JP2002047386A - Transparent and impact resistance acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an impact resistant acrylic or acrylic-aromatic vinyl resin composition having impact strength without hurting the original rigidity and transparency of the resins. SOLUTION: The acrylic aromatic resin composition which has transparency and impact resistance is consisting of 5-40 wt.% of a grafted copolymer obtained by polymerizing 60-15 pts.wt. of methyl methacrylate, butyl methacrylate and an aromatic monomer, a nitrile monomer, if necessary, to 40-85 pts.wt. diene rubber obtained by polymerizing 50-100 pts.wt. of a monomer of a conjugated diene, 50-0 pts.wt. of a copolymerizable vinyl monomer and 0-3 pts.wt. of a cross-linking monomer and 95-60 wt.% of an acrylic aromatic resin obtained by copolymerizing 45-100 pts.wt. of a methacrylic acid ester, 55-0 pts.wt. of an aromatic vinyl monomer and 0-20 pts.wt. of a vinyl monomer copolymerizable with these monomers to attain 100 pts.wt. in total.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin composition or an acrylic-aromatic vinyl copolymer resin composition, and more particularly, to an acrylic resin or acrylic-aromatic vinyl copolymer resin composition. The present invention relates to a resin composition having excellent balance of strength, transparency and processability, provided with impact resistance without impairing the transparency of the resin. As a field of application, it is suitable for molded articles requiring strength and transparency.

[0002]

2. Description of the Related Art As acrylic resins or acrylic-aromatic vinyl copolymer resins, those having various compositions are commercially available, but in general, their strength is not sufficient to meet market requirements. Therefore, USP 3,296,339,
As disclosed in JP-B-46-32748, those in which various rubbers are dissolved in monomers constituting a resin to increase the impact resistance by bulk polymerization or suspension polymerization, and JP-B-63-47745. JP-A-54-153884
The rubber-containing multilayer structure obtained by polymerizing butyl acrylate and butadiene as rubber components and emulsion polymerizing copolymerizable vinyl monomers and the like in the presence of them, as shown in Some are used as modifiers. However, in the former, the rubber content is restricted in terms of the solubility of the rubber, and therefore, the strength expression is not sufficient. In the latter case, it is necessary to reduce the addition amount of the impact modifier as small as possible in order not to impair the rigidity and transparency of the base resin. However, if an attempt is made to secure impact resistance using a conventional impact modifier, the amount of addition is increased, and it is difficult to maintain other qualities such as rigidity. In other words, if the amount of rubber is increased to a point where the strength can be secured, the rigidity, heat resistance, and transparency, which are the original characteristics, are reduced, and it is difficult to use practically. Therefore, if the impact resistance can be imparted without deteriorating the advantages of the base resin, it is expected that the resin can be used for various purposes.

[0003]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides an impact-resistant resin having an impact resistance without impairing the rigidity and transparency of an acrylic resin or an acrylic-aromatic vinyl resin. The present invention provides a hydrophilic acrylic or acrylic-aromatic vinyl resin composition.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned objects, that is, to impart impact resistance without impairing the excellent rigidity and transparency of an acrylic or acrylic-aromatic vinyl resin. Next, the inventors studied a graft copolymer and arrived at the present invention.

