JPH05230319A - Thermoplastic resin composition and molding produced therefrom - Google Patents

Abstract

PURPOSE:To obtain the subject composition giving a molding having excellent impact resistance, chemical resistance and thermal deformation resistance by compounding an aromatic polyester resin with a copolymer produced by grafting a polyfunctional monomer and an acrylic acid ester to a conjugated diene polymer. CONSTITUTION:The objective thermoplastic resin composition giving a molding having excellent impact resistance, chemical resistance and thermal deformation resistance and useful as a molding material, etc., can be produced by compounding (A) 45-99wt.% of a graft copolymer produced by dividedly polymerizing a polymerizable monomer for forming a rigid resin in the presence of a graft polymer rubber obtained either by the emulsion polymerization of a conjugated diene polymer and a polymerizable monomer mixture containing a polyfunctional monomer and an acrylic acid ester or by the emulsion polymerization of the polymerizable monomer mixture until the polymerization ratio reaches the range of 50-93wt.% with (B) 55-1wt.% of a thermoplastic aromatic polyester resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article excellent in impact resistance, chemical resistance and thermal deformation resistance, and a thermoplastic resin composition which is a molding material for the molded article.

[0002]

2. Description of the Related Art Acrylonitrile-acrylic rubber-styrene terpolymer (AAS resin) is used in a wide range of fields because of its excellent weather resistance, impact resistance and workability. Insufficient chemical resistance and heat resistance.
On the other hand, a thermoplastic aromatic polyester resin (hereinafter referred to as polyester) is already known as a resin having excellent chemical resistance and heat resistance. However, since this product is inferior in impact resistance, it has been proposed to blend polyester with ABS resin (acrylonitrile-polybutadiene rubber-styrene terpolymer composition), AAS resin, etc. No. 25261, JP-A-54-1
50457, JP-A-57-94038, etc.).

However, in the methods generally proposed so far, the compatibility between the ABS resin or the AAS resin and the polyester is poor, so that a composition having a sufficiently balanced physical property cannot be obtained.

On the other hand, in order to improve the weather resistance of the ABS resin or the surface quality of the injection-molded article, the core formed by the crosslinked diene rubber, the first outer shell formed by the crosslinked acrylic rubber and the resin-forming monomer are used. A graft polymer comprising a second shell formed from a polymerized copolymer is disclosed in Japanese Patent Publication No. 47-47863 and U.S. Pat. No. 4,393,172. These graft polymers also show excellent impact resistance. However, these prior arts do not describe such blends of graft polymers and polyesters. In addition, these prior arts disclose that the impact resistance of the resulting graft polymer is improved by stopping the polymerization halfway during the formation of the acrylic rubber or by dividing the resin-forming monomer and polymerizing the addition. There is no place to do it.

A graft polymer similar to the above, which is obtained by stopping the polymerization during the formation of acrylic rubber, is disclosed in Japanese Patent Publication No. 63-54729 (Japanese Patent Publication No. 58-187411). Although disclosed, this prior art is silent about blends of such graft polymers and polyesters.

US Pat. No. 4,417,026 discloses 1 to 40% by weight of the graft polymer disclosed in US Pat. No. 4,393,172 and 99 to 60% by weight of a saturated polyester. A thermoplastic polyester molding composition containing is disclosed. According to this prior art, it is possible to improve the impact resistance of the saturated polyester by mixing with the graft polymer, but according to the knowledge of the present inventors, in order to obtain a preferable impact resistance, Is insufficient. In particular, even if the above graft polymer itself exhibits excellent impact resistance, its impact resistance is significantly reduced by mixing with the polyester.

[0007]

DISCLOSURE OF THE INVENTION The present invention has both the chemical resistance and heat resistance of polyester while maintaining the impact resistance and processability of a graft copolymer containing a diene rubber, an acrylic rubber and a resin-forming component as much as possible. Another object of the present invention is to provide a thermoplastic resin composition useful as a molding material and a molded product obtained by molding the same.

[0008]

The present invention comprises (A) a graft copolymer and (B) a thermoplastic aromatic polyester resin, wherein the (A) graft copolymer is a graft polymer rubber (a). ) 5 to 50 parts by weight and the polymerizable monomer (b) 9
It is obtained by polymerizing the polymerizable monomer (b) in the presence of the graft polymer rubber (a), using 5 to 50 parts by weight so that the total amount thereof becomes 100 parts by weight. ,
The graft polymer rubber (a) comprises 95 to 60 parts by weight of the polymerizable monomer mixture (α) and the conjugated diene polymer (β) 5.
To 40 parts by weight so that the total amount thereof becomes 100 parts by weight, and is obtained by emulsion-polymerizing the polymerizable monomer mixture (α) in the presence of the conjugated diene polymer (β). And the polymerizable monomer mixture (α) is 0.1 to 20% by weight of the polyfunctional monomer (I) and the acrylic ester (II) 50 to 99. having an alkyl group having 1 to 13 carbon atoms. 9% by weight and 0 to 30% by weight of another vinyl compound (III) are blended so as to be 100% by weight in total, and the polymerizable monomer (b) is an aromatic vinyl compound ( IV)
0-100% by weight, methacrylic acid ester (V) 0-1
In the thermoplastic resin composition which is used so that the total amount of 100% by weight is 00% by weight and 0 to 40% by weight of the vinyl cyanide compound (VI), the (A) graft copolymer is i) In the presence of the graft polymer rubber (a), 5 to 30% by weight of the polymerizable monomer (b) is blended and polymerized, and then the rest of the polymerizable monomer (b) is blended. And (ii) in the presence of the conjugated diene-based polymer (β), the polymerizable monomer mixture (α) has a polymerization rate of 50% by weight or more and 93% by weight or less. To the polymerizable monomer (b) in the presence of the graft polymer rubber (a) obtained by emulsion polymerization until
A thermoplastic resin obtained by polymerizing (A) a graft copolymer and (B) a thermoplastic aromatic polyester resin in an amount of 45 to 99% by weight of the former and 55 to 1% by weight of the latter. The present invention relates to a composition and a molded article obtained by molding the thermoplastic resin composition.

The present invention will be described in detail below. In the present invention, the graft polymer rubber (a) used for producing the graft copolymer of the component (A) is a polyfunctional monomer (I) in an amount of 0.1 to 20% by weight and an alkyl group having 1 to 13 carbon atoms. 100% by weight of acrylic acid ester (II) having 50 to 99.9% by weight and other vinyl compound (III) copolymerizable with components (I) and (II) at 0 to 30% by weight.
95 to 60 parts by weight of the polymerizable monomer mixture (α) obtained by blending so that the conjugated diene polymer (β) 5
It is obtained by compounding in the presence of ˜40 parts by weight so that the total amount becomes 100 parts by weight and emulsion-polymerizing.

As the polyfunctional monomer (I), for example,
Polyvalent vinyl compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, divinylbenzene, diallyl phthalate, dicyclopentadiene acrylate, dicyclopentadiene methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, etc. Examples thereof include polyvalent allyl compounds, and among them, triallyl isocyanurate, triallyl cyanurate, dicyclopentadiene acrylate, and dicyclopentadiene methacrylate are particularly preferable from the viewpoint of impact resistance.

