a methacrylamide group in addition to the acrylamide group.

Such a compound is disclosed, for example, in JP-A-60 / 60.
It can be manufactured by the method described in No. 130580. That is, it is produced by condensing an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide in the presence of an acidic catalyst, and then glycidylating the hydroxyl group with epihalohydrin. You can As the aromatic hydrocarbon having at least one phenolic hydroxyl group, a phenolic compound having 6 to 23 carbon atoms is used.

Specific examples of the phenol compound include phenol, cresol, xylenol, carvacrol, thymol, naphthol, resorcin, hydroquinone, pyrogallol and phenanthrol. Among them, monohydric phenols having an alkyl substituent are preferred. For example, when 2,6-xylenol and N-methylol acrylamide are used as starting materials, structural formula (II):

[0021]

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The compound represented by the following formula can be obtained. When orthocresol and N-methylolacrylamide are used as starting materials, the structural formula (III)

[0023]

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The compound represented by can be obtained. Among these, the compound represented by the structural formula (II) is particularly preferably used.

The unsaturated glycidyl ester (b2-2) which is another component (b2) is, for example, glycidyl acrylate, glycidyl methacrylate, mono- or diglycidyl ester of itaconic acid, mono- or di-butenetricarboxylic acid. And triglycidyl esters, mono and diglycidyl esters of citraconic acid, endo-cis-bicyclo [2,2,1] hept-5-ene-
Mono- and diglycidyl esters of 2,3-dicarboxylic acid, endo-cis-bicyclo [2,2,1] hept-5
Examples include mono- and diglycidyl esters of -ene-2-methyl-2,3-dicarboxylic acid, mono- and diglycidyl esters of allyl succinic acid, glycidyl esters of p-styrenecarboxylic acid, etc., and these may be used alone or in combination of two or more. Used in combination. Of these, glycidyl methacrylate is preferable from the viewpoint of cost and performance balance.

It is one of the components of the component (B) (b
3) Examples of vinyl monomers include aromatic vinyl compounds such as styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, vinyltoluene, and divinylbenzene.
Examples of the methacrylic acid alkyl ester having 1 to 22 carbon atoms include methyl methacrylate, ethyl methacrylate,
I-propyl methacrylate, n-butyl methacrylate,
T-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate and the like are alkyl acrylates having 1 to 22 carbon atoms,
Methyl acrylate, ethyl acrylate, acrylic acid i-
Propyl, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the like are vinyl methyl ether, vinyl ethyl ether, vinyl as the vinyl alkyl ether having 1 to 22 carbon atoms. n-propyl ether, vinyl i-propyl ether, vinyl i-butyl ether, vinyl n-amyl ether, vinyl i-amyl ether,
Vinyl 2-ethylhexyl ether, vinyl octadecyl ether, and the like, unsaturated nitrile compounds such as acrylonitrile and methacrylnitrile, and unsaturated amino compounds such as acrylamide and methacrylamide, and maleic acid di-alkyl esters. Examples include maleic acid di-n-amyl ester, maleic acid di-n-butyl ester, maleic acid di-i-amyl ester, maleic acid di-i-butyl ester, maleic acid dimethyl ester, maleic acid di-n.
-Propyl ester, maleic acid di-octyl ester, maleic acid dinonyl ester, etc., as allyl alkyl ether having 1 to 8 carbon atoms, allyl ethyl ether, allyl n-octyl ether, etc., and as diene compound, Dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene, and 1,3.
-Cyclooctadiene and the like, and other vinyl monomers include allyl methacrylate, acrylic acid, maleic acid methacrylic acid, maleic anhydride, vinyl acetate and the like. These may be used alone or in combination of two or more.

Examples of the radical initiator (b4) used for producing the component (B) include, for example, methyl ethyl ketone peroxide, di-t-butyl peroxide, 1,1.
-Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-
Butyl peroxy) valerate, 2,5-dimethylhexane-2,5-dihydroperoxide, α, α'-
Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexyne-3, organic peroxides such as benzoyl peroxide, or, for example, 1,
1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo]
Formamide, 2-phenylazo-4-methoxy-2,
4-dimethyl-valeronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4,4-
Examples thereof include azo compounds such as trimethylpentane), 2,2′-azobis (2-acetoxypropane), and 2,2′-azobis (2-acetoxybutane). These may be used alone or in combination of two or more. . Further, these initiators can be appropriately selected as desired depending on the impregnation and polymerization conditions.