That is, the present invention relates to (A) (a1) 50 to 100% by weight of a conjugated diene monomer, (a2) 50 to 0% by weight of a vinyl monomer copolymerizable with a conjugated diene monomer, (a3) In the presence of 40 to 85 parts by weight of a diene rubber obtained by polymerizing 0 to 3% by weight of a crosslinkable monomer and 0 to 3% by weight of a chain transfer agent, (a4)
45 to 95% by weight of methyl methacrylate monomer, 5 to 50% by weight of butyl methacrylate monomer, 0 to 50% by weight of aromatic vinyl monomer and 0 to 20 of other vinyl monomers copolymerizable therewith. 60 to 15% by weight of a monomer mixture
5 to 40 parts by weight of a graft copolymer obtained by polymerizing parts by weight (the total amount of the diene rubber and 100 parts by weight) and (B) (b1) 45 to 100% by weight of a methacrylate monomer, b2) 55 to 0% by weight of an aromatic vinyl monomer and (b3)
95 to 60 parts by weight of an acrylic resin obtained by polymerizing 0 to 20% by weight of the other vinyl monomer copolymerizable therewith [100% by weight in total of (b1), (b2) and (b3)] [( A),
(B) 100 parts by weight in total) and a diene rubber having an average particle diameter of 500 to 300.
0% rubber particles, based on 100 parts by weight of the particles,
At least one unsaturated acid monomer of acrylic acid, methacrylic acid, itaconic acid, crotonic acid
% By weight, at least one of 1 to 12 carbon atoms in the alkyl group
5 to 30% by weight of at least one alkyl acrylate monomer, 20 to 80% by weight of at least one alkyl methacrylate monomer having 1 to 12 carbon atoms in an alkyl group, and other vinyl monomers copolymerizable therewith An average obtained by adding 0.1 to 15 parts by weight (as a solid content) of an acid group-containing latex obtained by polymerizing a monomer mixture consisting of 0 to 40% by weight (totaling 100% by weight) and coagulating and expanding. 2. A diene rubber having a particle size of 3500 to 20000%.
The present invention relates to the resin composition described in claim 2.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The diene rubber used in the present invention includes a conjugated diene monomer 50 to 100% by weight (hereinafter the same), a copolymerizable vinyl monomer 0 to 50%, a crosslinkable It is obtained by polymerizing 0 to 3% of a monomer and 0 to 3% of a chain transfer agent. Representative conjugated diene monomers include various butadiene-substituted products such as butadiene, isoprene and chloroprene. Examples of the copolymerizable vinyl monomer include vinyl monomers having an aromatic ring, such as styrene, vinyltoluene, α-methylstyrene, and the like.
Also, methacrylate compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Examples of vinyl cyanide include butyl methacrylate and the like, and acrylate compounds such as methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate. Examples of vinyl cyanide include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. In the field where transparency of a molded article is required, an acrylic (-aromatic vinyl) -based resin is intended for the refractive index of a graft copolymer obtained by polymerizing a vinyl monomer in the presence of the diene-based rubber. However, in the case of an acrylic (-aromatic vinyl) resin having a relatively high refractive index, an aromatic ring is used as a diene rubber from the viewpoint of adjusting the refractive index. A diene rubber containing a vinyl monomer unit having the same becomes practical. However, the target acrylic (-aromatic vinyl)
If the refractive index of the system resin is high and the refractive index of the diene rubber used is to match the value of the matrix, the ratio of vinyl monomer units having an aromatic ring increases, and the glass transition temperature of the copolymer rubber increases. As a result, the function as rubber may be reduced. In such a case, in the polymerization of the vinyl monomer copolymerized with the diene monomer constituting the diene rubber, a layer comprising the diene monomer, or a high concentration of the diene component It is advantageous to polymerize the diene rubber in multiple stages so as to contain a layer having For example, a monomer copolymerized with a diene monomer is separated and polymerized.First, a diene monomer or a system containing a high concentration of a diene monomer is polymerized, and in the presence thereof, The remaining monomers are polymerized to prepare a rubber having a layer with a low glass transition temperature, and if necessary, a known method, for example, after enrichment with hydrochloric acid, or a method of grafting while coagulating with a salt, or a resin From the viewpoint of further improving the impact resistance of the molded product of the composition, it is preferable to use a diene rubber having a large particle size by enlarging with a latex of an acid group-containing copolymer. It is also effective to carry out the polymerization order of the monomer to be copolymerized with the diene monomer in the reverse order to the above-mentioned order, and to enlarge later. These diene rubbers to be used are advantageously obtained by ordinary emulsion polymerization and have a particle size of 500 to 3