The polyfunctional monomer (I) is used in the polymerizable monomer mixture (α) within the range of 0.1 to 20% by weight, but within the range of 0.5 to 10% by weight. It is preferably used in. If this proportion is less than 0.1% by weight, the degree of crosslinking will be insufficient and the impact resistance and the appearance of the molded article will be poor. If it exceeds 20% by weight, the degree of crosslinking will be excessive and the impact resistance will decrease. Impact resistance tends to be insufficient.

The acrylate ester (II) having an alkyl group having 1 to 13 carbon atoms includes, for example, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Of these, butyl acrylate is particularly preferable. This acrylic ester (II)
Is used in the range of 50 to 99.9% by weight in the polymerizable monomer mixture (α), but is preferably used in the range of 65 to 99.5% by weight. This proportion is 50% by weight
If it is less than the above range, the properties of the acrylic rubber are deteriorated and the impact resistance tends to be insufficient.

Further, the above-mentioned acrylic ester (II)
Other vinyl compounds (III) copolymerizable with are acrylonitrile, styrene and the like. The proportion of these used is 0 to 30% by weight in the polymerizable monomer mixture,
It is preferably in the range of ˜25% by weight. If this proportion 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.

As the conjugated diene polymer (β),
For example, polybutadiene, a butadiene-styrene copolymer, etc. can be used. The conjugated diene polymer (β) is preferably crosslinked, and particularly preferably has a gel content of 50% by weight or more, more preferably 60% by weight or more, and most preferably 70% by weight or more.
The polymerizable monomer mixture (α) and the conjugated diene polymer (β) have a weight ratio of (β) / (α) of 5/95 to 40 /.
Used in a ratio of 60. If this ratio is less than 5/95, the impact resistance and the appearance of the molded product will be poor, and if it exceeds 40/60, the weather resistance will be poor, such being undesirable. The gel content is the ratio of the insoluble content after the dissolution treatment with the organic solvent.

Further, the conjugated diene polymer (β) is preferably used as a latex body dispersed in an aqueous medium in advance in order to facilitate the dispersion during emulsion polymerization.

The emulsion polymerization for obtaining the above graft polymer rubber (a) can be carried out by any known method. In the present invention, this emulsion polymerization is carried out by using the above-mentioned polymerizable monomer mixture (α). It may be carried out until the polymerization rate becomes 93 to 100% by weight, but 50% by weight or more and 93% by weight or less,
It is preferable to carry out the polymerization until it reaches 60% by weight or more and 90% by weight or less, in order to improve the compatibility with the polyester and obtain high impact resistance.
In this emulsion polymerization, the polymerizable monomer mixture (α)
When the polymerization rate is less than 50% by weight, the rate of copolymerization with the polymerizable monomer (b) at the time of copolymerization with the polymerizable monomer (b) is increased, and the heat distortion temperature is lowered.

In the emulsion polymerization, a small amount of an emulsifying agent can be used. Examples of the emulsifying agent include anionic emulsifying agents such as sodium oleate, sodium lauryl sulfate and sodium dodecylbenzenesulfonate, polyoxyethylene cetyl ether and the like. A nonionic emulsifier or the like can be used. Further, as the polymerization initiator,
What is used for usual emulsion polymerization, for example, the redox type composed of persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate is used.

The graft copolymer, which is the component (A) in the present invention, comprises the aromatic vinyl compound (IV) 0 to the aromatic vinyl compound (IV) in the presence of the graft polymer rubber (a) obtained as described above.
100% by weight, methacrylic acid ester (V) 0-100
% And vinyl cyanide compound (VI) 0-40% by weight
Is obtained by polymerizing the polymerizable monomer (b), which is compounded so that the total amount becomes 100% by weight. Here, if the amount of the vinyl cyanide compound (VI) is too large, the moldability will be deteriorated, so that it must be used within a range not exceeding 40% by weight. Further, when the aromatic vinyl compound (IV) is used in an amount of 30% by weight or more, the moldability is improved, and when the vinyl cyanide compound (VI) is used in an amount of 10% by weight or more,
Improves chemical resistance. Therefore, the polymerizable monomer (b)
As the component (IV) is 30 to 100% by weight, particularly 50 to 90% by weight, the component (V) is 0 to 70% by weight, particularly 0 to 40% by weight and the component (VI) is 0 to 30% by weight. It is particularly preferable to use it in a proportion of 10 to 30% by weight.

Examples of the aromatic vinyl compound (IV) constituting the polymerizable monomer (b) include α-substituted styrene such as α-methylstyrene and α-ethylstyrene, chlorostyrene, vinyltoluene and t-. Examples of the styrene are nuclei-substituted styrenes such as butylstyrene. Further, examples of the methacrylic acid ester (V) include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like, and examples of the vinyl cyanide compound (VI) include
Examples thereof include acrylonitrile and methacrylonitrile.

In the present invention, the graft polymer rubber (a) and the polymerizable monomer (b) are (a) 5 to 50.
It is used in a proportion of 95 to 50 parts by weight with respect to parts by weight, so that the total amount is 100 parts by weight. (A) /
When the weight ratio of (b) is less than 5/95, the impact resistance decreases, and when it exceeds 50/50, the mechanical strength and heat distortion resistance decrease.

In order to polymerize the polymerizable monomer (b) in the presence of the graft polymer rubber (a), various polymerization methods such as emulsion polymerization method, suspension polymerization method and solution polymerization method can be used. Can be adopted. At the time of polymerization, an emulsifier, a polymerization initiator, a chain transfer agent, etc. can be appropriately added. As the polymerization initiator, for example, a redox type initiator composed of persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate may be used as the monomer (b).
About 0.1 to 2% by weight is used. As the chain transfer agent, for example, tert-dodecyl mercaptan or the like is used in an amount within about 1% by weight with respect to the monomer (b). The polymerization temperature is preferably 20 to 100 ° C., particularly preferably 50 to 90 ° C. It should be noted that similar conditions may be adopted when producing the graft polymer rubber.

Further, the polymerizable monomer (b) to be polymerized in the presence of the graft polymer rubber (a) may be polymerized in a single amount at once, or may be polymerized in two or several divided portions, or Although any polymerization method such as a method of polymerizing while dropping all the monomers may be adopted, as a first step, after polymerizing 5 to 30% by weight of the polymerizable monomer (b). ,
As the second step, it is preferable to add and polymerize the remaining amount of the polymerizable monomer (b) once or in two or more divided portions. By adopting such a multi-step polymerization method, the fluidity and the heat distortion temperature are further increased, and the impact resistance is also improved. In the multistage polymerization method, the polymerization in the first stage is preferably in the range of 5 to 30% by weight of the polymerizable monomer (b). When this amount is less than 5% by weight, there is no difference from the case where the entire amount is polymerized in one step, and when it exceeds 30% by weight,
The effect of improving the impact resistance and the effect of improving the heat distortion temperature due to the divided addition of the polymerizable monomer (b) and polymerization are reduced. Further, at this time, it is preferable to add the remaining amount of the polymerizable monomer (b) and polymerize after the polymerization rate has progressed to 50% by weight or more. If the polymerization rate in the first stage polymerization is less than 50% by weight, the effect of improving the heat distortion temperature and impact resistance tends to be reduced. Here, the polymerization rate is [1- (total weight of unreacted residual monomer at the end of the first-stage polymerization) / (polymerizable monomer mixture contained in the used graft polymer rubber (a) ( The weight of the unreacted residual monomer of α + the weight of the polymerizable monomer (b) used in the first step)] × 100%.

