JPH0674359B2 - Thermoplastic resin composition having excellent retention heat stability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent heat resistance and retention heat stability. The composition of the present invention is used for automobile parts, electric / electronic parts, office work. It can be preferably used for machine parts, heat appliances and the like.

(Conventional Technology and Problems) A composition comprising a copolymer having an imide group in a side chain and one or more polymers selected from polycarbonate and polyester has been excellent in heat resistance and mechanical properties. It is widely known to have.

For example, a resin composition comprising a copolymer of styrene and maleimide and polycarbonate (US Pat. No. 4,160,792
No.), a rubber-modified imidized copolymer obtained by reacting a copolymer obtained by polymerizing a monomer mixture of styrene and maleic anhydride with ammonia and / or a primary amine in the presence of a rubbery block copolymer. A resin composition (US Pat. No. 4,122,130) comprising a polymer and a polycarbonate, and an imidized copolymer obtained by reacting a copolymer comprising styrene and maleic anhydride with ammonia and / or a primary amine;
A graft copolymer obtained by copolymerizing a monomer mixture of styrene, acrylonitrile, and a vinyl monomer copolymerizable therewith in the presence of a rubbery polymer, and at least one selected from polycarbonate and polyester resin. There is a resin composition composed of a polymer (JP-A-57-125241).

However, since the higher the heat resistance of these compositions is, the higher the molding temperature is, when they stay in the cylinder during molding, they start to decompose in a very short time and good molded products cannot be obtained. In this case, there is a problem of poor thermal stability of residence in that the impact strength is remarkably reduced.

The present inventors have found that residence heat stability during molding of a resin composition comprising a copolymer having an imide group and one or more polymers selected from polycarbonate and polyester, particularly residence heat stability during high temperature molding. The present invention has been achieved through intensive studies for the purpose of improving

(Means for Solving the Problems) The present invention comprises (A) component: rubbery polymer 0 to 40% by weight, aromatic vinyl monomer residue 30 to 90% by weight, unsaturated dicarboxylic acid imide derivative residue An imidized copolymer comprising 3 to 70% by weight and 0 to 40% by weight of a vinyl monomer residue other than these residues 2 to
98% by weight, (B) component: 2-98% by weight of one or more polymers selected from polycarbonate and polyester, and (C) component: 0-70% by weight of thermoplastic polymer. With respect to 100 parts by weight of the thermoplastic resin, organic phosphoric acid ester, organic phosphorous acid ester, acidic phosphoric acid ester, acidic phosphorous acid ester and / or their metal salts 0.01 to 1.0
It is a thermoplastic resin composition characterized by containing 0.01 part by weight of an organic carboxylic acid and / or an organic carboxylic acid anhydride in an amount of 0.01 to 5 parts by weight.

First, the imidized copolymer of the component A and its manufacturing method will be described.

As the method for producing the component (A) copolymer, an aromatic vinyl monomer, in the presence of a rubbery polymer, if necessary as the first production method,
Aromatic vinyl monomer, unsaturated dicarboxylic acid in the presence of a rubbery polymer, if necessary, as a second production method in which an unsaturated dicarboxylic acid imide derivative and a vinyl monomer mixture copolymerizable therewith are copolymerized Ammonia and / or a primary amine is reacted with a polymer obtained by copolymerizing an anhydride and a vinyl monomer mixture copolymerizable therewith to convert 40 to 100 mol% of an acid anhydride group into an imide group. The method is mentioned, and the imidized copolymer can be obtained by any method.

Aromatic vinyl monomers used in the first production of the component A copolymer are styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and substituted monomers thereof. Among these, styrene is particularly preferable.

