JPH0331352A - Thermoplastic resin composition excellent in impact and weather resistance and moldability - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in impact and weather resistance and moldability by polymerizing a monomer selected from aromatic vinyl compounds, etc., in the presence of a latex of a specific crosslinked acrylic rubber having a multiple structure. CONSTITUTION:A thermoplastic resin composition obtained by blending (A) 10-90 pts.wt. graft copolymer resin prepared by polymerizing (A2) 95-10 pts.wt. one or more monomers selected from aromatic vinyl compounds, etc., in the presence of (A1) 5-90 pts.wt. latex of a crosslinked acrylic rubber, containing a diene-based rubber enlarged with an acid group-containing copolymer latex in the interior of particles and obtained by using a graft crossing agent and a crosslinking agent in combination in the outer layer part with (B) 90-10 pts.wt. graft copolymer resin prepared by polymerizing (B2) 95-10 pts.wt. one or monomers selected from the aromatic vinyl compounds, etc., in the presence of (B1) 5-90 pts.wt. latex of a crosslinked acrylic acid ester-based polymer consisting essentially of an acrylic acid ester and prepared by using a graft crossing agent and a crosslinking agent in combination.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic resin composition having excellent impact resistance, weather resistance and moldability.

[Prior art] As an impact-resistant resin, AB consisting of a resin-rubber two-phase system
There is S resin. However, this ABS resin deteriorates when exposed to ultraviolet rays because the butadiene-based polymer, which is the rubber component that imparts impact resistance, has many chemically unstable double bonds in its main chain. It is well known that it has poor weather resistance.

As a method to improve the weather resistance of ABS resin, a method has been proposed to use a saturated rubbery polymer that has almost no double bonds in the main chain, and a typical example is the use of acrylic ester rubber. What has been done is known. Although this saturated rubber is stable against ultraviolet rays, it does not have crosslinking active sites or grafting active sites, so it is difficult to form rubber crosslinks or graft structures, which are essential requirements for resin-rubber two-phase resins. Compared to those using diene rubber, it has the disadvantages of being soft, having a low elastic modulus, and slowing recovery of elasticity. Therefore, when injection molding is performed using a resin composition similar to ABS resin that uses such saturated rubber as a molding material, the orientation of the rubber particles is marked and a pearl-like luster appears over the entire surface area of the molded product or in a certain direction of flow. is expressed.

Furthermore, when colored with pigments, etc., this tendency is further accentuated, resulting in a disadvantage that the commercial value decreases. In order to improve this drawback, a method of copolymerization by selecting the type of crosslinking agent, a method of performing peroxide crosslinking, etc., a method of using a multi-structure crosslinked acrylic rubber containing diene rubber inside the particles, and Japanese Patent Publication No. 47-47863 No. Publication, JP-A-56-8
6918, JP 56-133311, JP 57-167308, JP 58-1206
The method disclosed in Publication No. 63 and the like has been proposed.

However, the balance between gloss and impact resistance of molded products obtained by high-temperature molding was not always satisfactory.

As a countermeasure to this problem, a diene rubber latex with a small particle diameter manufactured by a specific method is enlarged with an acid group-containing copolymer latex, and the diene rubber latex is enlarged inside the particles, and a grafting agent and a crosslinking agent are used together. In the presence of a latex containing a multilayer acrylic rubber whose outer layer is a crosslinked acrylic ester polymer whose main component is an acrylic ester, aromatic vinyl compounds and ethylenic The above problems can be solved by producing a graft copolymer resin by polymerizing at least one monomer selected from the group consisting of unsaturated compounds. Gansho 6l-2453
3).

[Problems to be Solved by the Invention] Although this method has expanded the molding temperature range to higher temperatures, the reality is that in higher molding temperature ranges, the appearance of the molded product still deteriorates in gloss. there were.