Even when the polymerizable monomer (b) is divided and used as described above, the total amount of the component (IV) and the component (V) is
The use ratios of the component and the component (VI) are adjusted as described above. The use ratio may be different between the first stage and the second stage and thereafter, but it is preferable that the same mixing ratio is used in each stage.

When the polymerization is emulsion polymerization, the graft copolymer (A) obtained by polymerizing the polymerizable monomer (b) in the presence of the graft polymer (a) contains potassium after the polymerization. The copolymer is coagulated and separated using a method such as salting out in which alum is mixed with hot water dissolved, dehydrated and dried, and then pelletized in powder form or using an extruder or the like,
It can be used for blending with polyester.

The characteristics of the graft copolymer which is the component (A) in the present invention are as follows: (i) Polymerization of the polymerizable monomer (b) in the presence of the graft polymer rubber (a) After blending 5 to 30 wt% of the monomer (b) and polymerizing it (preferably, after polymerizing to 50 wt% or more at the above-defined polymerization rate), a polymerizable monomer ( The remaining part of b) is blended and polymerized. (ii) In the production of the graft polymer rubber (a) as the raw material, the polymerizable monomer mixture (in the presence of the conjugated diene polymer (β) ( The emulsion polymerization of α) is carried out until the polymerization rate becomes 50% by weight or more and 93% by weight or less and then the polymerization is stopped, or (iii) the above (i) and (ii) are performed.
Therefore, in the production of the graft polymer rubber (a),
Emulsion polymerization of the polymerizable monomer mixture (α) in the presence of the conjugated diene polymer (β) has a polymerization rate of 93% by weight.
Even if it goes beyond the above, it is sufficient that the above (i) is carried out. Further, the polymerization of the polymerizable monomer (b) in the presence of the graft polymer rubber (a) may not be carried out separately as described above, as long as the above (ii) is carried out. However, it is most preferable to perform both (i) and (ii) above. Due to such characteristics, the thermoplastic resin composition according to the present invention is excellent in a good balance of impact resistance, heat distortion resistance, and chemical resistance. In particular, due to the above characteristics, the graft copolymer (A) is added to the polyester (B). Even if mixed with, the impact resistance does not decrease much.

The thermoplastic aromatic polyester resin used as the component (B) in the present invention is a polyalkylene terephthalate obtained by a polycondensation reaction of terephthalic acid or its derivative with an aliphatic glycol, or a copolymerization mainly composed of this. An example is coalescence. As the polyalkylene terephthalate, polyethylene terephthalate,
Polybutylene terephthalate is a typical one. In addition to terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, etc. are mixed as an acid component in the production of the polyester resin. It can also be used. Examples of the aliphatic glycols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and the like, along with other diols or polyhydric alcohols, for example,
Cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, glycerin, pentaerythritol and the like can also be used in combination.

The polyester resin used in the present invention is o-
It is considered preferable that the intrinsic viscosity measured at 25 ° C. in chlorophenol alone or a mixture of phenol and tetrachloroethane (50/50 weight ratio) is 0.5 or more from the viewpoint of impact resistance.

In the thermoplastic resin composition of the present invention,
(A) / (B) is 99 /
It is blended so as to be 1 to 45/55 (weight ratio). If this ratio exceeds 99/1, the improvement effect of polyester (the effect of improving chemical resistance and heat distortion resistance) is low, and 4
If it is less than 5/55, the impact resistance decreases. In particular, (A) /
It is preferable that (B) is blended so as to be 95/5 to 50/50 (weight ratio), and (A) / (B) is 95/5 to 5/5.
Most preferably, it is blended so as to be 55/45 (weight ratio).

In the thermoplastic resin composition of the present invention, as the component (C), at least one monomer selected from aromatic vinyl compounds, vinyl cyanide compounds, methacrylic acid esters and N-substituted maleimide compounds is polymerized. The polymer thus obtained may be contained. Here, as the aromatic vinyl compound, for example, α-methylstyrene, α-
Examples include α-substituted styrene such as ethylstyrene, chlorostyrene, vinyltoluene, nuclear-substituted styrene such as t-butylstyrene, and styrene. Further, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the methacrylic acid ester include:
Examples thereof include methyl methacrylate, ethyl methacrylate and butyl methacrylate. As the N-substituted maleimide compound, N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N
-Methylphenylmaleimide, N-dimethylphenylmaleimide, N-chlorophenylmaleimide, N-methylmaleimide, N-ethylmaleimide and the like are mentioned, and among these, N-phenylmaleimide is preferable. In addition,
Specific preferred examples of the polymer which is the component (C) are as follows.
Acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, acrylonitrile-
There are α-methylstyrene-N-phenylmaleimide copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, styrene-N-phenylmaleimide copolymer, methylmethacrylate-styrene copolymer, and polymethylmethacrylate. .. As the polymerization method, various polymerization methods such as emulsion polymerization method, suspension polymerization method, solution polymerization method and bulk polymerization method can be adopted.

The blending amount of the component (C) is used in place of a part of the component (A) in the blending ratio of the components (A) and (B) described above. That is, the component (A),
The components (B) and (C) are [(A) + (C)] /
(B) is blended so as to be 99/1 to 45/55 (weight ratio). If this ratio exceeds 99/1, the effect of improvement by the polyester (the effect of improving chemical resistance and heat distortion resistance) is low, and if it is less than 45/55, the impact resistance decreases.
In particular, [(A) + (C)] / (B) is 95/5 to 50 /
50 (weight ratio) is preferably blended,
[(A) + (C)] / (B) is 95/5 to 55/45
Most preferably, it is blended so as to be (weight ratio).
The mixing ratio of the component (C) to the component (A) is (C) /
It is preferable that (A) is blended in a weight ratio of 0/100 to 70/30, and particularly 0/100 to 40/6.
It is preferably blended so as to be 0.

