JPH0798883B2 - Resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a heat-resistant resin composition having excellent moldability and solvent resistance, and more specifically, from methyl methacrylate and a specific type of N-substituted maleimide. A copolymer obtained by polymerizing a monomer mixture consisting of, and a molding processability and solvent resistance consisting of an alkyl acrylate or a graft copolymer containing an alkyl acrylate and a rubber component of 1,3-butadiene. The present invention relates to a heat resistant resin composition having excellent properties.

[Problems to be solved with conventional technology]

As a method for obtaining a thermoplastic resin excellent in heat resistance and impact resistance, a graft copolymer obtained by graft copolymerizing styrene or acrylonitrile with a diene rubber has
-Method of mixing a terpolymer consisting of methylstyrene, methyl methacrylate and acrylonitrile (JP-A-57
-70143) or a method of mixing a polycarbonate resin and a diene rubber (Japanese Patent Publication No. 38-15225). However, with these methods,
There is a problem that the flow processability is remarkably reduced, and a heat-resistant resin having moldability has not yet been developed.

Further, as another method for obtaining a heat resistant resin, for example, a method of copolymerizing methyl methacrylate, α-methylstyrene, styrene and maleic anhydride (JP-A-56-81322) and methacrylic acid and N-arylmaleimide A method of copolymerizing and (Japanese Patent Publication No. Sho 43-9753) is known,
Although the obtained copolymer has heat resistance, it has a low tensile elongation and therefore cracks during molding, resulting in poor productivity and problems in molding processability. In addition, the above-mentioned resin molded product has insufficient solvent resistance and may cause craze due to contact with the solvent.

[Means for solving problems]

An object of the present invention is to provide a heat resistant resin composition having excellent moldability and solvent resistance.

As a result of intensive studies to achieve the above object, the present inventors blended a copolymer containing methyl methacrylate and a specific N-substituted maleimide as a main component, and a specific graft copolymer. As a result, they have found that a heat-resistant resin composition having excellent moldability and solvent resistance can be obtained, and completed the present invention.

The resin composition according to the present invention has a methyl methacrylate content of 40 to 95.
%, N-cyclohexylmaleimide and / or N-alkylmaleimide having an alkyl group having 2 to 4 carbon atoms 5 to 35% by weight, vinyl aromatic monomer 0 to 25% by weight,
Copolymer [I] obtained by polymerizing a monomer mixture consisting of 0 to 10% by weight of another copolymerizable monomer 50 to 99% by weight
And 50% by weight of acrylic acid alkyl ester or acrylic acid alkyl ester and 1,3-butadiene monomer unit.
Graft copolymer obtained by polymerizing 10 to 1500 parts by weight of a monomer or monomer mixture containing 60% by weight or more of methyl methacrylate and / or styrene in the presence of 100 parts by weight of the elastic copolymer containing It is characterized in that it comprises 1 to 50% by weight of the combination [II].

The resin composition according to the present invention is characterized in that the solvent resistance is improved by the synergistic effect of the copolymer [I] of methyl methacrylate, vinyl aromatic compound and maleic anhydride and the graft copolymer [II]. It is in the point that it is possible to improve and to develop the characteristics that are well-balanced in moldability and heat resistance.

The copolymer [I] used in the present invention is methyl methacrylate.
40-95% by weight, N-cyclohexylmaleimide and /
Alternatively, it is composed of 5 to 35% by weight of an N-alkylmaleimide having an alkyl group having 2 to 4 carbon atoms, 0 to 25% by weight of a vinyl aromatic monomer, and 0 to 10% by weight of another copolymerizable monomer. It is a copolymer obtained by polymerizing a monomer mixture, and has the effect of mainly imparting heat resistance and fluidity to the final resin composition.

The proportion of each structural unit in the copolymer [I] is determined from the balance of heat resistance, weather resistance, polymerization rate, fluid processability of the copolymer [I], compatibility with the graft copolymer [II], and the like. However, if any of the monomer components is out of the above range, problems such as poor heat resistance and weather resistance and extremely deteriorated productivity occur.

