JPH03247651A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable for interior automotive trims, exterior automotive trims, etc., having improved water absorption properties, chemical resistance and heat resistance by blending a thermoplastic polyester with a specific copolymer and a diene-based graft copolymer in a specific ratio. CONSTITUTION:(A) 2-97wt.%, preferably 10-80wt.% thermoplastic polyester (e.g. polyl-4,-butylene terephthalate) is blended with (B) 2-97wt.% polymer obtained by copolymerizing B1: 100-70wt.% monomer comprising a vinyl aromatic compound, unsaturated dicarboxylic acid compound, etc., with B2: 0-30wt.% rubber-like polymer having <=0 deg.C glass transition temperature and having 3-35wt.% copolymerization ratio of unsaturated dicarboxylic acid anhydride in the whole resinous polymer and (C) 1-70 one or more diene-based graft copolymers selected from a butadiene-based graft copolymer, etc., prepared by subjecting C1: a vinyl aromatic compound, etc., to graft copolymerization in the presence of a conjugated diene-based polymer.

Description

[Detailed description of the invention] a. Industrial application field The present invention is directed to a thermoplastic resin that has excellent impact resistance, heat resistance, chemical resistance, surface appearance of molded products, and warpage resistance (performance that does not cause warpage). Regarding the composition.

b. Conventional technology Thermoplastic polyesters, represented by polybutylene terephthalate and polyethylene terephthalate, are used as molded products in a wide range of fields such as parts in the electrical and electronic fields due to their excellent properties. It has the disadvantages of low impact strength, easy molded products to warp, and low heat distortion temperature under high loads. For this reason, its use in large molded products has been restricted.

On the other hand, a copolymer consisting of styrene and maleic anhydride
Although it has the characteristic of having a high heat distortion temperature, it has the disadvantage of being inferior in impact resistance, chemical resistance, etc.

Japanese Patent Publication No. 63-12102 discloses a composition comprising polybutylene terephthalate and a styrene-maleic anhydride copolymer. However, although such compositions have good heat resistance, chemical resistance, molded product surface appearance, and molded product warpage, they have the drawback of poor impact resistance.

For the purpose of improving impact resistance, there is a method in which styrene and maleic anhydride are graft-polymerized in the presence of a rubbery polymer and blended with thermoplastic polyester, but the improvement in impact resistance was insufficient.

That is, the present inventors blended rubbery polymers such as polybutadiene and butadiene-acrylonitrile copolymer to improve the impact resistance of a composition composed of polybutylene terephthalate and styrene-maleic anhydride copolymer. However, the impact resistance was not improved at all, and the surface appearance of the molded product was significantly inferior.

C0 Problems to be Solved by the Invention The purpose of the present invention is to provide a thermoplastic resin composition that has excellent impact resistance, heat resistance, chemical resistance, surface appearance of molded products, and warpage resistance. .

60 Means for Solving the Problems The present inventors have developed a graft copolymer in which a resinous polymer is graft-polymerized to a thermoplastic polyester resin, a specific styrene-maleic anhydride copolymer, and a specific rubbery polymer. It was discovered that a thermoplastic resin composition having unprecedented performance could be obtained by blending the compounds, and the present invention was completed based on this knowledge.

That is, the present invention comprises (a) 2 to 97% by weight of a thermoplastic polyester resin, (b) a vinyl aromatic compound, an unsaturated dicarboxylic acid anhydride, and optionally another vinyl monomer copolymerizable with these. A copolymer obtained by copolymerizing 100 to 70% by weight of a monomer forming a resinous polymer and 0 to 30% by weight of a rubbery polymer having a glass transition temperature of 0 ° C or less, and a polymer in which the copolymerization ratio of unsaturated dicarboxylic acid anhydride in the resinous polymer is 3 to 35% by weight, 2 to 97% by weight, and (c) (c-1) a conjugated diene polymer. and (c -2) A vinyl aromatic compound, a vinyl cyanide compound, and a vinyl aromatic compound (methyl )
1 selected from the group consisting of acrylic acid alkyl esters
A thermoplastic resin composition comprising 1 to 70% by weight of at least one diene graft copolymer selected from a diene graft copolymer obtained by graft copolymerizing a species or two or more species. It provides:

The above thermoplastic polyester resin is a polyester compound consisting of a dicarboxylic acid and a diol compound, and is a relatively high molecular weight, almost linear thermoplastic polymer. Preferably, polymeric glycols of terephthalic acid and isophthalic acid are used. Examples include esters.