The thermoplastic resin composition of the present invention may further contain a plasticizer as the component (D) in order to improve impact resistance. Examples of the plasticizer include diisodecyl succinate, dioctyl adipate, diisodecyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate, dioctyl tetrahydrophthalate, dibasic acid esters of dibasic acid, dimethyl phthalate, and phthalate. Diethyl acid, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di2-ethylhexyl phthalate, diisooctyl phthalate, di-n-phthalate
Octyl, dinonyl phthalate, diisodecyl phthalate,
Phthalates such as ditridecyl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, butyllauryl phthalate and methyloleyl phthalate, diethylene glycol dibenzoate, glycol esters such as dipentaerythritol hexaester and pentaerythritol ester, butyl oleate, Fatty acid esters such as methyl acetylricinoleate, tricresyl phosphate,
Phosphate esters such as trioctyl phosphate, octyl diphenyl phosphate, triphenyl phosphate, epoxidized soybean oil, epoxy butyl epoxy stearate, octyl epoxy stearate, epoxy compounds such as benzyl epoxy stearate, trioctyl trimellitate, trimellitate Examples thereof include triisodecyl acid, tetraoctyl pyromellitic acid, ethylphthalylethyl glycolate, and butylphthalylbutyl glycolate.

The component (D) has a weight ratio of (D) / [(A) + (B) + (C)] to improve impact resistance.
It is preferably blended so as to be / 100 to 20/100, and particularly preferably blended so as to be 2/100 to 15/100. If the amount of component (D) is too small, the impact resistance improving effect tends to be low,
If it exceeds, the heat distortion resistance tends to decrease.

The thermoplastic resin composition of the present invention contains a reinforcing agent or filler such as glass fiber, metal fiber or carbon fiber, a dye, a pigment, a heat and light stabilizer, and AAS, if necessary.
Additives usually added to resins and the like can be included.

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

The thermoplastic resin composition of the present invention is produced by the casting method,
Various molded products 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.

[0036]

Next, the present invention will be described in more detail based on 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. Heat distortion resistance JIS 1 specified in JIS K 7113 with a plate thickness of 2 mm.
The dumbbell was left for 30 minutes in a constant temperature bath set at 150 ° C., and the deformation was measured, and the change rate was shown. MFR (melt flow rate) Measured at 230 ° C. and 10 kg according to JIS-K7210. Chemical resistance A plate obtained by injection-molding a thermoplastic resin composition was immersed in methanol or gasoline for 24 hours at 23 ° C, and then the plate surface was visually observed. Gel Content of Polybutadiene A precipitate is generated from methanol from the polybutadiene latex and collected. About 1 g of the collected precipitate is immersed in 100 ml of toluene and left at room temperature for 48 hours.
After that, the mixture is filtered and separated into a filtrate and a swollen gel which is a filtration residue. 20 ml of the filtrate is taken and dried to obtain a dry sol, and its weight (Z) is measured. The swollen gel is shaken out of toluene and left in a desiccator filled with toluene vapor for 5 hours to saturate the toluene. After this, the weight (G) of the swollen gel is measured. After that, the following formula is used for calculation. [S− (T + S−G) × Z ÷ F] ÷ S × 100% where S is the weight of the collected precipitate and T is 100 toluene.
ml weight, F is 20 ml filtrate weight

Reference Example 1 (Production of Graft Copolymer G-1) (a) Production of Graft Polymer Rubber Latex Blend Composition Component Polybutadiene Latex (SN-800T, trade name of Sumitomo Nogatac Co., Ltd., polybutadiene is crosslinked) The gel content is 82%) 300 parts (solid content) Component butyl acrylate 700 parts Triallyl isocyanurate 14 parts Component potassium persulfate 0.4 parts Sodium sulfite 0.04 parts Emulsifier (Nonsar TN-1 , A trade name of fatty acid soap manufactured by NOF CORPORATION) 9.2 parts Deionized water 1420 parts

Polymerization Operation Charge the reaction vessel and the uniformly dissolved ingredients,
After mixing and stirring, uniformly dissolved components were added, and after nitrogen substitution, the temperature was raised and polymerization was carried out at 60 to 65 ° C. for about 4 hours, followed by cooling to stop the polymerization. The polymerization rate at this time is 6
It was 7%. Here, the said 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: Weight of the solid content of the polybutadiene latex used ε: Used butyl acrylate and triallyl isocyanate Total weight with nurate Polymerization rate = [(α × β ÷ γ-δ) / ε] × 100% This polymerization rate is hereinafter referred to as polymerization rate A.

(B) Emulsion Polymerization in the Presence of Graft Polymer Rubber Latex Blending Composition Component Deionized Water 1425 parts Emulsifier (Nonsar TN-1) 10.6 parts Rongalit 2.8 parts Component styrene 507 parts Acrylonitrile 193 parts Cumene hydroperoxide 2.45 parts tert-dodecyl mercaptan 2.8 parts

Polymerization Procedure After the components and the components were charged into a reaction vessel and uniformly mixed by stirring, 300 parts of the graft polymer rubber latex obtained in the above (a) (solid content including residual monomer, which is the residual monomer (30% based on the total amount of the graft polymer rubber, styrene and acrylonitrile) was added, and the mixture was stirred and mixed for another 30 minutes while substituting with nitrogen. After that, it was polymerized at 65 ° C. for about 6 hours, and after confirming that the polymerization rate reached 90%, it was further polymerized at 90 ° C. for 2 hours,
A resin latex was obtained. The resin latex was salted out in hot water in which potassium alum was dissolved, dehydrated and dried to obtain a resin powder, and the powder was pelletized by an extruder (hereinafter, referred to as graft copolymer G-1). .. here,
The 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 collected reaction mixture γ: weight of the collected 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 used styrene and acrylonitrile Polymerization rate = [(α × β ÷ γ−δ + ε) / (ε + ζ)] × 1
00% This polymerization rate is hereinafter referred to as polymerization rate B.

Reference Example 2 (Graft copolymers G-2 and G
Production of -3) Polymerization rate A in the polymerization of the graft polymer rubber latex
Except that the polymerization was stopped at 55% and 90%.
The same operation as in Reference Example 1 was performed. The obtained resin pellets were used as a graft copolymer G-2 (polymerization rate A55%) and G-
3 (polymerization rate A 90%).

Reference Example 3 (Graft copolymers G-4 and G
Production of -5) Reference Example 1 except that the polymerization rate A was stopped at 45% or 95% during the production of the graft polymer rubber latex.
It operated exactly the same as. The resin pellets obtained are referred to as graft copolymers G-4 (polymerization rate A 45%) and G-5 (polymerization rate A 95%).

Reference Example 4 (Graft copolymers G-6 to G-
Production of 9) Polymerization was carried out according to the formulation shown in Table 1 to obtain pellets of the thermoplastic resin composition. Details of the polymerization operation are as follows.
Ingredients, ingredients, ingredients, ingredients and ingredients were sequentially placed in a reaction vessel, and the mixture was stirred at room temperature for about 1 hour while replacing with nitrogen. Then, the temperature was raised to 70 ° C., and the reaction was continued until the polymerization rate B reached 65%. Then, the components were added, and the components were added dropwise, and polymerization was performed at 74 ° C. for about 2 hours. After the dropping of the components was completed, the components were added and kept at 74 ° C. for 1 hour while keeping the temperature at 74 ° C., and then the components were added and kept at the same temperature for 2 hours. Thereafter, the obtained resin latex was salted out with an aqueous solution of potassium alum, dehydrated and dried to obtain graft copolymers G-6 to G-9. In the production of the graft copolymers G-6 to G-9, the addition rates of the first step of the monomer mixture (b) are 5%, 15%, 30% and 4 in order.
It was 0%.