As the unsaturated dicarboxylic acid imide derivative, maleimide, N-methylmaleimide, N-butylmaleimide, N
-Cyclohexylmaleimide, N-arylmaleimide (aryl groups include, for example, phenyl, 4-diphenyl, 1-naphthyl, 2-chlorophenyl, 4-bromophenyl and other mono- and dihalophenyl isomers, 2,4,
6-tribromophenyl, methoxyphenyl and the like can be mentioned. ) And other maleimide derivatives, N-methylitaconic acid imides and N-phenylitaconic acid imides, and other itaconic acid imide derivatives.

The aromatic vinyl monomer used in the second production method is as described above, and as the unsaturated dicarboxylic acid anhydride, there are anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Maleic anhydride is especially preferred.

As vinyl monomers copolymerizable with these, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile, and acrylic acid ester monomers such as methyl acrylic acid ester and ethyl acrylic acid ester. , Methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, and methacrylic acid amide. Monomers such as methacrylic acid ester, acrylic acid and methacrylic acid are preferred.

Further, the ammonia and the primary amine used in the imidization reaction may be in either anhydrous or aqueous solution, and examples of the primary amine include methylamine, ethylamine,
Examples thereof include alkylamines such as butylamine and cyclohexylamine, and aromatic amines such as chloro- or bromo-substituted alkylamines, aniline, tolylamine, naphthylamine, and halogen-substituted aromatic amines such as chloro- or bromo-substituted aniline.

Further, when the imidization reaction is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. Good. A catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is about 50 to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than 50 ° C, the reaction rate is slow and the reaction requires a long time, which is not practical. On the other hand, when the temperature exceeds 350 ° C, the physical properties are deteriorated due to thermal decomposition of the polymer.

The amount of ammonia and / or primary amine used is preferably 0.4 to 1.05 molar equivalent, particularly 0.7 to 1.0 molar equivalent with respect to the unsaturated dicarboxylic acid anhydride. If the amount is less than 0.4 molar equivalent, the acid anhydride group will increase in the imidized copolymer, and the thermal stability and hot water resistance will decrease, which is not preferable.

Further, the rubber-like polymer used in the first or second production method includes a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer. Polymers, block copolymers of butadiene and aromatic vinyl, acrylic acid ester polymers, and copolymers of acrylic acid esters and vinyl monomers copolymerizable therewith are used.

Component A copolymer is a rubber-like polymer 0 to 40% by weight, preferably 0 to 30% by weight, aromatic vinyl monomer residue 30 to 90% by weight
Preferably 40 to 70% by weight, unsaturated dicarboxylic acid imide derivative residues 3 to 70% by weight, preferably 3 to 60% by weight and vinyl monomer residues copolymerizable with these 0 to 40% by weight, preferably 0 to An imidized copolymer composed of 30% by weight,
When the amount of the rubber-like polymer exceeds 40% by weight, heat resistance, moldability and dimensional stability are impaired. When the amount of the aromatic vinyl monomer residue is less than 30% by weight, moldability and dimensional stability are impaired, and when it exceeds 90% by weight, impact strength and heat resistance are impaired. If the amount of the unsaturated dicarboxylic acid imide derivative residue is less than 3% by weight, the effect of improving heat resistance decreases. On the other hand, when the amount of the unsaturated dicarboxylic acid imide residue exceeds 70% by weight, the resin composition becomes brittle and the moldability is significantly deteriorated. When the amount of the vinyl monomer residue copolymerizable with these exceeds 40% by weight, dimensional stability and heat resistance are impaired.

Next, as the polycarbonate which can be used as the component (B), bisphenol A, (4,4'-dihydroxydiphenyl) ether and 2,2- (4,4'-dihydroxy-3,
Copolycarbonate having a carbonate bond synthesized from bisphenols such as 5,3 ', 5'-tetrobromodiphenyl) propane and phosgene or diphenylcarbonate, and different bisphenols as raw materials A modified polycarbonate resin such as a (homo-bonded copolymer) or a hetero-bonded copolymer having a carbonate bond and other bonds, for example, an ester bond, a urethane bond or a siloxane bond in the main chain can also be used.

