JPH0711094A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin excellent in impact resistance, moldability, heat distortion resistance and chemical resistance by improving compatibility of AAS resin with polyamide. CONSTITUTION:A mixture of butyl acrylate and triallyl cyanurate is polymerized in the presence of butadiene rubber or without using it. In the presence of the resultant rubbery polymer, monomers such as styrene and acrylonitrile are graft-polymerized to synthesize a graft copolymer (A). With the synthesized graft copolymer (A), a polyamide (B) and a carboxylic acid-containing modified vinyl copolymer (C) synthesized by using an unsaturated carboxylic acid as the essential component and copolymerizing styrene, acrylonitrile, etc., therewith are blended, thus affording the objective thermoplastic resin composition.

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 having excellent impact resistance, moldability, heat distortion resistance and chemical resistance.

[0002]

2. Description of the Related Art Acrylonitrile-acrylic rubber-styrene terpolymer composition (AAS resin) has weather resistance,
It is used in a wide range of fields because of its excellent impact resistance and molding processability, but its chemical resistance is not sufficient. On the other hand, a polyamide resin (hereinafter referred to as polyamide) is already known as a resin having excellent chemical resistance and heat distortion resistance, but it is inferior in impact resistance. A blend of the two has also been proposed (Japanese Patent Laid-Open No. 54-112954).
AS resin and polyamide have poor compatibility, and only a material having poor impact resistance can be obtained. In addition, a method of introducing a functional group having reactivity or affinity with polyamide into an ABS resin has been proposed. (JP-A-54-1159, JP-A-58-32656, JP-A-58-93745)

[0003]

However, with the methods proposed so far, it is not possible to obtain a composition having a well-balanced physical property. The present inventors, as a result of extensive studies to solve the above problems, by blending a graft copolymer obtained by copolymerizing an unsaturated carboxylic acid to a vinyl copolymer obtained by using a specific grafting method and a polyamide. It was found that a thermoplastic resin composition having impact resistance, moldability and chemical resistance was obtained, and the present invention was obtained.

[0004]

The present invention is directed to a graft copolymer obtained by using a specific acrylic rubber and a specific grafting method, and a polyamide and an unsaturated carboxylic acid-containing modified vinyl copolymer in a specific ratio. The above objects are achieved by blending. That is, the present invention is a multifunctional monomer (I) 0.1 to 20% by weight, carbon number 1 to
Acrylic ester (II) 5 having 13 alkyl groups
0-99.9% by weight and other vinyl compounds (III) 0-3
A rubbery polymer (a) 5 obtained by polymerizing a polymerizable monomer mixture obtained by adjusting 0% by weight to 100% by weight in the presence or absence of a conjugated diene polymer.
~ 70 parts by weight of aromatic vinyl compound (IV) 0
~ 100 wt%, methacrylic acid ester (V) 0-10
The rubber-like polymer (95 to 30 parts by weight) of the polymerizable monomer (b) is blended in such a proportion that 0% by weight and 0 to 40% by weight of the vinyl cyanide compound (VI) become 100% by weight in total. Graft copolymer (A) 10 to 90 parts by weight and polyamide (B) 5 to 9 which are obtained by blending and polymerizing a) and the polymerizable monomer (b) in a total amount of 100 parts by weight.
0 part by weight, 0.5 to 30% by weight of unsaturated carboxylic acid, and at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, acrylic acid esters and N-substituted maleimide compounds 70 to A carboxylic acid-containing modified vinyl copolymer (C) obtained by polymerizing 99.5% by weight of 0.1 to 30 parts by weight and an aromatic vinyl compound,
Polymers (D) 0 to 8 obtained by polymerizing at least one monomer selected from the group consisting of vinyl cyanide compound methacrylic acid ester and N-substituted maleimide compound
The present invention relates to a thermoplastic resin composition containing 0 parts by weight so that the total amount becomes 100 parts by weight.