Å is preferred. Those having an average particle size of 500 ° or less tend to be difficult to obtain stably by ordinary emulsion polymerization, while those having an average particle size of 3000 ° or more have a problem in productivity because the polymerization time is long. Next, as a crosslinkable monomer that can be used for preparing such a diene rubber, a compound having two or more polymerizable functional groups in a molecule, for example, allyl methacrylate, divinylbenzene, diallyl phthalate, etc. Is mentioned. Examples of usable chain transfer agents include n-dodecyl mercaptan and t-dodecyl mercaptan. These may be used as needed, but are preferably used in an amount of 0 to 3% by weight, and if it exceeds 3% by weight, the impact resistance of the final product is deteriorated, which is not suitable. Next, in order to carry out the present invention particularly effectively, it is preferable to use a latex of an acid group-containing copolymer to make a large particle diene rubber and carry out the process. Regarding the composition of the acid group-containing latex and the method for enlarging the latex, see JP-A-166-217, JP-A-58-6110.
2, Open 8-59704, Open 8-157502, etc. However, as a result of diligent studies on a method for enlarging an acid group-containing latex that is advantageous to the present invention, the acid group-containing latex contains at least one unsaturated acid 5 selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and crotonic acid. ~
25% (% by weight, the same applies hereinafter), and the number of carbon atoms of the alkyl group is 1
At least one alkyl acrylate of
0%, 20 to 80% of at least one alkyl methacrylate having 1 to 12 carbon atoms in the alkyl group, and 0 to 40% of a vinyl monomer copolymerizable therewith (a total of 100%). %) Is advantageous. That is, as the unsaturated acid used, acrylic acid, methacrylic acid or a mixture thereof is preferable from a practical point of view, and the proportion of the unsaturated acid is 5 to 25%. If it is less than 5%, the hypertrophic ability is poor, and if it is more than 25%, coagulum formation and latex thickening occur, which is not suitable for industrial production. Examples of the alkyl acrylate used include acrylates having an alkyl group having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Particularly, an alkyl group having 1 to 8 carbon atoms is preferable. These can be used alone or in combination of two or more. The proportion of alkyl acrylate is 5 to 30%, preferably 8 to 28%. If it is less than 5%, the hypertrophic capacity is reduced, and if it is 30% or more, the coagulum during the production of the acid group-containing latex increases. As the alkyl methacrylate to be used, esters of methacrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms are used. Among them, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate are used. Etc. In particular, the alkyl group has 1 to 1 carbon atoms.
8 is preferred. These can be used alone or in combination of two or more. The proportion of the alkyl methacrylate is 20 to 80%, preferably 25 to 75%, and outside this range, the hypertrophic ability is reduced. Examples of vinyl monomers copolymerizable therewith include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, allyl methacrylate, and polyethylene glycol dimethacrylate. And a monomer having two or more polymerizable functional groups in the molecule. These are used alone or in combination of two or more. The ratio of these copolymerizable vinyl monomers is 0 to 40%, preferably 0 to 35%. If it exceeds 40%, the hypertrophic ability decreases. If necessary, a chain transfer agent such as n-dodecyl mercaptan or t-dodecyl mercaptan may be used in an amount of 0 to 3%. Incidentally, the particle diameter of the acid group-containing latex is preferably 700 to 1500 °,
At 700 ° C or less, the expanding ability is weak, and at 2000 ° C or more, the rubber particle size distribution of the expanded rubber tends to be unhypertrophied, resulting in quality deterioration. Next, when the diene rubber is enlarged to an average particle diameter of 3500 to 20000 ° by the above-mentioned acid group-containing latex, the acid group-containing latex is a rubber polymer 100
It is preferable to use 0.1 to 15 parts (in terms of solid content) with respect to parts (parts by weight, hereinafter the same). If the amount is less than 0.1 part, the amount of the unexpanded diene rubber increases, and it is impossible to enlarge the desired average particle size. Thus, if it exceeds 15 parts, it is difficult to control the average particle size. And the physical properties of the final product tend to be reduced.
Further, it is practical to use 0.5 to 5 parts from the viewpoint that the amount of unexpanded diene rubber is small and the average particle diameter of enlarged particles is relatively uniform and can be stably obtained. Further, in order to sufficiently maintain the effect of imparting impact strength, the average particle size is 350
Preferably, it is 0 to 20000 °, more preferably 3500 to 9000 °. Next, in order to prepare a rubber-containing graft product of interest using the diene rubber obtained in this manner, an unexpanded diene rubber, or more preferably, an average particle diameter enlarged with an acid group-containing latex. 3500-200
(A4) in the presence of 40 to 85 parts of an enlarged diene rubber of 00Å
Methyl methacrylate 45-95%, butyl methacrylate 5-50%, aromatic vinyl 0-50%
And other vinyl compounds 0 to 2 copolymerizable therewith.
It is obtained by polymerizing 60 to 15 parts of a monomer consisting of 0% (the total amount with the diene rubber is 100 parts). Incidentally, as a graft composition used here, it is advantageous from the viewpoint of strength development to include a soft component, but as such a soft component, alkyl methacrylate is used rather than alkyl acrylate. The present inventors have found that these are more advantageous in terms of strength, transparency and rigidity, and have reached the present invention.