Specific examples of the method for producing the (B) graft-modified ethylene-vinyl acetate copolymer include (b)
1) component, (b2) component, (b3) component, and (b
4) Prepare an aqueous suspension containing the component, impregnate the (b1) component with the (b2) component and the (b3) component in the aqueous suspension, and polymerize the (b2) component and the (b3) component. There is a method of making it. In the case of this method, the component (b1),
The proportions of the component (b2) and the component (b3) are 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, and the component (b3) to 100 parts by weight of the component (b1). 0.1 to 500 parts by weight, preferably 0.1 to 100 parts by weight, 0.001 to 10 parts by weight of the component (b4) per 100 parts by weight of the total amount of the components (b2) and (b3). , Preferably 0.05 to 5 parts by weight. When the ratio of the component (b2) is higher than the above range, the fluidity and mechanical properties are deteriorated, and when the ratio is low, the modifying effect on the component (b1) is insufficient. Further, when the ratio of the component (b3) is higher than the above range, the polymerization of the vinyl-based monomers is predominant, so that excessive aggregation, fusion, agglomeration, etc. may occur in the aqueous suspension during the polymerization. If it occurs and is small, (b2)
It becomes difficult to uniformly impregnate the component (b1) and graft polymerization. Further, when the ratio of the component (b4) is higher than the above range, the component (b1) causes excessive crosslinking, and when it is low, the polymerization becomes insufficient.

As another method for producing the (B) graft-modified ethylene-vinyl acetate copolymer, after mixing the components (b1), (b2), (b3) and (b4), A method of polymerizing the (b2) component and the (b3) component with respect to the (b1) component by melt-kneading using a heating and kneading device such as an extruder can be mentioned. In the case of this method, the component (b1), the component (b2) and the component (b)
The ratio of the component (3) is 0.1 to 50 parts by weight, preferably 0.1% by weight, relative to 100 parts by weight of the component (b1).
1 to 30 parts by weight, component (b3) 0 to 100 parts by weight, preferably 0 to 50 parts by weight, component (b4) is 0 based on 100 parts by weight of the total amount of the components (b2) and (b3). ．
The amount is 001 to 10 parts by weight, preferably 0.05 to 5 parts by weight. When the ratio of the component (b2) is more than the above range,
If the flowability and mechanical properties are deteriorated and the amount is small, (b
1) The modifying effect on the component becomes insufficient. Also, (b
When the ratio of the component 3) is higher than the above range, not only the excess vinyl-based monomer is distilled off and the addition effect is not improved, but also the mechanical properties are deteriorated and the malodor may occur.
When the ratio of the component (b4) is higher than the above range,
If the component (b1) causes excessive cross-linking and the amount is small, the polymerization becomes insufficient.

The (B) graft-modified ethylene-vinyl acetate copolymer of the present invention may be used in the form of a composition containing an unmodified ethylene-vinyl acetate copolymer. In this case, the content of the unmodified ethylene-vinyl acetate copolymer is 0 to 9
It is in the range of 5% by weight, preferably 0 to 80% by weight. The blending ratio of the (A) polycarbonate resin and the (B) graft modified ethylene-vinyl acetate copolymer in the present invention is (B) with respect to 99 to 50% by weight of the (A) component.
Ingredient 1-50% by weight, preferably (A) ingredient 99-70
It is in the range of 1 to 30% by weight of component (B) with respect to% by weight. When the compounding ratio is out of the above range, the balance of physical properties such as heat resistance, impact resistance, rigidity, moldability, and surface property becomes insufficient.