Examples of the polyester that can be used as the component (B) include dicarboxylic acids such as terephthalic acid, adipic acid, sebacic acid, isophthalic acid, naphthalenedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, or dimethyl terephthalate, diethyl terephthalate and 1 Dicarboxylic acid derivatives such as dimethyl 4,4-cyclohexanedicarboxylate and ethylene glycol, 1,3-propylene diol, 1,4
-A polymer having an ester bond synthesized from a diol compound such as butanediol and poly (tetramethylene oxide) glycol, and also different dicarboxylic acids and their derivatives, and copolyesters made from different diol compounds as raw materials Can be used for

The composition of the present invention contains at least one polymer selected from these polycarbonates and polyesters as an essential component, but may of course contain two or more polymers.

Further, the thermoplastic resin that can be used as the component (C) is
A resin having good compatibility with the imidized copolymer as the component (A) and the polycarbonate and / or polyester as the component (B), for example, 30 to 90% by weight of an aromatic vinyl monomer, and a single amount of vinyl cyanide. A copolymer obtained by copolymerizing a monomer mixture comprising 0 to 50% by weight of a polymer and 0 to 50% by weight of a vinyl monomer copolymerizable therewith, and 5 to 80% by weight of a rubber-like polymer, Aromatic vinyl monomer 40 to 80% by weight, vinyl cyanide monomer 0 to 40% by weight, and monomer mixture 20 to 40% by weight copolymerizable vinyl monomer 0 to 40% by weight
95% by weight graft copolymer, polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, 6,6-nylon, 6-nylon, 12-nylon, polyphenylene oxide, styrene grafted Examples thereof include polymerized polyphenylene oxide, polyphenylene oxide, and the like, and one or more kinds of these resins can be used.

The aromatic vinyl monomer used as the component (C) is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, or a substituted monomer thereof. Particularly preferred are styrene and α-methylstyrene.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable.

Examples of vinyl monomers copolymerizable with them include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, and butyl acrylic acid ester, and methacrylic acid ester such as methyl methacrylic acid ester and ethyl methacrylic acid ester. Examples thereof include monomers, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, acenaphthylene, N-vinylcarbazole, N-alkyl-substituted maleimides, and N-aromatic-substituted maleimides.

Examples of the rubber-like polymer that can be used as the component (C) include a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, A block copolymer of butadiene and aromatic vinyl, an acrylic acid ester polymer, a copolymer of acrylic acid ester and a vinyl monomer copolymerizable therewith, and the like are used.

In the present invention, the proportion of blending each of the components (A), (B) and (C) is 2 to 98% by weight, preferably 10 to 90% by weight, and 2% by weight in the component (B). -98% by weight, preferably 10-90% by weight, (C) component 0-70% by weight
It is preferably in the range of 0 to 50% by weight. If the proportion of the component (A) exceeds 98% by weight, the impact strength will decrease, and if it is less than 2% by weight, the heat resistance will decrease. If the content of the component (B) exceeds 98% by weight, the hot water resistance decreases, and if it is less than 2% by weight, the impact strength and fluidity are impaired. The inclusion of the component (C) improves the fluidity and impact strength,
If the proportion of the component (C) exceeds 70% by weight, the heat resistance will be insufficient.

Examples of the organic phosphoric acid ester used as the stabilizer of the present invention include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and trixyl phosphate. Nyl phosphate, trinonyl phenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, octyl diphenyl phosphate, trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trioleyl phosphate Ato,
And these halogen-substituted phosphates and the like.

Examples of the organic phosphite include trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, trinonyl phenyl phosphite, cresyl. Diphenyl phosphite, trilauryl phosphite,
There are tricetyl phosphite, tristearyl phosphite, trioleyl phosphite, triphenyl trithiophosphite, trilauryl trithiophosphite, tristearyl trithiophosphite and halogen-substituted phosphite thereof.