More specifically, if the amount of methyl methacrylate is less than 40% by weight, the weather resistance and mechanical properties will be significantly deteriorated, and if it exceeds 95% by weight, the improvement in heat resistance will be small. The use of N-cyclohexylmaleimide and / or N-alkylmaleimide mainly improves the heat resistance. Satisfactory resins cannot be obtained with other N-substituted maleimides. For example, with N-phenylmaleimide, the resin obtained is colored, and with N-methylmaleimide, the water resistance decreases and the water absorption rate increases. It is not preferable to use an N-alkylmaleimide having an alkyl group having 5 or more carbon atoms, because the heat resistance improving effect is lowered. Among the N-alkylmaleimides used in the present invention, Nt-butylmaleimide is the best in consideration of the balance between water absorption and heat resistance.

The vinyl aromatic compound is not an essential component, but mainly N
Since it has the effect of improving the reactivity of the substituted maleimide and improving the physical properties of the final resin composition, it is preferably used in an amount of 25% by weight or less. In particular, in order to obtain higher heat resistance by copolymerizing a large amount of N-substituted maleimide, the combined use of a vinyl aromatic compound is particularly preferable. When a vinyl aromatic compound is used in combination, the ratio β / α of the number of moles (β) of the vinyl aromatic compound to the number of moles (α) of the N-substituted maleimide is preferably 0.2 to 5, and the ratio of 0.5 to 2 is More preferable.

As a preferable example of the vinyl aromatic compound, styrene,
Vinyltoluene and α-methylstyrene,
These may be used alone or in combination of two or more.

If necessary, 10% by weight or less of another copolymerizable monomer may be added as the fourth component. Examples of such a monomer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate, butyl methacrylate, and vinyl acetate.

The blending ratio of the copolymer [I] is 50 to 99% by weight, more preferably 60 to 90% by weight, and 50% by weight to the total resin composition.
If it is less than 100% by weight, heat resistance and fluid processability are poor, and if it exceeds 99% by weight, moldability tends to be poor.

The copolymer [I] is obtained by subjecting the above-mentioned monomer mixture to a radical polymerization initiator by suspension polymerization, bulk polymerization, solution polymerization, etc.
It can be produced by a commonly used polymerization method.

The graft copolymer [II] used in the present invention has an effect of imparting molding processability to the resin composition, and comprises an alkyl acrylate or an alkyl acrylate and 1,3-
It is composed of a graft copolymer containing 50% by weight or more of a butadiene monomer unit as a rubber component.

The graft copolymer [II] of the present invention can be prepared by, for example, an emulsion polymerization method, in the first step, the above-mentioned acrylic acid alkyl ester or a mixture of an acrylic acid alkyl ester and 1,3-butadiene, and if necessary, By copolymerizing a monomer mixture containing another copolymerizable vinyl monomer and a crosslinkable monomer to obtain an elastic copolymer, which is then preferably mixed with methacrylic acid in the presence of the elastic copolymer. It can be obtained by sequentially graft-polymerizing methyl ester and / or styrene and another copolymerizable vinyl monomer in one step or in two or more steps. The elastic copolymer is required to contain 50% by weight or more of polymerized alkyl acrylate unit or alkyl acrylate unit and 1,3-butadiene unit in its structure.

The total content of acrylic acid alkyl ester units or alkyl acid alkyl ester units and 1,3-butadiene units is 5
If it is less than 0% by weight, the moldability is poor, which is not preferable.

As the acrylic acid alkyl ester that can be used here,
It is an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and among them, butyl acrylate, 2-ethylhexyl acrylate and the like are particularly preferable. In obtaining the elastic copolymer, less than 50% by weight of another copolymerizable vinyl monomer can be copolymerized. As the other copolymerizable vinyl-based monomer used here, methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable. A cross-linking agent can be used in obtaining an elastic copolymer by polymerizing the acrylic acid alkyl ester or a mixture thereof with 1,3-butadiene. In particular, when the acrylic acid alkyl ester is the main component, crosslinking is preferred. The crosslinkable monomer used is not particularly limited. Preferably ethylene glycol dimethacrylate, ethylene glycol diacrylate,
1,3-butylene dimethacrylate, 1,4-butanediol diacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, allyl sorbate, diallyl maleate, Trimethylolpropane triacrylate, allyl cinnamate, etc. are mentioned, and these can be used individually or in combination.

