JP2001164040A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate having excellent mechanical properties such as weld portion strength, low-temperature impact strength, moldability, heat resistance, etc., and styrene resins such as ABS resin and ASA resin. And a method for molding the same. SOLUTION: Aromatic polycarbonate resin (A component)
1 to 99% by weight, styrene-based polymer or copolymer other than styrene-conjugated diene block copolymer (component B) 9
The total of 9 to 1% by weight is 100% by weight, and the total of 100 parts by weight of the component A and the component B,
Styrene-based elastomer block copolymer (component C)
0.2 to 15 parts by weight, 0 to 30 parts by weight of an aromatic polyester resin (D component), and 0 to 10 parts by weight of a styrene-conjugated diene block copolymer (E component).
When the ratio of the C component to the total of 100 parts by weight of the A component and the B component is c parts by weight, the ratio of the D component is d parts by weight, and the ratio of the E component is e parts by weight, these c, d, and e are specific. A thermoplastic resin composition satisfying the relational expression.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly to an aromatic polycarbonate and polystyrene, HIPS (high impact polystyrene), A
S resin (acrylonitrile / styrene resin), ABS resin (acrylonitrile / butadiene / styrene resin),
A styrene-based resin such as ASA resin (acrylonitrile-styrene-acrylate rubber resin), a polyester-styrene-based elastomer block copolymer, and optionally an aromatic polyester resin, and a styrene-conjugated diene block copolymer, more preferably The present invention relates to a thermoplastic resin composition comprising a polymer comprising a vinyl monomer having a specific weight average molecular weight and having excellent mechanical properties such as impact strength and strength of a weld portion.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are known as thermoplastic resins having excellent mechanical properties such as impact strength.
Styrene resins such as S resin are widely used in various applications such as automobiles and OA fields as thermoplastic resins having excellent balance of mechanical properties and excellent moldability. However, the aromatic polycarbonate resin has a problem that the impact strength in a low-temperature atmosphere is significantly inferior to that in a normal-temperature atmosphere in terms of moldability. On the other hand, A
Styrene resins such as BS resin and ASA resin have a problem in terms of heat resistance, and there is a problem that use in a high-temperature atmosphere is limited.

[0003] Aromatic polycarbonate resin and A
Many alloys with styrene resins such as BS resin have been developed and widely used for various applications. (JP-B-38-15225, JP-B-39-71, and JP-B-42-11496).

However, alloys of aromatic polycarbonate resins and resins made of styrene-based graft copolymers such as ABS resins are basically excellent in moldability, mechanical properties at room temperature, heat resistance, etc. Since the compatibility between the aromatic polycarbonate resin and the styrene-based resin is poor, there have been cases where improvement is required due to low low-temperature impact strength and low weld strength.

As a method of solving such a problem of compatibilization, the addition of a compatibilizing agent between an aromatic polycarbonate resin and a styrene-based resin can be mentioned.
A compound containing a group having reactivity with one or the other polymer or a catalytic compound that promotes a reaction between the polymers is considered to be preferable. Particularly, methods such as reactive processing have been actively tried and various proposals have been made. ing.

For example, Japanese Patent Application Laid-Open No. 9-324086 discloses the use of a specific epoxy-modified block copolymer as a compatibilizer for a graft copolymer such as an aromatic polycarbonate resin and an ABS resin. . However, when such a polymer containing an epoxy group is used, it is difficult to control the reactivity, and particularly when there is a dead space in the melt kneader, gelation occurs and a heterogeneous portion is included, so that the performance and the like are increased. Had the problem of becoming unstable.

On the other hand, JP-A-2-199217 discloses the use of a copolymer comprising an aromatic vinyl block and a block having an affinity for polyester as a compatibilizer. The resulting compatibilizer is
Aromatic polycarbonate resins were not satisfactory.

Japanese Patent Application Laid-Open No. 9-48901 proposes the use of a specific addition polymerization type block copolymer for an aromatic polycarbonate resin and a thermoplastic polyester resin.
Japanese Patent Application No. 0-158409 proposes specific block copolymers as modifiers for various polymers alone. However, any of these publications discloses a polymer alloy comprising a styrene resin, such as an aromatic polycarbonate and an ABS resin. There is no description about the modification, and it does not propose a solution to a specific problem in a polymer alloy of an aromatic polycarbonate resin and a styrene-based resin such as an ABS resin.

As described above, a resin composition comprising an aromatic polycarbonate and a graft copolymer such as an ABS resin, which is excellent in mechanical properties such as impact strength, moldability, weld strength, heat resistance and the like, is required. However, at present, a resin composition satisfying such requirements has not been obtained.

[0010]

An object of the present invention is to provide an aromatic polycarbonate, an ABS resin and an ASA resin which are excellent in mechanical properties such as weld strength, impact strength, etc., chemical resistance, molding workability, heat resistance and the like. Another object of the present invention is to provide a thermoplastic resin composition comprising a styrene resin such as

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that aromatic polycarbonate and ABS
When a specific polyester-styrene-based elastomer block copolymer is further added to a styrene-based resin such as a resin or an ASA resin, the weld strength is greatly improved, and the polyester or styrene-based material constituting the block copolymer is significantly improved. In the case where the composition further contains an elastomer block copolymer, they have found that they need to be within a specific ratio range, and have reached the present invention. Furthermore, they have found that the properties such as weld strength are further improved by adding a high molecular weight vinyl polymer having a specific molecular weight or more, and have reached the present invention.

[0012]

According to the present invention, there is provided an aromatic polycarbonate resin (component (A)) of 1 to 99% by weight,
A total of 99 to 1% by weight of the styrene-based polymer or copolymer (component B) other than the conjugated diene block copolymer is 100%
%, And the total of the A component and the B component is 100
Parts by weight, 0.2 to 15 parts by weight of a polyester-styrene elastomer block copolymer (component C), 0 to 30 parts by weight of an aromatic polyester resin (component D), and a styrene-conjugated diene block copolymer (E Component) 0-10
Parts by weight, and the total of component A and component B is 100
When the ratio of the C component to the parts by weight is c parts by weight, the ratio of the D component is d parts by weight, and the ratio of the E component is e part by weight, a thermoplastic resin composition satisfying the following formula (1) is obtained. Such is the case.

[0013]

(Equation 3)

The aromatic polycarbonate resin of the component A used in the present invention may be a resin obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer. Are polymerized by a solid-phase transesterification method, or obtained by ring-opening polymerization of a cyclic carbonate compound.

Representative examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4
-Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or in combination of two or more.

Bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and the oxidation of the dihydric phenol may be used. An inhibitor or the like may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When the composition contains a polyfunctional compound capable of producing such a branched polycarbonate resin, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.001 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may be generated as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (1).

[0023]

Embedded image

(Wherein A is a hydrogen atom or a group having 1 to 9 carbon atoms)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0026]

Embedded image

[0027]

Embedded image

(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. In the substituted phenols of the general formula (2), n is 1
Those having 0 to 30, particularly 10 to 26 are preferred, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol,
Docosyl phenol and triacontyl phenol can be exemplified.

