JPH01313549A - Production of n-arylmaleimide polymer and heat-resistant and impact-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve the heat resistance, impact resistance and flow of a thermoplastic resin composition by reacting an N-arylmaleimide with an aromatic vinyl compound and a specified compound in a pre-emulsified aqueous solution. CONSTITUTION:A pre-emulsified aqueous solution (E) is obtained by mixing water with 0.01-3wt.%, based on the monomer mixture to be reacted, chain transfer agent (e.g., t-dodecylmercaptan) and 0.5-7wt.%, based on the monomer mixture to be reacted, emulsifier (e.g., sodium lauryl-sulfonate). A monomer mixture comprising 10-60wt.% N-arylmaleimide (A) (e.g., N-phenylmaleimide), 16-65wt.% aromatic vinyl compound (B) (e.g., alpha-methylstyrene) and 60-15wt.% at least either (C) of a vinyl cyanide compound and a (meth)acrylate (e.g., acrylonitrile) is copolymerized in component E in the presence of a polymerization initiator (D) to obtain the title polymer of a weight-average MW of 50000-300000.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing an N-arylmaleimide copolymer useful for thermoplastic resins, and a method for producing an N-arylmaleimide copolymer that has excellent heat resistance, impact resistance, etc. using the same. The present invention relates to a thermoplastic resin composition.

(Prior art) Rubber-modified thermoplastic resins made by graft polymerizing acrylonitrile and styrene to rubber include so-called ABS resins,
There is something known as AAS resin. These resins have processability 1 mechanical strength.

Because it has excellent performance such as surface gloss and chemical resistance.

Widely used today. However, it cannot be said that it has sufficient heat resistance depending on the field of use.

As for the method of improving this heat resistance, it is generally known to replace part or all of styrene with α-methylstyrene. but.

Even with this method, there is a limit to the improvement in heat resistance.

This is not necessarily satisfactory in fields that require heat resistance, such as parts for automobiles and light electrical equipment.

On the other hand, copolymers of vinyl monomers such as styrene and N-substituted maleimides have high heat distortion temperatures and thermal decomposition temperatures (Kobunshi Ronsen Vol. 36).

No. 7, page 447, published by the Society of Polymer Science and Technology, 1979).

Poor mechanical properties such as impact resistance [Journal/
of Polymer Science (J, Polymer Science)
rSci, Vol. 36, p. 241, published in 1959].

Therefore, it has been proposed to obtain a copolymer with excellent impact resistance and heat resistance by reacting N-substituted maleimide, olefinically unsaturated nitrile, and aromatic vinyl in the presence of a rubber component (UK). Patent No. 3,721,7
Specification No. 24). but.

Performing a polymerization reaction of maleimide or the like in the presence of a rubber component induces a significant decrease in the polymerization rate. Additionally, the amount of copolymer that does not bond with the rubber component increases. Furthermore, the molecular weight tends to be low. Therefore, it has been difficult to achieve both heat resistance and impact resistance.

Also, N-fi? A thermoplastic resin composition comprising a blend of a copolymer containing converted maleimide and a graft copolymer based on a rubber-like polymer has been proposed (Japanese Patent Publication No. 46-34103; Japanese Patent Application Laid-open No. 117050/1982). (see publication). The thermoplastic resin composition proposed here is
Although it shows excellent impact resistance and heat resistance, it is difficult to say that it is sufficient.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems. That is, a thermoplastic resin composition containing a graft copolymer based on a rubbery polymer that has significantly improved impact resistance and heat resistance at the same time, and an N-arylmaleimide copolymer useful therein. The present invention provides a method for manufacturing.

(Means for Solving the Problems) The present invention involves adding 10 to 60% by weight of N-arylmaleimide, 16 to 65% of an aromatic vinyl compound, and vinyl cyanide to an aqueous solution that has been emulsified in advance by adding a chain transfer agent and an emulsifier. N-arylmale fA) imide copolymer, characterized in that a copolymerization reaction is carried out by adding a monomer containing 60 to 15% by weight of a compound, an acrylic ester and/or a methacrylic ester, and a polymerization initiator. N obtained by the production method and on μ
-7lyl maleimide copolymer.