[Means for Solving the Problems] In view of the current situation, the inventors of the present invention conducted extensive studies with the aim of improving the balance between impact resistance and gloss under molding conditions ranging from low temperatures to considerably high temperatures. A cross-linked acrylic acid obtained by using a graft cross-agent and a cross-linking agent together, containing a diene-based rubber made by enlarging a small-particle-diameter diene rubber latex produced by a specific method with an acid group-containing copolymer latex inside the particles. An aromatic vinyl compound and an ethylenically unsaturated compound are mixed in the presence of a latex containing a multilayer acrylic rubber whose outer layer is an ester polymer whose main component is an acrylic ester. A cross-linked acrylic ester whose main component is an acrylic ester obtained by combining a graft copolymer resin obtained by polymerizing at least one monomer selected from the group consisting of a graft cross-agent and a cross-linking agent. A graft copolymer resin is prepared by polymerizing at least one monomer selected from the group consisting of an aromatic vinyl compound and an ethylenically unsaturated compound in the presence of a polymer latex. The inventors have discovered that the above-mentioned problems can be solved and a thermoplastic resin composition excellent in all of impact resistance, weather resistance, and moldability can be obtained by mixing these, and the present invention has been achieved.

That is, the thermoplastic resin composition of the present invention having excellent impact resistance, weather resistance, and moldability contains 5 to 90% by weight of diene rubber (i) enlarged with acid group-containing copolymer latex inside the particles, A cross-linked acrylic ester polymer obtained by using a graft cross-linking agent and a cross-linking agent in combination, the main component of which is an acrylic ester (ii) l 0 to 95% by weight constitutes the outer layer. In the presence of 5 to 90 parts by weight (as solid content) of a latex of a multi-structure crosslinked acrylic rubber (1) consisting of an aromatic vinyl compound and a compound of the general formula % (wherein R is H or CHl, X is CN or C0O
R', where 5R' is an alkyl group having 1 to 8 carbon atoms. 095 to 10 parts by weight of a monomer selected from the group consisting of ethylenically unsaturated compounds represented by
Graft copolymer resin 010 to 90 parts by weight and graft copolymer resin 090 to 10 parts by weight (total amount of [3] and parts by weight),
The resin [6] is aromatized in the presence of 5 to 90 parts by weight of a latex of a crosslinked acrylic ester polymer (iii) whose main component is an acrylic ester obtained by using a grafting agent and a crosslinking agent together. Group vinyl compounds and -maximum % formula % (wherein R represents a hydrogen atom or a methyl group, and X represents a cyano group or a -〇〇〇R' group. Here, R1 represents 1 carbon atom
It is an alkyl group containing ~8. ) 95 to 10 parts by weight of one or more monomers selected from the group consisting of ethylenically unsaturated compounds represented by (iv) [
A thermoplastic resin composition with excellent impact resistance, weather resistance, and moldability, characterized in that it is obtained by subjecting the total amount of (iif) and (iv) to 100 parts by weight] to polymerization. or the composition further contains a thermoplastic resin [7
], and the total resin composition ([3] + [6] + [
7]), the content rate of the former ([3]+■) is 5 to 80
This is a thermoplastic resin composition having excellent impact resistance, weather resistance, and moldability, characterized in that it contains a hard thermoplastic resin [7] in a proportion of % by weight.

That is, a cross-linked acrylic ester rubber graft copolymer resin whose rubber source is a cross-linked acrylic ester polymer with a small particle size prepared separately is blended with a multi-layered acrylic rubber graft copolymer resin to obtain a particle size distribution. By doing so, the present inventor succeeded in expanding the molding temperature range to the required level to the high temperature side while maintaining a balance between impact resistance and molded appearance.

In the composition of the present invention, the enlarged diene rubber (i) constituting the inner layer of the particles of the multilayer acrylic rubber (i) is 1.3
-100-50% by weight of butadiene and 0-50% by weight of butadiene
(100% by weight in total), and 1
．． It is a 3-butadiene homopolymer or a copolymer composed of 50% by weight or more of 1,3-butadiene units.

Examples of the copolymer include butadiene-aromatic vinyl compound copolymers such as butadiene-styrene copolymer, butadiene-vinyltoluene copolymer; butadiene-acrylonitrile copolymer; butadiene-methacrylic copolymer; Nitrile copolymer; butadiene-methyl acrylate copolymer, butadiene-ethyl acrylate copolymer,
Butadiene-butyl acrylate copolymer, butadiene-
Butadiene-acrylic acid alkyl ester copolymers such as 2-ethylhexyl acrylate copolymer; butadiene-methacrylic acid alkyl ester copolymers such as butadiene-methyl methacrylate copolymer, butadiene-ethyl methacrylate copolymer, etc. including polymers;
Furthermore, it also includes a ternary coelectric material composed of 50% by weight or more of 1,3-butadiene units. These can usually be easily produced by known emulsion polymerization. Also,
Although various catalysts, emulsifiers, etc. can be used without particular limitation in the production of this diene rubber, the particle size of the obtained rubber is preferably 0.04 to 0.2 μm.