As the substituted phenols of the general formula (3), compounds wherein X is -R-CO-O- and R is a single bond are suitable, and n is 10-30, especially 10-26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

It is desirable that the terminal terminator is introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from dihydric phenol is more preferably 20 mol% or less, and particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was adjusted to 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

A polymerization catalyst may be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, the high-temperature properties and the like will be reduced. 10,00
0-40,000 is preferable, and 14,000-3
Particularly preferred are those having a molecular weight of 0000. Also, two or more polycarbonate resins may be mixed. The viscosity average molecular weight in the present invention is determined by inserting the specific viscosity (η _SP ) obtained from a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. into the following equation. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The styrene-based resin other than the styrene-conjugated diene block copolymer of the component B used in the thermoplastic resin composition of the present invention refers to a polymer block composed of various styrene-based monomers and a conjugated diene monomer. Styrene polymers other than block copolymers consisting of polymer blocks consisting of various styrene monomers, various styrene monomers and vinyl monomers copolymerizable with styrene monomers A styrene monomer, a rubbery polymer copolymerizable with a styrene monomer, and, if necessary, a graft copolymer composed of a vinyl monomer copolymerizable with a styrene monomer. Examples thereof include polymers and random copolymers.

The styrene monomer used for the styrene resin includes styrene, α-methylstyrene, o
-Methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert
-Styrene derivatives such as butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, with styrene being particularly preferred. These can be used alone or in combination of two or more.

Other vinyl monomers copolymerizable with the styrene monomer include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; and methyl acrylate. , Ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, alkyl esters of acrylic acid such as dodecyl acrylate, phenyl methacrylate, aryl methacrylate such as benzyl methacrylate,
Methyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, and epoxy group-containing methacrylates such as glycidyl methacrylate, maleimide , N-methylmaleimide, maleimide monomers such as N-phenylmaleimide, acrylic acid, methacrylic acid,
Α, β-unsaturated carboxylic acids such as maleic acid, maleic anhydride, phthalic acid and itaconic acid, and anhydrides thereof.

Examples of the rubbery polymer copolymerizable with the styrene monomer include polybutadiene, polyisoprene,
And diene copolymers such as styrene-butadiene copolymers, ethylene-propylene random copolymers, ethylene-butene random copolymers and other ethylene-α-olefin copolymers, ethylene-methacrylate copolymers Copolymer of ethylene and unsaturated carboxylic acid ester such as ethylene-butyl acrylate copolymer, copolymer of ethylene and aliphatic vinyl such as ethylene-vinyl acetate copolymer, ethylene-propylene-hexadiene copolymer Ethylene and propylene and non-conjugated diene terpolymer such as coalesced, acrylic rubber such as polybutyl acrylate, and polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component and polyisobutylene component so that they cannot be separated from each other. Composite rubber (hereinafter referred to as IP Type rubber) and the like.

Examples of the styrene resin include polystyrene, (PS), and high impact polystyrene (HIP).
S), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer Resins such as polymer (MABS resin), acrylonitrile / styrene / acrylate rubber copolymer (ASA resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin) and styrene / IPN type rubber copolymer, or These mixtures are mentioned. Incidentally, such a styrene-based thermoplastic resin may be one having a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst at the time of its production.
Further, in some cases, polymers and copolymers having a narrow molecular weight distribution, obtained by methods such as anionic living polymerization and radical living polymerization, and block copolymers, and polymers and copolymers having high stereoregularity are used. It is also possible. These can be used alone or in combination of two or more.

Among these, polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile
Styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene / acrylate rubber copolymer (AS
A resin), acrylonitrile, ethylene propylene rubber, styrene copolymer (AES resin), methyl methacrylate, butadiene, styrene copolymer (MBS resin) Preferably, ABS resin, ASA
Resins and AES resins are most preferred.

The resin used as the component B of the present invention has a weight average molecular weight of 500,0 of the soluble component in GPC (gel permeation chromatography) measurement.
It is intended for those having a value of 00 or less, and is distinguished from the F component described later. Here, the weight average molecular weight is obtained by GPC using a calibration curve with a standard polystyrene resin.
Calculated by measurement.

The ABS resin used in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is a mixture of coalescence. As the diene rubber component forming the ABS resin, for example, a rubber having a glass transition point of 10 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and the ratio thereof is 100% by weight of the ABS resin component. Preferably from 5 to 80% by weight,
Particularly preferably, it is 10 to 50% by weight. As the vinyl cyanide compound grafted to the diene rubber component,
The above-mentioned thing can be mentioned, and especially acrylonitrile can be used preferably. As the aromatic vinyl compound to be grafted to the diene rubber component, the above-mentioned ones can be similarly used, but styrene and α-methylstyrene are particularly preferably used. The proportion of the component grafted to the diene rubber component is preferably 95 to 20% by weight, and particularly preferably 5 to 20% by weight in 100% by weight of the ABS resin component.
0 to 90% by weight. Furthermore, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight based on 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, and the like can be mixed and used for a part of the components grafted to the diene rubber component. It is preferably 15% by weight or less. Further, various initiators, serial transfer agents, emulsifiers and the like used in the reaction can be used as required.

The ASA resin used in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing an acrylic rubber component with a vinyl cyanide compound and an aromatic vinyl compound, or the thermoplastic graft copolymer and vinyl cyanide. A mixture of a compound and a copolymer of an aromatic vinyl compound.
The acrylic rubber referred to in the present invention is one containing an alkyl acrylate unit having 2 to 10 carbon atoms, and further containing styrene, methyl methacrylate, and butadiene as other copolymerizable components as necessary. Is also good. Preferred examples of the alkyl acrylate having 2 to 10 carbon atoms include 2-ethylhexyl acrylate and n-butyl acrylate, and the alkyl acrylate is preferably contained at 50% by weight or more in 100% by weight of the acrylate rubber. Further, such an acrylate rubber is at least partially cross-linked, and examples of such a cross-linking agent include ethylene glycol diacrylate, butylene glycol diacrylate, ethylene glycol dimethacrylate, allyl methacrylate, and polypropylene glycol diacrylate. The crosslinking agent is preferably used in an amount of 0.01 to 3% by weight based on the acrylate rubber. Further, the ratio of the vinyl cyanide compound and the aromatic vinyl compound is such that the total amount of the vinyl cyanide compound is 5 to 50% by weight,
The content of the aromatic vinyl compound is 95 to 50% by weight, particularly the content of the vinyl cyanide compound is 15 to 35% by weight and the content of the aromatic vinyl compound is 85 to 65% by weight.

The AES resin used in the present invention is an ethylene-propylene rubber component or ethylene-propylene-
Thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component,
Alternatively, it is a mixture of the thermoplastic graft copolymer and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound.

The ABS resin and ASA resin of the present invention
In the AES resin, the rubber particle diameter is 0.1 to 5.0 μm.
m is preferable, and more preferably, it is 0.2 to 3.0 μm. As the distribution of the rubber particle diameter, either a single distribution or a distribution having two or more peaks can be used, and the morphology is such that the rubber particles form a single phase. Alternatively, the rubber particles may have a salami structure by containing an occlude phase around the rubber particles.

It is well known that ABS resins, ASA resins and AES resins contain a vinyl cyanide compound and an aromatic vinyl compound which are not grafted to the diene rubber component. ASA resins and AES resins may also contain free polymer components generated during such polymerization.

In the present invention, ABS resin, ASA resin,
The AES resin may be one produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be one-step copolymerization or multi-step copolymerization. Further, a blend of a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component with an ABS resin or the like obtained by such a production method can also be preferably used. The weight average molecular weight (Mw) of the vinyl compound polymer obtained by separately copolymerizing the aromatic vinyl compound and the vinyl cyanide component is 10,000 to 500,000.
0, preferably 50,000 to 200,000.