As a method for producing a resin composition comprising the (A) polycarbonate resin of the present invention and the (B) graft-modified ethylene-vinyl acetate copolymer, for example, the respective components are uniformly mixed using a stirrer or the like. After that, it is manufactured by melt-kneading. The method of melt-kneading is not particularly limited, and may be melt-kneaded using a conventionally known blender such as an extruder, a heat roll, a Brabender, a Banbury mixer.

As the filler added to the resin composition of the present invention, silica, talc, mica, glass fiber, glass beads, hollow glass beads, neutral clays, carbon fibers,
Examples thereof include aromatic polyamide fibers, aromatic polyester fibers, vinylon fibers, carbonized fibers, silicon carbide fibers, alumina fibers, potassium titanate fibers, and metal fibers. These may be used alone or in combination of two or more. When using the filler, 1 to 100 parts by weight to 100 parts by weight of the resin component in the resin composition of the present invention,
The ratio of 10 to 50 parts by weight is preferable. If it is less than the above range, the effect as a filler cannot be obtained, and if it is more than the above range, the molding fluidity decreases.

Further, as the flame retardant used in the resin composition of the present invention, tetrabromobisphenol A, 2,2
-Bis (4-hydroxy-3,5-dibromophenyl)
Propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4
-Hydroxyethoxy-3,5-dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, halogenated flame retardants such as chlorinated paraffin; ammonium phosphate,
Tricresyl phosphate, triethyl phosphate, tris chloroethyl phosphate, tris (B-
Chloroethyl) phosphate, trisdichloropropyl phosphate, cresyl phenyl phosphate,
Phosphorus flame retardants such as xylenyl diphenyl phosphate, acidic phosphoric acid esters, nitrogen-containing phosphorus compounds; red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, etc. Inorganic flame retardant, brominated polystyrene, brominated poly α-methylstyrene, brominated polycarbonate, brominated polyepoxy resin, chlorinated polyethylene, chlorinated poly α
Examples thereof include polymer flame retardants such as methylstyrene, chlorinated polycarbonate, and chlorinated polyepoxy resin. These may be used alone or in combination of two or more. When the flame retardant is used, it is 1 to 50 parts by weight, preferably 1 to 100 parts by weight of the resin component in the resin composition of the present invention.
A ratio of up to 30 parts by weight is preferable. When it is less than the above range, the effect of imparting flame retardancy cannot be obtained, and when it is more than the above range, the molding fluidity is deteriorated and the mechanical properties are deteriorated.

In the resin composition of the present invention, if necessary,
You may add a stabilizer, a catalyst etc. which improve the reactivity of a graft modified ethylene-vinyl acetate copolymer. The stabilizer is, for example, 2,4-bis (n) as an antioxidant.
-Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2-
Thiobis (4-methyl-6-t-butylphenol),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene and other phenolic compounds and thioether compounds,
Or tetrakis (2,4-di-t-butylphenyl)
Phosphorus compounds such as -4,4'-biphenylene phosphonite and tris (2,4-di-t-butylphenyl) phosphonite are listed, and the light stabilizer is dimethyl succinate-1. -(2-hydroxyethyl)
-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-
2,4-diyl] [(2.2.6.6-tetramethyl-
4-piperidyl) imino] hexamethylene [2,2,2
6,6-Tetramethylpiperidyl) imino]], 2-
(3,5-di-t-butyl-4-hydroxybenzyl)
Examples thereof include hindered amine compounds such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2-n-butylmalonate, which may be used alone or in combination of two or more. The amount of the stabilizer used is in the range of 0.01 to 20 parts by weight based on 100 parts by weight of the resin composition of the present invention. If it is less than the above range, the effect of adding the stabilizer is not sufficient, and if it is more than the above range, the mechanical properties are deteriorated.