Examples of the acidic phosphoric acid ester include monomethyl acid phosphate, dimethyl acid phosphate, monoisopropyl acid phosphate, diisopropyl acid phosphate, monobutyl acid phosphate, dibutyl acid phosphate, and monooctyl acid phosphate. , Dioctyl acitrated phosphate, monolauryl acitrated phosphate, dilauryl acitrated phosphate, monostearyl acitrated phosphate, distearyl acitrated phosphate, monophenyl acitrated phosphate, diphenylenyl acitrated phosphate, mono Cresyl azidophosphate, dicresyl azidophosphate, monononylphenyl azidophosphate, dinonylphenyl azidophosphate and their halogen-substituted acids There is the phosphate and the like.

Examples of the acidic phosphite include monomethyl acid phosphite, dimethyl acid phosphite, monoisopropyl acid phosphite, diisopropyl acid phosphite, monobutyl acid phosphite, dibutyl acid phosphite, monooctyl acid phosphite. Phyto, dioctyl acid phosphite, monolauryl acid phosphite, dilauryl acid phosphite, monostearyl acid phosphite, distearyl acid phosphite, monophenyl azido phosphite, diphenyl azido phosphite, Monocresyl acid phosphite, dicresyl acid phosphite, monononyl phenyl acid phosphite,
Examples thereof include dinonylphenyl acid phosphite and halogen-substituted acid phosphite.

Examples of the metal salt of the acidic phosphoric acid ester and the metal salt of the acidic phosphorous acid ester include the Mg salt, Zn salt, and aluminum salt of the acidic phosphoric acid ester and the acidic phosphorous acid ester.

The addition amount of these is 0.01 to 1.0 parts by weight, preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. If it is less than 0.01 parts by weight, the effect of improving the retention heat stability during high temperature molding is small, and if it exceeds 1.0 parts by weight,
There is a drawback that the heat resistance decreases and the retention heat stability is impaired again.

The stabilizer used in the present invention is an organic carboxylic acid and / or an anhydride thereof, and specific examples thereof include terephthalic acid, cyclopentanetetracarboxylic acid, trimellitic acid, transanicottate acid, homophthalic acid, and the like.
Difuenoic acid, maleic acid, itaconic acid, ββ'dithiodipropionic acid, furoic acid, etc., and anhydrides thereof include maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, dipyruenoic anhydride, cyclopentanecarboxylic anhydride. , Benzophenone tetracarboxylic acid anhydride, norbornene 2,3 dicarboxylic acid anhydride, methylendomethylene tetrahydrophthalic acid anhydride and the like.

The addition amount of these is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.

The present invention provides, as a stabilizer, at least one of an organic phosphoric acid ester, an organic phosphorous acid ester, an acidic phosphoric acid ester, an acidic phosphorous acid ester and / or a metal salt thereof, an organic carboxylic acid and an organic carboxylic acid anhydride. Characterized by using at least one kind together. In order to improve the residence heat stability with only a phosphorus compound as a stabilizer, the phosphorus compound must be used in an amount of more than 1.0 weight, which results in a decrease in heat resistance and a tendency to cause flashing during molding retention. Appears. Further, the use of only the organic carboxylic acid and / or the organic carboxylic acid anhydride as the stabilizer is insufficient to maintain the impact strength during high temperature molding retention.

The mixing method of the thermoplastic resin composition of the present invention is not particularly limited, and known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, a single-screw or twin-screw extruder, and the like.
Examples of the mixing form include ordinary melt mixing, multi-stage melt mixing using a master pellet, and solution blending.

Further antioxidant in the composition of the present invention, flame retardant, ultraviolet absorber, plasticizer, lubricant, glass fiber, carbon fiber,
It is also possible to add a filler such as calcium carbonate, a coloring agent, a metal powder or the like.

The present invention will be further described below with reference to examples. All parts and% in the examples are expressed on a weight basis.