The polyester of the component C used in the present invention
The styrene-based elastomer block copolymer is a block copolymer having a polyester-based block (P) and an aromatic vinyl-based polymer block (Q), for example, one polyester block (P) and one aromatic block. Diblock copolymer to which aromatic vinyl polymer block (Q) is bonded, and one aromatic vinyl polymer block (Q) bonded to both sides of one polyester block (P) A triblock copolymer, a polyester block (P) in which one polyester block (P) is bonded to both sides of one aromatic vinyl-based block (Q). ) And an aromatic vinyl polymer block (Q) are alternately bonded in a total of 4 or more, such as a polyblock copolymer or the like. Consisting of seeds or more.

The polyester block (P) of the component C of the present invention may be any polymer block derived from a thermoplastic polyester polymer, such as polyethylene terephthalate resin and polybutylene terephthalate. Resin, polyethylene naphthalate resin, polybutylene naphthalate resin, poly-1,4
And polymer blocks derived from polyester polymers such as cyclohexane dimethylene terephthalate resin, polycaprolactone resin, p-hydroxybenzoic acid polyester resin, and polyarylate resin. Among them, the polyester block (P) in the polyester compatibilizer (C) is derived from at least one of a polyethylene terephthalate resin and a polybutylene terephthalate resin in view of compatibility with the aromatic polycarbonate resin. The polymer block is preferably a polymer block derived from polybutylene terephthalate.

If the polyester block (P) in the component C of the present invention is 30 mol% or less based on the total structural units thereof, a dicarboxylic acid other than the dicarboxylic acid units constituting the basic structure and / or You may have other diol units other than the diol unit which comprises a structure. That is, the polybutylene terephthalate-based resin refers to a resin in which a unit exceeding 70 mol% based on all structural units is composed of a polybutylene terephthalate unit.

Examples of the dicarboxylic acid unit which can be contained in the polyester block (P) in the component C include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, 5-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, aromatic dicarboxylic acids such as sodium 5-sulfoisophthalate, adipic acid, sebacic acid, azelaic acid,
Aliphatic dicarboxylic acids such as dodecanedioic acid and 1,3-
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and dicarboxylic acid units derived from ester-forming derivatives thereof. The polyester block (P) in the component C of the present invention may have only one type of the above-described dicarboxylic acid units, or may have two or more types.

Examples of the diol unit which can be contained in the polyester block (P) in the component C of the present invention include ethylene glycol, propylene glycol,
Aliphatic diols having 2 to 10 carbon atoms such as 4-butanediol, neopentyl glycol, 2-methylpropanediol, and 1,5-pentanediol, alicyclic diols such as cyclohexanedimethanol and cyclohexanediol, diethylene glycol, and polyethylene glycol And diol units derived from polyalkylene glycols having a molecular weight of 6000 or less, such as poly-1,3-propylene glycol and polytetramethylene glycol. The polyester block (P) in the component C of the present invention is one or two of the above diol units.
It may have more than one species.

Further, the polyester block (P) in the component C of the present invention contains 1 mol% based on the total structural units.
If it is the following, it may have a structural unit derived from a trifunctional or higher functional monomer such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid.

The polyester block (P) in the component C of the present invention has an intrinsic viscosity of 0.3 to 1.5 when measured in a phenol / tetrachloroethane (weight ratio = 1/1) mixed solvent. It is preferably derived from a certain polyester polymer.

The aromatic vinyl block (Q) in the component C of the present invention is a polymer block (q1) mainly composed of an aromatic vinyl compound unit or a polymer block (q1) mainly composed of an aromatic vinyl compound unit and hydrogen. A polymer block (qa) composed of any of the added polybutadiene blocks (q2) having a 1,2-bond content of less than 30% and a hydrogenated polyisoprene block (q3); 30-80 binding amount
% Of a polybutadiene block (q4) and a hydrogenated isoprene / butadiene copolymer block (q5) and at least one polymer block (qb) selected from the group consisting of an aromatic vinyl-based block copolymer (qα). ) And an aromatic vinyl block copolymer (qβ) consisting mainly of a polymer block (qc) consisting mainly of aromatic vinyl compound units and a polyisobutylene block (qd). .

The component C of the present invention is derived from an aromatic vinyl block copolymer (qα) comprising a polymer block (qa) and a polymer block (qb) which can constitute the aromatic vinyl block (Q). Examples of the block structure of the aromatic vinyl block (Qα) include those represented by the following general formulas (1) to (5). (Ab) _e (ba) _f a- (ba ′) _g b- (ab ′) _h (where a and a ′ each represent a polymer block (qa), b and b ′ each represent a polymer block (qb), and e, f, g and h each independently represent an integer of 1 or more.) The aromatic vinyl-based block (Qα )), The number of repetitions e, f, g and h can be arbitrarily determined, but is usually preferably an integer in the range of 1 to 5. As the aromatic vinyl-based block (Qα), among the aromatic vinyl-based blocks represented by the above general formulas (1) to (4), the aromatic vinyl represented by the formula: ab in which e = 1 in the above general formula More preferred are an aromatic vinyl block or an addition-polymerized triblock represented by the formula: aba ′ in which g = 1 in the above general formula.

The aromatic vinyl polymer block (qc) and the polyisobutylene block (qd) which can constitute the aromatic vinyl block (Q) in the component C of the present invention.
Examples of the block structure of the aromatic vinyl-based block (Qβ) derived from the aromatic vinyl-based block copolymer (qβ) include those represented by the following general formula or c- (dc ′) _j d- (cd ′) _k (wherein c and c ′ each represent an aromatic vinyl polymer block (qc), and d and d ′ each represent a polyisobutylene block (Qd), and j and k each independently represent an integer of 1 or more.) J and k in the aromatic vinyl-based block (Qβ) represented by the above general formula or are each arbitrarily determined. Usually, it is preferably an integer in the range of 1 to 5. Among the aromatic vinyl-based blocks (Qβ) represented by the general formula or the above, the aromatic vinyl-based triblock represented by the formula cdc ′ in which j = 1 in the general formula or the aromatic vinyl-based block (Qβ) Is more preferably an aromatic vinyl-based triblock represented by the formula dcd ′ in which k = 1 in the general formula.

In the polymer block (q1) which may constitute the aromatic vinyl block (Qα) and the polymer block (qc) which may constitute the aromatic vinyl block (Qβ), the aromatic As the aromatic vinyl compound forming the vinyl compound unit, styrene,
Examples thereof include α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, and vinylanthracene. Among them, from the viewpoint of compatibility with the component B, a polymer block (q1) which may constitute an aromatic vinyl block (Qα) and a polymer block which may constitute an aromatic vinyl block (Qβ). (Q
The aromatic vinyl compound forming the aromatic vinyl compound unit of c) is preferably composed of one or two selected from styrene and α-methylstyrene,
Of these, those composed of styrene are particularly preferred.