The catalyst is not particularly limited and is generally selected from the compounds which promote the reaction between the carboxylic acid group, the hydroxyl group, the ester group and the glycidyl group, or a combination of two or more thereof is preferable. , Tertiary amines,
It is an amine compound such as a quaternary ammonium salt, a phosphonium salt, a phosphorus compound such as phosphine, or an imidazole. Of these, phosphorus compounds are particularly preferable from the viewpoint of heat resistance stability, and specifically, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium chloride, tri-n-butylmethylphosphonium iodide. , Phosphonium salts such as tri-n-butylbenzylphosphonium chloride and tri-n-butylallylphosphonium bromide, and phosphines such as triphenylphosphine. The amount of the catalyst used is 100% by weight of the resin composition of the present invention.
0.001 to 2 parts by weight, preferably 0.
It is in the range of 005 to 1 part by weight. When the amount is less than the above range, the reaction promoting effect cannot be obtained, and when the amount is more than the above range, mechanical properties are deteriorated and coloring is caused. Furthermore, the resin composition of the present invention, if necessary, within the range not impairing the features of the present invention,
A pigment, an antistatic agent, a nucleating agent, or a thermoplastic crystalline resin or amorphous resin other than the present invention may be added.

[0036]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples, and can be changed as appropriate without departing from the scope of the invention. In the following description,
“Parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Reference Example 1 Graft-modified ethylene-vinyl acetate copolymer (MEV
1) Preparation of ethylene-vinyl acetate copolymer (Evaflex 360 manufactured by Mitsui DuPont Polychemical Co., Ltd .: vinyl acetate content 25%, melt flow rate 2 dg / min) per 4200 parts of pure water in a pressure-resistant closed reaction tank. ) 1400 copies,
Styrene 400 parts, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 200 parts, 1,1-bis (t-butylperoxy) 3,3.
6.0 parts of 3,5-trimethylcyclohexane, 30 parts of tribasic calcium phosphate, and 1.0 part of an emulsifier (Latemul PS manufactured by Kao Corporation) were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous solution was stirred at 100 ° C. for 1 hour and then at 110 ° C. for 3 hours to complete the polymerization. The obtained particles were washed with water to remove tricalcium phosphate and latemur PS, and then dried to obtain a graft-modified ethylene-vinyl acetate copolymer (MEV1).

Reference Example 2 Graft-modified ethylene-vinyl acetate copolymer (MEV
2) Production In a pressure tight reaction vessel, ethylene-vinyl acetate copolymer (Evaflex 260 manufactured by Mitsui DuPont Polychemical Co., Ltd .: vinyl acetate content 28%, melt flow rate 6 dg / min) was added to 4200 parts of pure water. ) 1400 copies,
Styrene 300 parts, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 200 parts, glycidyl methacrylate 100 parts, 1,1
-Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 6.0 parts, calcium triphosphate 30
Part and emulsifier (Latemul PS manufactured by Kao Corporation)
0 parts were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous solution was stirred at 100 ° C. for 1 hour and then at 110 ° C. for 3 hours.
The polymerization was completed by stirring for a period of time. The obtained particles were washed with water to remove tricalcium phosphate and latemur PS, and then dried to obtain a graft-modified ethylene-vinyl acetate copolymer (MEV2).

Reference Example 3 Graft-modified ethylene-vinyl acetate copolymer (MEV
3) Production of 100 parts of ethylene-vinyl acetate copolymer (Evaflex 360 manufactured by Mitsui DuPont Polychemical Co., Ltd .: vinyl acetate content 25%, melt flow rate 2 dg / min),
Styrene 5 parts, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 5
Parts, and α, α′-bis (t-butylperoxy-m-isopropyl) benzene 0.1 part by dry blending,
The mixture was charged into a twin-screw extruder at a rate of 15 kg / hour, melt-kneaded at a cylinder temperature of 190 ° C., and pelletized. The pellets were dried at 50 ° C for 12 hours to obtain a graft-modified ethylene-vinyl acetate copolymer (MEV3).

Reference Example 4 Graft-modified ethylene-vinyl acetate copolymer (MEV
4) Production of 100 parts of ethylene-vinyl acetate copolymer (Evaflex 260 manufactured by Mitsui DuPont Polychemical Co., Ltd .: vinyl acetate content 28%, melt flow rate 6 dg / min)
Styrene 10 parts, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 5
Part, 5 parts of glycidyl methacrylate, and 0.1 part of α, α′-bis (t-butylperoxy-m-isopropyl) benzene were dry blended, and then 1 hourly in a twin-screw extruder.
It was charged at a rate of 5 kg, melted and kneaded at a cylinder temperature of 190 ° C., and pelletized. The pellets were dried at 50 ° C. for 12 hours to obtain a graft modified ethylene-vinyl acetate copolymer (MEV4).