These polymers are already commercially available and can be manufactured by known manufacturing techniques (US Pat. No. 2,465,319, US Pat. No. 3,047,539).

In other words, it can be produced by alcoholysis of phthalate ester with glycol and subsequent polymerization reaction, and it can also be produced by polymerization reaction by heating free phthalic acid or its halide derivative and glycol, or similar production methods. It can also be produced by a method.

A preferred thermoplastic polyester resin (a) is one composed of a high molecular weight polymeric glycol terephthalate or glycol isophthalate having a repeating unit represented by the following formula, or a mixture of these esters.

[In the formula, n is preferably an integer of 2 to 10, and particularly preferably 2 to 4 in view of the physical properties of the composition. ] Copolymers of terephthalic acid and isophthalic acid containing up to 30% of isophthalic acid units can also be suitably used.

Preferred thermoplastic polyester resins (a) are poly-ethylene terephthalate and poly-1,4-butylene terephthalate, particularly preferably poly-1,4-butylene terephthalate.

Branched poly-ethylene terephthalate and branched poly-1,4-butylene terephthalate can also be used. Such a branched polymer may contain a small amount of a branching component having at least three ester-forming groups, for example up to 5 mol % based on the terephthalic acid units.

The branching component may form a branch on the polyol unit in addition to the acid unit of the polyester (or may be a mixture of both. Examples of such a branching component include:
tri- or tetracarboxylic acids, such as trimesic acid,
such as trimellitic acid, pyromellitic acid and lower alkyl esters thereof, or polyols, preferably tetrols, such as pentaerythritol and triols, such as trimethylolpropane, or dihydroxycarboxylic acids and hydroxydicarboxylic acids and their derivatives, such as hydroxy Examples include dimethyl terephthalate.

These branched polyesters are described, for example, in U.S. Pat.
It can be produced by the same production method as the branched poly(1°4-butylene terephthalate) resin described in No. 53.404.

Copolyesters are also useful as thermoplastic polyester resins (a), such as those described in U.S. Pat. No. 3,651,01.
4, U.S. Pat. No. 3.763.109 and U.S. Pat. No. 3.766,146 Polyester can be suitably used.

The amount of component (a) used in the composition of the present invention is 2 to 9
7% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight. If the amount used is less than 2% by weight, the chemical resistance and impact resistance will be poor, and if it exceeds 97% by weight, the impact resistance and heat resistance will be poor and the molded product will be likely to warp.

Component (i) of the present invention usually contains a vinyl aromatic compound, an unsaturated dicarboxylic anhydride, and optionally another vinyl monomer copolymerizable therewith under bulk or solution polymerization conditions. Obtained by radical copolymerization of 100 to 70% by weight of a monomer forming a resinous polymer having a glass transition temperature with 0 to 30% by weight of a rubbery polymer having a glass transition temperature of 0°C or lower. . The preferred copolymerization method is to first dissolve the above-mentioned rubbery polymer in a vinyl aromatic compound and, in some cases, other vinyl monomers that can be copolymerized therewith, and then add a molecular weight regulator and a polymerization solvent as necessary. In addition, in the presence of a radical polymerization initiator, continuous polymerization is performed so that the concentration ratio of the vinyl aromatic compound or its mixture with vinyl monomer and the unsaturated dicarboxylic acid anhydride remains substantially constant during the polymerization period. This is a method in which an unsaturated dicarboxylic acid anhydride is added to the mixture, and polymerization is carried out at a reaction temperature of 40 to 170°C.

The above-mentioned vinyl aromatic compound is not particularly limited, and examples include styrene, α-methylstyrene, P-methylstyrene,
-Methylstyrene, nuclear-substituted halogenated styrene, indene, etc. can be used, with styrene being particularly preferred.

In addition, unsaturated dicarboxylic acid anhydrides (but not limited to)
For example, maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, phenylmaleic anhydride, aconintic anhydride, etc. can be used, and maleic anhydride is particularly preferred. . Two or more of these vinyl aromatic compounds and unsaturated dicarboxylic acid anhydrides may be used in combination.