[0045]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Composition (unit: copies) ━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft co-copolymer G-6 G-7 G -8 G-9 ──────────────────────────────────── Ingredient Reference Example 1 (a) The obtained graft polymer latte 300 300 300 300 300 x (solid content including residual monomer) Component Deionized water 635 685 775 820 Emulsifier (Emar 2F) 0.73 0.73 0.73 0.73 Emulsifier (KS Soap) ) 0.83 2.16 4.19 5.52 Component Styrene 10 37.5 100 150 Acrylonitrile 10.5 31.5 58 77 Cumene hydroperoxide 0.1 3 0.368 0.735 0.98 component Styrene 14.5 36 52 53 t-dodecyl mercaptan 0.14 0.42 0.84 1.12 component Rongalit 3.01 3.01 3.01 3.01 deionized Water 115 115 115 115 115 Component Potassium Carbonate 7.84 7.84 7.84 7.84 Deionized Water 70 70 70 70 70 Component Styrene 483 434 355.5 304.5 Acrylonitrile 182 161 161 134.5 115.5 t-Dodecyl mercaptan 2.66 2.38 1.96 1.68 Cumene hydroperoxide 2.33 2.08 1.72 1.47 Emulsifier (KS Soap) 12.4 11.1 9.11 7.81 Deionized water 440 390 320 275 components emulsifier (KS soap) 0.27 0.24 0.20 0.17 deionized water 120 120 120 100 100 Potassium persulfate 1.37 1.37 1.37 1.37 Deionized water 70 70 70 70 70 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━

Reference Example 5 (Production of Graft Copolymer G-10) The amount of the graft polymer rubber in Reference Example 1 was set to 15% with respect to the total amount of the graft polymer rubber (including residual monomer), styrene and acrylonitrile. The operation was performed in the same manner as in Reference Example 1 except that the above was performed. The resin pellet thus obtained is referred to as a graft copolymer G-10.

Examples 1 to 10 and Comparative Examples 1 to 5 Polybutylene terephthalate (hereinafter abbreviated as PBT. 1401-X06 manufactured by Toray Industries, Inc., intrinsic viscosity 1.6 measured at 25 ° C. in o-chlorophenol). The graft copolymers G-1 to G-9 were added so as to have the composition shown in Table 2 and kneaded with a 30 mmφ twin-screw extruder (vent type) at 250 ° C. Then, using an injection molding machine, the molding temperature was set to 250 ° C. and the mold temperature was set to 50 ° C., and predetermined test pieces were molded. The physical properties were evaluated using this test piece, and the results are shown in Table 3.

[0048]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 Composition (weight part) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PBT type Compound amount Compound amount ───── ─────────────────────────────── Example 1 G-1 70 30 Example 2 G-2 70 30 Example 3 G-3 70 30 Example 4 G-6 70 30 Example 5 G-7 70 30 Example 6 G-8 70 30 Example 7 G-9 70 30 Example 8 G-1 95 5 Example 9 G- 1 65 35 Example 10 G-1 55 45 ──────────────────────────────────── Comparative Example 1 G-4 70 30 Comparative Example 2 G-5 70 30 Comparative Example 3 -5 100 0 Comparative Example 4 G-1 100 0 Comparative Example 5 0 100 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━

[0049]

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 3 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 min) Methanol Gasoline ──────────────────────────────────── Example 1 431 .6 11.7 No change No change Example 2 44 1.5 12.0 No change No change Example 3 41 1.6 1.6 12.1 No change No change Example 4 50 1.4 12.5 No change Change None Example 5 52 1.5 12.7 No change No change Example 6 49 1.6 1.6 11.9 No change No change Example 7 42 1.4 12.2 No change No change Example 8 45 3.5 8 .1 No change No change Example 9 40 1.2 18.3 No change No change Example 10 32 32 1.0 25.5 No change No change ───────────────── ──────────────────── Comparative Example 1 42 7.6 11.9 No change No change Comparative Example 2 16 1.5 1.5 13.2 No change No change Comparative Example 3 30 28.0 2.8 Whitening Whitening Comparative Example 4 45 29.5 3.5 Whitening Whitening Comparative Example 5 3.9 0.8 37.2 No change No change ━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Examples 11 to 20 and Comparative Examples 6 to 8 PBT (Mitsubishi Rayon Co., Ltd. Toughpet N120)
0, weight ratio of tetrachloroethane / phenol = 1/1
The test was carried out in the same manner as in Examples 1 to 10 by adding the intrinsic viscosity at 25 ° C. of 1.26) in the mixed solvent of 1. and the graft copolymers G-1 to G-9 in the proportions shown in Table 4. The physical properties were evaluated using the pieces, and the results are shown in Table 5.

[0051]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 4 Composition (parts by weight) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PBT type Compound amount Compound amount ───── ─────────────────────────────── Example 11 G-1 70 30 Example 12 G-2 70 30 Example 13 G-3 70 30 Example 14 G-6 70 30 Example 15 G-7 70 30 Example 16 G-8 70 30 Example 17 G-9 70 30 Example 18 G-1 95 5 Example 19 G- 1 65 35 Example 20 G-1 55 45 ──────────────────────────────────── Comparative Example 6 G-4 70 30 Comparative Example 7 G-5 0 30 Comparative Example 8 0 100 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0052]

[Table 5] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 5 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 minutes) Methanol Gasoline ──────────────────────────────────── Example 11 51 1 . 5 9. 7 No change No change Example 12 51 1. 5 9. 8 No change No change Example 13 50 1. 6 9. 7 No change No change Example 14 58 1. 5 9. 9 No change No change Example 15 60 1. 4 9. 8 No change No change Example 16 57 1. 4 9. 5 No change No change Example 17 50 1. 6 9. 6 No change No change Example 18 45 3. 4 7. 5 No change No change Example 19 55 1. 1 12. 1 No change No change Example 20 35 0. 9 18. 6 No change No change ──────────────────────────────────── Comparative Example 6 52 7. 7 9. 9 No change No change Comparative Example 7 18 1. 4 9. 7 No change No change Comparative Example 8 6. 1 0. 8 31. 2 No change No change ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Examples 21 to 30 and Comparative Examples 9 to 10 Table 6 shows polyethylene terephthalate (hereinafter abbreviated as PET. PET-J135 manufactured by Mitsui Pet Resin Co., Ltd.) and graft copolymers G-1 to G-9. The above composition was added and kneaded with a 30 mmφ twin-screw extruder (vent type) at 260 ° C. Next, using an injection molding machine, a molding temperature of 260 ° C. and a mold temperature of 70 ° C. were set, and predetermined test pieces were molded. Physical properties were evaluated using this test piece, and the results are shown in Table 7.