(Bl in the presence of 1 to 15 parts by weight of a rubbery polymer.

A monomer mixture containing 50 to 85 parts by weight of an aromatic vinyl compound and 15 to 50 parts by weight of a vinyl cyanide compound 85 to 9 parts by weight
in the presence of a graft copolymer obtained by polymerizing 9 parts by weight and 30 to 80 parts by weight of (C) a rubbery polymer.

Monomer mixture 70-2 containing 60-80% by weight of an aromatic vinyl compound and 20-40% by weight of a vinyl cyanide compound
0 parts by weight, (A1 component is 10 to 80% by weight, (B
The total amount of component ) and component (C) is 90 to 20% by weight.

The ratio of component (B)/component (C) is 1/99 to 99 by weight
It relates to a heat-resistant and impact-resistant thermoplastic resin composition which is blended so that: /1.

First, the method for producing an N-arylmaleimide copolymer and the obtained copolymer [i.e. (component copolymer c hereinafter, "
copolymer (A)] will be explained.

N-arylmaleimide, which is a copolymerization component, has a molecular weight of 10 to 60
% by weight, preferably 12-55%. N-
When the amount of arylmaleimide is less than 10% by weight, it is obtained by blending the copolymers.

The heat resistance of the thermoplastic resin composition (hereinafter simply referred to as the resin composition) decreases, and when the weight ratio exceeds 60, the fluidity and impact resistance of the resin composition decrease. Aromatic vinyl compounds are 1
6-65% by weight, preferably 18-60% by weight is used. When the content of the aromatic vinyl compound is 16% by weight, the impact resistance of the resin composition decreases, and when it exceeds 65% by weight, the heat resistance decreases. The vinyl cyanide compound, acrylic ester and/or methacrylic ester is used in an amount of 60 to 15% by weight, preferably 55 to 18% by weight.

If the amount of these monomers is less than 15% by weight, the fluidity and WJ impact resistance of the resin composition will decrease, and if it exceeds 60% by weight, the heat resistance of the resin composition will decrease. Note that other copolymerizable monomers may be used in an amount of 30% or less by weight based on the total monomers. The above monomers are adjusted so that the total amount is 100% by weight.

Copolymer (A) is obtained by emulsion polymerization.

A chain transfer agent is added to adjust the molecular weight between copolymers and improve moldability. During polymerization, chain transfer agents are generally used after being dissolved in monomers. However, in the present invention, a chain transfer agent is previously present together with an emulsifier to produce an emulsified aqueous solution, and then monomers and a polymerization initiator are added to carry out a copolymerization reaction. This improves heat resistance and impact resistance. This is because monomers move into emulsifier micelles incorporating chain transfer agents and polymerization progresses.

This is because the concentration of the chain transfer agent relative to the monomer changes, resulting in a broader molecular weight distribution and improved compatibility with the graft copolymer. From this, in the present invention, solution polymerization, suspension polymerization, bulk polymerization, etc.

Other polymerization methods cannot be used.

n-dodecylmercaptan as a chain transfer agent.

Examples include t-dodecyl mercaptan, xanthogen disulfide, terpene, and tetrahydronaphthalene. The chain transfer agent is preferably used in an amount of 0.01 to 3% by weight based on the monomer.

As the emulsifier, anionic, cationic or nonionic surfactants can be used. Anionic surfactants are particularly preferred, and specific examples include sodium lauryl sulfate, potassium oleate, disproportionated potassium rosinate, sodium dioctyl sulfo/phosphate, and sodium dodecylbenzenesulfonate. These are 0 for monomers.
．． Preferably, it is used for weights of 5 to 7. However, in order to improve emulsion stability, sulfates, chlorides, carbonates, etc. of alkali metals such as sodium and potassium may be used.

