JP3164888B2 - Acrylic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an acrylic resin composition. More specifically, the present invention relates to an acrylic resin composition which is very useful for the purpose of forming an acrylic resin surface layer on the surface of a molded article by coextruding with a vinyl chloride resin for the purpose of supplementing the weather resistance of the molded article. This molded product is, for example, a window frame, a bench material, a decorative column, or the like.

[0002]

2. Description of the Related Art Conventionally, for products having a high designability, such as window frames, bench materials, decorative columns, etc., a vinyl chloride resin having good workability is used as a material in terms of the degree of freedom of the surface and the shape. Have been. When using this processed vinyl chloride resin outdoors, it is necessary to supplement the weather resistance of the vinyl chloride resin. From this point, there is conventionally known a technique in which a resin mainly composed of an acrylic resin is coextruded with a vinyl chloride resin to form a weather-resistant acrylic resin layer on the surface of the molded product.

In this case, it is necessary to adjust the fluidity of the acrylic resin to some extent to the fluidity of the vinyl chloride resin so that coextrusion molding with the vinyl chloride resin becomes possible. Therefore, there is a limitation in selecting the composition of the acrylic resin.

Further, this molded article has a drawback that it is weak against an impact applied from the acrylic resin side. For the purpose of imparting impact resistance, it is conceivable to add elastic particles further containing an acrylic rubber in the acrylic resin, but this addition reduces the fluidity of the resin and reduces the co-extrusion moldability with the vinyl chloride resin. There is a tendency.

[0005]

SUMMARY OF THE INVENTION The present invention solves the problems of the prior art in forming a weather-resistant acrylic resin surface layer by the above-mentioned co-extrusion molding of a vinyl chloride resin (substrate) and an acrylic resin. It was done to solve it.

[0006] That is, an object of the present invention is to both impart sufficient impact resistance to the obtained molded article and to have the same fluidity so that coextrusion molding with a vinyl chloride resin can be performed well. An object of the present invention is to provide an acrylic resin composition having a good balance.

[0007]

The above objects can be achieved by the acrylic resin composition of the present invention described in detail below. That is, the present invention provides (I) an alkyl methacrylate (i-1) having an alkyl group having 1 to 4 carbon atoms,
A polymer obtained by polymerizing 00% by weight and 0 to 20% by weight of an alkyl acrylate (i-2) having an alkyl group having 1 to 8 carbon atoms.
An acrylic polymer dissolved in 00 ml and having a reduced viscosity η _SP / C measured at 25 ° C. of 0.1 liter / g or less 5
0 to 90 parts by weight, (II) a multilayer polymer having an acrylic rubber containing an acrylic acid alkyl ester as a main component in the innermost layer
50 parts by weight, and (III) the innermost layer is 100 to 50 % by weight of 1,3 butadiene.
And the following groups copolymerizable therewith

Embedded image 0 to 50% by weight (total 100% by weight)
Multilayer polymer composed of diene rubber composed of
1 to 50 based on 100 parts by weight of the total of the components (I) and (II)
Co-extrusion with polyvinyl chloride consisting mainly of parts by weight
An acrylic resin composition for molding.

[0008]

The acrylic resin composition of the present invention has a very good balance by blending three specific components at a specific ratio. The acrylic polymer (I)
The effect of improving the weather resistance, mechanical properties, fluidity, etc. is particularly exhibited by selecting a specific monomer and the degree of polymerization, and the multilayer structure polymer (II) imparts particularly impact resistance and elongation. The multi-layered polymer (III) has an effect to further improve the impact strength, and furthermore, when these components are blended in a specific composition ratio, the respective effects are synergistically synergistic with each other, so that the whole is very Excellent characteristics will be obtained.

Hereinafter, the present invention will be described in more detail.

In the acrylic polymer (I) which is one component of the resin composition of the present invention, methyl methacrylate is the most preferred alkyl methacrylate (i-1) having an alkyl group having 1 to 4 carbon atoms. preferable. In addition, carbon number 1
Acrylic acid alkyl ester having an alkyl group of from 8 to 8
Examples of (i-2) include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. No.

The ratio of the alkyl methacrylate (i-1) to the alkyl acrylate (i-2) is 80 to 100% by weight of the alkyl methacrylate (i-1) and the alkyl acrylate (i- 2) 0-20% by weight. When the alkyl acrylate (i-2) exceeds 20% by weight, mechanical properties such as strength and elongation of the resin composition are reduced, and heat resistance is significantly reduced.