The amount of the cross-linking agent used as necessary is 0.1 to 10% by weight.
Is the range.

It is known to graft-polymerize a monomer having a high glass transition temperature in the presence of an elastic copolymer, but in the case of the present invention, the compatibility with the copolymer [1] is improved, and From the viewpoint of improving the gloss, fluidity and mechanical properties of the resin composition, it is particularly preferable to graft-polymerize methyl methacrylate or styrene. Other copolymerizable vinyl-based monomers that are optionally used in the graft polymerization include methacrylic acid alkyl esters such as ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, acrylic acid. Methyl, ethyl acrylate,
Acrylic alkyl esters such as butyl acrylate and 2-ethylhexyl acrylate, styrene and its derivatives, acrylonitrile, methacrylic acid, acrylic acid,
Examples thereof include itaconic acid, maleic acid, fumaric acid, vinyltoluene, and the like, and preferable examples include acrylic acid alkyl esters such as methyl acrylate and ethyl acrylate. The amount of these other copolymerizable vinyl-based monomers is not particularly limited depending on the kind of the graft copolymer, but is less than 40% by weight in the grafting monomer.

In the method for producing the graft copolymer [II] of the present invention,
It is not necessary for the first step and the second step or more to have a homogeneous composition in each step, and it is possible to change the composition within a composition range that does not impair the object of the present invention.

In the resin composition obtained by dispersing the graft copolymer [II] used in the present invention in the copolymer [I], particles of the graft copolymer are used in order to balance appearance characteristics and molding processability. Diameter 0.015 to 0.45 μm, especially 0.05 to 0.35
It is preferably in the range of μm.

Preferred examples of the graft copolymer [II] constituting the composition of the present invention include (1) 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of another copolymerizable vinyl monomer, and In the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing a monomer mixture consisting of 0.1 to 10% by weight of a polymerizable crosslinkable monomer, methyl methacrylate and / or 60 to 100% by weight of styrene and A graft copolymer obtained by polymerizing 10 to 1,000 parts by weight of a monomer or a mixture thereof with 0 to 40% by weight of another vinylic monomer copolymerizable therewith, (2) alkyl acrylate Ester 50 to 99.9% by weight, other copolymerizable vinyl-based monomer 0 to 40% by weight and other copolymerizable vinyl-based monomer 0 to 40% by weight, and copolymerizable crosslinkable monomer 0.1 to Existence of 100 parts by weight of an elastic copolymer obtained by polymerizing a 10% by weight monomer mixture. Under the present circumstances, a monomer or a mixture thereof comprising 60 to 100% by weight of methyl methacrylate and 0 to 40% by weight of another vinyl monomer copolymerizable therewith.
Graft copolymer obtained by polymerizing 10 to 1,500 parts by weight in at least two stages in any composition and ratio within the above range, and (3) 1,3-butadiene 1 to 95% by weight, alkyl acrylate 100 parts by weight of an elastic copolymer obtained by polymerizing a monomer mixture comprising 99 to 5% by weight of an ester and 0 to 20% by weight of another copolymerizable vinyl monomer and / or a crosslinkable monomer. In the presence of 70% methyl methacrylate and / or styrene
Examples thereof include a graft copolymer obtained by polymerizing 10 to 1,000 parts by weight of a monomer consisting of 100% by weight and 30 to 0% by weight of another copolymerizable monomer or a mixture thereof.

The blending amount of the graft copolymer [II] is 1 in the total resin composition.
-50% by weight, more preferably 10-40% by weight. If it is less than 1% by weight, the moldability is poor, and if it exceeds 50% by weight, the heat resistance is lowered.

The composition of the present invention is selected from other resins [III] depending on the purpose of use, for example, methacrylic resin, polycarbonate resin, AS resin, methyl methacrylate-styrene copolymer, polystyrene, polyester, nylon. At least one resin can be added up to 50% by weight. Further, a stabilizer, a lubricant, a plasticizer, a face wash, an ultraviolet absorber and the like can be added if necessary.