The hydrogenated polybutadiene block (q2) which can be a constituent block of the polymer block (qa) in the aromatic vinyl-based block (Qα) has less than 30% of 1,2-bonds in the polybutadiene block. And more preferably 25% or less. The hydrogenated polybutadiene block (q2) is a polybutadiene block in which part or all, preferably 90% or more, of unsaturated bonds have been converted to saturated bonds by hydrogenation. Before hydrogenation, the polybutadiene constituting the hydrogenated polybutadiene block (q2) preferably has a vinylethylene group (1,2-bonded butadiene unit) of less than 30 mol%, more preferably 25 mol% or less.
And the remainder is a 2-butene-1,4-diyl group (1,4
-Butadiene units of linkage).

The hydrogenated polyisoprene block (q3), which can be a constituent block of the polymer block (qb) in the aromatic vinyl block (Qα), is composed of unsaturated bonds of polyisoprene mainly composed of monomer units derived from isoprene. It is preferable that the polymer block is a polymer block in which a part or all of the polymer has been hydrogenated to form an unsaturated bond. In the hydrogenated polyisoprene block (q3), before hydrogenation, units derived from isoprene include a 2-methyl-2-butene-1,4-diyl group (1,4-bonded isoprene unit) and an isoprene unit. Propenylethylene group (3,4-
It is preferably composed of at least one selected from the group consisting of a bond isoprene unit) and a 1-methyl-1-vinylethylene group (1,2-bond isoprene unit).

The hydrogenated polybutadiene block (q4) which can be a constituent block of the polymer block (qb) in the aromatic vinyl-based block (Qα) has a 1,2-bond amount in the polybutadiene block of preferably 30 to 30.
The polybutadiene block is 80%, more preferably 35 to 60%, and further has a part or all of the unsaturated bonds that have become saturated by hydrogenation. In the polybutadiene constituting the hydrogenated polybutadiene block (q4), preferably 30 to 80 mol%, more preferably 35 to 60 mol% thereof is a vinylethylene group (1,2-bonded butadiene unit) before hydrogenation, Preferably 70 to 20 mol%, more preferably 65 to 40 mol%
Is a 2-butene-1,4-diyl group (butadiene unit having a 1,4-bond).

A hydrogenated isoprene / butadiene copolymer block (q) which can be a constituent block of the polymer block (qb) in the aromatic vinyl-based block (Qα)
5) is an isoprene / butadiene copolymer mainly composed of units derived from isoprene and units derived from butadiene, and a part or all of the unsaturated bonds are saturated by hydrogenation. It is a copolymer block. In the hydrogenated isoprene / butadiene copolymer block (q5), before hydrogenation, units derived from isoprene include a 2-methyl-2-butene-1,4-diyl group, an isopropenylethylene group and At least one group selected from the group consisting of -methyl-1-vinylethylene group, and the unit derived from butadiene is vinylethylene group and / or 2
-Butene-1,4-diyl groups are preferred, but the proportion of those groups in the isoprene / butadiene copolymer block before hydrogenation is not particularly limited. In the hydrogenated isoprene / butadiene copolymer block (q5), the unit derived from butadiene and the unit derived from isoprene may be in any of random, block, and tapered block configurations. .

The aromatic vinyl block (Qα)
As described above, in the hydrogenated polybutadiene block (q2), the hydrogenated polyisoprene block (q3), the hydrogenated polybutadiene block (q4) and the hydrogenated isoprene / butadiene copolymer block (q5) Some or all of the carbon-carbon double bonds may be hydrogenated, but the carbon in the butadiene unit and / or the isoprene unit in the aromatic vinyl block (Qα) It is preferable that 50 mol% or more, particularly 80 mol% or more, of the carbon-carbon double bond is hydrogenated from the viewpoint of improving the heat aging resistance and weather resistance of the component C.

The polyisobutylene block (q) in the aromatic vinyl block (Qβ) of the component C of the present invention
d) is a polymer block mainly composed of isobutylene units.

In the polyester-styrene-based elastomer block copolymer of the present invention, {the total content of the polymer blocks (qa)} in the aromatic vinyl-based blocks (Qα): {the total of the polymer blocks (q2 and qb) Content} and {total content of polymer block (qc)} in the aromatic vinyl-based block (Qβ): {total content of polymer block (qd)} are 1: 9 to
It is preferably in the range of 9: 1 (weight ratio), and 2: 8
It is particularly preferable that the ratio be in the range of 7 to 3 (weight ratio).

The number average molecular weight of the polymer block (q1) in the aromatic vinyl block (Qα) and the polymer block (qc) in the aromatic vinyl block (Qβ) of the component C according to the present invention are as follows. Is 2,500
Preferably it is in the range of ~ 50,000. The number average molecular weights of the polymer block (q2 or qb) in the aromatic vinyl block (Qα) and the polyisobutylene block (qd) in the aromatic vinyl block (Qβ) are 10,000 to 100,000, respectively.
Is preferably within the range. Further, the polyester-styrene-based elastomer block copolymer of the present invention may have one or more kinds of aromatic vinyl-based blocks (Qα) and / or one or more kinds of aromatic vinyl-based blocks. It may have a vinyl block (Qβ).

The component C of the present invention has a number average molecular weight of 2,7.
It is preferably in the range of 00 to 300,000,
More preferably, it is in the range of 5,000 to 200,000. The number average molecular weight shown here is calculated by GPC measurement using a calibration curve using a standard polystyrene resin.

The method for producing the component C according to the present invention is not particularly limited. For example, a polyester resin and an aromatic vinyl polymer having a functional group capable of reacting with the polyester resin in the molecule are mixed under melting conditions. , Followed by solid phase polymerization, and a production method of extracting and recovering a block copolymer having a polyester block (P) and an aromatic vinyl block (Q) from the resulting polyester-based reaction product is preferred. As a method. Another method is to transesterify an aromatic dicarboxylic acid derivative with a diol and an aromatic vinyl-hydrogenated conjugated diene type block copolymer having a functional group capable of reacting with a polyester resin in the presence of a transesterification catalyst. Examples of the method include a method of reacting or further performing solid phase polymerization, and a method of subjecting a polyester or a low molecular weight compound having an ester bond to a polyester in a transesterification reaction in the presence of a transesterification catalyst.

In the above-mentioned production method, the melt kneading of the polyester resin and the aromatic vinyl polymer can be carried out using a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, and a Banbury mixer. it can. Melt kneading conditions can be appropriately selected according to the type of polyester resin or aromatic vinyl polymer used, the type of equipment, and the like.
It is good to do for about a minute. Also, solid-state polymerization after melt kneading,
After solidifying and granulating the resin obtained by melt-kneading the polyester-based resin and the aromatic vinyl polymer, the resin is transferred to an appropriate solid-state polymerization reactor, and subjected to a pretreatment of 120%.
Drying, crystallization, and the like can be performed at a temperature of about 180 ° C., followed by solid phase polymerization. The solid-state polymerization reaction is usually carried out 5 to 6 times higher than the melting point of the polyester resin.
The heat treatment may be performed under an inert gas stream or under vacuum while maintaining the temperature at about 0 ° C. lower. Solid-state polymerization may be performed in either a batch system or a continuous system, by appropriately adjusting the residence time and the treatment time in the solid-state polymerization reaction device,
The desired degree of polymerization and reaction rate can be obtained.

In the above, extraction and recovery of a block copolymer having a polyester-based block (P) and an aromatic vinyl-based block (Q) from a polyester-based reaction product obtained by solid-phase polymerization is carried out, for example, by a polyester-based reaction product. The product is dissolved in a mixed solvent of hexafluoroisopropanol / chloroform, and the solution is poured into tetrahydrofuran to precipitate. The chloroform solution can be concentrated, dried and solidified to recover a block copolymer having a polyester block (P) and an aromatic vinyl block (Q) as a solid content.