The acrylic polymer (I) has a polymer content of 0.1.
It is important that 1 g is dissolved in 100 ml of chloroform and the reduced viscosity measured at 25 ° C. should be such that η _SP / C is 0.1 liter / g or less. When the reduced viscosity exceeds 0.1 liter / g, the fluidity decreases, and other components (II) and (III)
When mixed with, the fluidity of the resin composition itself is greatly reduced.

The multi-layered polymer (II), which is one component of the resin composition of the present invention, is a component for imparting impact resistance and elongation to the resin composition. It has a system rubber in the innermost layer.
For example, a multilayer structure polymer having a two-layer structure as disclosed in JP-B-54-18298,
No. 0841, a three-layered polymer as described in JP-A-57-140161 and JP-A-52-561.
For example, a polymer having a four-layer structure as shown in No. 50 can be used.

The multilayer polymer (III), which is one component of the resin composition of the present invention, is used to further improve the impact strength of the resin composition, and the innermost layer is made of a diene rubber. Things. For example, as such a crosslinked polymer having a multilayer structure, Japanese Patent Publication No. 47-47863,
6-86918, JP-A-56-13331, JP-A-57-167308, JP-A-58-120666.
JP-A-62-181312, JP-A-57-102
No. 940 and JP-A-2-47118 can be used.

That is, as long as the innermost layer is a polymer made of a diene rubber, various known multi-layered polymers can be used.

In the present invention, the diene rubber constituting the innermost layer of the multilayer polymer (III) refers to 100 to 50% by weight of 1,3-butadiene and the following groups copolymerizable therewith.

[0017]

Embedded image And a copolymer comprising 50% by weight or more of 1,3-polybutadiene homopolymer or 1,3-polybutadiene unit. It is. Examples of the copolymer include a butadiene-aromatic vinyl compound copolymer such as a butadiene-styrene copolymer and a butadiene-vinyltoluene copolymer; a butadiene-acrylonitrile copolymer; a butadiene-methacrylonitrile Copolymer; butadiene-methyl acrylate copolymer; butadiene-ethyl acrylate copolymer; butadiene-butyl acrylate copolymer, butadiene-acrylic acid 2-
Butadiene-alkyl acrylate copolymer such as ethylhexyl copolymer; butadiene-alkyl methacrylate copolymer such as butadiene-methyl methacrylate copolymer; butadiene-ethyl methacrylate copolymer; And a terpolymer composed of 50% by weight or more of 1,3-butadiene units. These can usually be easily produced by known emulsion polymerization.

In the present invention, the acrylic polymer (I), the multilayer polymer (II) and the multilayer polymer (II)
The composition ratio of (I) is extremely important for performing coextrusion molding with a vinyl chloride resin. The composition ratio of the acrylic polymer (I) and the multilayer polymer (II) is (I) 50 to 90 parts by weight and (II) 10 to 50 parts by weight. Multilayer polymer (I
If I) is less than 10 parts by weight, the impact strength of the resin molded product becomes insufficient. On the other hand, when the amount of the multilayer polymer (II) exceeds 50 parts by weight, the fluidity of the resin composition is lowered and the elastic modulus is also lowered. As for the composition ratio of the total amount of the two components (I) and (II) and the multilayer polymer (III), 1 to 50 parts by weight of (III) and 100 parts by weight of the total of (I) and (II) were used. Department. If the amount of the multilayer polymer (III) exceeds 50 parts by weight, the impact strength is not so improved and the fluidity is reduced. If the amount of the multilayer polymer (III) is less than 1 part by weight, sufficient impact strength cannot be obtained. Also, if the impact strength is to be improved only by adding a large amount of the multi-layered polymer (II) without blending the multi-layered polymer (III), the fluidity is reduced, and the co-extrusion with the vinyl chloride resin is performed. Molding becomes difficult.

Further, an appropriate matting agent can be added to the resin composition of the present invention in order to obtain a matte surface. As the matting agent, for example, an inorganic matting agent such as silicon oxide or calcium carbonate can be used, and further, a polymer matting agent can be used. In order to further improve the weather resistance, a known ultraviolet absorber can be added.
Further, a suitable coloring agent may be added. In order to suppress the deformation of the molded article outdoors, it is also possible to add a coloring agent that does not absorb the wavelength in the infrared region.