Comparative Reference Example 1 Preparation of Graft-Modified Ethylene-Vinyl Acetate Copolymer (M
EV5) The same as in Reference Example 1, except that N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide was not added, and the graft-modified ethylene-vinyl acetate copolymer (MEV5) was used. ) Got.

Comparative Reference Example 2 Preparation of Graft-Modified Propylene-Ethylene Copolymer (M
PE1) In Reference Example 4, instead of the ethylene-vinyl acetate copolymer, a propylene-ethylene copolymer (ethylene content 3
%, Melt flow rate 0.5 g / 10 min) was used in the same manner to obtain a graft-modified propylene-ethylene copolymer (MPE1).

Examples 1 to 4 and Comparative Examples 1 to 4 (A) Polycarbonate resin, (B) Graft-modified ethylene-vinyl acetate copolymer
A resin composition was produced in a combination and a mixing ratio of each component shown in Table 1 to prepare a test piece for each characteristic evaluation. (A) Polycarbonate resin Polycarbonate (Taflon A manufactured by Idemitsu Petrochemical Co., Ltd.
2200) (B) Graft-modified ethylene-vinyl acetate copolymer (MEV1 to MEV4) prepared in Reference Examples 1 to 4 and MEV5 and MPE1 prepared in Comparative Reference Examples 1 and 2. Further, EVA in the table represents an unmodified ethylene-vinyl acetate copolymer (Evaflex 260 manufactured by Mitsui DuPont Polychemical Co., Ltd .: vinyl acetate content 28%, melt flow rate 6 dg / min).

The resin composition and the test piece were manufactured by the following methods. Dry blending of the components in the proportions shown in Table 1 was performed with a 45 mm twin-screw extruder at a cylinder temperature of 26.
The mixture was melt-kneaded at 0 to 275 ° C and pelletized. After the pellets were vacuum dried to obtain a desired resin composition, injection molding was performed at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. by an injection molding machine to prepare a test piece.

Next, each test piece was evaluated by the following items and methods, and the results are shown in Table 1. (1) Impact resistance According to ASTM D256, thickness 1/4 inch and 1
A / 8 inch test piece (bar) was used to measure notched Izod impact values at -30 ° C and 23 ° C. (2) Rigidity The flexural modulus at 23 ° C. was measured according to ASTM D790. (3) Heat resistance According to ASTM D648, the heat distortion temperature under a load of 4.6 kg was measured. (4) Organic solvent resistance A test piece having a thickness of 2 mm was immersed in xylene at 23 ° C for 6 hours, and then the surface condition was visually observed. Out of 20 test pieces, one in which no crack was generated was evaluated as ◯, one in which one or two cracks were generated was evaluated as Δ, and one in which more cracks were generated was evaluated as x.

[0046]

[Table 1]

[0047]

As described in detail above, the thermoplastic resin composition of the present invention has improved impact resistance and organic solvent resistance at low temperature and in thick-walled molded products, and further has rigidity, heat resistance and molding. It is a resin composition having an excellent balance of physical properties such as properties and can be widely used for molded article applications.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kenji Kurimoto 2-9-30-12 Maikodai, Tarumi-ku, Kobe-shi, Hyogo

Claims (10)