The rubber-like polymer (a) of the present invention comprises a polyfunctional monomer (I) in an amount of 0.1 to 20% by weight and an alkyl acrylate (II) 5 having an alkyl group having 1 to 13 carbon atoms.
A polymerizable monomer mixture obtained by blending 0 to 99.9% by weight and 0 to 30% by weight of another vinyl compound (III) copolymerizable therewith so that the total amount is 100% by weight is a conjugated diene. The polymer is obtained by polymerizing in the presence or absence of a base polymer, and is obtained by polymerizing 95 to 60 parts by weight of a polymerizable monomer mixture in the presence of 5 to 40 parts by weight of a conjugated diene polymer. Those having excellent impact resistance are preferable. If the amount of the conjugated diene polymer is less than 5 parts by weight, the effect of improving the impact resistance tends to be small, and if it exceeds 40 parts by weight, the weather resistance tends to be poor. As the conjugated diene-based polymer, polybutadiene, butadiene-styrene copolymer and the like can be used, and in particular, crosslinked ones are preferable. As the polyfunctional monomer (I), ethylene glycol dimethacrylate,
Polyvalent vinyl compounds such as diethylene glycol dimethacrylate, ethylene glycol diacrylate, divinylbenzene, diallyl phthalate, dicyclopentadiene acrylate, and dicyclopentadiene methacrylate,
Examples include polyallyl compounds such as triallyl cyanurate, triallyl isocyanurate, and diallyl phthalate. Among them, triallyl isocyanurate, triallyl cyanurate, dicyclopentadiene acrylate, and dicyclopentadiene methacrylate are impact resistant. From the viewpoint of, it is particularly preferable. The polyfunctional monomer (I) to be copolymerized is 0.1 to 20 in the polymerizable monomer mixture.
It is used in an amount of 0.5% by weight, preferably 0.5 to 10% by weight. If it is less than 0.1% by weight, the degree of crosslinking is insufficient and the impact resistance and the appearance of the molded product are poor. If it exceeds 20% by weight, the degree of crosslinking is excessive and the impact resistance is lowered. Also, carbon number 1
Examples of the acrylic acid ester (II) having 13 alkyl groups include ethyl acrylate, butyl acrylate, 2
-Ethylhexyl acrylate and the like, of which butyl acrylate is particularly preferable. The acrylic ester (II) is contained in the monomer mixture in an amount of 50 to 99.9% by weight,
Preferably 65 to 99.5% by weight is used. If it is less than 50% by weight, the properties of the acrylic rubber are deteriorated and the impact resistance tends to be insufficient. Other vinyl compounds (III) copolymerizable with the acrylic ester (II) include acrylonitrile, styrene and the like.
It is used in the range of 0 to 30% by weight, preferably 0 to 25% by weight. If this ratio exceeds 30% by weight, the properties as an acrylic rubber will deteriorate when the polymerizable monomer mixture is polymerized, and the impact resistance tends to be insufficient.

Further, it is preferable to use the above conjugated diene polymer as a latex which is previously dispersed in an aqueous medium, in order to facilitate the dispersion during emulsion polymerization. The emulsion polymerization for obtaining the rubbery polymer (a) can be carried out by a method generally known to those skilled in the art. In this emulsion polymerization, the polymerization is not performed up to a conversion of 100% by weight
High impact resistance can be obtained by stopping at 50 to 93% by weight, preferably 60 to 90% by weight. This polymerization rate is 50% by weight
When it is less than 1, the ratio of copolymerization with the polymerizable monomer (b) during the polymerization of the polymerizable monomer (b) becomes high, and the heat distortion temperature tends to decrease. When the polymerization rate exceeds 93% by weight, the effect of improving impact resistance cannot be sufficiently obtained. In the absence of the conjugated diene polymer, it is preferable to carry out the polymerization at a polymerization rate of 95% by weight or more.

In emulsion polymerization for obtaining the rubbery polymer (a), anionic emulsifiers such as sodium oleate, sodium lauryl sulfate and sodium dodecylbenzene sulfonate, and polyoxyethylene cetyl ether are used as a small amount of an emulsifier. Any nonionic emulsifier can be used. As the polymerization initiator, those used in ordinary emulsion polymerization, for example, redox type ones composed of persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate are used.

Then, in the presence of the rubber-like polymer (a), the aromatic vinyl compound (I) is used as the polymerizable monomer (b).
V) 0 to 100% by weight, methacrylic acid ester (V) 0
~ 100 wt% and vinyl cyanide compound (VI) 0 ~
It is compounded and polymerized at a ratio of 40% by weight so that the whole amount becomes 100% by weight. Here, if the amount of the vinyl cyanide compound (VI) is too large, the moldability is deteriorated, so the amount of the vinyl cyanide compound (VI) should be 40% by weight or less. Further, when the aromatic vinyl compound (IV) is used in an amount of 30 parts by weight or more, the moldability is improved and the vinyl cyanide compound is used in an amount of 10 parts by weight or more.
If it is used in an amount of more than weight%, the chemical resistance will improve. Therefore, as the polymerizable monomer (b), the above (IV) is 30 to 1
00% by weight, especially 50 to 90% by weight, (V) 0 to 70
% By weight, in particular 0-40% by weight, and (VI) 0-30
Preference is given to using it in a proportion by weight, in particular 10 to 30% by weight.