In the present invention, an acid group-containing copolymer latex is used to enlarge the latex of the diene rubber. This acid group-containing copolymer latex must contain an acid group-containing monomer and an acrylic acid alkyl ester as essential components. Examples of acid group-containing monomers include unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid, and crotonic acid. Further, as the acrylic acid alkyl ester, at least one type of acrylic acid alkyl ester in which the alkyl group has 1 to 12 carbon atoms is selected.

Even when a monomer such as methacrylic ester, styrene, or acrylonitrile is used instead of acrylic acid alkyl ester, no enlargement effect is observed. However, it is possible to replace half or less of the acrylic acid alkyl ester with the other monomers mentioned above.

The acid group-containing monomer is used in an amount of 3 to 30% by weight of the constituent monomers of the acid group-containing copolymer. If it is less than 3% by weight, the enlargement ability is small, and if it exceeds 30% by weight, the enlargement ability is too strong. This is not very preferable because it tends to produce particles that are larger than Lll.

Furthermore, the optimum amount of the acid group-containing monomer varies depending on the degree of hydrophilicity of the alkyl acrylate ester used. When the hydrophilicity of the acrylic acid alkyl ester is high, the enlargement effect is exhibited in areas where the amount of acid group-containing monomer is small, but if the amount of acid group-containing monomer is large (the latex may be destroyed). On the other hand, if the hydrophilicity of the alkyl acrylate ester is low, the enlarging effect will be small in the region where the amount of the acid group-containing monomer is low. A sufficient effect cannot be achieved unless the amount exceeds a certain level.For example, in the case of highly hydrophilic acrylic acid alkyl esters such as methyl acrylate and ethyl acrylate, the amount of acid group-containing monomer is 5 to 10% by weight. However, in the case of butyl acrylate and 2-ethylhexyl acrylate, which are hydrophobic acrylic acid alkyl esters in which the alkyl group has 4 or more carbon atoms, the amount of acid group-containing monomer is It is optimal when the amount is 13 to 20% by weight.If a highly hydrophilic acrylic acid alkyl ester is used, the system becomes unstable even when the amount of acid group-containing monomer is 5 to 10% by weight. This is why caret (
The disadvantage is that large particles (coarse particles) are likely to be produced. On the other hand, if a hydrophobic acrylic acid alkyl ester is used, the system will not become unstable (and uniform enlarged particles can often be obtained.

In addition to the above monomers, the acid group-containing monomers include cinnamic acid,
There are maleic anhydride, butenetricarboxylic acid, etc., but these are not practical because of their small enlargement ability.

This acid group-containing copolymer is used in the form of a latex, the particle size of which has a large effect on its ability to enlarge. The preferred average particle diameter is in the range of 0.05 to 0.2 μm. If it is smaller than 0.05 μm, its enlargement ability will be significantly reduced, and if it is larger than 0.2 μm,
Since the rubber particle diameter after enlargement becomes too large, it becomes unstable and tends to aggregate when graft polymerization is subsequently carried out.

The diene rubber is enlarged by adding an acid group-containing copolymer latex to a diene rubber latex having a small particle size of 0.04 to 0.2 μm. The amount of acid group-containing copolymer latex added is 0.1-1 parts by weight (as solid content) per 100 parts by weight of the base diene rubber latex.
0 parts by weight (as solid content), particularly preferably 0 parts by weight (as solid content)
．． It is 5 to 5 parts by weight. The particle size of the latex of the enlarged diene rubber (i) in such an amount added is 0.15 to
Adjusted to 1 g, ra. The particle size of the crosslinked acrylic acid ester polymer latex containing this rubber inside is preferably 0.30 to 3 μm in terms of impact resistance and molded appearance.
m range.

In addition, the particle size of the crosslinked acrylic acid ester polymer rubber constituting the graft copolymer resin (■), which is separately adjusted and blended, is an important point in the present invention, and is important for improving the gloss of the molded product during high-temperature molding. In order to maintain the appearance, the thickness is preferably 0.2 μm or less.