The composition of the present invention is prepared by mixing the copolymer [I], the graft copolymer [II] and other additives with a V-type blender, a Henschel mixer or the like, and using a screw type extruder or the like.
It is preferably produced by melt mixing in the temperature range of to 300 ° C.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples.
Parts in the examples are parts by weight, and% is% by weight.

The evaluations in the examples were performed using the following methods.

(1) Molding workability Under the following molding conditions, 10 shot molding was performed, and it was evaluated by how many normal products could be molded.

Molding conditions: Injection molding machine: V-17-65 type screw type automatic injection molding machine manufactured by Japan Steel Works, Ltd. Injection molding conditions: Cylinder temperature 240 ° C, cycle 60 seconds,
Mold temperature 50 ° C., injection pressure 700 kg / cm ₂ mold ... ASTM D 638-77a, Type 4 (2) solvent resistance sheet thickness 2 mm, width 25 mm, by molding a specimen of length 110 mm, the specimen A stress of 4000 psi is applied to the fulcrum, and the fulcrum is wetted with isopropyl alcohol.
Measure the time until a crack occurs.

(3) HDT (℃) Heat distortion temperature, measured by ASTM D648.

(4) MRF (g) Melt Flow Rate, ASTM D123
Measured with 8-52T. (Number of g in 10 minutes under load of 230 kg at 230 ° C) (5) Tensile elongation (%) Measured by ASTM D638.

(6) Total Light Transmittance and Haze Value A sample having a plate thickness of 2 mm was molded and measured according to ASTM D-1003.

Production of Copolymer [I] Copolymer [I-1] Using a pressure resistant polymerization kettle having an internal volume of 50 l, methyl methacrylate 68
Parts, 2 parts of methyl acrylate, 8 parts of α-methylstyrene,
Styrene 5 parts, N-cyclohexylmaleimide 17 parts, n
-Octyl mercaptan 0.11 part, azobisisobutyronitrile 0.35 part, UV absorber Tinuvin-p (manufactured by Ciba Geigy) 0.05 part, mold release agent stearic acid monoglyceride 0.
18 kg of a monomer mixture consisting of 1 part was charged in 27 kg of deionized water containing 90 g of sodium sulfate as a dispersant, 3 g of a copolymer consisting of a sodium salt of 2-sulfoethylmethacrylic acid, and 200 rpm. Nitrogen was bubbled through the system with stirring to remove oxygen in the system, heated to 80 ° C for 4 hours to carry out suspension polymerization, heated to 120 ° C and held for 15 minutes, then cooled, washed with water and dried to obtain an average particle size. A 0.25 mm beaded polymer was obtained.

Copolymer [I-2] Except that the composition of the monomer mixture was changed as follows, [I-
Copolymerization was performed in exactly the same manner as 1] to obtain a bead-shaped polymer.

Methyl methacrylate 75 parts, α-methylstyrene 10 parts, Nt-butylmaleimide 15 parts, n-octyl mercaptan 0.08 parts, azobisisobutyronitrile 0.5 parts, stearic acid monoglide 0.1 parts.

Copolymer [I-3] Copolymerization was carried out in the same manner as in [I-1] except that the composition of the monomer mixture was changed as follows and the polymerization time was 2 hours to obtain a bead-shaped polymer. .

Methyl methacrylate 85 parts, N-cyclohexyl maleimide 15 parts, azobisisobutyronitrile 0.1 part n-octyl mercaptan 0.25 part, stearic acid monoglyceride 0.1 part.

Copolymer [I-4] A bead-like polymer was obtained by copolymerization in the same manner as in [I-3] except that N-cyclohexylmaleimide was used as N-ethylmaleimide.

Copolymer [I-5] Except that the composition of the monomer mixture was changed as follows, [I-
Copolymerization was performed in exactly the same manner as 1] to obtain a bead-shaped polymer.

Methyl methacrylate 84 parts, α-methyl styrene 5 parts, styrene 1 part, N-cyclohexyl maleimide 10 parts, n-octyl mercaptan 0.15 parts, azobisisobutyronitrile 0.30 parts, stearyl stearate 0.10 parts, tinuvin 320 (Ciba Geigy) 0.20 parts.

Copolymer [I-6] (Comparative Example) Except that the composition of the monomer mixture was changed as follows, [I-
Copolymerization was performed in exactly the same manner as in 3) to obtain a polymer.