As the above aromatic vinyl compound (IV),
α-Substituted styrenes such as α-methylstyrene and α-ethylstyrene, nuclear-substituted styrenes such as chlorostyrene, vinyltoluene, t-butylstyrene, styrene, and the like, and as the methacrylic acid ester (V), methyl methacrylate and methacrylic acid. As the vinyl cyanide compound (VI) such as ethyl or butyl methacrylate, acrylonitrile or methacrylonitrile can be used.

In the present invention, the above rubber-like polymer (a)
And, the polymerizable monomer (b) is preferably used in an amount of 95 to 30 parts by weight with respect to 5 to 70 parts by weight of (a). If the weight ratio of (a) / (b) is less than 5/95, the impact resistance decreases, and if it exceeds 70/30, the mechanical strength and heat distortion resistance decrease. Further, in order to polymerize the polymerizable monomer (b) in the presence of the rubbery polymer (a), a polymerization method such as an emulsion polymerization method, a suspension polymerization method or a solution polymerization method can be adopted. At the time of polymerization, an emulsifier, a polymerization initiator, a chain transfer agent, etc. are appropriately added. As the polymerization initiator, a redox type initiator such as persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate is used in an amount of about 0.1 to 2% by weight based on the polymerizable monomer (b).
As the chain transfer agent, tert-dodecyl mercaptan or the like is used in an amount of about 1% by weight or less with respect to the polymerizable monomer (b). The polymerization temperature is 20 to 100 ° C., especially 50 to 9
It is preferably carried out in the range of 0 ° C. It should be noted that similar conditions may be adopted when producing the rubber-like polymer. The monomers to be polymerized in the presence of the rubbery polymer (a) may be polymerized in a single amount at once, or may be polymerized while dropping all the monomers. However, as the first step, among the polymerizable monomers (b),
After 30% by weight is polymerized to a polymerization rate of 50% or more, it is preferable to add the remaining amount of the polymerizable monomer (b) and polymerize as the second stage. By adopting such a two-step polymerization method, the fluidity and the heat distortion temperature are further high, and the impact resistance is further improved, which is a desirable method. First of all, 5 of the polymerizable monomers (b) are polymerized.
The range is preferably from 30 to 30% by weight, and when it is less than 5% by weight, there is no difference from the case where the whole amount is polymerized in one step, and when it exceeds 30% by weight, the resistance to polymerization by adding the polymerizable monomer (b) is increased. The effect of improving impact resistance and the effect of improving heat distortion temperature are reduced. Further, at this time, it is preferable that the remaining amount of the polymerizable monomer (b) is added and polymerized after the rate of polymerization advances by 50% or more. If the polymerization rate is less than 50%, the effect of improving the heat distortion temperature and impact resistance tends to be reduced.

Even when the polymerizable monomer (b) is divided and used as described above, the total amount of the above-mentioned (IV), (IV),
The polymerizable monomers (b), which are blended in such a manner that the proportions of (V) and (VI) are used, are divided into the first stage and the second stage, and the polymerizable monomers (b) are each aromatic vinyl. Compound (I
V) 0 to 100% by weight, methacrylic acid ester (V) 0
~ 100 wt% and vinyl cyanide compound (VI) 0 ~
It is preferably 40% by weight and used in such a proportion that the total amount becomes 100% by weight.

The mixing ratios in the first and second stages may be the same or different. When the polymerization is emulsion polymerization, the graft copolymer (A) obtained by polymerizing the polymerizable monomer (b) in the presence of the rubber-like polymer (a) is a latex after polymerization and potassium alum. The resin is coagulated and separated using a method such as salting out in which it is mixed with hot water that has been melted, dehydrated and dried, and then palletized in powder form or using an extruder or the like, and used for blending with polyamide.

Polyamide resin (B) used in the present invention
As, nylon-6, nylon-11, nylon-
Ring-opening polymerization of lactams such as 12, Nylon-6,6, Nylon 12,12, Nylon 4,6, Nylon 6,10, Nylon-6,12, Polyhexamethylenediamine terephthalamide, Polyhexamethylenediamine isophthalamide, etc. The polyamide obtained by (1) or the polyamide obtained from an aliphatic, alicyclic or aromatic diamine and a dicarboxylic acid can be used, and a mixture or copolymer of two or more of these can also be used.