[0020]

The present invention will be described in more detail with reference to the following examples. In the examples, the terms “%” and “parts” mean “% by weight” and “parts by weight”, respectively, unless otherwise specified. In the examples, the particle diameter is determined by the electron microscope method for rubber or resin latex, or the wavelength of a diluted solution (0.15 g / liter) of the latex is 700.
A calibration curve was prepared from the relationship with the absorbance in nm, and the absorbance of the latex was measured to obtain the calibration curve.

<Preparation Example of Multilayer Structure Polymer (II) (II-1)> A multilayer structure polymer (II) having an acrylic rubber having an alkyl acrylate as a main component in the innermost layer by the following three-step process. ) Was prepared.

(1) First stage In a stainless steel reaction vessel having a content of 50 liters, 25 kg of deionized water, 8 g of sodium N-lauroylsarcosine (hereinafter referred to as S-LN), and 100 g of boric acid
g, sodium carbonate 10 g, ferrous sulfate 0.01 g, and ethylenediamine-4-acetic acid-2-sodium 0.2 g.
01 g was charged. While stirring the inside of the reaction vessel, 802.4 g of the monomer mixture (A-1) shown below was put in a lump, nitrogen gas was blown into the reaction vessel to make it substantially free of oxygen, and then the temperature was raised to 70 ° C.

[Monomer mixture (A-1)] 320 g of butyl acrylate, 76 g of styrene, 392 g of methyl methacrylate, 1,4-butanediol diacrylate (C
_4- DA) 12 g, tertiary butyl hydroperoxide 2.4 g, total 802.4 g.

Next, 50 I of deionized water is placed in the reaction vessel.
0 g and 40 g of sodium-formaldehyde sulfoxylate (hereinafter referred to as Rongalit) were added, and polymerization was carried out for 60 minutes. Thereafter, 803.6 g of the following monomer mixture (A-2) was continuously added into the reaction vessel over 30 minutes to carry out polymerization, and polymerization was continued for 90 minutes after the addition was completed.

[Monomer mixture (A-2)] 320 g of butyl acrylate, 76 g of styrene, 392 g of methyl methacrylate, 1,4-butanediol diacrylate (C
_4- DA) 12 g, tertiary butyl hydroperoxide 3.6 g, total 1203.6 g.

By the above first step, an acrylic rubber latex was obtained.

(2) Second Step 500 g of deionized water is placed in the same container containing 2 kg of polymer solid content of the semi-soft crosslinked resin obtained in the first step.
A mixed aqueous solution of 50 g of (S-LN) and 20 g of (Rongalit) was added, and the internal temperature was raised to 80 ° C. In this,
A mixture obtained by adding 32 g of tertiary butyl hydroperoxide (hereinafter abbreviated as t-BH) to 8 kg of a crosslinkable acrylate monomer mixture (B) shown below,
Polymerization was carried out with continuous addition over 150 minutes, and polymerization was continued for another 180 minutes after the addition was completed.

[Crosslinkable acrylate monomer mixture (B)] 81% of butyl acrylate, 17.
5%, triallyl isocyanurate (hereinafter abbreviated as Taik) 1.1% 1,4-butanediol diacrylate (C ₄ -DA) 0.4% Total 100%: 8 kg.

By the above second step, a polymer latex containing the resin of the first step inside the particles and having an elastomer layer formed on the outer layer was obtained. As a result of measuring the polymer particle size of this latex by an absorbance method, it was 0.28 μm.

(3) Third stage 500 g of deionized water and 40 g of (S-LN) are added to the same container containing 10 kg of polymer solid content of the copolymer latex having a two-stage structure obtained in the second stage. Then, the internal temperature was maintained at 80 ° C. while stirring. The monomer mixture (C) shown below was continuously added thereto at a rate of 40 g / hour. Thereafter, polymerization was continued for another hour.

[Monomer mixture (C)] A total of 6 kg of 95% of methyl methacrylate and 5% of methyl acrylate,
Normal octyl mercaptan (nC ₈ SH) 13.8
g, and 9 g of (tBH).

Thus, a multi-structure methacrylic resin was obtained in the form of a latex. The polymerization rate of the monomer mixture (C) is 99.
It was 5% or more. This latex was coagulated, washed and dried by the methods described below to obtain a powder. A stainless steel container was charged with 100 kg of a 1.0% sulfuric acid aqueous solution, and the temperature was raised to 70 ° C. with stirring, and 40 kg of the latex previously produced was added to 1 kg.
Add continuously over 5 minutes, then raise the internal temperature to 90 ° C
And kept for 5 minutes. After cooling to room temperature, the polymer was separated by filtration, washed with deionized water to obtain a white creamy polymer, and dried at 70 ° C. for 24 hours to obtain a multilayer as a white powdery polymer. A structural polymer (II) was obtained.