When transparency is required here,
The refractive index of the obtained graft and the target acrylic (-
The difference in the refractive index of the (aromatic vinyl) resin is within 0.003,
It is preferable to set the value so as to be preferably within 0.0004. If there is a difference exceeding 0.003, only a substantially opaque one is obtained. Of course, the refractive index referred to here is a comparison with actual measurement values, but as a guideline for prescription setting, it is necessary to set the rubber composition and graft composition by calculation from the refractive index values according to the literature such as the polymer handbook. Realistic. As a matter of course, it is advantageous for the graft formulation to be as close as possible to the composition of the matrix and to introduce a soft component, so that the refractive index of the impact-resistant reinforcing agent matches the refractive index of the target matrix. Therefore, the range of the composition that can be arbitrarily changed is limited.

Next, the acrylic (-aromatic vinyl) resin used in the present invention includes 45 to 100% of a methacrylate monomer and 55 to 0% of an aromatic vinyl monomer.
It is a resin obtained by polymerizing 0 to 20% of other copolymerizable vinyl monomers. Here, typical examples of the aromatic vinyl monomer used as a component of the acryl-aromatic vinyl resin include styrene, vinyl toluene, α
-Methylstyrene, and examples of the methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Other vinyl monomers copolymerizable therewith include acrylate monomers such as methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate. Further, vinyl cyanide such as acrylonitrile and methacrylonitrile may be used in some cases. These can be used alone or in combination of two or more.

Next, in order to produce the impact-resistant acrylic (-aromatic vinyl) resin composition, which is the object of the present invention, the aforementioned diene rubber or the previously described diene rubber is treated with an acid group. -Containing latex graft copolymer obtained by emulsion-polymerizing a vinyl monomer with a large-particle-diameter enlarged rubber obtained by adding and laminating a latex-containing latex, and an acrylic (-aromatic vinyl) -based A mixture is obtained by melt-kneading 95 to 60 parts of the resin. At that time, various stabilizers, lubricants, pigments, fillers and the like can be used alone or in combination of two or more, so long as the advantage of the acrylic (-aromatic vinyl) resin is not impaired. A molded product can be manufactured by extrusion molding, injection molding, or the like using the melt-kneaded product obtained in this manner. Hereinafter, the composition of the present invention will be described with reference to Examples, but the present invention is not limited thereto.

[0010]

EXAMPLES Example 1 (1) Polymerization of butadiene-styrene rubber 200 parts of water and 0.2 parts of potassium persulfate were placed in a 100-liter pressure-resistant polymerization machine, stirred, and sufficiently replaced with nitrogen to remove oxygen. After that, 1 part of sodium oleate, 2 parts by weight of sodium rosinate, 73 parts of butadiene and 27 parts of styrene were charged into the system, and the temperature was raised to 60 ° C. to initiate polymerization. The polymerization was completed in 12 hours. 96% polymerization conversion,
The average particle size of the rubber latex was 860 °. In addition, the measurement of the average particle diameter was performed using Nikkiso Co., Ltd. Microtrac particle size analyzer model 9230UPA including the following measurements.

(2) Polymerization of acid group-containing latex 200 parts of water and 0.5 part of sodium dioctylsulfosuccinate were placed in an 8 liter polymerization machine, and the temperature was raised to 70 ° C. while stirring and flowing nitrogen. 0.3 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate,
After adding 0.01 part of ethylenediaminetetraacetic acid, and after several minutes, 2 parts of butyl methacrylate, 23 parts of butyl acrylate, 2 parts of methacrylic acid, 0.125 t-dodecyl mercaptan
, A mixture of 0.025 parts of cumene hydroperoxide was continuously dropped at a rate of 20 parts / hour using a metering pump. After the addition of the above mixture, further 58 parts of butyl methacrylate, 2 parts of butyl acrylate, 13 parts of methacrylic acid,
A mixture of 0.3 part of t-dodecyl mercaptan and 0.08 part of cumene hydroperoxide was similarly added dropwise at 20 parts / hour, and the polymerization was terminated 1.5 hours after the completion of the addition. The polymerization conversion was 99.7%, the average particle size was 1050 °, the concentration was 33%, and the pH was 2.8.