Other vinyl monomers that can be copolymerized with the vinyl aromatic compound and unsaturated dicarboxylic acid anhydride used as optional components include vinyl cyanide compounds such as acrylonitrile and methacrylate, methyl methacrylate, methyl acrylate, and ethyl methacrylate. methacrylate, n-
Examples include (meth)acrylic acid alkyl esters such as butyl acrylate and 2-ethylhexyl acrylate, and two or more of these can also be used as a mixture.

The copolymerization amount of these other vinyl monomers is preferably 35% by weight or less of the resinous polymer.

The copolymerization ratio of the unsaturated dicarboxylic acid anhydride is 3 to 35% by weight, preferably 5 to 30% by weight, based on the resinous polymer.
More preferably, it is 5 to 25% by weight. If the amount is less than 3% by weight, the heat resistance of the final resin composition will not be sufficiently improved. Moreover, if it exceeds 35% by weight, the fluidity and thermal stability during molding of the resin composition finally obtained will be significantly reduced, and the surface appearance of the molded product will be poor.

Examples of rubbery polymers having a glass transition temperature of 0°C or lower include butadiene homopolymer rubber, styrene-butadiene copolymer rubber, butadiene-(meth)acrylic acid alkyl ester copolymer rubber, acrylonitrile-butadiene copolymer rubber, etc. butadiene-based rubbery polymers, chloroprene-based rubbery polymers, isoprene-based rubbery polymers,
Examples include natural rubber, chlorinated polyethylene, ethylene-propylene copolymer rubbery polymer, ethylene-diene copolymer rubbery polymer, and cycloolefin rubbery polymer.

The proportion of rubbery polymer in component (b) is 30% by weight.
It is as follows. If it exceeds 30% by weight, the viscosity of the polymerization solution becomes extremely high, making it difficult to carry out polymerization in practice.

In addition, the rubbery polymer is dispersed in a plurality of particles having an average particle size of preferably 0.02 to 30μ, particularly preferably 0.1 to 10μ, in the rubbery polymer component. It is preferable to continue stirring the polymerization system during the polymerization so that most of the resinous polymer is grafted onto the polymerization system.

The amount of component (b) used in the composition of the present invention is 2 to 9
7% by weight, preferably 5-90% by weight, more preferably 10-80% by weight. If the amount used is less than 2% by weight, the heat resistance will be poor and the molded product will be likely to warp.

Moreover, if it exceeds 97% by weight, impact resistance and chemical resistance will be poor.

Component (C) of the present invention is obtained by grafting one or more selected from the group consisting of vinyl aromatic compounds, vinyl cyanide compounds, and (meth)acrylic acid alkyl esters in the presence of a conjugated diene polymer. A copolymerized butadiene-based graft copolymer (c-1), and a hydrogenated product of an ethylene-α/olefin-based copolymer and/or a conjugated diene alone or a copolymer consisting of a conjugated diene and a vinyl aromatic compound. vinyl aromatic compounds in the presence of
At least one kind selected from butadiene-based graft copolymers (c-2) obtained by graft copolymerizing one or more kinds selected from the group consisting of vinyl cyanide compounds and (meth)acrylic acid alkyl esters. It is a diene-based graft copolymer.

As the conjugated diene polymer used in component (c-1), all of the butadiene rubber polymers exemplified as rubbery polymers having a lath transition temperature of O''CC or lower in component (b) can be used. As the vinyl aromatic compound, vinyl cyanide compound, and alkyl (meth)acrylate ester, all of the vinyl aromatic compounds, vinyl cyanide compounds, and alkyl (meth)acrylate exemplified in component (b) can be used.

Component (c-1) is a compound selected from the group consisting of vinyl aromatic compounds, vinyl cyanide compounds, and (meth)acrylic acid alkyl esters (hereinafter referred to as "specific compounds") in the presence of a conjugated diene polymer. It is a graft copolymer obtained by polymerizing a species or two or more species, and the amount of conjugated diene polymer in component (c-1) is 10% from the viewpoint of impact resistance of the composition.
-70% by weight is preferred, more preferably 40-70%
% by weight, particularly preferably from 50 to 65% by weight. (c
In component -1), polymer constituents made of specific compounds include polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer,
Styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile-α-methylstyrene copolymer, etc. are preferred. Here, the acrylonitrile content in the styrene-acrylonitrile copolymer is 5 to 3.
5% by weight is preferable, and the methyl methacrylate content in the styrene-methyl methacrylate copolymer is 10 to 90% by weight.
is preferred.