Methyl methacrylate 50 parts, N-cyclohexyl maleimide 50 parts, azobisisobutyronitrile 0.1 part, n-octyl mercaptan 0.25 part.

Production of Graft Copolymer [II] Graft Copolymer [II-1] (a) First Step Deionized water (hereinafter, abbreviated as “DW”) 32 kg, Nonsar® TK-1 (NOF Corporation) In the following, abbreviated as "TK-1") 200 g, ferrous sulfate 0.01 g, ethylenediaminetetraacetic acid disodium 0.5 g, and sodium formaldehyde sulfoxynate 25 g are charged into a 50 l SUS reaction vessel, butyl acrylate 98.7 g, Allyl methacrylate 1.0%, tertiary isobutyl hydroperoxide (hereinafter referred to as "t-B
Abbreviated as "H") 3 kg of a 0.3% mixture was charged, oxygen in the reaction vessel was replaced with nitrogen, and the mixture was polymerized at 70 ° C for 2 hours with stirring, and then 1 kg of a 5% aqueous solution of TK-1 was added. Thereafter, 7 kg of a mixture having the same composition as that previously polymerized was continuously added over 2 hours, and the polymerization was continued for another 2 hours after the addition was completed.

(B) Second step 1 kg of 5% TK-1 aqueous solution was added to the same reaction vessel where the first step was completed, and 96.7% methyl methacrylate and 3% methyl acrylate were added under the same conditions of 70 ° C as the first step. , Normal dodecyl mercaptan (hereinafter abbreviated as "n-Dm") 0.3
%, T-BH 0.2%, 6 kg was continuously added over 90 minutes, and the polymerization was further continued for 1 hour after the addition was completed.

The latex particle size calculated by the absorbance method was 0.12 μm.

The latex of the obtained graft copolymer [II] has a viscosity of 0.25
% Sulfuric acid water, coagulated under the conditions of latex / water = 1/2 and 50 ° C. 30 times the DW of the obtained slurry white polymer
After washing with water, dehydration, and drying at 75 ° C. for 36 hours.

Graft copolymer [II-2] (a) First stage DW 42 kg, TK-1, 300 g, ferrous sulfate 0.01 g, ethylenediaminetetraacetic acid disodium 0.5 g, sodium formaldehyde sulfoxynate 25 g reaction made of 50 l SUS In the container, butyl acrylate 98.7%, allyl methacrylate 1.
After charging 3 kg of a mixture of 0% and t-BH 0.3% and replacing oxygen in the reaction vessel with nitrogen, polymerization was carried out at 70 ° C. for 2 hours under stirring, and then 1 kg of a 5% aqueous solution of TK-1 was added. . Thereafter, 7 kg of a mixture having the same composition as that previously polymerized was continuously added over 2 hours, and the polymerization was continued for another 2 hours after the addition was completed.

(B) Second step 0.5 kg of 5% TK-1 aqueous solution was added to the same reaction vessel where the first step was completed, and 59% methyl methacrylate and 40% butyl acrylate were added under the same conditions of 70 ° C as the first step. , 2 kg of a mixture of allyl methacrylate 1.0%, n-Dm 0.3%, t-BH 0.2%
Add continuously for 30 minutes, then add 1 more after addition
Polymerization was continued for an hour.

(C) Third step 1 kg of 5% TK-1 aqueous solution was added to the same reaction vessel where the second step was completed, and under the same conditions of 70 ° C. as in the first step, 97.7% methyl methacrylate and 2% methyl acrylate. , N-Dm0.3
%, T-BH 0.2%, 6 kg was continuously added over 90 minutes, and the polymerization was further continued for 1 hour after the addition was completed.

The latex particle size calculated by the absorbance method was 0.14 μm.

The latex of the obtained graft copolymer [II] has a viscosity of 0.25
% Sulfuric acid water, coagulated under the conditions of latex / water = 1/2 and 50 ° C. 30 times the DW of the obtained slurry white polymer
It was washed with water, dehydrated and dried at 75 ° C. for 36 hours.