<Preparation Example of Multilayer Polymer (III) (III-1)
> A multilayer polymer (III) having a diene rubber in the innermost layer was synthesized by the following process.

(1) Synthesis of enlarged diene rubber (A) 66 parts of 1,3-butadiene, n-butyl acrylate 9
Parts, styrene 25 parts, diisopropylbenzene hydroperoxide 0.2 part, potassium oleate 1.0 part,
It consists of 1.0 parts of disproportionated potassium rosinate, 0.5 parts of sodium pyrophosphate, 0.005 parts of ferrous sulfate, 0.3 parts of textrose, 0.3 parts of anhydrous sodium sulfate, and 200 parts of ion-exchanged water. The composition was polymerized at 50 ° C. in a 100 liter autoclave. The polymerization was almost completed in 9 hours, and a rubber latex (base rubber a-1) having a conversion rate of 97%, a particle diameter of 0.08 μm, and a pH of 9.0 was obtained.

Separately, 85 parts of n-butyl acrylate, 15 parts of methacrylic acid, 2 parts of potassium oleate, 1 part of sodium dioctyl sulfosuccinate, 0.4 part of cumene hydroperoxide, 0 parts of sodium formaldehyde sulfoxylate A composition comprising 0.3 parts and 200 parts of ion-exchanged water was polymerized in another polymerization apparatus at 70 ° C. for 4 hours. As a result, the conversion was 98% and the average particle size was 0.08.
An acid group-containing copolymer (B) latex for enlargement of μm was obtained.

Next, 2 parts (solid content) of the acid group-containing copolymer (B) latex was added to 100 parts (solid content) of the base rubber (a-1) latex with stirring, and 3 parts were further added.
Stirring was continued for 0 minutes to obtain an enlarged diene rubber latex (A-1) having an average particle diameter of 0.27 μm.

(2) Multi-structure crosslinked acrylic rubber (C)
Production of the enlarged diene rubber latex (A) obtained as described above
-1) 20 parts (solid content) were transferred to a reaction vessel, 1 part of disproportionated potassium rosinate and 150 parts of ion-exchanged water were added, the atmosphere was replaced with nitrogen, and the temperature was raised to 70 ° C (internal temperature). A solution prepared by dissolving 0.12 parts of potassium persulfate in 10 parts of ion-exchanged water was added thereto, and a monomer mixture (c) shown below, which had been replaced with nitrogen, was continuously dropped over 2 hours.

[Monomer mixture (c)] 80 parts of n-butyl acrylate, 0.32 parts of allyl methacrylate, 0.16 parts of ethylene glycol dimethacrylate, a total of 8
0.48 parts.

Although the internal temperature does not rise at the same time as the completion of the dropping, if the temperature is further raised to 80 ° C. and the reaction is continued for 1 hour, the polymerization rate reaches 98.8% and the multi-layered structure containing an enlarged diene rubber inside. A crosslinked acrylic rubber (C-1) was obtained. The swelling degree of this multi-structure crosslinked acrylic rubber was 6.4, the gel content was 93.0%, and the particle size was 0.28 μm.

(3) Production of Graft Copolymer (D) Latex The multi-structure crosslinked acrylic rubber (C-
1) 30 parts of latex (solid content) was placed in a reaction vessel, and 140 parts of ion-exchanged water was added for dilution, and the temperature was raised to 70 ° C.

Separately, 70 parts of a monomer mixture for graft polymerization consisting of acrylonitrile / styrene = 29/71% was prepared, and benzoyl peroxide was added to the mixture.
After dissolving 35 parts, the atmosphere was replaced with nitrogen.

This monomer mixture was added at a rate of 15 parts / hr using a metering pump into a reaction system containing the multi-structure crosslinked acrylic rubber (C-1) latex. After the completion of the injection of the entire monomer mixture, the temperature in the system was raised to 80 ° C.
The stirring was continued for 30 minutes, and the graft copolymer latex (D-
1) was obtained. The conversion was 99%. Dilute sulfuric acid was added to a part of this latex (D-1), and the solidified and dried powder was subjected to direct extraction under reflux of methyl ethyl ketone.
_{When SP} / C was measured at 25 ° C. using dimethylformalide as a solvent, it was 0.67.

(4) Salting Out and Pelletization of Polymer The latex (D-1) produced by the above-described process was used in an amount of aluminum chloride (AlCl ₃ ) three times the total latex.
(6H ₂ O) was poured into a 0.15% aqueous solution (90 ° C.) while stirring to coagulate. After the addition of all the latex was completed, the temperature in the coagulation bath was raised to 93 ° C., and the mixture was allowed to stand for 5 minutes. After cooling, the mixture was drained and washed by a centrifugal dehydrator, and dried to obtain a multilayer polymer (III).

Examples 1 to 8 Resin compositions having the respective compositions shown in Table 1 were prepared. Here, as the acrylic polymer (I), methyl methacrylate 8
7 parts of methyl 13 parts of acrylic acid a polymer obtained by copolymerizing a polymer 0.1g chloroform 100 m
reduced viscosity eta _SP / C as measured by dissolved in l 25 ° C. 0.05
An acrylic polymer of 61 l / g was used. Also,
As the multilayer polymer (II), the polymer obtained in the above Production Example (II-1) was used, and as the multilayer polymer (III), the above Production Example was used.
The polymer obtained in (III-1) was used. The melt index (MI) (g / 10 minutes, 230 ° C.) of each resin composition was measured, and the results are shown in Table 1. In addition, each resin composition was extruded into a 0.2 mm sheet, and bonded to a 1 mm thick polyvinyl chloride sheet (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Clearlite, hereinafter referred to as a PVC sheet) by a hot press. Impact strength (Dainstadt impact strength, kg · cm / cm) from the resin composition side of this PVC sheet
² ) was measured. Table 1 also shows the impact strength of the PVC sheet alone for comparison.

The multilayer polymer (II) used here
The pure rubber content of (Production Example (II-1)) was about 60%, and the pure rubber content of the multilayer polymer (III) (Production Example (III-1)) was about 50%. The composition in Comparative Example 1 is such that the pure rubber components are substantially the same. Similarly, the compositions in Examples 7 and 8 and Comparative Example 2 are such that the pure rubber content is the same.

[0046]

[Table 1] As shown in Table 1, the composition of Comparative Example 1 containing no multilayer polymer (III) had an impact strength of 11.4 kg · cm.
/ Cm ^2, which is significantly lower than the impact strength of the PVC sheet alone. On the other hand, in the compositions of Examples 1 to 6, it can be seen that the impact strength increases as the amount of the multilayer polymer (III) increases. Example 7
Comparative Examples 2 to 8 and Comparative Example 2 show cases where the rubber component was increased as compared with Examples 1 to 6 and the like. Therefore, the multilayer polymer (I
II), the composition of Comparative Example 2 containing no
The impact strength is improved. However, Examples 7 and 8
Although the composition of Comparative Example 2 contains only a rubber component equivalent to that of Comparative Example 2, it shows a superior impact strength.

<Examples 9 to 12> Table 2 shows that the resin composition containing the three components (I) to (III) used in the above examples was further added with an appropriate amount of a matting agent (manufactured by Mitsubishi Rayon Co., Ltd.). The same evaluation results are shown for the composition to which (name: Metablen F410) was added.

[0048]

[Table 2] As shown in Table 2, the addition of the matting agent (F410) tends to greatly reduce the impact strength. Comparative Example 3 is shown in Table 1.
However, when the matting agent was further added to the composition of Comparative Example 1 shown in (1), the impact strength was reduced to 2.5. However, it can be seen that the compositions of Examples 9 to 11 exhibited better impact resistance than Comparative Example 3 even when the matting agent was added.

<Examples 13 to 19> Table 3 shows Production Example (III-1)
The same evaluation results are shown for a resin composition using a commercial product of a multilayer polymer having an innermost layer made of a diene rubber in place of the polymer (III) obtained in the above. Commercial products used herein are trade names Metablen E920, Metablen C20
1. Metablen W800 (all commercially available MBS resins,
Mitsubishi Rayon Co., Ltd.).

[0050]

[Table 3] As shown in Table 3, it can be seen that similarly good results were obtained when various commercial products were used as the multilayer structure polymer (III).

<Application Example 1 and Comparative Application Example 1> The acrylic resin composition of the present invention and a vinyl chloride resin are coextruded to obtain a molded article of a vinyl chloride resin having a weather-resistant acrylic resin surface layer. An application example of the present invention will be described.

First, the following polyvinyl chloride resin composition was prepared. [Vinyl chloride resin composition (PVC)] 100 parts (php) of polyvinyl chloride (number average molecular weight P = 1100), 2 parts of tribasic lead sulfate, 0.5 parts of dibasic lead stearate,
0.8 parts of lead stearate, calcium stearate
2 parts, (METABLEN P551) 1.5 parts, (METABLEN P710) 1.0 parts, (METABLEN S2001) 8.0
Department.

Separately, the following acrylic resin composition (a) of the present invention and the conventional acrylic resin composition (b)
Was prepared.

[Acrylic resin composition (a) of the present invention]
Acrylic resin (same as polymer (I) used in Examples) 68
Parts, 32 parts of the multilayer structure polymer obtained in Preparation Example (II-1), 10 parts of the multilayer structure polymer obtained in Preparation Example (III-1), 30 parts of (METABLEN F410), (METABLEN L1000)
1.0 part, tris (mono, dinonylphenyl) phosphite 0.4 part, (Tinuvin P, Ciba-Geigy) 0.
One copy.

[Conventional Acrylic Resin Composition (b)] Acrylic resin (trade name: Acrypet VH) 68 parts, acrylic resin (multilayer structure polymer obtained in Production Example (II-1)) 32
Part, (METABLEN F410) 30 parts, (METABLEN L1
000) 1.0 part, tris (mono, dinonylphenyl)
0.4 parts of phosphite, 0.1 part (Tinuvin P, manufactured by Ciba Geigy).

The above vinyl chloride resin composition (PVC),
The acrylic resin (a) or (b) was co-extruded. This extrusion molding was performed using a sizing die having a width of 10 cm at a molding temperature of 210 ° C. for acrylic resin and 200 ° C. for PVC. The obtained molded article was a PVC sheet having an acrylic resin layer on one side, and the thickness of the acrylic resin layer was adjusted to 0.15 to 0.2 mm, and the thickness of PVC was adjusted to 2 mm.

Table 4 shows the Dainstadt impact strength of each sheet measured from the acrylic resin layer side. For comparison, the impact strength of the PVC sheet alone is also shown.

[0058]

[Table 4] As shown in Table 4, the impact strength in the application example 1 using the acrylic resin of the present invention is almost the same as that of the PVC sheet alone, but the impact strength is significantly reduced in the comparative application example 1 using the conventional acrylic resin. You can see that

Further, the sheet obtained in Application Example 1 was exposed for 200 hours using an eye super exposure tester (manufactured by Dainippon Plastics Co., Ltd.), but no decrease in surface gloss was observed, and sufficient weather resistance was obtained. Indicated.

[0060]

The acrylic resin composition of the present invention described above can be favorably co-extruded with a vinyl chloride resin. Furthermore, when a weather-resistant acrylic resin layer is formed on the surface of a vinyl chloride resin molded product by the co-extrusion molding, the impact strength of the conventional acrylic resin decreases, but the impact strength of the acrylic resin of the present invention decreases. Can be suppressed. That is, the acrylic resin composition of the present invention,
The resulting molded article is provided with both good impact resistance and good fluidity so that co-extrusion with a vinyl chloride resin can be performed well.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Abe 20-1, Miyuki-cho, Otake City, Hiroshima Prefecture Inside the Mitsubishi Rayon Co., Ltd. Otake Works (56) References JP-A-61-14246 (JP, A) JP-A-61-14246 JP-A-62-230841 (JP, A) JP-A-63-135440 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 33/10-33/12 B32B 27/00-27 / 42 C08L 51/00-51/10 C08J 5/00-5/24

Claims (1)

(57) [Claims] 1. An alkyl methacrylate (i-1) having an alkyl group having 1 to 4 carbon atoms (I-1).
% By weight and 0 to 20% by weight of an alkyl acrylate (i-2) having an alkyl group having 1 to 8 carbon atoms.
reduced viscosity was measured in dissolved 25 ° C. in ml eta _SP / C is 0.
Acrylic polymer of 1 liter / g or less
90 parts by weight, (II) a multilayer polymer having an acrylic rubber having an alkyl acrylate as a main component in the innermost layer
50 parts by weight, and (III) the innermost layer is 100 to 50 % by weight of 1,3 butadiene.
And the following groups copolymerizable therewith : 0 to 50% by weight (total 100% by weight)
Multilayer polymer composed of diene rubber composed of
1 to 50 based on 100 parts by weight of the total of the components (I) and (II)
Co-extrusion with polyvinyl chloride consisting mainly of parts by weight
Acrylic resin composition for shapes .