[0054]

[Table 6] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 6 Composition (weight parts) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PET type Compound amount Compound amount ───── ─────────────────────────────── Example 21 G-1 70 30 Example 22 G-2 70 30 Example 23 G-3 70 30 Example 24 G-6 70 30 Example 25 G-7 70 30 Example 26 G-8 70 30 Example 27 G-9 70 30 Example 28 G-1 95 5 Example 29 G- 1 65 35 Example 30 G-1 55 45 ──────────────────────────────────── Comparative Example 9 G-4 70 30 Comparative Example 10 G- 70 30 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0055]

[Table 7] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 7 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 minutes) Methanol Gasoline ──────────────────────────────────── Example 21 38 1 .2 13.5 No change No change Example 22 37 1.2 1.2 1 No change No change Example 23 38 38 1.1 14.0 No change No change Example 24 42 1.1 14.2 No change Change None Example 25 43 1.3 1.3 1 No change No change Example 26 43 1.2 1.2 13.9 No change No change Example 27 37 1.2 1.2 13.6 No change No change Example 8 40 3.4 8.8 No change No change Example 29 33 0.8 22.4 No change No change Example 30 25 0.6 63.1 No change No change ─────────── ────────────────────────── Comparative Example 9 39 7.0 13.4 No change No change Comparative Example 10 10 1.2 1.2 13.5 No change No change ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Examples 31 to 35 and Comparative Examples 11 to 12 Graft copolymers G-1 to G-7 were treated with PBT (1401-X06 manufactured by Toray Industries, Inc.) and dioctyl adipate (D).
(Abbreviated as OA)) in a ratio shown in Table 8 and kneaded by a 30 mmφ twin-screw extruder (vent type) at 250 ° C. Then, using an injection molding machine, a molding temperature of 250
C. and the mold temperature were set to 50.degree. C. and predetermined test pieces were molded. The physical properties are evaluated using this test piece,
The results are shown in Table 9.

[0057]

[Table 8] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 8 Composition (parts by weight) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PBT DOA type compounding amount compounding amount compounding amount ── ────────────────────────────────── Example 31 G-1 70 30 5 Example 32 G-2 70 30 5 Example 33 G-3 70 30 5 Example 34 G-6 70 30 30 Example 35 G-7 70 30 5 ─────────────────────── ─────────────── Comparative Example 11 G-4 70 30 5 Comparative Example 12 G-5 70 30 5 ━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━

[0058]

[Table 9] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 9 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 min) Methanol Gasoline ──────────────────────────────────── Example 31 60 1 .9 17.6 No change No change Example 32 62 1.8 1.8 18.0 No change No change Example 33 60 1.9 18.2 No change No change Example 34 69 69 1.7 18.9 No change Change None Example 35 61 1.8 18.3 No change No change ─────────────────────────────────── -Comparative Example 11 58 10.1 1 7.9 No change No change Comparative example 12 23 1.8 19.8 No change No change ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━

Examples 36 to 39 and Comparative Examples 13 to 14 Graft copolymer G-10 was treated with PBT (1 manufactured by Toray Industries, Inc.).
401-X06) and dioctyl adipate (abbreviated as DOA) in the proportions shown in Table 10,
It was kneaded by a 30 mmφ twin-screw extruder (vent type) at 250 ° C. Then, using an injection molding machine, a molding temperature of 250 ° C.,
The mold temperature was set to 50 ° C. and predetermined test pieces were molded. The physical properties were evaluated using this test piece, and the results are shown in Table 11.

[0060]

[Table 10] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 10 Composition (weight part) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PBT DOA type compounding amount compounding amount compounding amount ── ────────────────────────────────── Example 36 G-10 70 30 5 Example 37 G-10 70 30 2 Example 38 G-10 95 5 15 Example 39 G-10 55 45 5 ─────────────────────────────── Comparative Example 13 G-10 70 30 25 Comparative Example 14 G-10 100 0 5 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━

[0061]

[Table 11] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 11 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 minutes) Methanol Gasoline ──────────────────────────────────── Example 39 30 1 .7 31.6 No change No change Example 37 24 1.6 2.6 28.5 No change No change Example 38 36 2.0 4.0 45.8 No change No change Example 39 15 1.1 1.1 51.3 No change Change None ──────────────────────────────────── Comparative Example 13 40 7.4 7.4 38.7 No change Change None Comparative Example 14 10 31. 22.1 whitening whitening ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Examples 40 to 44 and Comparative Examples 15 to 16 The graft copolymers G-1 to G-7 are shown in Table 12 together with PET (PET-J135 manufactured by Mitsui Pet Resin Co., Ltd.) and DOA.
30mmφ at 260 ℃
It was kneaded with a twin-screw extruder (vent type). Next, using an injection molding machine, the molding temperature was set to 260 ° C. and the mold temperature was set to 70 ° C., and predetermined test pieces were molded. The physical properties of the test pieces were evaluated, and the results are shown in Table 13.

[0063]

[Table 12] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 12 Composition (parts by weight) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PET DOA type compounding amount compounding amount compounding amount ── ────────────────────────────────── Example 40 G-1 70 30 5 Example 41 G-2 70 30 5 Example 42 G-3 70 30 5 Example 43 G-6 70 30 5 Example 44 G-7 70 30 5 ─────────────────────── ─────────────── Comparative Example 15 G-4 70 30 5 Comparative Example 16 G-5 70 30 5 ━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━

[0064]

[Table 13] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 13 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 minutes) Methanol Gasoline ──────────────────────────────────── Example 40 50 1 .5 20.1 No change No change Example 41 52 52 1.4 21.3 No change No change Example 42 49 1.5 1.5 21.2 No change No change Example 43 60 1.4 22.0 No change Change None Example 44 48 1.4 21.7 No change No change ──────────────────────────────────── -Comparative Example 15 50 9.7 21.7 No change No change Comparative example 16 17 1.3 22.5 No change No change ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━

Examples 45 to 48 and Comparative Example 17 Graft copolymer G-10 was added to PET (PET-J135 manufactured by Mitsui Pet Resin Co., Ltd.) and DOA so as to have the composition shown in Table 14, and the temperature was adjusted to 260 ° C. It was kneaded with a 30 mmφ twin-screw extruder (vent type). Next, using an injection molding machine, the molding temperature was set to 260 ° C. and the mold temperature was set to 70 ° C., and predetermined test pieces were molded. Physical properties were evaluated using this test piece, and the results are shown in Table 15.