(Examples of the Invention) Experimental Example- (1) Component (A) of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence of a rubbery polymer. Manufacturing 100 parts of styrene, 50 parts of methyl ethyl ketone, 24 parts of polybutadiene rubber (NF35AS, Asahi Kasei Co., Ltd.) cut into small pieces were placed in an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and the rubber was stirred overnight at room temperature. Dissolved. After adjusting the temperature to 80 ° C., a solution prepared by dissolving 67 parts of maleic anhydride and 0.3 part of benzoyl peroxide in 400 parts of methyl ethyl ketone was continuously added over 8 hours. The temperature was maintained at 80 ° C for another 3.5 hours after the addition. A portion of the viscous reaction liquid was sampled, unreacted monomers were quantified by gas chromatography, and the polymerization rate and the content rate of maleic anhydride in the polymer were calculated. The polymerization rate was 98%, the polymerization rate of maleic anhydride was 99%, and the content rate of maleic anhydride in the copolymer was 35.2%. Next, aniline 63 was added to the polymerization solution.
Parts (100% molar equivalent of added maleic anhydride), 2 parts of triethylamine, and 1 part of Irganox 1076 (Ciba Geigy) as an antioxidant were added, and the mixture was heated to 140 ° C. and reacted for 7 hours to carry out imidization reaction. . The reaction solution was cooled to 100 ° C., and the stainless steel bag was purged with the reaction solution. Further, it was vacuum dried at 180 ° C. for 3 hours, desolvated and then pulverized to obtain a yellowish white powder copolymer. C-13
From the NMR analysis, the conversion rate of acid anhydride groups to imide groups was 95%. This copolymer was designated as Polymer A-1.

Experimental Example- (2) Component (A) A copolymer obtained by polymerizing aromatic vinyl, unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable therewith in the presence of a rubbery polymer was imidized. Production of Polymer 100 parts of styrene and 17 parts of acrylonitrile were used in place of 100 parts of styrene in Experimental Example (1), and 67 parts of maleic anhydride was added.
Except for using 50 parts and using 35 parts instead of 63 parts of aniline, the same operation as in Experimental Example (1) was performed to obtain an imidized polymer. This is designated as Polymer A-2. The average conversion at this time was 95% and the conversion to imide groups was 74%.

Experimental Example- (3) Production of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the absence of the component (A) rubber-like polymer Experimental Example- Except for not using the polybutadiene of (1), the same operation as in Experimental Example- (1) was performed to obtain an imidized polymer. This is designated as Polymer A-3. At this time, the average polymerization rate was 99% and the conversion rate to an imide group was 98%.

Experimental Example- (4) Component (A) Production of polymer having imide group in side chain by copolymerization of aromatic vinyl monomer and N-substituted maleimide in the presence of rubbery polymer Polybutadiene rubber (Asahi Kasei Co., Ltd. Diene NF35AS ) 24 parts of 100 parts of styrene and 50 parts of methyl ethyl ketone were dissolved in an autoclave and kept at 80 ° C to obtain N-phenylmaleimide.
A solution of 100 parts and 0.3 part of benzoyl peroxide dissolved in 400 parts of methyl ethyl ketone was continuously added over 8 hours.
Further, polymerization was carried out at 80 ° C. for 3.5 hours. The polymer solution was vacuum dried and pulverized to obtain a powdery copolymer. This is designated as Polymer A-4. The average polymerization rate at this time was 95%.
It was.

Experimental Example- (5) Component (C): Production of Graft Copolymer 80 parts by weight of polybutadiene latex (solid content 50%, average particle size: 0.
35μ, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetyl citrate
0.03 parts, 0.003 parts of ferrous sulfate and 200 parts of water were charged into an autoclave replaced with nitrogen gas. After heating to a temperature of 65 ° C., 60 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 0.3 parts t-dodecyl mercaptan.
And 0.2 parts of Kyumen hydroperoxide were continuously added over 4 hours, and after the completion of addition, polymerization was continued for 6 hours at 6 ° C. The polymerization rate was 96%. After adding an antioxidant to the obtained latex, salting out with calcium chloride and washing with water
After drying, a white powdery polymer C-1 was obtained.