Component (c-1) can be produced by known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and polymerization methods that combine these. From the viewpoint of product surface appearance, it is preferable to manufacture by emulsion polymerization method.

The average particle size of the conjugated diene polymer used in emulsion polymerization is usually 600 to 8,000, preferably 1,000 to 5,000.
000, and the amount of gel (toluene solvent) in the conjugated diene polymer is preferably 20% by weight or more. In addition, the amount of polymer consisting of a specific compound grafted to the conjugated diene polymer, that is, the grafting rate (methyl ethyl ketone solvent)
is preferably 20% by weight or more of the polymer made of the specific compound. Also, as emulsion polymerization catalysts, persulfates such as potassium persulfate and ammonium persulfate, hydroperoxides and reducing agents (sugar-containing pyrophosphoric acid formulation, sulfoxylate formulation)
A redox initiator such as a combination of the following is preferably used.

The ethylene-α/olefin copolymers used for component (c-2) include ethylene-α/olefin copolymers and ethylene-α/olefin-polyene terpolymers. ′
The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, pentene-1, hexene-1, heptene-1,4-methylhebutene. -1,4-methylpentene-
1, etc., but propylene is preferred.

As polyene compounds, 1.4-pentadiene, 1.5
-hexadiene, 2methyl-1,5-hexadiene, 3
, 3-dimethyl-1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 6-methyl-1,5-
hexadiene, 1,4-hexadiene, 7-methyl-1
゜6-octadiene, 9-methyl-1,9-undecane, isoprene, 1,3-pentadiene, 4-vinyl-1
-Cyclohexane, cyclopentadiene, 2-methyl-
2,5-norbornadiene, 5-methyl 2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, dicyclopentadiene,
Examples include tricyclopentadiene, and the iodine value is 5.
A range of 40 to 40 is preferable.

The weight ratio of ethylene and α-olefin is 90:10~
A range of 40:60 is preferred. In addition, the Mooney viscosity (
MLI-4,1°. ℃) is preferably 50 or less.

As the conjugated diene homopolymer, 1,3-butadiene,
2-methyl-1,3-butadiene, 2,3-dimethyl-
1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene substituted linear conjugated pentadiene, linear and side chain conjugated hexadiene, etc. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene polymers are preferred, and 1,3-butadiene polymers are particularly preferred.

Copolymers of conjugated dienes and vinyl aromatic compounds include block copolymers, random copolymers, and combinations thereof, and block copolymers have the general formula: (1-B-)-
, (A-BhA, (1-B-)=X [where A is a polymer block mainly composed of a vinyl aromatic compound, B is a polymer block mainly composed of a conjugated diene compound, and X is a coupling agent residue. group, n is an integer of 1 or more.] Here, the polymer block mainly composed of a vinyl aromatic compound is a polymer block containing 90 weight or more of a vinyl aromatic compound. A polymer block mainly composed of a conjugated diene compound means that the conjugated diene compound block contains a conjugated diene compound alone or a conjugated diene compound in an amount of 60% by weight or more, preferably 80% by weight.
The copolymer block of the above-contained conjugated diene compound and vinyl aromatic compound may have any structure having one or more so-called tapered blocks in which vinyl aromatic compounds are randomly bonded or gradually increased.

As the conjugated diene compound, the same compounds as mentioned above can be used, and 1,3-butadiene is particularly preferred. Also,
As the vinyl aromatic compound, all of the vinyl aromatic compounds exemplified for component (b) can be used, but styrene is particularly preferred.

Furthermore, as a copolymer consisting of a conjugated diene and a vinyl aromatic compound, polymer blocks A, B, and C are included in the molecule.
However, A is a polymer block mainly composed of a vinyl aromatic compound containing 90% by weight or more of a vinyl aromatic compound, and B is a polymer block having 30 to 9 1,2-vinyl bonds.
0% polybutadiene polymer block, C indicates a polybutadiene polymer block with less than 30% of 1,2-vinyl bonds), the content of polymer A in the block copolymer is 10
~50% by weight, a block copolymer in which the content of polymer block B is 30 to 80% by weight, and the content of polymer block C is 10 to 40% by weight, or the block copolymer unit is a coupling agent residue. A block copolymer in which the molecular chain of the polymer unit is linear or branched, or 1.2- Vinyl structure is 20
% or less polybutadiene block segment (C) and a block segment (D) consisting of polybutadiene or a vinyl aromatic compound-butadiene copolymer having a 1°2-vinyl structure of 30 to 95%. and the general formula: (C-D-h, (C-D-)-TC, (C
-DhX [wherein X is a coupling agent residue and n is an integer of 1 or more. ] can be used.