Modified vinyl copolymer containing carboxylic acid (C)
In, unsaturated carboxylic acid is an essential component. As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or the like can be used. The amount of unsaturated carboxylic acid in the copolymer is preferably 0.5 to 30% by weight. If it is less than 0.5% by weight, the compatibility of the final composition is poor and the impact resistance is low. If it exceeds 30% by weight, the fluidity is lowered and the impact resistance is lowered, which is not preferable.

Modified vinyl copolymer containing carboxylic acid (C)
As the aromatic vinyl compound, methacrylic acid ester and vinyl cyanide compound in the above, those exemplified above as the aromatic vinyl compound (IV), methacrylic acid ester and (V) and vinyl cyanide compound (VI) are used, respectively. As an N-substituted maleimide compound, N-
Phenylmaleimide, N-cyclohexylmaleimide,
N-hydroxyphenyl lumaleimide, N-methylphenyl maleimide, N-dimethylphenyl maleimide, N
-Chlorophenyl maleimide, N-methyl maleimide,
N-ethyl maleimide etc. are mentioned.

Modified vinyl copolymer containing carboxylic acid (C)
As a method for producing the above, known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization are used.

The polymer of the component (D), which is an optional component in the present invention, is at least one monomer selected from the group consisting of aromatic vinyl compounds, methacrylic acid esters, vinyl cyanide compounds and N-substituted maleimide compounds. Is obtained by polymerizing. Here, as the aromatic vinyl compound, the methacrylic acid ester and the vinyl cyanide compound, the aromatic vinyl compound (I
V), methacrylic acid ester and (V) and vinyl cyanide compound (VI) can be used, and the N-substituted maleimide compound can be the N-substituted maleic compound exemplified as the component of the carboxylic acid-containing modified vinyl copolymer. Maleimide compounds can be used. As the polymerization method, various polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be adopted.

In the thermoplastic resin composition of the present invention, (A) 10 to 90 parts by weight, based on 100 parts by weight as a whole,
(B) 5 to 90 parts by weight, (C) 0.1 to 50 parts by weight and (D) 0 to 80 parts by weight are preferably blended, (A) 30 to 80 parts by weight, (B) ) 10 to 70 parts by weight, (C) 3 to 20 parts by weight and (D) 0 to 50 parts by weight are more preferable. If (A) is less than 10 parts by weight, the impact resistance will decrease, and if it exceeds 90 parts by weight, the heat resistance and chemical resistance will decrease. When (B) is less than 5 parts by weight, heat resistance and chemical resistance are poor, and when it exceeds 90 parts by weight, impact resistance is lowered. If the content of (C) is less than 0.1 parts by weight, the impact resistance decreases,
If it exceeds 30 parts by weight, the fluidity is lowered and the impact resistance is also lowered. If (D) exceeds 80 parts by weight, the impact resistance is poor.

The thermoplastic resin composition of the present invention is usually added to a reinforcing agent or filler such as glass fiber, metal fiber or carbon fiber, dye, pigment, heat stabilizer, AAS resin, etc., if necessary. Additives may be included.

The thermoplastic resin composition of the present invention is prepared by blending the above-mentioned components and uniformly mixing them with a two-roll, Banbury mixer, extruder, or any other mixing machine. You can

The thermoplastic resin composition of the present invention is produced by the casting method,
Various molded articles can be produced by molding by various methods such as an extrusion molding method, an injection molding method, a hollow molding method, and a vacuum molding method.

[0022]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, "part" and "%"
Indicates "part by weight" and "% by weight", respectively. Also,
The physical properties of the molding material were measured by the following methods.

Izod impact strength Measured according to ASTM-D256 with a 1/8 "notch.

Thermal deformation resistance A JIS No. 1 dumbbell having a plate thickness of 2 mm was allowed to stand in a constant temperature bath set at 150 ° C for 30 minutes, and the deformation was measured, and the change rate was shown.