In the present invention, when enlarging diene rubber, the pH of the base diene rubber latex is preferably maintained at 7 or higher (preferably; if the pH value is on the acidic side, the acid group-containing copolymer Even if a combined latex is added, the enlarging effect is low, making it difficult to advantageously produce the resin composition targeted by the present invention.

The operation of adjusting the po of the base diene rubber latex to 7 or more may be carried out during the polymerization of the base diene rubber latex, or may be carried out separately before the enlargement treatment.

The crosslinked acrylic ester polymer (H) constituting the outer layer of the multilayered crosslinked acrylic rubber in the present invention and the crosslinked acrylic ester rubber are obtained by using a grafting agent and a crosslinking agent in combination. The acrylic ester that is the main component (5.0% by weight or more) of the polymer (ii) is, for example, a carbon ester in which the ester moiety is methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, n-lauryl, etc. Alkyl esters of number 1 to 12; haloalkyl esters such as chloroethyl acrylate; aromatic esters such as benzyl acrylate or phenethyl; and the like.

Examples of monomers copolymerizable with these acrylic esters include methacrylic esters such as methyl methacrylate and butyl methacrylate; acrylonitrile; and styrene;
It may be used in an amount of 0% by weight or less, if desired.

By the way, in order for this acrylic ester-based polymer to form a crosslinked structure, a grafting agent or a crosslinking agent is individually added to the monomer or monomer mixture containing the acrylic ester as a main component, and polymerization is performed. The most common method is to However, in the present invention, when forming a crosslinked structure in this acrylic ester polymer, by using a combination of a grafting crosslinking agent and a crosslinking agent, it is possible to create a crosslinked structure by using a conventional grafting crosslinking agent or a crosslinking agent alone. It is characterized by being able to solve the problem of moldability that had not been achieved previously.

Examples of the grafting cross-agent in the present invention include allyl esters such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, cyanuric acid, and isocyanuric acid. Examples of the crosslinking agent include those containing two or more unsaturated aliphatic groups in one molecule, such as diacrylate or dimethacrylate of polyalkylene glycol and divinylbenzene.

When producing the thermoplastic resin composition of the present invention, the following method may be used to incorporate the enlarged diene rubber (i) inside the particles of the crosslinked acrylic ester polymer (ii).

First, the enlarged diene rubber (i) is prepared by emulsion polymerization of the diene rubber and subsequent enlargement treatment by adding an acid group-containing polymer latex. Next, 2 to 80% by weight of this enlarged diene rubber latex, preferably 5 to 80% by weight,
20 to 98% by weight of a crosslinked acrylic ester polymer constituent monomer mixture in the presence of 50% by weight (as solid content)
, preferably 95 to 50% by weight, is carried out in a so-called seed polymerization. The degree of swelling of the multi-structure crosslinked acrylic rubber (■) polymerized in this way (the ratio of the swollen weight to the absolute dry weight after standing in methyl ethyl ketone at 30°C for 24 hours) is the external impact strength of the molded product. Considering the balance of resin properties, the number is preferably 4 to 16, preferably 6 to 9.

In order to adjust the degree of swelling within this range, the grafting agent and the crosslinking agent may be added in a total amount of 0.1 to 10% by weight based on the constituent monomers of the acrylic ester polymer. Preferably, when the total amount of the graft cross-linking agent and the cross-linking agent is less than 0.1% by weight, the degree of swelling will be outside the above range,
This is unfavorable for the appearance of the molded product (if the amount exceeds 10% by weight, the impact strength tends to decrease. In addition, such seed polymerization may cause the crosslinked acrylic rubber to completely cover the enlarged diene rubber). Not done to achieve the desired appearance,
Resin with excellent weather resistance cannot be obtained.

Next, regarding the graft polymerization of the thus obtained multi-structure crosslinked acrylic rubber (1) and crosslinked acrylic ester rubber (2), aromatic Group vinyl monomers and general formula CHa・CRX (wherein R represents -H or -CL, X!; t -CN or -COOR1, where R1 is an alkyl group having 1 to 8 carbon atoms) 095 to 10 parts by weight of at least one monomer selected from the group consisting of ethylenically unsaturated compounds represented by Each graft copolymer can be obtained by adding the entire amount of monomer (1) to the latex all at once or in portions or continuously and polymerizing it. When a large amount of monomer is added, a continuous injection method is desirable in order to maintain the melt fluidity of the resulting polymer and to assist in the production of the graft polymer.