In the present invention, a conjugated diene homopolymer and a copolymer of a conjugated diene and a vinyl aromatic compound are hydrogenated before use, and the hydrogenation rate is such that at least 80% or more of the olefinic unsaturated bonds in the polymer are hydrogenated. It is preferably 90% or more, particularly preferably 95% or more.

The weight average molecular weight of the hydrogenated polymer is preferably 10,000 to soo, ooo, more preferably 2
It is 0.000 to 400,000.

Component (c-2) is the above-mentioned ethylene-α/olefin copolymer, a hydride of a conjugated diene homopolymer, and a hydride of a copolymer of a conjugated diene compound and a vinyl aromatic compound (hereinafter referred to as "rubber prize component"). ) at least one selected from
It is a graft copolymer obtained by polymerizing a specific compound similar to component (c-1) in the presence of seeds, and the amount of rubbery polymer in component (c-2) is determined by the impact resistance of the composition. 10-5 in terms of
It is preferably 0% by weight, more preferably 20 to 50% by weight. Furthermore, in component (c-2), examples of the polymer component made of a specific compound include those similar to component (c-1).

Component (c-2) can be polymerized by a known polymerization method, but a solution polymerization method is particularly preferred.

The amount of component (C) used in the composition of the present invention is 1 to
The amount used is 70% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight. If the amount used is less than 1% by weight, the impact resistance will be poor, and if it exceeds 70% by weight, the heat resistance will be poor.
Poor chemical resistance.

The thermoplastic resin composition of the present invention can be produced by using various extruders, Banbury mixers, kneaders, rolls, etc.
It can be obtained by kneading each component at a temperature of 0°C. The order of addition of each component during melt-kneading is not particularly limited, but it is manufactured by a method of mixing and kneading all the components, or a multi-stage kneading method such as kneading any two components and then adding and kneading the remaining components. can do.

When using the thermoplastic resin composition of the present invention, various fillers can be added.

For example, glass fiber, carbon fiber, metal fiber, glass beads, asbestos, glass flakes, wollastonite,
Fillers such as calcium carbonate, talc, barium sulfate, mica, potassium titanate whiskers, fluororesin, molybdenum disulfide, carbon black, and titanium oxide can be used alone or in combination.

Among these fillers, those in the form of fibers such as glass fiber and carbon fiber have a fiber diameter of 6 to 60μ and a fiber diameter of 30μ.
It is preferable to have a fiber length of - or more.

These fillers can be used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

Additionally, known additives such as flame retardants, antioxidants, lubricants, ultraviolet absorbers, and plastic nucleating agents may be added.

Further, depending on the required performance, other polymers such as polyamide, polyethylene, polypropylene, polycarbonate, polysulfone, polyethersulfone, polyimide, PPS, polyetheretherketone, polyphenylene ether, etc. may be blended as appropriate.

The thermoplastic resin composition of the present invention can be used by being molded into various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, or the like.

The various molded products obtained by the above-mentioned molding method can be used for the exterior and interior parts of automobiles, various electrical and electronic related parts, housings, etc. by taking advantage of their excellent performance.

e. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the content of the present invention.

Note that in each side below, parts and % indicate parts by weight and % by weight, respectively.

Components (a), (b) and (C) used in the following Examples and Comparative Examples are as follows.

1. (a) Component The following polybutylene ethylene terephthalate obtained from dimethyl terephthalate and butanediol and the following polyethylene terephthalate obtained from dimethyl terephthalate and ethylene glycol were used. [η] was dissolved in O-chlorophenol at 90 to 100°C and measured at 25°C.

A-1 Polybutylene terephthalate [η) =0.8
A-2 Polybutylene terephthalate [η] = 1.2
A-3 Polyethylene terephthalate [η) =0.82
, (B) Component B-1 Styrene Lid 850 g of styrene, 400 g of methyl ethyl ketone, and 2 g of benzoyl peroxide were charged into a stainless steel reactor equipped with a stirring device. After replacing the air inside with nitrogen, the jacket was filled with hot water (90 g ℃) and heated. When the internal temperature of the reactor reached 50° C., a solution consisting of 128 g of maleic anhydride and 800 g of methyl ethyl ketone was added at the following rate using a variable flow rate continuous addition device.