Chemical resistance A plate obtained by injection molding a thermoplastic resin composition was immersed in methanol and gasoline for 24 hours at 23 ° C. and the surface was visually observed. ○: No change ×: Whitening

Synthesis Example 1 (Graft Copolymer A) (a) Production of Rubbery Polymer Latex Blending Composition Component (1) Polybutadiene Latex (SN-800T Sumitomo Nogatac Co., Ltd. trade name) 300 parts Component (2) Acrylic Butyl acid 700 parts Triallyl isocyanurate 8.4 parts Component (3) Potassium persulfate 0.4 parts Sodium sulfite 0.04 parts Emulsifier (Nonsar TN-1, trade name of fatty acid soap manufactured by NOF Corporation) 9.2 Deionized water 1420 parts

Polymerization Operation Component (1) and component (3) dissolved uniformly are charged into a reaction vessel, mixed and stirred, then component (2) dissolved uniformly is added, the atmosphere is replaced with nitrogen, and the temperature is raised to 60. After polymerizing at about 65 ° C. for about 4 hours, it was cooled to terminate the polymerization. The polymerization rate at this time was 63%.

The above-mentioned polymerization rate was measured as follows. Method for Measuring Polymerization Rate A small amount of the reaction mixture was sampled from the polymerization system, its weight was measured, then it was heated with an infrared lamp, dried, and the weight of the remaining non-volatile content was measured, and calculated by the following formula. α: Total weight of reaction mixture present in polymerization system β: Weight of nonvolatile content of sampled reaction mixture γ: Weight of sampled reaction mixture δ: Weight of solid content of polybutadiene latex used ε: Used butyl acrylate and triallyl isocyanate Total weight with nurate Polymerization rate = [(α × β ÷ γ-δ) / ε] × 100%

(B) Emulsion Polymerization in the Presence of Rubbery Polymer Latex Blending Composition Component (4) Rubbery Polymer Latex of (a) (Converted to Solid Content Including Residual Monomer) 507 Parts Component (5) Deionized Water 200 parts Emulsifier (Emar 2F (Kao, sodium lauryl sulfate)) 0.78 part Emulsifier (KS Soap (Kao, semi-hardened tallow fatty acid potassium)) 3.7 parts Component (6) Sodium sulfite 0.6 part Deionized Water 100 parts Component (7) Glucose 6.34 parts Deionized water 200 parts Component (8) Potassium carbonate 8.54 parts Deionized water 150 parts Component (9) Styrene 60.3 parts t-Dodecyl mercaptan 0.4 parts Component (10) Acrylonitrile 29.1 parts Cumene hydroperoxide 0.16 parts Component (11) Rongalit 3.26 parts Deionized water 100 parts Component (12) Sodium pyrophosphate 6.34 parts Sodium sulfite 0.31 part Deionized water 100 parts Component (13) Ferrous sulfate 0.12 parts Deionized water 50 parts Component (14) Styrene 415.4 parts Acrylonitrile 188 Parts t-dodecyl mercaptan 3.0 parts component (15) cumene hydroperoxide 0.54 parts styrene 68 parts component (16) KS soap 10.74 parts deionized water 550 parts component (17) potassium persulfate 0.74 parts Deionized water 40 parts

In the reaction vessel, the components (4), (5),
After adding (6), (7), (8) and (9) and stirring for 10 minutes, the component (10) was added and the temperature was raised to 40 ° C. to about 3
Continue stirring for 0 minutes. Ingredient (11) is added and the temperature is 70 ° C.
After 2 hours of polymerization, it was confirmed that the polymerization rate was 56% by weight, and the components (12) and (13) were added.
Raise the temperature to ℃. Furthermore, the components (14), (15), (1
6) was uniformly mixed, added over about 2 hours, and then polymerized at 73 ° C for about 2 hours. After adding the component (17), the temperature was raised to 80 ° C and the polymerization was continued for about 30 minutes. , The polymerization was completed. This resin latex was salted out in hot water in which potassium alum was dissolved, dehydrated and dried to obtain a resin powder (hereinafter referred to as a graft polymer A).

The above-mentioned polymerization rate was measured as follows. Method for Measuring Polymerization Rate A small amount of the reaction mixture was sampled from the polymerization system, its weight was measured, then it was heated with an infrared lamp, dried, and the weight of the remaining non-volatile content was measured, and calculated by the following formula. α: Total weight of the reaction mixture present in the polymerization system β: Weight of the nonvolatile content of the sampled reaction mixture γ: Weight of the sampled reaction mixture δ: Solid weight of the graft polymer rubber latex used ε: Graft polymer used Weight of unreacted residual monomer in rubber latex ζ: Total weight of styrene and acrylonitrile used Polymerization rate = [(α × β ÷ γ-δ + ε) / (ε + ζ)] × 1
00%

Synthetic Example 2 (Unsaturated carboxylic acid-containing modified vinyl copolymer C-1) 2000 parts of deionized water and 1 potassium persulfate were placed in a reaction vessel.
Parts, and 1 part of sodium sulfite were charged, and the mixture was stirred for about 1 hour while substituting with nitrogen and then heated to 70 ° C. to give styrene 6
65 parts, acrylonitrile 285 parts, methacrylic acid 50
Part, a monomer solution containing 5 parts of t-dodecyl mercaptan, and an emulsifier solution containing 20 parts of sodium lauryl sulfate are added dropwise in about 3 hours. Then, the temperature was raised to 75 ° C. and polymerization was carried out for 2 hours to obtain a resin latex. This latex was salted out in hot water in which potassium alum was dissolved, dehydrated and dried to obtain a resin powder (C-1).