As a polymerization initiator used during polymerization.

Examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, water-soluble peroxides such as cumene hydroperoxide, and combinations of these with compounds that form redox systems. These are usually used in an amount of 0.05 to 5 times per monomer.

The aryl group of the N-arylmaleimide is Teha, phenyl group, 4-diphenyl group, 1-naphthyl group, mono- or dimethylphenyl 42.6-dinitylphenyl group, mono- or dihalogenated phenyl group, 2,4.6-dolichlorophenyl group enyl group, 2.4.6-driphromophenyl group 14
-n-butylphenyl group, 2-methyl-4-n-butylphenyl group, 4-benzylphenyl group, 3- or 4-
Methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 2-methoxy-5-bromophenyl g, 'zs-
dimethoxy-4-chlorophenyl group, 2.3-1 is 4-
Ethoxyphenyl group, 2.5-jethoxyphenyl group,
4-phenoxyphenyl group, 4-methoxycarbonylphenyl group, 4-cyanophenyl group, 2.3- or 4-nitrophenyl group, 2.3-.

2.4-, 2.5- or 4.3-methylchlorophenyl groups, etc. Particularly preferred are those having a phenyl group or an O-methylphenyl group.

Aromatic vinyl compounds used in the production of copolymer (A) include styrene and α-methylstyrene.

O-methylstyrene, m-methylstyrene, p-methylstyrene, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, α-ethylstyrene, methyl-α-methylstyrene.

Examples include dimethylstyrene and vinylnaphthalene.

Among these, styrene and α-methylstyrene are preferred.

Vinyl cyanide compounds used in the production of copolymer fAl include acrylonitrile, methacrylonitrile, etc., and acrylic esters and methacrylic esters include methyl ester, ethyl ester, and phthyl ester of acrylic acid or methacrylic acid. , hexyl esters, etc. are preferred, and methyl acrylate and methyl methacrylate are preferred.

The weight average molecular weight of the copolymer (Al) is preferably in the range of 50,000 to 300,000. If it is less than 50,000, impact resistance tends to decrease, and if it exceeds 300,000, fluidity tends to decrease.

Note that the weight average molecular weight in the present invention is measured by gel permeation chromatography.

This is a value calculated in terms of standard polystyrene.

Next, the heat-resistant and impact-resistant thermoplastic resin composition (hereinafter simply referred to as resin composition) of the present invention containing a copolymer (Al as one component) will be described in detail.

The graft copolymer (hereinafter referred to as "graft copolymer (B)") which is the fB) component of the resin composition will be explained.

Graft copolymer (Bl is a graft copolymer obtained by polymerizing monomers in the presence of a small amount of rubbery polymer, and such a graft copolymer is combined with the above copolymer + A).
) and the fCIE graft copolymer described below in a specific amount, they can be easily made to be compatible with each other.
The impact resistance can be improved without completely reducing the heat resistance of the resin composition.

The rubbery polymer used to prepare the graft copolymer CB) is used in an amount of 1 to 15% by weight, preferably 3 to 10% by weight. In addition, the monomer to be graft-polymerized is 99 to 8
59-85 ft or 97-90% by weight is used.

If the rubber-like polymer is less than 1% by weight, the impact resistance of the resin composition will decrease, and if it exceeds 15% by weight, the ability to make the graft copolymer of the co-electrolyte (A) and component (C) compatible will be reduced. The heat resistance of the resin composition decreases.

The monomer to be graft-polymerized is an aromatic vinyl compound 50
-85% by weight, preferably 65-75% by weight and 50-15% by weight of heptavinyl compound.

Preferably it contains 35 to 25% by weight. In addition, if necessary, other copolymerizable monomers such as methacrylic esters, acrylic esters, vinyl acetate, etc. are preferably included in a proportion of 30 or less, particularly preferably 25 or less, by weight based on the total monomers. It's okay to stay.