215etj of a solution of maleic anhydride! / at the speed of time 2
Add time, then add 3 hours at 96mf/hr, then 57wj! Added at the speed of / hour for 5 hours, and 30 seconds + 4 until the addition was complete! / Added at the speed of time. After the addition of the maleic anhydride solution was completed, stirring was continued for 2 hours while keeping the internal temperature at 90°C. The polymerization conversion rate was 85%.

The copolymerized amount of maleic anhydride in the polymer is 15.7% by weight
Met.

After the polymerization was completed, 5 g of 2,2'-methylene-bis-(4-methyl-6-1-butylphenol) was added as an antioxidant, and then the residual monomer and solvent were removed under reduced pressure and the mixture was dried.

483 g of styrene, 207 g of acrylonitrile, and 340 g of methyl ethyl ketone in a stainless steel reactor equipped with a stirring device.
and 2 g of benzoyl peroxide.

After replacing the internal air with nitrogen, fill the jacket with warm water (8
5°C) and heated. When the internal temperature of the reactor reached 50°C, a solution consisting of 128 g of maleic anhydride and 800 g of methyl ethyl ketone was added at the following rate using a variable flow rate continuous addition device.

A solution of maleic anhydride at 28B++/! / at the speed of time 2
Add for 3 hours, then add at a rate of 115 mf/hr for 3 hours, then add at a rate of 77 mf/hr until the addition is complete.

After the addition of the maleic anhydride solution was completed, stirring was continued for 2 hours while keeping the internal temperature at 85°C. The polymerization conversion rate was 99%. The copolymerized amount of maleic anhydride in the polymer was 15.8%.
Met.

After the polymerization was completed, 5 g of 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) was added as an antioxidant, and then the residual monomer and solvent were removed under reduced pressure and the mixture was dried.

B-3 to B-6 Styrene-gong Malein Kita Muu Y Change the amounts of styrene and maleic anhydride under the polymerization conditions of Polymer B-1, and keep the monomer concentration in the polymerization system constant as under the polymerization conditions of Polymer B-1. Polymerization was carried out using the following methods to obtain a polymer having the following maleic anhydride content.

B-322,2% B-48,5% B-547,5% B-62,3% By performing polymerization in the presence of polybutadiene under the polymerization conditions of Polymer B-1, the polybutadiene content was 20%.
So, the maleic anhydride content in the resinous polymer is 15.7%.
A polymer was obtained.

3. (c-1) In the presence of polybutadiene latex with an average particle diameter of 2,700, styrene and acrylonitrile are used as polymerization catalysts, and potassium persulfate is used as a polymerization catalyst to perform a graft reaction by emulsion polymerization, coagulation, and drying to obtain a polybutadiene content of 6.
1%, acrylonitrile content in resinous polymer 25.4
% of polymer C-1 was obtained.

Polymers C-2 and C-3 were obtained by changing the amounts of styrene and acrylonitrile used under the polymerization conditions for polymer C-X, and polymer C-4 was obtained by using methyl methacrylate instead of acrylonitrile.

4. Component (c-2) In the presence of the following rubbery polymer, styrene and acrylonitrile or styrene and methyl methacrylate are subjected to a graft reaction by solution polymerization to obtain polymers C-5 to 9.
I got it.

Notes: JIY body, 22 ecotylene-propylene-ethylidene norbornene copolymer, iodine value 10, propylene content 40%, Mooney viscosity (M
L, 4.1°. C) 35 Rubber -2A-B-A Pro Type A block copolymer hydride of styrene-butadiene-styrene, Kraton@G1650 manufactured by Shell Co., Ltd., was used.