Experimental Example- (6) Component (C): Production of Copolymer of α-Methylstyrene and Acrylonitrile 70 parts of α-methylstyrene, 30 parts of acrylonitrile, 2.5 parts of sodium stearate, 0.6 parts of t-dodecyl mercaptan and 250 parts of water. Part to 70 ° C. and add potassium persulfate to it.
Polymerization was initiated by adding 0.05 part. After 5 hours from the initiation of polymerization, 0.03 part of potassium persulfate was further added, the temperature was raised to 75 ° C. and maintained for 3 hours to complete the polymerization. Polymerization rate is 97%
Reached The obtained latex is coagulated with calcium chloride, washed with water and dried to obtain a white powdered copolymer, which is a copolymer C.
-2.

Experimental Example- (7) Evaluation of physical properties of thermoplastic resin composition As component (A), imidized copolymers of A-1 to 4, and as component (B) polycarbonate (Panlite K1300W manufactured by Teijin Chemicals Ltd.)
Hereinafter referred to as PC), polybutylene terephthalate (hereinafter referred to as PBT manufactured by Polyplastics Co., Ltd., and hereinafter referred to as PBT), and polyester elastomer (tolerated by Toyobo Co., Ltd., referred to as Perprene P70B and below referred to as TPE), C-1 to C-2 A composition was prepared by mixing a stabilizer with a thermoplastic resin containing each of the copolymers, and the respective physical properties were measured and are shown in Table 1.

The physical properties were measured by the following methods.

(1) Bicat softening point: Weight 5 kg, according to ASTM-D-1525 (2) Impact strength: Notched Izod impact strength According to ASTM-D-256 (3) Residence stability: Molded product in high temperature retention molding (4) Molding conditions Ordinary molding: Cylinder temperature 270 ° C, mold clamping time 45 seconds Molding retention molding: Cylinder temperature 270 ° C, mold clamping time 180 High temperature retention molding in seconds ... Cylinder temperature 300 ° C, mold clamping time 1
Molded in 80 seconds.

(Effect of the invention) An organic phosphate ester is used as a stabilizer in a resin composition containing an imidized copolymer and one or more polymers selected from polycarbonate and / or polyester as essential components.
By using an organic phosphite ester, an acidic phosphite ester, an acidic phosphite ester and / or a metal salt thereof in combination with an organic carboxylic acid and / or an organic carboxylic acid anhydride, the impact strength during high temperature retention molding can be improved. It was possible to suppress the decrease, and it was possible to remarkably suppress the coloring of the molded product and the occurrence of flashing.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08L 51/04 LKY 7308-4J 67/00 LPA 8933-4J 69/00 LPP 9363-4J (56) References Kai 57-61047 (JP, A) JP 58-183729 (JP, A) JP 62-18466 (JP, A) JP 61-19656 (JP, A)

Claims (1)

[Claims] 1. Component (A): 0-40% by weight of a rubber-like polymer,
An imidization copolymer comprising 30 to 90% by weight of an aromatic vinyl monomer residue, 3 to 70% by weight of an unsaturated dicarboxylic acid imide derivative residue, and 0 to 40% by weight of a vinyl monomer residue other than these residues. 2 to 98% by weight of polymer, (B) component: 2 to 98% by weight of one or more polymers selected from polycarbonate and polyester, and (C) component: 0 to 70% by weight of thermoplastic polymer. With respect to 100 parts by weight of the thermoplastic resin containing, organic phosphoric acid ester, organic phosphorous acid ester, acidic phosphoric acid ester, acidic phosphorous acid ester and / or their metal salts 0.01 to 1.0
A thermoplastic resin composition comprising 0.01 part by weight and 0.01 to 5 parts by weight of an organic carboxylic acid and / or an organic carboxylic acid anhydride.