(3) Preparation of enlarged butadiene-styrene rubber The butadiene produced in (1) was placed in an 8 liter polymerization machine.
100 parts (solid content) of styrene rubber and 20 parts of water were added, and the temperature was raised to 60 ° C. while flowing nitrogen under stirring. 0.1 parts of sodium hydroxide and 2.2 parts (solid content) of the acid group-containing latex polymerized in (2) were added, and stirring was continued for 1 hour to enlarge the butadiene-styrene rubber. Water 200
And 0.4 parts of sodium dodecylbenzenesulfonate, and further stirred for 30 minutes to complete the hypertrophy. A butadiene-styrene enlarged rubber having an average particle size of 5500 ° was obtained.

(4) Graft copolymerization of butadiene-styrene enlarged rubber 70 parts (solid content) of the butadiene-styrene enlarged rubber of (3) were charged into an 8 liter polymerization machine, and 6 parts were introduced under nitrogen flow and stirring.
Heat to 0 ° C. 0.18 parts of sodium formaldehyde sulfoxylate, 0.001 parts of ferrous sulfate and 0.004 parts of ethylenediaminetetraacetic acid are added, 12.7 parts of methyl methacrylate, 3.8 parts of butyl methacrylate, 13.5 parts of styrene. To 30 parts of a mixture of the monomers consisting of 30 parts by weight, 0.2 part of t-butyl hydroperoxide was added, and the mixture was continuously dropped into the polymerization machine at a rate of 10 parts / hour using a metering pump. During the addition of the monomer mixture, 0.2 parts of sodium dioctyl sulfosuccinate was added to the polymerization machine three times every one hour in order to maintain the stability of the latex. After the completion of the addition of the monomer mixture, the mixture was further stirred for 1 hour to complete the polymerization. The polymerization conversion was 96%, and the average particle size of the latex was 6,400 °. After adding 0.5 parts by weight of dilauryl-3,3'-thiodipropionate (DLTP) and 2,6-di-t-butyl-4-methylphenol (BHT) to the latex, calcium chloride 5 A part by weight was added for salting out, heated at 90 ° C., dehydrated and dried to obtain a dry powder. The refractive index was 1.535.

(5) Polymerization of acrylic-aromatic vinyl resin An acrylic-aromatic vinyl resin composed of styrene and methyl methacrylate was obtained by suspension polymerization as follows. 1
200 parts of water, 0.02 parts of sodium dodecylbenzenesulfonate and 1 part of calcium phosphate were put into a 00 liter polymerization machine, and after sufficient deoxidation, the temperature was raised to 85 ° C and styrene 45
, 55 parts of methyl methacrylate and 0.8 parts of benzoyl peroxide were added all at once, and the mixture was stirred for 5 hours to complete the reaction. It was further dehydrated and dried to obtain an aromatic resin. The refractive index was 1.535.

(6) Production of Impact-Resistant Acrylic-Aromatic Vinyl Resin Composition 75 parts of the acryl-aromatic vinyl resin produced in (5), 25 parts of the graft copolymer produced in (4) and A hindered phenol-based stabilizer (0.1 part) is mixed and melt-kneaded using an HW-40-28 extruder manufactured by Tabata Machine Co., Ltd. to form pellets of an impact-resistant acrylic-aromatic vinyl resin composition. did. Further, the pellets were molded into a 150 mm × 100 mm × 3 mm plate for measuring transparency and a piece for measuring Izod impact strength using a 160 MSP10 injection molding machine manufactured by Mitsubishi Heavy Industries, Ltd.

(7) Evaluation of Physical Properties of Impact-Resistant Acrylic-Aromatic Vinyl Resin Composition A molded article of the impact-resistant acrylic-aromatic resin composition produced in (6) was subjected to an impact resistance of ASTM D-256. Was measured for the Izod impact strength, and the transparency was measured for the haze according to JIS K 6714. Table 1 shows the results.

COMPARATIVE EXAMPLE 1 16.5 parts of methyl methacrylate and 13.5 parts of styrene were polymerized in the presence of the enlarged rubber made of the acid group-containing latex of Example 1 to obtain a graft. Then, it carried out similarly to Example 1 and set it as Comparative Example 1. The graft composition was set by calculation so that the refractive index would be the same as in the examples.

Comparative Example 2 Methyl methacrylate 13 parts, butyl acrylate 3 parts, and styrene 14 parts were polymerized in the presence of the enlarged rubber of the acid group-containing latex of Example 1 in the presence thereof to obtain a graft. Thereafter, the same operation as in Example 1 was performed, and Comparative Example 2 was performed.
And The graft composition was set by calculation so that the refractive index would be the same as in the examples.