Graft copolymer [II-3] (a) First step Butyl acrylate 4kg 1,3-Butadiene 6kg Diisopropylbenzene hydroperoxide 20g Beef tallow fatty acid potassium 200〃 Sodium N-lauroyl sarcosinate 100〃 Sodium pyrophosphate 50〃 Ferrous sulphate 0.5〃 Dextrose 30〃 DW 20kg Of the substances with the above composition ratios, except for 1,3-butadiene, replace the oxygen contained in it with nitrogen,
The state was set such that the polymerization reaction was not substantially inhibited. Then, all the substances were charged into a 40 l autoclave and polymerized at 50 ° C. The polymerization was almost completed in 9 hours, the conversion rate was 97%, and the particle size was 0.1.
A rubber latex of 30 μm was obtained.

(B) Second step DW 9 kg, sodium formaldehyde sulfoxylate 20 g, and sodium N-lauroyl sarcosinate 50 g were added to a polymerization reaction vessel containing a latex containing 10 kg of polymer solid content of the rubbery copolymer. The internal temperature was raised to 75 ° C., and the following raw materials were continuously added for 90 minutes for polymerization.

Methyl methacrylate 3800 g Styrene 350 g Normal octyl mercaptan 6.75 g Cumene hydroperoxide 16 g After the addition was completed, the polymerization was continued for another 60 minutes. The conversion of methyl methacrylate was almost 100%.

Styrenated phenol 58 was added to the obtained polymer latex.
g, dilauryl thiodipropionate 44g, triphenyl phosphite 58g, added at 0.25% at 50 ° C
The mixture was coagulated with latex / water = 1/2 with the sulfuric acid water of, and kept at 85 ° C. for 5 minutes.

The slurry polymer obtained is washed and dehydrated, and the polymer is dried at 65 ° C.
After drying for an hour, a white powder was obtained.

Graft copolymer [II-4] To a 10 l separable flask equipped with a stirring blade and a condenser, 5.7 kg of DW, 25 g of sodium dioctylsulfosuccinate as an emulsifier, and 1.2 g of Rongalit as a reducing agent were added and uniformly dissolved. As a first step, methyl methacrylate 191g,
Add a mixture of 19 g of styrene, 0.8 g of allyl methacrylate and 0.2 g of diisopropylbenzene hydroperoxide, and add 80
Polymerized at ° C. After the polymerization was completed, a mixture of butyl acrylate 1251 g, styrene 374 g, diethylene glycol acrylate 20 g, allyl methacrylate 13.0 g, and diisopropylbenzene hydroperoxide 1.6 g was added dropwise over 70 minutes as the second step, and then 50 minutes later. The polymerization was completed. Then, as the third stage, 385 g of methyl methacrylate, styrene 11
5 g, diisopropylbenzene hydroperoxide 0.45
A mixture of 1.8 g of g and n-octyl mercaptan was added and the polymerization was completed in 60 minutes. The obtained latex was put into a 0.5% aluminum chloride solution to coagulate the polymer, washed with warm water, and dried to obtain a polymer.

Graft copolymer [II-5] First, the following raw materials (a) and (b) were charged into a stainless steel reaction vessel having an internal volume of 50 l in respective proportions,
After blowing nitrogen under stirring to make it substantially unaffected by oxygen, raise the temperature to 65 ° C. and add the following raw materials (C),
The temperature was further raised to 80 ° C. and the polymerization was continued for 90 minutes. Thereafter, 5 kg (50 parts) of the raw material having the same composition as shown in (b) was continuously added for 90 minutes, and polymerization was further performed for 120 minutes to obtain an acrylic elastic body.

(A) DW 30 kg N-acyl sarcosinate sodium salt 100 g Boric acid 100 g Sodium carbonate 10 g (b) Butyl acrylate 3.9 kg Styrene 1.1 kg Allyl methacrylate 50 g Cumene hydroperoxide (CHP) 15 g (C) DW 500 g Rongalit 50 g Obtained latex Had a particle size of about 0.08 μm and a polymerization rate of 98% or more.