Synthetic Example 3 (Unsaturated carboxylic acid-containing modified vinyl copolymer C-2) In Synthetic Example 2, 420 parts of styrene, 180 parts of acrylonitrile, and 400 parts of methacrylic acid were synthesized. (C
-2)

Synthetic Example 4 (unsaturated carboxylic acid-containing modified vinyl copolymer C-3) Synthetic Example 2 was synthesized using 560 parts of styrene, 240 parts of acrylonitrile and 200 parts of methacrylic acid.
(C-3)

As the polyamide (B), nylon-6 (Ube Nylon 1013B, manufactured by Ube Industries, Ltd.) was used.

The gelaft copolymer A obtained in the above synthesis example, the unsaturated carboxylic acid-containing modified vinyl copolymers C-1 to C-3, polyamide and acrylonitonyl-styrene copolymer (abbreviated as AS, manufactured by Asahi Kasei Kogyo Co., Ltd.) Style rack 70
3) was blended in the proportions shown in Table 1, Table 2 and Table 3, and 30
Kneading and granulation were carried out at 250 ° C. using a mmφ twin-screw extruder.
Then, a test piece was injection-molded at a cylinder temperature of 250 ° C and a mold temperature of 50 ° C. Table 1 shows the results of evaluating various characteristics by changing the compounding ratio of the components.

Table 2 shows the results of evaluating various properties by changing the unsaturated carboxylic acid content of the unsaturated carboxylic acid-containing modified vinyl copolymer (C).

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

The thermoplastic resin composition according to claim 1 or 2 is a molding material useful for obtaining a molded article having excellent impact resistance, chemical resistance, and heat distortion resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 101/08 LSY

Claims (2)

[Claims] 1. A polyfunctional monomer (I) in an amount of 0.1 to 20% by weight, an acrylate ester (II) having an alkyl group of 1 to 13 carbon atoms in an amount of 50 to 99.9% by weight, and other vinyl compounds. (III) A rubber-like polymer obtained by polymerizing a polymerizable monomer mixture obtained by adjusting 0 to 30% by weight to 100% by weight in the presence or absence of a conjugated diene polymer. (A) In the presence of 5 to 70 parts by weight, 0 to 100% by weight of an aromatic vinyl compound (IV), 0 to 100% by weight of a methacrylic acid ester (V) and a vinyl cyanide compound (V
I) The rubber-like polymer (a) and the polymerizable monomer (a) are added in an amount of 95 to 30 parts by weight of the polymerizable monomer (b) blended in a proportion such that 0 to 40% by weight is 100% by weight in total. The graft copolymer (A) is mixed in an amount of 10 to 90 parts by weight, the polyamide (B) is added to 5 to 90 parts by weight, and the unsaturated carboxylic acid is added in an amount of 0. 5-3
0% by weight of at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, acrylic acid esters and N-substituted maleimide compounds 70-
Consists of 0.1 to 30 parts by weight of a carboxylic acid-containing modified vinyl copolymer (C) obtained by polymerizing 99.5% by weight, an aromatic vinyl compound, a vinyl cyanide compound methacrylic acid ester and an N-substituted maleimide compound. A thermoplastic resin composition comprising 0 to 80 parts by weight of a polymer (D) obtained by polymerizing at least one monomer selected from the group so that the total amount thereof becomes 100 parts by weight. 2. When polymerizing the polymerizable monomer (b) in the presence of the rubber-like polymer (a), 5 to 30% by weight of the polymerizable monomer (b) is converted into 50% by weight. % Of the polymerizable monomer (b), and then the rest of the polymerizable monomer (b) is added and polymerized. Each of the divided polymerizable monomers (b) is an aromatic vinyl compound (IV) 0-100. 2. The thermoplastic resin composition according to claim 1, which comprises 100% by weight of 0% to 100% by weight of methacrylic acid ester (V) and 0 to 40% by weight of vinyl cyanide compound (VI). object.