[Claims] 1. (A) Polycarbonate resin 99 to 50
% By weight, and (b2) the following general formula (I): with respect to 100 parts by weight of (B) (b1) ethylene-vinyl acetate copolymer. (Wherein, Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms bonded to at least one glycidyloxy group;
Represents a hydrogen atom or a methyl group. ) 0.1 to 50 parts by weight of the compound (b2-1) having a glycidyl group and / or the unsaturated glycidyl ester (b2-2), and (b3) 0 to 500 parts by weight of the vinyl monomer. , Graft-modified ethylene-vinyl acetate copolymers 1 to 50 polymerized in the presence of 0.001 to 10 parts by weight of (b4) radical initiator per 100 parts by weight of the components (b2) and (b3) in total. A resin composition comprising 100% by weight. 2. The ethylene-vinyl acetate copolymer (b1) comprises ethylene in an amount of 50 to 99% by weight and vinyl acetate in an amount of 50 to 99% by weight.
The resin composition according to claim 1, which is an ethylene-vinyl acetate copolymer composed of 1% by weight and having a melt flow rate according to JIS K6730 of 0.1 to 500 g / 10 min. 3. The compound (b2-1) having a glycidyl group in the component (b2) has the following structural formula (II): The resin composition according to claim 1, which is a compound represented by: 4. The resin composition according to claim 1, wherein the unsaturated glycidyl ester (b2-2) in the component (b2) is glycidyl methacrylate. 5. The component (b2) is a compound (b2-1) having a glycidyl group, represented by the following structural formula (II): The resin composition according to claim 1 or 2, which is a mixture of 1 to 99% by weight of the compound represented by and 99 to 1% by weight of glycidyl methacrylate as the unsaturated glycidyl ester (b2-2). 6. The (b3) vinyl monomer is an aromatic vinyl compound, an alkyl acrylate having an alkyl group having 1 to 22 carbon atoms, and an alkyl group having 1 to 22 carbon atoms.
Methacrylic acid alkyl ester, vinyl alkyl ether whose alkyl group has 1 to 22 carbon atoms, vinyl alcohol, unsaturated nitrile compound, unsaturated amino compound, maleic acid dialkyl ester whose alkyl group has 1 to 9 carbon atoms At least one selected from the group consisting of an allyl alkyl ether having an alkyl group having 1 to 8 carbon atoms, an allyl acrylic ester, a diene compound, maleic anhydride, maleic acid, acrylic acid, methacrylic acid, and vinyl acetate. Item 6. The resin composition according to any one of items 1 to 5. 7. The graft-modified ethylene-vinyl acetate copolymer (B) comprises 100 parts by weight of the component (b1), 0.1 to 50 parts by weight of the component (b2), and 0.1 to 500 parts by weight of the component (b3). , And (b4) component in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total of the components (b2) and (b3), and b
The resin according to claim 1, which is obtained by impregnating the component (b1) with the component (2) and the component (b3) and polymerizing the component (b2) and the component (b3). Composition. 8. The graft-modified ethylene-vinyl acetate copolymer (B) comprises 100 parts by weight of the component (b1), 0.1 to 50 parts by weight of the component (b2), 0 to 100 parts by weight of the component (b3),
And a total of 100 of the components (b2) and (b3)
It is obtained by melt-kneading 0.001 to 10 parts by weight of component (b4) with respect to parts by weight, and polymerizing component (b2) and component (b3) with component (b1). The resin composition according to any one of 1 to 6. 9. Silica, talc, mica, glass fiber, glass beads, hollow glass beads, neutral clays, carbon with respect to 100 parts by weight of the resin composition according to claim 1. 1 to 100 parts by weight of at least one filler selected from the group consisting of fibers, aromatic polyamide fibers, aromatic polyester fibers, vinylon fibers, carbonized fibers, silicon carbide fibers, alumina fibers, potassium titanate fibers, and metal fibers. A resin composition prepared by blending. 10. A total of 100 parts by weight of the resin component in the resin composition according to claim 1.
Tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy) -3,5-Dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, chlorinated paraffin, ammonium phosphate, tricresyl phosphate, triethyl phosphate, trischloroethyl phosphate , Tris (B-chloroethyl) phosphate, trisdichloropropylphosphate, cresylphenylphosphate, xylenyldiphenylphosphate, acidic phosphate ester, nitrogen-containing phosphorus compound, red phosphorus,
Tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, brominated polystyrene, brominated poly α-methylstyrene, brominated polycarbonate, brominated polyepoxy resin, chlorinated polyethylene, chlorine A resin composition comprising 1 to 50 parts by weight of at least one flame retardant selected from the group consisting of chlorinated poly α-methylstyrene, chlorinated polycarbonate, and chlorinated polyepoxy resin.