DW 500 g and N-acyl sarcosinic acid sodium salt 25 g were added to the same reactor in which a latex containing solid content 10 kg (100 parts) of the above latex was added and stirred, and then 5.5 kg of methyl methacrylate while maintaining the temperature at 80 ° C., Styrene 0.48k
A monomer mixture consisting of g, normal octyl mercaptan 25 g, and LHP 24 g was continuously added dropwise for 90 minutes, and then the polymerization was continued for 90 minutes. The polymerization rate of the monomer was 99% or more.
25 kg of this latex was charged in a stainless steel container with 50 kg of 1.0% sulfuric acid water, heated to 80 ° C., and continuously added over 20 minutes. Thereafter, the temperature was raised to 90 ° C., the temperature was maintained for 5 minutes, cooling, washing and drying were performed to obtain a white powder polymer.

Examples 1 to 14 and Comparative Examples 1 to 5 Copolymer [I] and graft copolymer [II] were blended in a Henschel mixer in the types and proportions shown in Table 1, and a cylinder temperature of 200 was obtained using a screw extruder. The mixture was melt-kneaded and pelletized at 270 ° C and a die temperature of 260 ° C. Physical properties were evaluated using the pellets. The obtained results are shown in Tables 1 and 2.

Upon blending, 0.1 part of Mark LA-57 and 0.2 part of Mark-P (both manufactured by ADEKA ARGUS CORPORATION) were added as stabilizers to 100 parts of the resin. In the table, Acrypet VH (trademark) manufactured by Mitsubishi Rayon Co., Ltd. was used as the methacrylic resin.

[Effects of the Invention] As described in detail above, the resin composition of the present invention is
It is particularly useful for vehicle parts, illuminator parts and the like because it has excellent moldability, solvent resistance and heat resistance.

Claims (5)

[Claims] 1. Methyl methacrylate 40 to 95% by weight, N-cyclohexylmaleimide and / or N-alkylmaleimide having an alkyl group having 2 to 4 carbon atoms 5 to 35% by weight, vinyl aromatic monomer 0 to 25. 50% to 99% by weight of a copolymer [I] obtained by polymerizing a monomer mixture consisting of 0% to 10% by weight of another copolymerizable monomer and an alkyl acrylate or alkyl acrylate. Esters and 1,3
-Monomers or monomer mixtures containing 60% by weight or more of methyl methacrylate and / or styrene in the presence of 100 parts by weight of an elastic copolymer comprising 50% by weight or more of butadiene monomer units; A resin composition comprising 1 to 50% by weight of a graft copolymer [II] obtained by polymerizing parts by weight. 2. The resin composition according to claim 1, wherein the vinyl aromatic monomer is at least one monomer selected from styrene and α-methylstyrene. 3. A graft copolymer [II] comprising 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of another copolymerizable vinyl monomer, and 0.1 to 0.1% of a copolymerizable crosslinkable monomer. ~ 1
In the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing a monomer mixture consisting of 0% by weight, 60 to 100% by weight of methyl methacrylate and / or styrene and another vinyl type copolymerizable therewith The resin composition according to claim 1, which is obtained by polymerizing 10 to 1,000 parts by weight of a monomer comprising 0 to 40% by weight of a monomer or a mixture thereof. 4. A graft copolymer [II] comprising 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of another copolymerizable vinyl monomer, and 0.1 to 0.1% of a copolymerizable crosslinkable monomer. ~ 1
In the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing a monomer mixture consisting of 0% by weight, 50-100% by weight of methyl methacrylate and / or styrene and another vinyl type copolymerizable therewith A monomer obtained by polymerizing 10 to 1,500 parts by weight of a monomer or a mixture thereof, which comprises 0 to 50% by weight of the monomer, in at least two stages and in any composition and ratio within the above range. The resin composition according to claim 1. 5. A graft copolymer [II] comprising 1,3-butadiene in an amount of 1 to 95% by weight and an acrylic acid alkyl ester in an amount of 99 to 5
In the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing a monomer mixture consisting of 0 to 20% by weight of other copolymerizable vinyl monomers and / or crosslinkable monomers. Obtained by polymerizing 10 to 1,000 parts by weight of a monomer or a mixture thereof, which comprises 70 to 100% by weight of methyl methacrylate and / or styrene and 0 to 30% by weight of another copolymerizable vinyl monomer. The resin composition according to claim 1, which is