[0019]

[Table 1] Example 2 Using the rubber obtained by polymerization of (1) butadiene-styrene rubber in Example 1, a graft was obtained by the following method. That is,
70 parts of the unexpanded butadiene-styrene rubber described above and 2.5 parts of sodium sulfate were added, and 0.18 parts of sodium formaldehyde sulfoxylate and 0.001 of ferrous sulfate were added.
Parts, 0.0004 parts of ethylenediaminetetraacetic acid,
The temperature was raised to ° C. To a mixture of 30 parts of a monomer mixture consisting of 12.7 parts of methyl methacrylate, 3.8 parts of butyl methacrylate and 13.5 parts of styrene, 0.2 part of t-butyl hydroperoxide was added. It was dropped into the polymerization machine continuously at a rate of parts / hour. During the addition of the monomer mixture, 0.2 parts by weight of sodium dioctyl sulfosuccinate was added to the polymerization machine three times every one hour in order to maintain the stability of the latex. After the completion of the addition of the monomer mixture, the mixture was further stirred for 1 hour to complete the polymerization. The polymerization conversion was 96%, and the average particle size of the latex was 2,300 °. Dilauryl-3,3'-thiodipropionate (DLTP) for latex
And 0.5 parts of 2,6-di-t-butyl-4-methylphenol (BHT) were added thereto, and 5 parts of calcium chloride was added for salting out. Thus, a dried powder was obtained. The refractive index was 1.5356. After that, it carried out similarly to Example 1. The results are shown in Table 2.

Comparative Example 3 Example 2 was repeated except that the graft composition was changed to 16.5 parts of methyl methacrylate and 13.5 parts of styrene.
Was performed in the same manner as described above. Table 2 shows the results.

Comparative Example 4 The procedure of Example 2 was repeated, except that the graft composition was changed to 13 parts of methyl methacrylate, 3 parts of butyl acrylate, and 14 parts of styrene. Table 2 shows the results.

[0022]

[Table 2]

[0023]

From the results shown in Tables 1 and 2, it can be seen that the resin composition of the present invention has high impact strength at ordinary temperature and low temperature and excellent transparency.

Claims (2)

[Claims] (A) (a1) a conjugated diene monomer 50 to 10
0% by weight, (a2) 50 to 0% by weight of a vinyl monomer copolymerizable with a conjugated diene-based monomer, (a3) 0 to 3% by weight of a crosslinkable monomer
And (a4) 45 to 95% by weight of a methyl methacrylate monomer, 5 to 95% by weight of a butyl methacrylate monomer in the presence of 40 to 85 parts by weight of a diene rubber obtained by polymerizing 0 to 3% by weight of a chain transfer agent. 50% by weight, aromatic vinyl monomer 0 to 50% by weight
And other vinyl monomers 0 to 20 copolymerizable therewith.
5 to 40 parts by weight of a graft copolymer obtained by polymerizing 60 to 15 parts by weight of a monomer mixture composed of 100% by weight (total amount with a diene rubber) and (B) (b1) methacrylic acid 45 to 100% by weight of an ester monomer, 55 to 0% by weight of an aromatic vinyl monomer (b2) and 0 to 20% by weight of another vinyl monomer copolymerizable therewith [(b1), b2)
95 to 60 parts by weight of an acrylic resin obtained by polymerizing 100% by weight of (b3) and (b3) [10% in total of (A) and (B)]
0 parts by weight]. 2. The diene rubber having an average particle diameter of 500 to 3
000 ° rubber particles, and 100 parts by weight of the particles, at least one unsaturated acid monomer of acrylic acid, methacrylic acid, itaconic acid, crotonic acid
25% by weight, 5 to 30% by weight of at least one alkyl acrylate monomer having 1 to 12 carbon atoms in the alkyl group,
A monomer mixture comprising 20 to 80% by weight of at least one alkyl methacrylate monomer having 1 to 12 carbon atoms of an alkyl group and 0 to 40% by weight of another vinyl monomer copolymerizable therewith ( (Total amount of 100% by weight in total).
The resin composition according to claim 1, wherein the resin composition is a diene rubber having an average particle diameter of 3500 to 20000 ° obtained by adding a part by weight (as a solid content) to cause coagulation and enlargement.