[0066]

[Table 14] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 14 Composition (parts by weight) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PET DOA type compounding amount compounding amount compounding amount ── ────────────────────────────────── Example 45 G-10 70 30 5 Example 46 G-10 70 30 2 Example 47 G-10 95 5 15 Example 48 G-10 55 45 5 ──────────────────────────────── Comparative Example 17 G-10 70 30 25 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━

[0067]

[Table 15] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 15 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 min) Methanol Gasoline ──────────────────────────────────── Example 45 25 1 .2 35.1 No change No change Example 46 20 1.2 1.2 33.4 No change No change Example 47 34 34 1.8 49.2 No change No change Example 48 14 0.7 55.5 No change Change None ──────────────────────────────────── Comparative Example 17 36 6.4 48.7 No change Change None ━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━

Reference Example 6 (Production of Graft Copolymer G-11) (1) Emulsion Polymerization in the Presence of Graft Polymer Rubber Latex Blending Composition Component (a) Deionized Water 1425 Parts Emulsifier (Nonsar TN-1) 10. 6 parts Rongalit 2.8 parts Component (b) Styrene 435 parts Acrylonitrile 165 parts Cumene hydroperoxide 2.1 parts tert-Dodecyl mercaptan 2.4 parts

Polymerization Operation After uniformly dissolving the components (a) and (b) in a reaction vessel and uniformly stirring and mixing, the graft polymer rubber latex obtained in (a) of Reference Example 1 was converted into solid content. At 400
Parts (solid content including residual monomer: graft polymer rubber,
40% based on the total amount of styrene and acrylonitrile)
Was added, and the mixture was further stirred and mixed for 30 minutes while purging with nitrogen. After that, it is polymerized at 65 ° C. for about 6 hours, and the polymerization rate is 90.
%, It was further polymerized at 90 ° C. for 2 hours to obtain a resin latex. 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 graft copolymer G-1.
1)).

Reference Example 7 (Production of Graft Copolymer G-12) A graft polymer rubber latex obtained in the same manner as in Reference Example 1 (a) was further supplemented with 0.33 parts of potassium persulfate and K.
Add 0.8 parts of S-Soap and 50 parts of deionized water to 65 ° C
It was polymerized for 3 hours. The polymerization rate A at this time was 95%. 100 parts of this graft polymer rubber latex in terms of solid content was charged into a reaction vessel, the following component (1) was further charged, nitrogen substitution was carried out, and after heating at 73 ° C., the following component (2) was added.
Was added dropwise over about 3 hours. After completion of the dropping, polymerization was continued for 3 hours, salting out was performed in hot water in which potassium alum was dissolved, and dehydration drying was performed to obtain a resin powder. This was designated as graft copolymer G-12.

Component (1) Sodium sulfite 0.12 parts Potassium carbonate 1.69 parts Potassium persulfate 2.43 parts Deionized water 240 parts Component (2) Styrene 112.6 parts Acrylonitrile 37.5 parts t-dodecyl mercaptan 0 68 parts Emar 2F 0.15 parts KS Soap 2.85 parts Deionized water 40 parts

Reference Example 8 (Production of Graft Copolymer G-13) (a) Production of Graft Polymer Rubber Latex Blend Composition Component (1) Polybutadiene Latex (same as used in Reference Example 1) 300 parts (solid) Min) Component (2) Butyl acrylate 700 parts Triallyl isocyanurate 14 parts Component (3) Potassium persulfate 0.4 parts Sodium sulfite 0.04 parts Emulsifier (Nonsar TN-1, manufactured by NOF Corporation, fatty acid soap product) Name) 9.2 parts Deionized water 1420 parts Component (4) Potassium persulfate 0.33 parts Emulsifier (KS Soap) 0.8 parts Deionized water 50 parts

Polymerization Operation Component (1) and component (3) dissolved uniformly were charged into a reaction vessel, mixed and stirred, then component (2) dissolved uniformly was added, and after nitrogen replacement, the temperature was raised to 60. After polymerizing at ˜65 ° C. for about 4 hours, the component (4) was added and further polymerized at 65 ° C. for 3 hours. The polymerization rate A at this time was 96%, which was substantially complete.

(B) Emulsion Polymerization in the Presence of Graft Polymer Rubber Latex Component (1) Graft Polymer Rubber Latex Obtained as Above (Converted to Solid Content Including Residual Monomer) 507 Parts Component (2) Deionization Water 778 parts Emulsifier (Emar 2F (Kao, sodium lauryl sulfate) 0.92 parts Emulsifier (KS soap) 4.33 parts Component (3) Styrene 29.8 parts Acrylonitrile 28.9 parts Cumene hydroperoxide 0.312 Part Ingredient (4) Styrene 30.4 part t-Dodecyl mercaptan 0.285 part Ingredient (5) Rongalit 3.28 part Deionized water 126 part Ingredient (6) Potassium carbonate 8.52 part Deionized water 78.0 part Ingredient (7) Styrene 483.6 parts Acrylonitrile 188 parts t-dodecyl mercaptan 2.15 parts Kumenha Idropoperoxide 1.88 parts KS Soap 12.5 parts Deionized water 440 parts Ingredient (8) KS Soap 0.27 parts Deionized water 127 parts Ingredient (9) Potassium persulfate 1.49 parts Deionized water 72 parts

Polymerization Operation The above component (1), component (2), component (3), component (4) and component (5) were successively placed in a reaction vessel and stirred for about 1 hour while substituting with nitrogen. Then, the temperature was raised to 70 ° C., and after polymerization for 1 hour, it was confirmed that the polymerization rate B was 60% by weight, and the component (6) was added, and further the component (7) was added.
Was added dropwise over about 2 hours to polymerize at 74 ° C. After the dropping of the component (7), the component (8) was added, and after 1 hour, the component (9) was added, and the polymerization was continued for another 2 hours. The obtained resin latex is salted out with an aqueous solution of potassium alum, dehydrated and dried to give a graft copolymer G-1.
A resin powder of 3 was obtained.

Examples 49 to 50 and Comparative Examples 18 to 21 Resin powders of the graft copolymers G-11 to G-13 obtained above, acrylonitrile-styrene copolymer resin (Styrac 703 manufactured by Asahi Kasei Kogyo KK) , And hereinafter referred to as AS-1) and PBT (1401-X06 manufactured by Toray Industries, Inc.) were blended at a ratio shown in Table 16, and kneaded and granulated at 250 ° C. using a 30 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. Various characteristics were evaluated by a predetermined method. As a result, Table 1
7 shows.

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[Table 16] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 16 Composition (weight part) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer Rigid resin Polyester seeds Blends Blends Blends Blends Compounding amount ──────────────────────────────────── Example 49 G-11 50 AS-1 20 PBT 30 Example 50 G-13 50 AS-1 20 PBT 30 ────────────────────────────────────── -Comparative Example 18 G-12 50 AS-1 20 PBT 30 Comparative Example 19 G-12 71.5 AS-1 28.5 0 Comparative Example 20 G-11 71.5 AS-1 28.5 0 Comparative Example 21 G -13 71.5 A -1 28.5 0 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

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[Table 17] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 17 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 minutes) Methanol gasoline ──────────────────────────────────── Example 49 231 .7 20.0 No change No change Example 50 21 1.4 18.0 No change No change ──────────────────────────── ───────── Comparative Example 18 11 1.6 17.6 No change No change Comparative Example 19 28 27.0 13.0 Whitening Whitening Comparative Example 20 33 27.5 12.5 Whitening Whitening Comparative Example 21 32 26.0 12.8 Whitening Whitening ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Examples 51 to 56 and Comparative Examples 22 to 25 Graft copolymer G-1 or G-5, PBT (1401)
-X06) and the plasticizer were mixed in the composition shown in Table 18, and 2
The mixture was kneaded with a 30 mmφ twin-screw extruder (vent type) at 50 ° C. Then, using an injection molding machine, a molding temperature of 250 ° C.,
The mold temperature was set to 50 ° C. and a predetermined test piece was molded. The results of evaluation of physical properties using this test piece are shown in Table 19.
Shown in. As the plasticizer, diisodecyl phthalate (DIDP), trioctyl phosphate (TOP), epoxidized soybean oil (ESO) or triisodecyl trimellitate (TIDT) was used.