The above monomers are adjusted to have a total weight of 10,000%. If there is too little aromatic vinyl compound or too much vinyl cyanide compound.

Fluidity tends to decrease. If there is too much aromatic vinyl compound or too little cyanide vinyl compound,
Impact resistance tends to decrease. Also.

If the amount of other copolymerizable monomers is too large, impact resistance tends to decrease.

The rubbery polymer is polybutadiene.

Butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polyisoprene, poly-2,3-dimethylbutadiene, polypiperylene.

Polychloroprene, diene copolymers such as ethylene-propylene-diene copolymers, ethylene-propylene rubber, acrylic rubber, composite rubbers obtained by synthesizing acrylic rubber in the presence of diene copolymers, etc. .

The above acrylic rubber is a polyfunctional monomer with 1 to 13 carbon atoms.
It is obtained by copolymerizing an acrylic acid ester having an alkyl group and, if necessary, other monomers copolymerizable therewith.

Examples of polyfunctional monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and ethylene glycol diacrylate.

Examples include polyvalent vinyl compounds such as divinylbenzene, diallyl phthalate, synchronopentadiene acrylate, and dicyclopentadiene methacrylate, and polyvalent allyl compounds such as triallyl cyanurate, triallyl isocyanurate, and diallyl phthalate. , triallyl isocyanurate and triallyl cyanurate are particularly preferred. The polyfunctional monomer preferably has a weight ratio of 0.1 to 20, particularly preferably 0.
．． It is used within the range of 5 to 10 weight factors. 0.1% by weight
If it is less than 20 mm by weight, the degree of crosslinking will be insufficient and the impact resistance and appearance of the molded product will tend to be poor; if it exceeds 20 mm by weight, the degree of crosslinking will be excessive and the impact resistance will tend to decrease. Examples of the acrylic ester having an alkyl group having 1 to 13 carbon atoms include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and among these, butyl acrylate is particularly preferred. The acrylic ester is preferably used in an amount of 50 to 99.9% by weight, particularly preferably 65 to 99.5% by weight, based on the total monomers. If it is less than 50% by weight, impact resistance tends to decrease.

Other monomers that can be copolymerized with acrylic esters include styrene, acrylonitrile, and vinyl acetate.

There are acrylic acid, methacrylic acid, methacrylic acid alkyl ester (methyl ester, butyl ester, etc.), and the amount is 0 to 30% by weight based on the total monomer.

It is preferably used in a range of 0 to 25% by weight.

If it exceeds 30% by weight, sufficient impact resistance will not be obtained.

The composite rubber contains, in the presence of the diene polymer rubber, the polyfunctional monomer described above, an acrylic ester having an alkyl group having 1 to 13 carbon atoms, and others copolymerizable with these as necessary. It is obtained by copolymerizing a polymerizable monomer containing the following monomers. The weight ratio of the diene polymer and the polymerizable monomer is preferably 5/95 to 40.
/60, particularly preferably 20/80 to 35/65. If this ratio is less than 5/95.

Impact resistance and molded product appearance tend to be poor, and if it exceeds 40/60, weather resistance tends to be poor. Also.

In the composite rubber, the polymerization rate of the polymerizable monomer is preferably 50.
Particularly preferred is a rubbery resin composition obtained by stopping the polymerization in a range of 1% to 93% by weight, particularly preferably 55 to 75% by weight. It is preferable to use a graft copolymer obtained using such a rubbery resin composition in terms of impact resistance and heat resistance. That is, the 9 polymerization rate is 93
If it exceeds 5% by weight, the effect of improving impact resistance tends to decrease.
If it is less than 0% by weight, heat resistance tends to decrease. The composition of the polymerizable monomer used in the production of the composite rubber is the same as in the production of the acrylic rubber.

The polymerization for producing the acrylic rubber and composite rubber can be carried out by a known emulsion polymerization method. In this emulsion polymerization, the polymerization initiators include potassium persulfate, sodium persulfate, ammo persulfate, persulfates such as rum, and water-soluble peroxides such as cumene hydroperoxide, which together form a redox system. Anionic, cationic, or nonionic surfactants can be used as emulsifiers, with anionic surfactants being particularly preferred.

The aromatic vinyl compound used in the production of the graft copolymer (B) is the same as that used in the production of the copolymer (B), and the vinyl cyanide compound is
Acrylonitrile, methacrylate trile, etc. Among other copolymerizable monomers used as necessary, methacrylic esters and acrylic esters are similar to those used in the production of copolymers. Things can be used.

Next, the graft copolymer of component (C) (hereinafter referred to as "graft copolymer (C)") will be explained.

The graft copolymer (C1 has a larger proportion of rubbery polymer than the graft copolymer CB+) and is used to improve the impact resistance of the heat-resistant thermoplastic resin composition according to the present invention.

The monomers to be combined with the rubbery polymer used in the production of the graft copolymer fcl each have a weight range of 30 to 80% by weight, preferably 40 to 70% by weight, and a range of 70 to 20% by weight, preferably If the rubber-like polymer used is less than 30 parts by weight, the impact resistance will decrease, and if it exceeds 800 parts by weight, the heat resistance will decrease.

The monomer to be graft-polymerized is an aromatic vinyl compound 60
~80% by weight, preferably 65-78% by weight and 20-40% by weight of the vinyl cyanide compound.

Preferably, the weight range is 20 to 35, and if necessary, methacrylic ester and acrylic ester.

It may also contain other copolymerizable monomers such as vinyl acetate, preferably in an amount of 30 weight percent or less, particularly preferably 25 weight percent or less, based on the total monomers. The total of the above monomers is 1
0000 parts by weight. If the amount of aromatic vinyl compound is too small or the amount of vinyl cyanide compound is too large, fluidity tends to decrease. There are too many aromatic vinyl compounds.

If the vinyl cyanide compound is too small, impact resistance tends to decrease.

The rubber-like polymer, aromatic vinyl compound, vinyl cyanide compound, and other copolymerizable monomers used are the same as those used in the graft copolymer (B), and are preferred. 4 which can be used as -.

In addition, both graft copolymers (B) and (C).

The weight average molecular weight of those acetone soluble parts is 50,000 to 3
Preferably, it is 0,000. If the weight average molecular weight of the acetone soluble portion of these graft copolymers is too small, impact resistance tends to decrease, and if it is too large, moldability tends to decrease.

The above copolymer (A), graft copolymer fB) and graft copolymer (C) are copolymer FA) 10 to 80
By weight, preferably 20-70% by weight and the total of graft copolymer fB) and graft copolymer fc) 90-20%
weight, preferably 80 to 30% by weight, and the ratio of graft copolymer (B) to graft copolymer (C) is 1/99 to 99/1. Preferably 10/90-95
15 to obtain a heat-resistant and impact-resistant thermoplastic resin composition according to the present invention. Copolymer (Nga 10
If it is less than 0 parts by weight, heat resistance will decrease, and if it exceeds 80 parts by weight, fluidity and impact resistance will decrease. In addition, the ratio of graft copolymer CB)/graft copolymer fc) is a weight ratio,
If it is less than 1/99, heat resistance tends to decrease;
If it exceeds 50%, impact resistance tends to decrease.

(Examples) The present invention will be described in more detail below using nine examples.

[Production of copolymer (A)]

Production Example 1 (Synthesis of copolymer (A-t)) 200 parts by weight of ion-exchanged water was charged into a reactor, the atmosphere was replaced with nitrogen, and the mixture was heated to 60°C, followed by 2 parts by weight of sodium lauryl sulfate and 0.0 parts by weight of t-dodenlumerbutane. Prepare 4 parts by weight, 1
The mixture was stirred for 0 minutes to emulsify t-dodecylmercaptan. Next, 0.15 parts by weight of potassium persulfate and 0.015 parts by weight of sodium sulfite were charged, and a monomer consisting of 20 parts by weight of N-phenylmaleimide, 60% by weight of α-methylstyrene, and 31% by weight of acrylonitrile was added. 100 parts by weight was continuously dropped over 3 hours at 60°C after the dropping was completed.
Polymerization was carried out at 80°C for 1 hour and at 80°C for 2 hours. After the polymerization was completed, the polymerization rate was determined using a gas chromatograph.

It was 98chi. Moreover, the weight average molecular weight (abbreviated as Mw) of this copolymer is measured by gel permeation chromatography and converted to standard polystyrene.

) was 120,000. This latex is referred to as copolymer (A-1).

Production Example 2 (Synthesis of Copolymer (A-2)) 200 parts by weight of ion-exchanged water was charged into a reactor, the atmosphere was replaced with nitrogen, and the mixture was heated to 60°C. Prepare the weight part, 1
The mixture was stirred for 0 minutes to emulsify t-dodecylmercaptan. Next, 0.14 parts by weight of potassium persulfate and sulfite)
Incorporating 0.028 parts by weight of IJum, 10 parts by weight of a monomer consisting of 41 parts by weight of N-phenylmaleimide, 28 parts by weight of α-methylstyrene, and 31 parts by weight of methyl methacrylate.
0 parts by weight was continuously added dropwise over 3 hours, and after the completion of 2 drops, polymerization was carried out at 60°C for 1 hour and at 80°C for 2 hours. The obtained copolymer had an Mw of 120,000 and a polymerization rate of 98. This latex is referred to as copolymer (A-2).

Production Example 3 (Synthesis of Copolymer (A-3)) The procedure of Production Example 2 was followed except that methyl acrylate was used instead of methyl methacrylate.

A copolymer (A-3) was obtained. The obtained copolymer had an Mw of 120,000 and a polymerization rate of 98.

Production Example 4 (Synthesis of copolymer (A-4)) N-phenylmaleimide 41 was adjusted to 29% by weight, α
- Copolymer (A-4) was obtained in the same manner as in Production Example 2, except that methylnuthylene 28% by weight was changed to 20% by weight and methyl methacrylate 31% by weight was changed to 51% by weight. The obtained copolymer had an Mw of 120,000 and a polymerization rate of 98.

Production Example 5 (Synthesis of Copolymer (A-5)) The procedure of Production Example 2 was followed except that t-dodecylmercaptan was dissolved in the monomer and added dropwise, and copolymer (A-5) was produced.
I got it. The obtained copolymer had an Mw of 120,022 and a polymerization rate of 98.

Production Example 6 (Synthesis of copolymer (A-6')) N-phenylmaleimide 41 was adjusted to 50% by weight, α
- Copolymer (A-6) was obtained by simply following Production Example 2 except that methyl styrene 28 weight percent was changed to 40 weight percent and methyl methacrylate 31 weight percent was changed to 10 weight percent. The obtained copolymer had a Mw of 130,009 and a polymerization rate of 99.
It was Chi.

Production Example 7 (Synthesis of copolymer (A, -7)) N-phenylmaleimide 41 was adjusted to 30% by weight, α
- A copolymer (A-7) was obtained in accordance with Production Example 2 except that 28% by weight of methylstyrene was changed to 10% by weight and 31% by weight of methyl methacrylate was changed to 60% by weight. The polymerization rate was 96.

[Manufacture of rubber latex]

Production Example 8 In a reactor purged with nitrogen, 240 parts by weight of ion-exchanged water, 1.0 parts by weight of potassium oleate, 1 part of polybutadiene latex 30M (solid content), 70 parts by weight of butyl acrylate, 1.4 parts by weight of triallyl isocyanurate (parts by weight, 0.04 parts by weight of potassium persulfate, and 0.04 parts by weight of potassium persulfate).
004 parts by weight was added, the temperature was raised after nitrogen substitution, and the temperature was raised to 60 to 65°C.
After polymerization was carried out for 4 hours, the polymerization was stopped by cooling. The polymerization rate determined from the solid content of the latex at this time was 67%. This is called rubber latex (D).

[Graft copolymer (production of Bl)]

Production Example 9 (Synthesis of graft copolymer (B-1'l)) In a reactor were placed 200 parts by weight of ion-exchanged water, 5 parts by weight of rubber latex fDl as a solid content (including unreacted monomers), and 70 parts by weight of α-methylstyrene. Heavy!: H, 95 parts by weight of a monomer mixture consisting of 30% by weight of acrylonitrile and 0.8 parts by weight of t-dodecylmercaptan were charged, and after purging with nitrogen, 1 part by weight of sodium phonate and persulfuric acid were added to dodecylbenzene 7S. Potassium 0
．． 15 parts by weight were added and polymerized at 60°C for 3 hours and at 90°C for 2 hours. After the polymerization was completed, the polymerization rate was determined by gas chromatography and was found to be 98%. Also.

The Mw of the acetone soluble portion of this polymer was 98,000.

Production Example 10 (Synthesis of graft copolymer (B-2)) 70% by weight of α-methylstyrene [4] and 30% by weight of acrylonitrile,
α-methylstyrene 60% by weight, acrylonitrile 20%
A graft copolymer (B-2) was obtained in the same manner as in Production Example 9 except that the weight was 9% by weight and the methyl methacrylate was 20% by weight.

The polymerization rate was 98%.

[Production of graft copolymer (C)]

Production Example 11 (Synthesis of Graft Copolymer (C-1)) 240 parts by weight of ion-exchanged water, 1.0 parts by weight of potassium oleate, and 0.0 parts by weight of sodium formaldehyde sulfoxylate were placed in a reaction vessel.
14 parts by weight, 160 parts by weight of rubber latex CD (including solid content and unreacted monomers), 28 parts by weight of styrene, 12 parts by weight of acrylonitrile, 0.14 parts by weight of cumene hydroperoxide, and 0 parts by weight of t-dodecyl mercaptan.
．． A 16-layer polymer was added, the temperature was raised after purging with nitrogen, and polymerization was carried out at 65°C for 6 hours and at 90°C for 2 hours. The polymerization rate was calculated from the solid content of the latex after polymerization and was found to be 95%. This latex is referred to as a graft copolymer (C-1). The Mw of the acetone soluble portion was 140,000.

Production Example 12 (Synthesis of Graft Copolymer (C-2)) Instead of rubber latex fDl, 9 reactions were carried out in Production Example 8 until the polymerization rate was 90, and at this point the temperature was raised to 90°C, and the polymerization was further carried out for 2 hours. The procedure was as in Production Example 11 except that a rubber latex obtained by the reaction until the polymerization rate reached 98 was used. The obtained latex was mixed with a graft copolymer (C-2
). The polymerization rate was 96%, and the graft copolymer (C-
The Mw of the acetone soluble component in 2) was 140,000.

Production Example 13 (Synthesis of Graft Copolymer (C-3)) The procedure of Production Example 11 was repeated except that the rubber latex (Dl was changed to butadiene rubber (manufactured by Sumitomo Naugatac, trade name 5N-800, latex)). Ta.

The obtained latex was used as a graft copolymer (C-3'). The polymerization rate was 96%, and the graft copolymer (C-3)
The Mw of the acetone soluble portion was 130,000.

Production Example 14 (Synthesis of Graft Copolymer (C-4)) Same as Production Example 11 except that the rubber latex obtained without using butadiene rubber in Production Example 8 was used instead of rubber latex (D). I went alone. The obtained latex was used as a graft copolymer (C-4). The polymerization rate was 97%.

In the above, in order to determine the polymerization rate by gas chromatography, a portion of the latex is sampled.

This was added to dimethylformamide and dissolved.

It was determined from the amount that was subjected to gas chromatography analysis and compared with a calibration curve.