The functional groups of the component C of the present invention include:
There is no particular limitation as long as it is a functional group capable of reacting with the polyester resin, and examples thereof include a hydroxyl group, a carboxyl group, an ester group, an amide group, an amino group, an epoxy group, a thiol group, a thioester group, and a cyclic imino such as a 2-oxazoline group. Ether group, succinic anhydride-2-yl group, succinic anhydride-
Examples thereof include groups having an acid anhydride structure such as a 2,3-diyl group. Particularly preferred are a hydroxyl group, a carboxyl group, an epoxy group, and a 2-yl succinic anhydride group which have no decomposing action on the aromatic polycarbonate resin. In the aromatic vinyl polymer having a functional group capable of reacting with the polyester resin, the functional group is located at any position in the molecular main chain or the molecular side chain of the aromatic vinyl polymer or at any of the molecular terminals. However, it is preferably located at the molecular end. Further, the content of the functional group is preferably 0.5 or more per molecule on average, and 0.7 to
More preferably, the number is one.

In the present invention, an aromatic polyester resin may optionally be contained as the D component. The D component is a resin obtained by a polycondensation reaction from a dicarboxylic acid unit or a derivative thereof and a diol unit or a derivative thereof, and one of the dicarboxylic acid unit and the glycol unit has an aromatic group.

Examples of the dicarboxylic acid unit which can be contained in the component D of the present invention include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, 1,5-naphthalene Dicarboxylic acid, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, aromatic dicarboxylic acid such as sodium 5-sulfoisophthalate and adipic acid, sebacic acid, azelaic acid, aliphatic dicarboxylic acid such as dodecanedioic acid and 1, 3-cyclohexanedicarboxylic acid,
Examples thereof include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and dicarboxylic acid units derived from ester-forming derivatives thereof and the like, having only one of the above-described dicarboxylic acid units. Or two or more kinds.

Examples of the diol unit which can be contained in the component D of the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 2-methylpropanediol, 1,5-pentanediol and the like. Alicyclic diols such as aliphatic diols having 2 to 10 carbon atoms, cyclohexane dimethanol and cyclohexane diol, and molecular weight 600 such as diethylene glycol, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc.
Examples thereof include diol units derived from 0 or less polyalkylene glycol, and may have one or more of the above diol units.

Further, the component D of the present invention may be a tri- or higher-functional monomer such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, pyromellitic acid, etc. if it is 1 mol% or less based on the total structural units. May have a structural unit derived from

The D component of the present invention preferably has an intrinsic viscosity of 0.3 to 1.5 when measured in a phenol / tetrachloroethane (weight ratio = 1/1) mixed solvent.

Specific examples of the aromatic polyester resin which is the component D of the present invention include, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, poly-1,4
-Cyclohexane dimethylene terephthalate, polycaprolactone, p-hydroxybenzoic acid-based polyester resin, polyarylate-based resin, and the like. Among these, from the viewpoint of compatibility with the aromatic polycarbonate resin, at least one of polyethylene terephthalate and polybutylene terephthalate is preferable, and polybutylene terephthalate is particularly preferable.

In the present invention, styrene-
It may contain a conjugated diene block copolymer. The component E is a block copolymer composed of a block composed of a polymer of a styrene monomer and a block composed of a polymer of a conjugated diene monomer such as polybutadiene and polyisoprene, and hydrogenates the unsaturated bond thereof ( Hydrogenation)
This is the block copolymer obtained. Specific examples thereof include a hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS) and a hydrogenated styrene / isoprene / styrene copolymer (hydrogenated SIS). The form of the block copolymer may be any of diblock, triblock and multiblock. Further, the shape of the block may be basically any of linear, radial, branched, etc., but a linear shape is more preferable.

The styrene monomer includes styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. Among them, those composed of styrene are particularly preferable.

Examples of the conjugated diene monomer component include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like. In particular, butadiene and isoprene are preferable, and a copolymer of both is also used. it can. Further, the hydrogenated block copolymer that can be used in the present invention is a hydrogenated block copolymer in which 50% or more, more preferably 80% or more of the carbon-carbon unsaturated bond in the polymer block of the conjugated diene monomer is hydrogenated. is there.

The block copolymer before hydrogenation is prepared by a method of sequentially polymerizing conjugated diene and styrene monomers in the presence of alkyl lithium such as butyl lithium and styryl lithium as a catalyst. Polymerization reaction was carried out separately, and the obtained polymer was
It can be obtained by a method of bonding with a functional coupling agent or the like.

Further, as a method for hydrogenating the obtained block polymer, a method in which a metal such as nickel, palladium, platinum or ruthenium is supported on a material having a small surface area such as carbon, alumina or diatomaceous earth, Raney nickel, Urushibara Using a heterogeneous catalyst such as nickel, or a homogeneous catalyst such as a Ziegler catalyst obtained by combining a transition metal compound with an alkylated product such as aluminum, an alkaline earth metal, or an alkali metal, at a temperature of 20 to 200 ° C.
A method of contacting with a hydrogen gas of 0.1 to 20 MPa for 0.1 to 100 hours can be given.

The amount of the block of the styrene polymer in the component E of the present invention is 10 to 50% by weight, and preferably 15 to 35% by weight. Further, the styrene-based polymer block molecular weight is a number average molecular weight of 4,
000 to 80,000, preferably 8.0
00 to 60,000. The molecular weight of the hydrogenated block copolymer is 30,000 to 500, in number average molecular weight.
000. In addition, the number average molecular weight shown here is G using a calibration curve with a standard polystyrene resin.
It is calculated by PC measurement.

The aromatic polycarbonate resin (A) of the present invention
Component), a styrene-based polymer or copolymer other than the styrene-conjugated diene block copolymer (component B), a polyester-styrene elastomer block copolymer (component C), an aromatic polyester resin (component D), and The ratio of the styrene-conjugated diene block copolymer (E component) is as follows.

The ratio of the component A to the component B is as follows:
%, B component 99-1% by weight, preferably A component 20
~ 90 wt%, B component 80 ~ 10 wt%, more preferably A component 40 ~ 90 wt%, B component 60 ~ 10 wt%,
Particularly preferably, component A is 50 to 90% by weight, component B is 50 to 90% by weight.
10% by weight, and the sum of the component A and the component B is 100% by weight.

Further, the proportions of the components C, D and E are based on 100 parts by weight of the total of the components A and B.
Component C is 0.2 to 15 parts by weight, preferably 0.5 to 12 parts by weight.
Parts by weight, more preferably 1 to 10 parts by weight, and the D component is 0 to
30 parts by weight, preferably 0.6 to 20 parts by weight, more preferably 1 to 15 parts by weight, E component 0 to 10 parts by weight, preferably 0.1 to 7 parts by weight, more preferably 0.3 to 5 parts by weight. Parts by weight, and the total of the A component and the B component is 1
When the ratio of the C component to 00 parts by weight is c parts by weight, the ratio of the D component is d parts by weight, and the ratio of the E component is e part by weight,
It satisfies the following expression (1).

[0088]

(Equation 4)

A total of 100% by weight of the components A and B
When the content of the component A is less than 1% by weight and the content of the component B is more than 99% by weight, the effect of improving the heat resistance becomes insufficient.
If the amount of component B is less than 1% by weight and the amount of component A exceeds 99% by weight in 0% by weight, the effect of improving the processability of the aromatic polycarbonate resin and the effect of improving the impact in a low-temperature atmosphere are insufficient. When the amount of the component C is less than 0.2 part by weight based on 100 parts by weight of the total of the components A and B, the effect of improving the compatibility becomes insufficient, and the effect of improving the strength of the weld portion and the low-temperature impact strength becomes insufficient. If the amount exceeds 15 parts by weight, the further improvement effect is saturated and is not recognized or reduced, but on the other hand, heat resistance and impact strength are undesirably reduced. If the component D exceeds 30 parts by weight, the impact strength decreases, and if the component E exceeds 10 parts by weight, heat resistance, weld strength, etc. decrease, which is not preferable.

If the above formula (1) is not satisfied, the effect of the component C as a compatibilizer is undesirably inhibited by the components D and E. On the other hand, within the range satisfying the expression (1), almost the same behavior as the component C can be taken.

That is, it is considered that the present invention improves the adhesion at the interface between the aromatic polycarbonate resin as the component A and the styrene resin as the component B by including the component C. When the E component is added more than necessary, the C component is not at the interface between the A component and the B component,
It is expected that the structure will be closer to the layer composed of the D component and the E component having a higher affinity and a higher affinity, and will not contribute to the interfacial adhesion between the A component and the B component.

On the other hand, the D component and the E component of the present invention enter into the phase of the C component up to a certain amount, and can have the same behavior as the C component as a whole, and the C component is substantially increased. It is considered that the effect is accompanied.

In the present invention, it is preferable that the relationship among c, d, and e satisfies the following expression (2).

[0094]

(Equation 5)

Further, in the present invention, a more preferable relational expression related to the expression (1) is represented by the following expression (3).

[0096]

(Equation 6)

Further, according to the present invention, the F component has a weight average molecular weight (Mw) of 1,000,000 to 10,000,000,
An aromatic vinyl monomer which is 0, a vinyl cyanide monomer,
By including a polymer obtained by polymerizing at least one monomer selected from an acrylate monomer and a methacrylate monomer, the weld strength is further improved, and the appearance such as jetting is improved. It is possible to obtain a thermoplastic resin composition having excellent chemical resistance and the like. In this respect, it is more preferable to include the F component.

With respect to the various monomers used in the component F, the styrene monomer, the vinyl cyanide compound, the various acrylates,
The same methacrylates can be used. Preferable examples include styrene, acrylonitrile, ethyl acrylate, and methyl methacrylate. That is, a homopolymer of these, and a copolymer containing two or more of these can be used, and a styrene-acrylonitrile polymer is particularly preferable. If the weight-average molecular weight (Mw) of the F component is less than 1,000,000, the effect of improving the strength of the weld portion is not sufficient, and the content of 10,000,000 is not sufficient.
If it exceeds 000, the influence of the deterioration of the fluidity on the improvement effect becomes large. The weight average molecular weight (Mw) of the polymer used in the component F of the present invention is calculated by GPC measurement using a calibration curve using a standard polystyrene resin.

The proportion of the component F is preferably from 0.1 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, particularly preferably from 0.7 to 10 parts by weight, per 100 parts by weight of the total of the components A and B. 2.5 parts by weight. Within such a range, it is possible to further improve weld strength while maintaining good moldability.

In the present invention, an inorganic filler can be further contained as a G component. Inorganic fillers include glass fiber (chopped strand), carbon fiber, metal-coated carbon fiber, metal fiber, wollastonite, zonotolite, potassium titanate whisker, aluminum borate whisker, and basic magnesium sulfate whisker. Fillers, plate-like fillers such as talc, mica, glass flakes, graphite flakes, short glass fibers (milled fibers), short carbon fibers, glass beads, glass balloons, ceramic balloons, silica particles, titania particles, alumina particles, kaolin , Clay, calcium carbonate, titanium oxide and the like. And the above various inorganic fillers by plating, vapor deposition, methods such as sputtering, gold, silver, nickel, copper, chromium, various metals typified by aluminum and the like, titanium oxide, iron oxide,
An inorganic filler coated with a metal oxide represented by tin oxide, zirconium oxide, cerium oxide, or the like can be given.

In the present invention, talc, mica, wollastonite, kaolin, clay, glass flake, etc.
It is particularly useful for inorganic fillers that cause a decrease in weld strength even when blended with a resin having good weld strength. In the present invention, even when such an inorganic filler is used, the weld strength can be effectively improved.

The proportion of the G component is preferably 1 to 100 parts by weight based on 100 parts by weight of the total of the A component and the B component.
More preferably 2 to 50 parts by weight, particularly preferably 3 to 4 parts by weight.
0 parts by weight. Within such a range, further improvement in weld strength can be achieved while maintaining good moldability, and it can be used in fields where higher strength and rigidity are required and improvement in weld strength is particularly required.

Further, various heat-resistant organic fillers, phosphorus-based heat stabilizers, antioxidants, ultraviolet absorbers, mold release agents, antistatic agents, flame retardants, flame retardant additives are added to the thermoplastic resin composition of the present invention. Agent,
Blowing agents, dyes and pigments and the like can also be blended.

The heat-resistant organic fillers are those which do not melt at the molding temperature of the aromatic polycarbonate resin as the component A of the present invention. Examples of such fillers include fibrous fillers such as aramid fibers and polyarylate fibers. , Aramid powder, polytetrafluoroethylene powder, phenol resin particles, crosslinked styrene particles, crosslinked acryl particles, and other particulate fillers.

Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. (2,
4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite Phyte, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert -Butylphenyl)
Octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t
phosphite compounds such as tert-butylphenyl) pentaerythritol diphosphite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl Phosphate compounds such as phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and tetrakis (2,4-
Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-ter
t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite,
Bis (2,4-di-tert-butylphenyl) -4-
Examples thereof include phosphonite compounds such as biphenylenephosphonite. Of these, trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert)
-Butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl)
Phosphite, triphenyl phosphate, trimethyl phosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)-
4-Biphenylenephosphonite is preferred. These heat stabilizers may be used alone or in combination of two or more. The amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, based on 100 parts by weight of the total of the component A and the component B.
0.002 to 0.3 parts by weight is more preferred.

Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and triethylene glycol-bis. [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-)
Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, tetrakis (4,4′-biphenylenediphosphosphinate) (2,4-di-t-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {-2,4,8,10
-Tetraoxaspiro (5,5) undecane and the like. The compounding amount of these antioxidants is preferably 0.0001 to 1 part by weight based on 100 parts by weight of the total of the component A and the component B.

As the ultraviolet absorber, for example, 2,2'-
A benzophenone-based ultraviolet absorber represented by dihydroxy-4-methoxybenzophenone;
(3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H -Benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and 2- (3,5-di-tert- Examples thereof include benzotriazole-based ultraviolet absorbers represented by (amyl-2-hydroxyphenyl) benzotriazole. Further, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, bis (1,2,2,6,6-
It is also possible to use hindered amine light stabilizers represented by (pentamethyl-4-piperidyl) sebacate and the like. The amount of the ultraviolet absorber and the light stabilizer is
0.0 to 100 parts by weight of the total of the component A and the component B
1 to 5 parts by weight is preferred.

In order to further improve the releasability from the mold at the time of melt molding, a releasing agent may be added to the thermoplastic resin composition of the present invention as long as the object of the present invention is not impaired. It is. Examples of such release agents include olefin waxes, silicone oils, organopolysiloxanes, higher fatty acid esters of monohydric or polyhydric alcohols, paraffin wax, beeswax and the like. The amount of the release agent is based on 100 parts by weight of the total of the A component and the B component.
0.01 to 2 parts by weight is preferred.

The flame retardant is not particularly limited, but is typified by red phosphorus or stabilized red phosphorus in which the surface of red phosphorus is microencapsulated with a known thermosetting resin and / or inorganic material. Red phosphorus flame retardant: Tetrabromobisphenol A, oligomer of tetrabromobisphenol A, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene Halogen flame retardants represented by ether, polydibromophenylene ether, decabromodiphenyl oxide bisphenol condensate and halogenated phosphoric ester; triphenyl phosphate as monophosphate compound, condensation Organic phosphate ester flame retardants represented by resorcinol bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and pentaerythritol diphenyl diphosphate as acid esters; ammonium polyphosphate, aluminum phosphate, phosphorus Inorganic phosphates such as zirconium oxide, hydrates of inorganic metal compounds such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc metaborate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide, etc. Inorganic flame retardants represented by: potassium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, potassium diphenylsulfon-3-sulfonate, diphthamine Vinyl sulfonic -
Organic alkali (earth) metal salt-based flame retardants represented by potassium 3,3'-disulfonate; (poly) organosiloxane compounds containing phenyl, vinyl and methyl groups, and (poly) organosiloxane and polycarbonate resins And phosphazene-based flame retardants represented by phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers. The red phosphorus-based flame retardant is preferably melt-mixed in advance with the resin of the component A or the component B, and more preferably a master batch.

An antistatic agent can be added to the thermoplastic resin composition of the present invention within the scope of the effects of the present invention. Examples of such antistatic agents include polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, monoglyceride maleic anhydride, diglyceride maleic anhydride, and the like. The compounding amount of the antistatic agent is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the total of the component A and the component B.

The thermoplastic resin composition used in the present invention comprises:
Combine the above components simultaneously or in any order in a tumbler, V
It can be manufactured by mixing with a mixer such as a mold blender, a Nauter mixer, a Banbury mixer, a kneading roll, and an extruder. Further, a nucleating agent, a flame retardant, a foaming agent, a dye and the like which are usually used in the resin composition may be contained as long as the object of the present invention is not impaired. Although the thermoplastic resin composition obtained by the present invention is particularly suitable for injection molding, such injection molding methods include not only ordinary injection molding, but also injection compression molding, gas injection hollow molding, and two-color molding. It is also useful in high-speed injection molding and other various injection molding methods.

[0112]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples. Parts and% in the examples are parts by weight and% by weight, and the evaluation was made by the following methods.

The evaluation was performed according to the following method. (1) Impact resistance: 23 according to ASTM D-256
Atmospheric impact resistance at -30 ° C and -30 ° C was measured. (1/8 "with Izod notch) (2) Heat resistance: Deflection temperature under load was measured in accordance with ASTM D-648. (3) Strength measurement of weld portion: ASTM D-638
The gates were formed at both ends of the dumbbell using the tensile dumbbell described in (1), and the tensile strength (Y1) was measured such that a weld was formed at the center of the dumbbell. Also ASTM
In accordance with D-638, ordinary tensile strength (Y2) was measured, and the retention of weld strength was calculated according to the following equation.
The weld retention is preferably 70% or more for practical use, and particularly preferably 75% or more. Strength retention (%) = (Y1 / Y2) × 100%

(4) Appearance: A tensile dumbbell described in ASTM D-638 was molded, and the presence or absence of jetting and flow marks was visually determined. The judgment was made as follows. ○ ・ ・ ・ No defective jetting and flow mark appearance × ・ ・ ・ No defective jetting or flow mark appearance (5) Formability: Injects an Archimedes-type spiral flow length with a channel thickness of 2 mm and a channel width of 8 mm The measurement was performed using a molding machine “SG150U manufactured by Sumitomo Heavy Industries, Ltd.” at a cylinder temperature of 260 ° C., a mold temperature of 80 ° C. and an injection pressure of 98 MPa. In addition, evaluation was performed as follows. ○: Spiral flow length of 20 cm or more ×: Spiral flow length of less than 20 cm

[Examples 1 to 32 and Comparative Examples 1 to 21,
Reference Examples 1-4] After mixing the components shown in Tables 1 to 7 at the mixing ratios shown in the table with a V-type blender, the screw diameter was 3
0mm vent type twin screw extruder [KTX manufactured by Kobe Steel Ltd.]
−30], and pelletized at a cylinder temperature of 260 ° C. After the pellets were dried at 110 ° C. for 6 hours, a desired test piece was prepared at 260 ° C. cylinder temperature and 80 ° C. mold temperature by an injection molding machine [T-150D manufactured by FANUC Corporation], and the evaluation results were shown. (However, for Comparative Example 3 and Reference Examples 1 to 4, the cylinder temperature during extrusion was 290 ° C.).

The symbols indicating the components described in the table are as follows. The weight average molecular weight (Mw) is usually calculated by GPC measurement using a calibration curve using a polystyrene resin.

(Component A) PC: Linear aromatic polycarbonate resin having a viscosity average molecular weight of 22,500 produced from bisphenol A and phosgene: "Panlite L-1225" manufactured by Teijin Chemicals Ltd.

(Component B) ABS: ABS resin ("Santac U" manufactured by Mitsui Chemicals, Inc.)
T-61 "Mw of AS component = 120,000) AES: AES resin (" AXS resin E700N "manufactured by Ube Sykon Co., Ltd. Mw of AS component = 130,000) ASA: ASA resin (manufactured by Ube Sykon Co., Ltd.) AXS resin A600N ”Mw of AS component = 130,000) AS: Acrylonitrile-styrene copolymer (“ Stylac AS769 ”manufactured by Asahi Kasei Corp.) Mw = 14
0000)

(Component C) Polyester-styrene elastomer (C-1): polybutylene terephthalate resin (“Hauser S1000F” manufactured by Kuraray Co., Ltd .: intrinsic viscosity [η] = 0.85) 70
Parts by weight and hydrogenated SBIS-OH {polystyrene block having a hydroxyl group at one end (number average molecular weight 6000) /
Triblock copolymer composed of hydrogenated copolymer block of 1,3-butadiene and isoprene (number average molecular weight 28,000) / polystyrene block (number average molecular weight 6000), hydroxyl group content = 0.8 / molecule, Styrene content before hydrogenation = 30% by weight, 1,3-butadiene / isoprene molar ratio = 1/1, number average molecular weight = 4000
0 to 30 parts by weight were preliminarily mixed and melt-kneaded at 250 ° C. using a twin-screw extruder (“TEX44C” manufactured by Japan Steel Works, Ltd.) to produce pellets. The pellets were transferred to a solid-state polymerization apparatus and pretreated at 120 ° C. for about 4 hours. Thereafter, the pressure in the solid-state polymerization apparatus was reduced to 0.2 mmHg, and the temperature was raised to 200 ° C. to start the polymerization reaction. After about 14 hours, nitrogen gas was introduced into the reactor to return to normal pressure, the reaction product obtained was dissolved in a mixed solvent of hexafluoroisopropanol / chloroform (1/1), and the solution was injected into tetrahydrofuran. A precipitate was obtained. After further heating and refluxing in chloroform, the mixture was filtered off, and the chloroform solution was concentrated to dryness to separate the copolymer in which the target polyester and hydrogenated SBIS were bonded.
-1).

The following points confirmed that the polyester-styrene-based elastomer (C-1) obtained above was a block copolymer in which a polybutylene terephthalate block and a hydrogenated SBIS block were bonded.
That is, a polyester-styrene-based elastomer (C-
The peak (8.1, 4.1, 4.1) derived from the chemical structure of polybutylene terephthalate by ¹ H-NMR measurement of 1)
2.2 ppm) and peaks derived from the chemical structure of hydrogenated SBIS-OH (7.0, 6.6, 0.7 to 2.0).
ppm) and the hydrogenated SBIS-
The chemical shift of the peak of the methylene proton adjacent to the hydroxyl group at the molecular end observed in OH was shifted. Also, in GPC measurement, it shows a single molecular weight, and the number average molecular weight is the number average molecular weight of polybutylene terephthalate used as a raw material and hydrogenated SBIS.
That is, it was almost equal to the total number average molecular weight of —OH.

Polyester-styrene elastomer (C-2): Instead of SBIS-OH used in C-1, hydrogenated SI-OH−polystyrene block having a hydroxyl group at a polystyrene block terminal (number-average molecular weight: 1000)
0) / Diblock copolymer composed of hydrogenated polyisoprene block (number average molecular weight 20,000), hydroxyl group content = 0.8 / molecule, styrene content in block copolymer before hydrogenation = 33 A solid-phase polymerization reaction product containing a polyester-aromatic vinyl-based block copolymer was obtained in the same manner as in C-1 using weight% and a number average molecular weight of 30,000 °. The obtained solid-phase polymerization reaction product was treated with hexafluoroisopropanol / chloroform (1/1).
It was dissolved in the mixed solvent of 1), and the solution was poured into tetrahydrofuran to obtain a precipitate. After further heating and refluxing in chloroform, the mixture was filtered off and the chloroform solution was concentrated to dryness to obtain the desired polyester-styrene-based elastomer (C-2). The fact that this was a block copolymer was confirmed by the same method as in C-1.

(Component D) PBT: polybutylene terephthalate resin (“Hauser S1000F” manufactured by Kuraray Co., Ltd.): intrinsic viscosity [η] = 0.
85) (E component) SBIS: Hydrogenated SBIS-OH used for producing C-1 SI: Hydrogenated SI-OH used for producing C-2 (F component) UHMAS: Acrylonitrile-styrene copolymer (General Electric Company, Inc.) “Blendex 869” Mw = 7,000,000) (G component) WSN: Wollastonite (NYGLOS manufactured by NYCO)
4) Talc: Talc (HST 0.8, manufactured by Hayashi Kasei Co., Ltd.) GF: Glass fiber (ECS, manufactured by NEC Corporation)
03T-511)

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

[0129]

[Table 7]

As is evident from the table, the inclusion of the specific polyester-styrene elastomer block copolymer which is the component C of the present invention significantly improves the weld strength and the low-temperature impact resistance. . This point is clear from comparison between Examples 10 and 11 and Comparative Example 5, for example. Further, from a comparison with Example 10, when the component C was not contained, the effect of improving the weld strength was not obtained even when the component D or the component E was present (Comparative Example 6). It can be seen that while the improvement in the resistance is saturated, the impact resistance and the heat resistance are reduced (Comparative Example 7). Further, even when the C component is present, if the ratio does not satisfy the specific relational quantity (Equation (1)), the weld strength is not sufficiently improved (Comparative Example 8). I understand.

On the other hand, it can be seen from a comparison of Examples 5 and 10 that the weld strength is further improved when the composition further contains a high molecular weight vinyl polymer as the F component. Further, when the C component satisfies the more preferable specific ratio (formula (2)), it can be seen from the comparison between Examples 10 and 12 that a better weld strength and the like are achieved. Examples 10 and 1
From the comparison of No. 1, it can be seen that the presence of the D component and the E component to some extent can obtain better characteristics.

Further, when comparison was made with the case where inorganic fillers such as talc and wollastonite were added, as shown in Reference Examples 1 to 4, the aromatic polycarbonate resin alone showed a sufficient improvement in weld strength even with the blending of the C component. However, in the resin composition of the present invention, as can be seen from the comparison between Examples 14 and 15 and Comparative Examples 9 and 10, improvement in weld strength due to the blending of the C component is observed.

[0133]

According to the present invention, the strength of the weld portion can be improved.
Aromatic polycarbonate and ABS resin, AS with excellent mechanical properties such as impact strength at low temperature, moldability, heat resistance, etc.
It is possible to obtain a thermoplastic resin composed of a styrene resin such as A resin, and it is extremely useful for various industrial uses such as the automotive field, OA equipment field, and electronic / electric equipment field. Use, interior material use,
It is most suitable for applications requiring relatively large molded products such as electronic equipment housings.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 55/00 C08L 55/00 67/02 67/02 69/00 69/00 (72) Inventor Hidekazu Ito 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Teijin Chemicals Co., Ltd. F-term (reference) 4J002 AC07X AC08X BC02U BC03X BC04X BC06U BC06X BC08X BC09X BC11X BC12X BC13X BG04U BG06U BG06X BG10U BG10X CF05 CF05 BP15Z03 CF18Z CG01W CG02W DA016 DA026 DA066 DE136 DE146 DE186 DE236 DG046 DJ006 DJ016 DJ036 DJ046 DJ056 DK006 DL006 FA016 FA046 FA066 FA086 FB076 FD016 FD050 FD060 FD070 FD100 FD130 FD160 FD200 GN00 GP00 GQ00

Claims (4)

[Claims] 1. An aromatic polycarbonate resin (A component)
1 to 99% by weight, styrene-based polymer or copolymer other than styrene-conjugated diene block copolymer (component B) 9
The total of 9 to 1% by weight is 100% by weight, and the total of 100 parts by weight of the component A and the component B,
Styrene-based elastomer block copolymer (component C)
0.2 to 15 parts by weight, 0 to 30 parts by weight of an aromatic polyester resin (D component), and 0 to 10 parts by weight of a styrene-conjugated diene block copolymer (E component).
When the ratio of the C component to the total of 100 parts by weight of the A component and the B component is c parts by weight, the ratio of the D component is d parts by weight, and the ratio of the E component is e parts by weight, the following formula (1) is satisfied. A thermoplastic resin composition comprising: (Equation 1) 2. The thermoplastic resin composition according to claim 1, further satisfying the following formula (2). (Equation 2) 3. A weight-average molecular weight (Mw) of 1,000, based on 100 parts by weight of the total of the component A and the component B.
Obtained by polymerizing at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, an acrylate monomer, and a methacrylate monomer having a molecular weight of 1,000 to 10,000,000. Polymer (F component) 0.1-1
3. The thermoplastic resin composition according to claim 1, comprising 0 parts by weight. 4. The heat according to claim 1, further comprising 1 to 100 parts by weight of an inorganic filler (G component) based on 100 parts by weight of the total of the component A and the component B. Plastic resin composition.