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[Table 18] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 18 Composition (parts by weight) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PBT DIDP TOP ESO TIDT species compounding amount compounding amount compounding Amount Compounding amount Compounding amount Compounding amount ──────────────────────────────────── Example 51 G-1 70 30 5 0 0 0 Example 52 G-1 70 30 0 5 0 0 Example 53 G-1 70 30 0 0 5 0 Example 54 G-1 70 30 0 0 0 5 Example 55 G-1 70 30 2 0 0 Example 56 G-1 70 30 15 0 0 0 ──────────────────────────────────── — Comparative Example 22 G-5 0 30 5 0 0 0 Comparative Example 23 G-5 70 30 0 5 0 0 Comparative Example 24 G-5 70 30 30 0 0 5 0 Comparative Example 25 G-5 70 30 0 0 0 0 5 5 ━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━

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[Table 19] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 19 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 min) Methanol Gasoline ──────────────────────────────────── Example 51 59 1 .8 17.8 No change No change Example 52 57 57 1.8 17.9 No change No change Example 53 60 1.9 17.9 No change No change Example 54 62 1.9 18.0 No change Change None Example 55 55 1.6 14.0 No change No change Example 56 70 70 2.0 22.5 No change No change ────────────────────── ─── Comparative Example 22 22 18 1.8 19.9 No change No change Comparative Example 23 20 18 1.8 18.7 No change No change Comparative Example 24 21 1.9 19.0 No change No change Comparative Example 25 23 1.9 19.2 No change No change ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━

Examples 57 to 62 and Comparative Examples 26 to 29 PBT (1401-X06) was replaced with PET (PET-J13).
The procedure was carried out according to Examples 51 to 56 and Comparative Examples 22 to 25, except that the procedure of 5) was changed. The formulations are shown in Table 20, and the evaluation results of physical properties are shown in Table 21.

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[Table 20] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 20 Combination (weight part) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Graft copolymer PET DIDP TOP ESO TIDT species compounding amount compounding amount compounding Amount Compounding amount Compounding amount Compounding amount ──────────────────────────────────── Example 57 G-1 70 30 5 0 0 0 Example 58 G-1 70 30 0 5 0 0 Example 59 G-1 70 30 0 0 5 0 Example 60 G-1 70 30 0 0 0 5 Example 61 G-1 70 30 2 0 0 Example 62 G-1 70 30 15 0 0 0 ──────────────────────────────────── -Comparative Example 26 G-5 0 30 5 0 0 0 Comparative Example 27 G-5 70 30 0 5 0 0 Comparative Example 28 G-5 70 30 30 0 0 5 0 Comparative Example 29 G-5 70 30 0 0 0 0 5 5 ━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━

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[Table 21] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 21 Evaluation of physical properties ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Izod impact strength Heat distortion resistance MFR Chemical resistance Productability (kgcm / cm) (% ) (G / 10 minutes) Methanol Gasoline ──────────────────────────────────── Example 57 501 .5 21.0 No change No change Example 58 49 1.5 1.5 20.5 No change No change Example 59 49 1.4 20.7 No change No change Example 60 51 1.4 1.4 20.8 No change Change None Example 61 45 1.3 17.9 No change No change Example 62 62 1.9 25.2 No change No change ────────────────────── ─── Comparative example 26 16 1.4 1.4 21.2 No change No change Comparative example 27 15 15 1.4 21.4 No change No change Comparative example 28 17 1.5 21.7 No change No change Comparative example 29 17 1.4 21.3 No change No change ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━

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The thermoplastic resin composition according to claim 1 or 2 is excellent in impact resistance, chemical resistance and thermal deformation resistance. The molded article according to claim 3 is excellent in impact resistance, chemical resistance and thermal deformation resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 3-343329 (32) Priority date Hei 3 (1991) December 25 (33) Priority claim country Japan (JP) (72) Inventor Isamu Hattori 14 Goi Minami Coast, Ichihara City, Chiba Hitachi Chemical Co., Ltd. Goi Factory

Claims (3)

[Claims] 1. A graft copolymer (A) and a thermoplastic aromatic polyester resin (B) are contained. The graft copolymer (A) is polymerized with 5 to 50 parts by weight of a graft polymer rubber (a). The polymerizable monomer (b) is used in an amount of 95 to 50 parts by weight so that the total amount thereof is 100 parts by weight, and the polymerizable monomer (b) is polymerized in the presence of the graft polymer rubber (a). And a graft polymer rubber (a)
However, 95 to 60 parts by weight of the polymerizable monomer mixture (α) and 5 to 40 parts by weight of the conjugated diene polymer (β) are used so that the total amount thereof is 100 parts by weight. It is obtained by emulsion-polymerizing the polymerizable monomer mixture (α) in the presence of the polymer (β), and the polymerizable monomer mixture (α) is a polyfunctional monomer (I). 1 to 20% by weight,
50 to 99.9% by weight of an acrylic ester (II) having an alkyl group having 1 to 13 carbon atoms and other vinyl compounds (I
II) It is used by blending 0 to 30% by weight so that the total amount becomes 100% by weight, and the polymerizable monomer (b) is
Aromatic vinyl compound (IV) 0 to 100% by weight, methacrylic acid ester (V) 0 to 100% by weight and vinyl cyanide compound (VI) 0 to 40% by weight are used so that the total amount becomes 100% by weight. In the thermoplastic resin composition, the (A) graft copolymer is (i) a polymerizable monomer (b) in the presence of the graft polymer rubber (a).
Of the conjugated diene polymer (β) obtained by blending 5 to 30% by weight of the above and polymerizing, and then blending and polymerizing the rest of the polymerizable monomer (b). In the presence of the above, the polymerization rate of the polymerizable monomer mixture (α) is 50% by weight.
After emulsion polymerization until above and 93% by weight or less,
It is obtained by polymerizing a polymerizable monomer (b) in the presence of a graft polymer rubber (a) obtained by terminating the polymerization, wherein (A) a graft copolymer and (B) a thermoplastic aroma. A thermoplastic resin composition comprising a group polyester resin and the former 45 to 99% by weight and the latter 55 to 1% by weight. 2. The thermoplastic resin composition according to claim 1, wherein the polyfunctional monomer (I) is triallyl isocyanurate or triallyl cyanurate. 3. A molded product obtained by molding the thermoplastic resin composition according to claim 1 or 2.