Rubber Person -3A-B-C Pro Type Bustyrene-
Hydrogenated unhydrogenated polymer of butadiene-butadiene block copolymer A block: Polystyrene Proportion 15.2% B block: Polybutadiene 1.2 Vinyl bond amount 39% Proportion 54.9% C block: Polybutadiene 1.2 Vinyl Bond amount 12% Ratio 29.9% Hydrogenation rate of butadiene portion of hydrogenated polymer 99% Weight average molecular weight 110,000 rubber People -4
A-B Pro ri Hydrogenated unhydrogenated polymer A block of a block copolymer of ibstyrene-styrene/butadiene random copolymer; Polystyrene proportion 12.1% Styrene content 20% Hydrogenation of the butadiene portion of the hydrogenated polymer Weight average molecular weight 99% 160,000 Composition ratios of polymers C-5 to C-9 Examples 1 to 15, Comparative Examples 1 to 7 The various polymers were sufficiently dried and mixed in the composition ratios shown in Table 1. Then, the mixture was melt-mixed and pelletized using an extruder NVC50mm (made by Nakatani Kikai ■) at a barrel temperature of 240°C to 260°C. After sufficiently drying the obtained pellets in a dehumidifying dryer, test pieces for evaluation were molded in an injection molding machine and evaluated using the following evaluation method. The evaluation results are shown in Table-1.

Evaluation method Impact resistance: Thickness 1/8# according to ASTM D256
Izot impact strength was measured at 23°C with a notch.

Heat resistance, 1/4' thickness according to ASTM 064B
, measured at a load of 18.6 kg/d.

Chemical resistance: 1% strain applied to 1/8# thick UL bar D
Soaked in OP and brake oil.

Cracks were observed in molded products for brake oil after 10 minutes and for DOP after 10 hours.

○: No change ×: Crank occurrence or fracture Surface appearance of the molded product; Front gloss of the molded product was measured using a color difference meter manufactured by Suga Test Instruments ■.

Warpage of the molded product: Molding a direct gate disc and checking the warpage ○: Almost no warpage △: Some warpage ×: Large warpage Examples 1-15
The composition has excellent impact resistance, heat resistance, chemical resistance, and the surface appearance of molded products, and there is almost no warpage in the molded products.

On the other hand, in the composition of Comparative Example 1, the amount of component (C) used was less than the range of the present invention, and the impact resistance was poor.

In the composition of Comparative Example 2, the amount of unsaturated dicarboxylic acid anhydride in component (b) was larger than the range of the present invention, and the molded product foamed and had a poor appearance.

In the composition of Comparative Example 3, the amount of unsaturated dicarboxylic anhydride in component (b) is less than the range of the present invention, and the composition has poor heat resistance.

In the composition of Comparative Example 4, the amount of component (a) used was less than the range of the present invention, and the composition had poor chemical resistance and impact resistance.

In the composition of Comparative Example 5, the amount of component (b) used was less than the range of the present invention, the heat resistance was poor, and the molded product warped.

In the compositions of Comparative Examples 6 and 7, the amount of component (C) used was greater than the range of the present invention, and the heat resistance and chemical resistance were poor.

f3 Effects of the Invention According to the present invention, a thermoplastic resin composition can be obtained that has excellent impact resistance, chemical resistance, heat resistance, and surface appearance of a molded article, and has less warpage of the molded article.

Because the composition of the present invention has such highly balanced performance, it can be preferably used as molded products such as automobile exteriors and interior parts, various electric/electronic parts, and housings that require high quality. The industrial value is extremely large.

Claims (1)

[Scope of Claims] (a) 2 to 97% by weight of thermoplastic polyester resin, (b
) 100 to 70% by weight of a monomer forming a resinous polymer containing a vinyl aromatic compound, an unsaturated dicarboxylic acid anhydride, and optionally other vinyl monomer copolymerizable with these and a temperature below 0°C. A copolymer obtained by copolymerizing 0 to 30% by weight of a rubbery polymer having a glass transition temperature, and the copolymerization ratio of unsaturated dicarboxylic acid anhydride in the resinous polymer is 3 to 35%. and (c) a vinyl aromatic compound, a vinyl cyanide compound, and a (meth)acrylic acid alkyl ester in the presence of a conjugated diene polymer (c) (c-1). A butadiene-based graft copolymer obtained by graft copolymerizing one or more selected from the group, and (c-2) an ethylene-α-olefin-based copolymer and/or a conjugated diene alone or with a conjugated diene. Graft copolymerization of one or more selected from the group consisting of vinyl aromatic compounds, vinyl cyanide compounds, and (meth)acrylic acid alkyl esters in the presence of a hydrogenated copolymer consisting of vinyl aromatic compounds. 1 to 70% by weight of at least one diene-based graft copolymer selected from: