JP2699945B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing an N-arylmaleimide-based copolymer and having excellent heat resistance and impact resistance.

[0002]

2. Description of the Related Art Rubber-modified thermoplastic resins obtained by graft-polymerizing acrylonitrile and styrene onto rubber include those known as so-called ABS resins and AAS resins. These resins are widely used today because of their excellent properties such as processability, mechanical strength, surface gloss, and chemical resistance. However, it is hard to say that it has sufficient heat resistance depending on the field of use. As for the method of improving the heat resistance, it is generally known that part or all of styrene is used in place of α-methylstyrene. However, even with this method, there is a limit to the improvement in heat resistance, and it is not always satisfactory in fields requiring heat resistance, such as parts of automobiles and light electric appliances. On the other hand, a copolymer of a vinyl monomer such as styrene and an N-substituted maleimide has a high thermal deformation temperature and a high thermal decomposition temperature (Polymer Transactions, Vol. 36, No. 7, p. 447). 1979), poor mechanical properties such as impact resistance [Journal of Polymer Science (J. Polyme
r Sci.) 36, 241, 1959].

[0003] Therefore, it has been proposed to obtain a copolymer having excellent impact resistance and heat resistance by reacting N-substituted maleimide, olefinically unsaturated nitrile and aromatic vinyl in the presence of a rubber component. (GB 3,721,724). However, performing a polymerization reaction of maleimide or the like in the presence of a rubber component induces a remarkable reduction in the polymerization rate. Also, the amount of the copolymer that does not bond with the rubber component increases. Further, the molecular weight tends to be low. Therefore, it has been difficult to achieve both heat resistance and impact resistance. In addition, a thermoplastic resin composition has been proposed in which a copolymer containing an N-substituted maleimide is blended with a graft copolymer based on a rubber-like polymer (Japanese Patent Publication No. Sho 4).
6-34103, JP-A-53-117050). Although the thermoplastic resin composition proposed here exhibits excellent impact resistance and heat resistance, it is hardly sufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a thermoplastic resin composition having significantly improved impact resistance and heat resistance.

[0005]

According to the present invention, there is provided (A) an aqueous solution preliminarily emulsified by adding a chain transfer agent and an emulsifier to 10 to 60% by weight of an N-arylmaleimide,
6 to 65% by weight and a vinyl cyanide compound, an acrylic ester and / or a methacrylic ester 60 to 15
In the presence of an N-arylmaleimide-based copolymer obtained by performing a copolymerization reaction by adding a monomer containing a% by weight and a polymerization initiator, and (B) 1 to 15 polymerized parts of a rubbery polymer, Monomer mixture 85 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 30 to 80 parts by weight of a graft copolymer obtained by polymerizing -99 parts by weight and (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
It contains a graft copolymer obtained by polymerizing 0 parts by weight, the component (A) is 10 to 80% by weight, and the total of the components (B) and (C) is 90 to 20% by weight. ,
The ratio of component (B) / component (C) is 1/99 to 99 by weight.
The present invention relates to a thermoplastic resin composition which is blended so as to be / 1.

The present invention relates to a heat-resistant and impact-resistant thermoplastic resin composition wherein the rubbery polymer is a diene rubber, an ethylene-propylene rubber and / or an acrylic rubber. In the present invention, in the thermoplastic resin composition, the rubber-like polymer is a polyfunctional monomer in an amount of 0.1 to 20% by weight and an acrylate having an alkyl group having 1 to 13 carbon atoms in an amount of 50 to 99.9. Polymerizable monomer 95 in which 0% to 30% by weight of another vinyl compound copolymerizable therewith is blended so that the total amount is 100% by weight.
To 60 parts by weight in the presence of 5 to 40 parts by weight of a diene polymer, and a thermoplastic resin which is a rubbery resin composition obtained by terminating the polymerization at a conversion of 50 to 93% by weight. Composition. The present invention further relates to a thermoplastic resin composition wherein the polyfunctional monomer in the thermoplastic resin composition is triallyl isocyanurate and / or triallyl cyanurate.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a method for producing an N-arylmaleimide copolymer and the obtained copolymer [ie, a copolymer of component (A) (hereinafter referred to as "copolymer (A)")] explain.

The N-arylmaleimide as a copolymer component is used in an amount of 10 to 60% by weight, preferably 12 to 55% by weight. When the N-arylmaleimide is less than 10% by weight, the heat resistance of a thermoplastic resin composition (hereinafter, simply referred to as a resin composition) obtained by blending the copolymer (A) is reduced, and 60% by weight is reduced. If it exceeds, the fluidity and impact resistance of the resin composition decrease. The aromatic vinyl compound is used in an amount of 16 to 65% by weight, preferably 18 to 60% by weight. If the amount of the aromatic vinyl compound is less than 16% by weight, the impact resistance of the resin composition is reduced, and if it is more than 65% by weight, the heat resistance is reduced. Vinyl cyanide compounds, acrylates and / or
Alternatively, the methacrylate is used in an amount of 60 to 15% by weight, preferably 55 to 18% by weight. These monomers are 1
If it is less than 5% by weight, the fluidity and 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 another copolymerizable monomer may be used in an amount of 30% by weight or less based on all monomers. The above monomers are adjusted so as to be 100% by weight in total.

[0009] The copolymer (A) is obtained by emulsion polymerization. A chain transfer agent is added to adjust the molecular weight of the copolymer (A) and improve the moldability. The chain transfer agent is generally used by dissolving in a monomer during polymerization. However, in the present invention, a chain transfer agent is previously present together with an emulsifier, an emulsified aqueous solution is produced, and then a monomer and a polymerization initiator are added to carry out a copolymerization reaction. Thereby, heat resistance and impact resistance are improved. This is because the monomer moves to the emulsifier micelle incorporating the chain transfer agent and the polymerization proceeds, so that the concentration of the chain transfer agent with respect to the monomer changes and the molecular weight distribution broadens, resulting in compatibility with the graft copolymer. Is to improve. For this reason, in the present invention, other polymerization methods such as solution polymerization, suspension polymerization and bulk polymerization cannot be used.

Examples of the chain transfer agent include n-dodecyl mercaptan, t-dodecyl mercaptan, xanthogen disulfide, terpene, tetrahydronaphthalene and the like.
The chain transfer agent is preferably used in an amount of 0.01 to 3% by weight based on the monomer. As an emulsifier, an anionic, cationic or nonionic surfactant can be used. In particular, anionic surfactants are preferable, and specific examples thereof include sodium lauryl sulfate, potassium oleate, disproportionated potassium rosinate, sodium dioctylsulfosuccinate, and sodium dodecylbenzenesulfonate. These are preferably used in an amount of 0.5 to 7% by weight based on the monomer. Also, in order to improve the emulsion stability, sodium,
Sulfates, chlorides, carbonates and the like of alkali metals such as potassium may be used. In the polymerization, the polymerization initiators used include potassium persulfate, sodium persulfate, persulfates such as ammonium persulfate, water-soluble peroxides such as cumene hydroperoxide, and compounds forming a redox system with these. And the like. These are usually used in an amount of 0.05 to 5% by weight based on the monomers.

The aryl group of the N-arylmaleimide includes a phenyl group, a 4-diphenyl group, a 1-naphthyl group, a mono- or dimethylphenyl group, a 2,6-diethylphenyl group, a mono- or dihalogenated phenyl group,
4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 4-n-butylphenyl group, 2-methyl-4-n-butylphenyl group, 4-benzylphenyl group, 2,3- or 4-methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 2-methoxy-5-bromophenyl group, 2,5-dimethoxy-4-chlorophenyl group, 2,3- or 4-ethoxyphenyl group, 2,5 -Diethoxyphenyl group, 4-phenoxyphenyl group, 4-
Methoxycarbonylphenyl group, 4-cyanophenyl group, 2,3- or 4-nitrophenyl group, 2,3-,
And a 2,4-, 2,5- or 4,3-methylchlorophenyl group. Particularly, those having a phenyl group and an o-methylphenyl group are preferable.

Examples of the aromatic vinyl compound used for producing the copolymer (A) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, chlorostyrene, and dichlorostyrene. , Bromostyrene, dibromostyrene, α-ethylstyrene, methyl-α-methylstyrene, dimethylstyrene,
And vinyl naphthalene. Styrene and α
-Methylstyrene is preferred.

Examples of the vinyl cyanide compound used in the production of the copolymer (A) include acrylonitrile and methacrylonitrile, and examples of the acrylate and methacrylate include methyl ester of acrylic acid or methacrylic acid; There are ethyl ester, butyl ester, hexyl ester and the like, and methyl acrylate and methyl methacrylate are particularly preferable. The weight average molecular weight of the copolymer (A) is preferably in the range of 50,000 to 300,000. If it is less than 50,000, the impact resistance tends to decrease, and if it exceeds 300,000, the fluidity tends to decrease. The weight average molecular weight in the present invention is a value measured by gel permeation chromatography and calculated in terms of standard polystyrene.

Next, the thermoplastic resin composition of the present invention containing the copolymer (A) as one component (hereinafter, simply referred to as a resin composition)
Will be described in detail. The graft copolymer (hereinafter, referred to as “graft copolymer (B)”) as the component (B) of the resin composition will be described. The graft copolymer (B) is a graft copolymer obtained by polymerizing a monomer in the presence of a small amount of a rubbery polymer. ) And a later-described component (C), by blending in a specific amount with the graft copolymer, to facilitate the compatibility thereof and improve the impact resistance without lowering the heat resistance of the resin composition. it can.

The rubbery polymer used for producing the graft polymer (B) is used in an amount of 1 to 15% by weight, preferably 3 to 10% by weight. Further, the monomer to be graft-polymerized is
It is used in an amount of 99 to 85% by weight, preferably 97 to 90% by weight. If the amount of the rubbery polymer is less than 1% by weight, the impact resistance of the resin composition is reduced. If the amount exceeds 15% by weight, the ability to make the graft copolymer of the copolymers (A) and (C) compatible with each other is insufficient. And the heat resistance of the resin composition decreases.

The monomer to be graft-polymerized contains 50 to 85% by weight, preferably 65 to 75% by weight of an aromatic vinyl compound and 50 to 15% by weight, preferably 35 to 25% by weight of a vinyl cyanide compound. If necessary, other copolymerizable monomers such as methacrylic acid esters, acrylic acid esters, and vinyl acetate are preferably contained in an amount of preferably 30% by weight or less, more preferably 25% by weight or less, based on all monomers. You may go out. The above monomers are adjusted so as to be 100% by weight in total. If the amount of the aromatic vinyl compound is too small or the amount of the vinyl cyanide compound is too large, the fluidity tends to decrease. If the amount of the aromatic vinyl compound is too large or the amount of the vinyl cyanide compound is too small, the impact resistance tends to decrease. On the other hand, if the amount of other copolymerizable monomers is too large, the impact resistance tends to decrease.

The rubbery polymer includes polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polyisoprene, poly-2,3
-Obtained by synthesizing acrylic rubber in the presence of diene-based copolymers such as dimethylbutadiene, polypiperylene, polychloroprene, ethylene-propylene-diene copolymer, ethylene-propylene rubber, acrylic rubber, and diene-based copolymer. There is a composite rubber or the like. The acrylic rubber is
It is obtained by copolymerizing a polyfunctional monomer, an acrylate ester having an alkyl group having 1 to 13 carbon atoms, and another monomer copolymerizable therewith, if necessary.

Examples of the polyfunctional monomer include polyvalent vinyl compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, divinylbenzene, diallyl phthalate, dicyclopentadiene acrylate, and dicyclopentadiene methacrylate; Examples thereof include polyvalent allyl compounds such as nurate, triallyl isocyanurate and diallyl phthalate. Of these, triallyl isocyanurate and triallyl cyanurate are particularly preferred. The polyfunctional monomer is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 1% by weight, based on all monomers.
It is used within the range of 0% by weight. If the amount is less than 0.1% by weight, the degree of crosslinking is insufficient and the impact resistance and the appearance of the molded article tend to be inferior. Examples of the acrylate having an alkyl group having 1 to 13 carbon atoms include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Of these, butyl acrylate is particularly preferable. This acrylate is based on all monomers
Preferably 50 to 99.9% by weight, particularly preferably 65%.
９９99.5% by weight. If it is less than 50% by weight, the impact resistance tends to decrease. Other monomers copolymerizable with the acrylic acid ester include styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, methacrylic acid alkyl esters (methyl ester, butyl ester, etc.), and the like. 0-30% by weight
Preferably, it is used in the range of 0 to 25% by weight. If it exceeds 30% by weight, sufficient impact resistance cannot be obtained.

The above-mentioned composite rubber is prepared by adding the above-mentioned polyfunctional monomer and carbon number 1 to 13 in the presence of the above-mentioned diene polymer rubber.
And a polymerizable monomer obtained by blending an acrylate having an alkyl group as described above and another monomer copolymerizable therewith, if necessary. The diene polymer and the polymerizable monomer preferably have a former / latter ratio of 5 to 5 by weight.
/ 95 to 40/60, particularly preferably 20/80 to 35
/ 65 used. If the ratio is less than 5/95, the impact resistance and the appearance of the molded article tend to be inferior.
If it exceeds 30, the weather resistance tends to be poor. Further, the composite rubber is a rubber-like resin composition obtained by terminating the polymerization at a polymerization rate of the polymerizable monomer of preferably 50 to 93% by weight, particularly preferably 55 to 75% by weight. Is particularly preferred. Use of a graft copolymer obtained by using such a rubber-like resin composition is preferable in terms of impact resistance and heat resistance. That is, if the polymerization rate exceeds 93% by weight, the effect of improving impact resistance tends to decrease, and if it is less than 50% by weight, heat resistance tends to decrease. The composition of the polymerizable monomer used for producing the composite rubber is the same as that for producing the acrylic rubber.

The polymerization for producing the acrylic rubber and the composite rubber can be performed by a known emulsion polymerization method. In this emulsion polymerization, polymerization initiators include potassium persulfate, sodium persulfate, persulfates such as ammonium persulfate, water-soluble peroxides such as cumene hydroperoxide, and combinations of these with compounds that form a redox system. As the emulsifier used, an anionic, cationic, or nonionic surfactant can be used, and an anionic surfactant is particularly preferable.

The aromatic vinyl compound used for the production of the graft copolymer (B) is the same as that used for the production of the copolymer (A). Among acrylonitrile, methacrylonitrile, etc., among other copolymerizable monomers used as needed, methacrylic acid esters and acrylic acid esters are used in the production of copolymer (A). The same can be used.

Next, the graft copolymer of the component (C) (hereinafter referred to as "graft copolymer (C)") will be described. The proportion of the rubbery polymer in the graft copolymer (C) is larger than that in the graft copolymer (B), and is used for improving the impact resistance of the thermoplastic resin composition according to the present invention. The rubbery polymer used for the production of the graft copolymer (C) and the monomer to be graft-polymerized are each 30 to
80% by weight, preferably 40-70% by weight and 70-2%
0% by weight, preferably 60 to 30% by weight is used. If the amount of the rubbery polymer is less than 30% by weight, the impact resistance is reduced, and
If it exceeds 0% by weight, the heat resistance decreases.

The monomer to be graft-polymerized contains 60 to 80% by weight, preferably 65 to 78% by weight of an aromatic vinyl compound and 20 to 40% by weight, preferably 20 to 35% by weight of a vinyl cyanide compound. According to the above, other copolymerizable monomers such as methacrylic acid ester, acrylic acid ester, vinyl acetate, etc.
% By weight, particularly preferably 25% by weight or less. The above monomers are adjusted so that the total amount is 100% by weight. Too little aromatic vinyl compound,
If the amount of the vinyl cyanide compound is too large, the fluidity tends to decrease. If the amount of the aromatic vinyl compound is too large or the amount of the vinyl cyanide compound is too small, the impact resistance tends to decrease.

The above rubbery polymer, aromatic vinyl compound,
Those used as the vinyl cyanide compound and other copolymerizable monomers are the same as those in the graft copolymer (B), and the same ones that can be preferably used are also the same. It is preferred that both the graft copolymers (B) and (C) have a weight average molecular weight of 50,000 to 300,000 in their acetone-soluble component. If the weight average molecular weight of the acetone-soluble component of these graft copolymers is too small, the impact resistance tends to decrease, while if too large, the moldability tends to decrease.

The copolymer (A), the graft copolymer (B) and the graft copolymer (C) are 10 to 80% by weight, preferably 20 to 70% by weight of the copolymer (A).
And graft copolymer (B) and graft copolymer (C)
90 to 20% by weight, preferably 80 to 30% by weight
Wherein the ratio of graft copolymer (B) / graft copolymer (C) is 1/99 to 99/1, preferably 10/90 to 95/5 by weight, and A heat-resistant impact-resistant thermoplastic resin composition according to the present invention is obtained. When the amount of the copolymer (A) is less than 10% by weight, the heat resistance decreases, and
If it exceeds 0% by weight, the fluidity and the impact resistance are reduced. Further, graft copolymer (B) / graft copolymer (C)
If the ratio is less than 1/99, the heat resistance tends to decrease, and if it exceeds 99/1, the impact resistance tends to decrease.

[0026]

[Production of copolymer (A)]

Production Example 1 (Synthesis of Copolymer (A-1))
After adding 00 parts by weight and heating to 60 ° C. after purging with nitrogen, 2 parts by weight of sodium lauryl sulfate and 0.4 part by weight of t-dodecyl mercaptan were charged and stirred for 10 minutes to emulsify t-dodecyl mercaptan. Next, 0.15 parts by weight of potassium persulfate and 0.015 parts by weight of sodium sulfite were charged, 20% by weight of N-phenylmaleimide, 60% by weight of α-methylstyrene, and 20% by weight of acrylonitrile.
Was continuously dropped over 3 hours, and after completion of the dropping, polymerization was carried out at 60 ° C. for 1 hour and at 80 ° C. for 2 hours. After completion of the polymerization, the conversion was determined by gas chromatography to be 98%. The weight average molecular weight (abbreviated as Mw; measured by gel permeation chromatography, converted to standard polystyrene, hereinafter the same) of this copolymer was 120,000. This latex is referred to as a copolymer (A-1).

Production Example 2 (Synthesis of Copolymer (A-2))
After adding 00 parts by weight and heating to 60 ° C. after purging with nitrogen, 2 parts by weight of sodium lauryl sulfate and 0.5 part by weight of t-dodecylmercaptan were charged and stirred for 10 minutes to emulsify t-dodecylmercaptan. Next, 0.14 parts by weight of potassium persulfate and 0.028 parts by weight of sodium sulfite were charged, and 41% by weight of N-phenylmaleimide, 28% by weight of α-methylstyrene, and 31% by weight of methyl methacrylate 31 were used.
100 parts by weight of a monomer consisting of 100% by weight was continuously added dropwise over 3 hours.
Polymerized for hours. The obtained copolymer had an Mw of 120,000 and a polymerization rate of 98%. This latex is referred to as a copolymer (A-2).

Production Example 3 (Synthesis of copolymer (A-3)) Copolymer (A-3) was obtained in the same manner as in Production Example 2 except that methyl acrylate was used instead of methyl methacrylate. . The obtained copolymer had an Mw of 120,000 and a polymerization rate of 98%.

Production Example 4 (Synthesis of copolymer (A-4)) 41% by weight of N-phenylmaleimide was added to 29% by weight, 28% by weight of α-methylstyrene was added to 20% by weight, and 31% by weight of methyl methacrylate was added. Except having changed to 51 weight%, it carried out according to manufacture example 2, and obtained copolymer (A-4). The obtained copolymer had an Mw of 120,000 and a polymerization rate of 98%.

Production Example 5 (Synthesis of copolymer (A-5)) Copolymer (A-5) was prepared in the same manner as in Production Example 2 except that t-dodecylmercaptan was dissolved in a monomer and added dropwise. ) Got. The obtained copolymer had Mw of 120,000 and a polymerization rate of 98%.

Production Example 6 (Synthesis of Copolymer (A-6)) N-phenylmaleimide (41% by weight), α-methylstyrene (28% by weight), 40% by weight, and methyl methacrylate (31% by weight) A copolymer (A-6) was obtained in the same manner as in Production Example 2 except that the amount was changed to 10% by weight. The obtained copolymer had an Mw of 130,000 and a conversion of 99%.

Production Example 7 (Synthesis of Copolymer (A-7)) N-phenylmaleimide (41% by weight), α-methylstyrene (28% by weight), 10% by weight, and methyl methacrylate (31% by weight) A copolymer (A-7) was obtained in the same manner as in Production Example 2 except that the amount was changed to 60% by weight. The conversion was 96%.

Production of Rubber Latex Production Example 8 240 parts by weight of ion-exchanged water, 1.0 part by weight of potassium oleate, 30 parts by weight of polybutadiene latex (solid content), 70 parts by weight of butyl acrylate were placed in a nitrogen-purged reactor. , 1.4 parts by weight of triallyl isocyanurate, 0.04 parts by weight of potassium persulfate, and 0.04 parts by weight of sodium sulfite
After adding 04 parts by weight, the temperature was raised after purging with nitrogen, polymerization was carried out at 60 to 65 ° C for 4 hours, and then the polymerization was stopped by cooling. At this time, the polymerization rate determined from the solid content of the latex was 67%. This is designated as rubber latex (D).

[Production of Graft Copolymer (B)] Production Example 9 (Synthesis of Graft Copolymer (B-1)) In a reactor, 200 parts by weight of ion-exchanged water and rubber latex (D) were added as solid components. 5 parts by weight (including unreacted monomers), 95 parts by weight of a monomer mixture composed of 70% by weight of α-methylstyrene and 30% by weight of acrylonitrile, and 0.1 part of t-dodecyl mercaptan.
After charging 8 parts by weight and purging with nitrogen, 1 part by weight of sodium dodecylbenzenesulfonate and 0.1 part of potassium persulfate were added.
5 parts by weight were charged and polymerized at 60 ° C. for 3 hours and at 90 ° C. for 2 hours. After the completion of the polymerization, the conversion was determined by gas chromatography to be 98%. Further, Mw of the acetone-soluble component of this polymer was 98,000.

Production Example 10 (Synthesis of graft copolymer (B-2)) 70% by weight of α-methylstyrene and 30% by weight of acrylonitrile
-A graft copolymer (B-2) was obtained according to Production Example 9, except that 60% by weight of methylstyrene, 20% by weight of acrylonitrile and 20% by weight of methyl methacrylate were used. The conversion was 98%.

[Production of Graft Copolymer (C)] Production Example 11 (Synthesis of Graft Copolymer (C-1)) In a reaction vessel, 240 parts by weight of ion-exchanged water, 1.0 part by weight of potassium oleate, sodium Formaldehyde sulfoxylate 0.
14 parts by weight, rubber latex (D) 60 parts by weight (including solid content, unreacted monomer), styrene 28 parts by weight, acrylonitrile 12 parts by weight, cumene hydroperoxide 0.14 parts by weight, and t-dodecyl mercaptan 0.16 Parts by weight, and the temperature was raised after purging with nitrogen.
Polymerization was conducted at 90 ° C. for 2 hours. The degree of polymerization was calculated from the solid content of the latex after polymerization to be 95%. This latex is referred to as a graft copolymer (C-1). The Mw of the acetone-soluble component was 140,000.

Production Example 12 (Synthesis of Graft Copolymer (C-2)) Instead of rubber latex (D), the reaction was allowed to proceed to a polymerization rate of 90% in Production Example 8, at which point the temperature was raised to 90 ° C. The polymerization was carried out in the same manner as in Production Example 11 except that a rubber latex obtained by polymerizing for 2 hours and reacting until the conversion reached 98% was used. The obtained latex is graft copolymerized (C-2)
And The conversion was 96%, and the graft copolymer (C-
Mw of the acetone-soluble component in 2) was 140,000.

Production Example 13 (Synthesis of Graft Copolymer (C-3)) Production Example 11 except that the rubber latex (D) was changed to butadiene rubber (manufactured by Sumitomo Nogatack, trade name SN-800, latex). It went according to. The obtained latex was used as a graft copolymer (C-3). The polymerization rate was 96%, and Mw of the acetone-soluble portion of the graft copolymer (C-3) was 130,000.

Production Example 14 (Synthesis of Graft Copolymer (C-4)) Except that rubber latex obtained without using butadiene rubber in Production Example 8 was used instead of rubber latex (D). Performed according to Production Example 11. The obtained latex was used as a graft copolymer (C-4). The conversion was 97%.

In the above, in order to determine the polymerization rate by gas chromatography, a part of latex is collected, added to dimethylformamide and dissolved, subjected to gas chromatography analysis, and determined from the amount collated with the calibration curve. Was. The polymerization rate from the solid content of the latex was determined by taking a part of the latex and heating it to evaporate the remaining monomer and water to obtain the solid content (% by weight), and from this value (a), the following formula was used.

[0041]

(Equation 1) However, the non-volatile components are those which do not volatilize during the preparation and during the preparation, and include a resin, an emulsifier, a polymerization initiator and the like.

Examples 1 to 10 and Comparative Examples 1 to 3 The latexes of the obtained copolymer (A), graft copolymer (B) and graft copolymer (C) are shown in Tables 1 and 2.
Was mixed according to the formula shown in Table 1. Next, it was dehydrated and dried after coagulation with potassium alum. The obtained resin powder was pelletized by an extruder and further molded by an injection molding machine. Tables 1 and 2 show the measurement results of the physical properties of the molded article.

[0043]

[Table 1]

[0044]

[Table 2]

As can be seen from Tables 1 and 2, Comparative Example 1 using the copolymer (A-5) as the copolymer (A) has low heat resistance and impact resistance, and cannot be put to practical use. . Comparative Example 2 using the copolymer (A-6) as the copolymer (A) has extremely low impact resistance and fluidity, and cannot be put to practical use. Comparative Example 3 using the copolymer (A-7) as the copolymer (A) has a remarkably low heat resistance and cannot be put to practical use. In Example 8 using the graft copolymer (C-2) as the graft copolymer (C), the heat resistance and the fluidity were excellent, but the impact resistance tended to be slightly inferior.

[0046]

The thermoplastic resin composition according to any one of claims 1 to 4 comprises a graft copolymer (graft copolymers (B) and (C)) and an N-substituted maleimide-based copolymer (copolymer (A) )) Are well compatible, and the composition is excellent in heat resistance, impact resistance and fluidity.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 55/02 C08L 55/02 // C08F 2/24 C08F 2/24 Z 2/38 2/38 212/06 212/06 220/10 220/10 220/44 7824-4J 220/44 222/40 222/40 (72) Inventor Isamu Hattori 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Inside the plant (72) Inventor Hisashi Takagame 14 Goi south coast, Ichihara city, Chiba prefecture Hitachi Chemical Co., Ltd.In the Goi plant (72) Inventor Kiyotaka 14 bottom Goi south coast, Ichihara city, Chiba prefecture Hitachi Chemical Co., Ltd. Inside the Goi Plant (56) References JP-A-64-87651 (JP, A) JP-A-59-232138 (JP, A)

Claims (4)

(57) [Claims] 1. An aqueous solution emulsified in advance by adding a chain transfer agent and an emulsifier (A) to an aqueous solution of N-arylmaleimide 10 to 60.
A copolymerization reaction is carried out by adding a monomer containing 16% to 65% by weight of an aromatic vinyl compound, 16% to 65% by weight of an aromatic vinyl compound, and 60% to 15% by weight of a vinyl cyanide compound, an acrylate and / or a methacrylate, and a polymerization initiator. The aromatic vinyl compound 5 in the presence of 1 to 15 parts by weight of the rubbery polymer (B)
A graft copolymer obtained by polymerizing 85 to 99 parts by weight of a monomer mixture containing 0 to 85% by weight and 15 to 50% by weight of a vinyl cyanide compound; and (C) a rubbery polymer 3
In the presence of 0 to 80 parts by weight, the aromatic vinyl compound 60 to
80% by weight and 20 to 40% by weight of a vinyl cyanide compound
A graft copolymer obtained by polymerizing 70 to 20 parts by weight of a monomer mixture containing
0 to 80% by weight, and the total of the components (B) and (C) is 90%
A thermoplastic resin composition which is blended so that the ratio of component (B) / component (C) is 1/99 to 99/1 by weight. 2. The thermoplastic resin composition according to claim 1, wherein the rubbery polymer is a diene rubber, an ethylene-propylene rubber and / or an acrylic rubber. 3. The rubbery polymer according to claim 1, wherein the polyfunctional monomer is 0.1 to 0.1.
20% by weight, 50 to 99.9% by weight of an acrylic acid ester having an alkyl group having 1 to 13 carbon atoms and 0 to 30% by weight of another vinyl compound copolymerizable therewith are 100% by weight.
95 to 60 parts by weight of a polymerizable monomer blended so as to be 5% by weight in the presence of 5 to 40 parts by weight of a diene polymer, and the polymerization is stopped when the polymerization rate is in the range of 50 to 93% by weight. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a rubber-like resin composition obtained by the reaction. 4. The thermoplastic resin composition according to claim 3, wherein the polyfunctional monomer is triallyl isocyanurate and / or triallyl cyanurate.