The polymerization rate from the solid content of the latex was determined by taking a portion of the latex, heating it to volatilize the remaining monomers and water to determine the solid content (weight 4), and using this value (al) using the 9th equation.

However, the nonvolatile components are those that do not volatilize during the charging composition and include resins, emulsifiers, polymerization initiators, and the like.

Examples 1 to 10 and Comparative Examples 1 to 3 The obtained latexes of copolymer (3), graft copolymer (B), and graft copolymer (C) were mixed in the formulations shown in Table 1. Next, the coagulated water was removed with IJ alum and dried.

The obtained resin powder was pelletized using an extruder and then molded using an injection molding machine. Table 1 shows the results of measuring the physical properties of the molded product.

As can be seen from Table 1, Comparative Example 1 using copolymer (A-5) as copolymer (A) has low heat resistance and impact resistance, and cannot be put to practical use. Comparative Example 2 in which copolymer (A-6) was used as copolymer (A) had extremely low impact resistance and fluidity, and could not be put to practical use.

Furthermore, Comparative Example 3 in which copolymer (k-7> was used as the copolymer (Al) had extremely low heat resistance and could not be put to practical use.

Further, Example 8 in which the graft copolymer (C-2) was used as the graft copolymer (C) had excellent heat resistance and fluidity, but showed a tendency to be slightly inferior in impact resistance (effect of the invention). The thermoplastic resin composition according to the invention is characterized in that the graft copolymers (graft copolymers (B) and (C)) and the N-substituted maleimide copolymer (copolymer (At)) are well compatible with each other. Therefore, the composition has excellent heat resistance, impact resistance, and fluidity.

Claims (1)

[Claims] 1. 10 to 60% by weight of N-arylmaleimide, 16 to 65% by weight of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic ester to an aqueous solution previously emulsified by adding a chain transfer agent and an emulsifier. A method for producing an N-arylmaleimide copolymer, which comprises adding a monomer containing 60 to 15% by weight of a methacrylic acid ester and a polymerization initiator to carry out a copolymerization reaction. 2. (A) N obtained by the production method according to claim 1
- arylmaleimide copolymer, (B) a monomer mixture containing 50 to 85% by weight of an aromatic vinyl compound and 15 to 50% by weight of a vinyl cyanide compound in the presence of 1 to 15 parts by weight of a rubbery polymer; In the presence of a graft copolymer obtained by polymerizing 85 to 99 parts by weight and 30 to 80 parts by weight of (C) rubbery polymer, 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyanide compound. contains a graft copolymer obtained by polymerizing 70 to 20 parts by weight of a monomer mixture containing 10 to 80 parts by weight of component (A) and 10 to 80 parts by weight of component (B).
The total of component ) and component (C) is 90 to 20% by weight, and the ratio of component (B)/component (C) is 1/99 to 9 by weight.
A heat-resistant and impact-resistant thermoplastic resin composition having a ratio of 9/1. 3. The heat-resistant and impact-resistant thermoplastic resin composition according to claim 2, wherein the rubbery polymer is diene rubber, ethylene-propylene rubber and/or acrylic rubber. 4. Rubbery polymer contains 0.1 to 20% by weight of polyfunctional monomer
, a polymerization in which 50 to 99.9% by weight of an acrylic ester having an alkyl group having a carbon number of 1 to 13 and 0 to 30% by weight of another vinyl compound copolymerizable with this are blended so that the total amount is 100% by weight. A rubbery resin composition obtained by polymerizing 95 to 60 parts by weight of a monomer in the presence of 5 to 40 parts by weight of a diene polymer, and stopping the polymerization when the polymerization rate is in the range of 50 to 93% by weight. The heat-resistant and impact-resistant thermoplastic resin composition according to claim 2. 5. The heat-resistant and impact-resistant thermoplastic resin composition according to claim 4, wherein the polyfunctional monomer is triallyl isocyanurate and/or triallyl cyanurate.