Typical examples of the aromatic vinyl compound include styrene, a-methylstyrene, vinyltoluene, and the like. Typical ethylenically unsaturated compounds represented by -maximum CH2=CRX include acrylonitrile, methacrylonitrile, and methyl, ethyl, propyl, butyl esters of acrylic acid or methacrylic acid.

Graft copolymer resin (b) which is also separately adjusted and blended
In the presence of 50 to 90 parts by weight (as solid content) of the latex of the crosslinked acrylic ester polymer (4), the main component of which is an acrylic ester obtained using a combination of a grafting agent and a crosslinking agent, Aromatic vinyl compounds and -maximum C)1
．． =CRX (wherein, R is H or CH@, X is C
N or COOR1, where R1 is an alkyl group having 1 to 8 carbon atoms. ) at least one monomer selected from the group consisting of ethylenically unsaturated compounds (iV
) is a graft copolymer resin obtained by polymerizing 95 to 10 parts by weight (total amount of (4) + (iV): 100 parts by weight). This graft copolymer resin (6) includes an acrylic ester used in the crosslinked acrylic ester polymer (ii) constituting the outer layer of the multilayer crosslinked acrylic rubber;
Grafting agents and crosslinking agents can be used, and examples of acrylic esters include those in which the ester moiety is methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, n-
- C1-12 alkyl ester such as lauryl;
Haloalkyl esters such as chloroethyl acrylate; aromatic esters such as benzyl acrylate or phenethyl acrylate; and the like are used.

Examples of monomers copolymerizable with these acrylic esters include methacrylic esters such as methyl methacrylate and butyl methacrylate; acrylonitrile; and styrene.

Examples of gelabut crossagents include allyl esters such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, cyanuric acid, and isocyanuric acid. Examples of the crosslinking agent include diacrylate or dimethacrylate of polyalkylene glycol, divinylbenzene, and the like. The total amount of graft cross-linking agent and cross-linking agent used is 0.
．． It ranges from 1 to 10% by weight.

The particle size of the rubber of the crosslinked acrylic ester polymer (ii) is an important point in the present invention, and in order to maintain the molded appearance such as gloss of the molded product obtained during high temperature molding, it is necessary to
．． The thickness is preferably 2 μm or less.

Further, the aromatic vinyl monomer and general ethylenically unsaturated compound represented by 2CH,=CRX to be grafted to the crosslinked acrylic ester polymer (4) include styrene, a-methylstyrene, vinyltoluene, acrylonitrile, Examples include methacrylonitrile, methyl, ethyl, propyl, and butyl esters of acrylic acid or methacrylic acid.

The thus obtained graft copolymer resin mixture ■+[
6] can be used as it is as the thermoplastic resin composition of the present invention, but if the separately produced hard thermoplastic resin [7] is added to the total resin composition ([3]+■+■ sum). It can also be used as a resin composition in which the graft copolymer resin ■+■ is mixed in a proportion such that the graft copolymer resin ■+■ is 5 to 80% by weight. As the above-mentioned hard thermoplastic resin (2), it can be used without any particular restriction as long as it is hard at room temperature, but aromatic vinyl compound-acrylonitrile copolymer, aromatic vinyl compound-acrylonitrile-methyl methacrylate ternary Suitable examples include copolymers, aromatic vinyl compound-acrylonitrile-lower alkyl acrylate terpolymers, acrylonitrile-lower alkyl acrylate copolymers, and polycarbonates.

Further, the method of mixing the graft copolymer of the multi-structure crosslinked acrylic rubber and the graft copolymer of the crosslinked acrylic ester rubber may be a latex blend or a dry powder triblend.

The thermoplastic resin composition of the present invention, which has excellent impact resistance, weather resistance, and moldability, may contain various colorants such as dyes and pigments, light or heat stabilizers, inorganic or organic granules, powders, or Fibrous fillers, blowing agents, antistatic agents, etc. can be added. This composition can also be injection molded,
It can be molded by various processing methods such as extrusion molding, and can be used as various molded products with excellent impact resistance and weather resistance, and as a component of laminate structures, such as the outermost layer exposed to sunlight.

[Example] EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, "%" and "part" represent weight % and weight part, respectively, and the particle size is rubber or methyl methacrylate/acrylonitrile/styrene = 20/20/60 (weight %).
) A calibration curve was created from the relationship between the particle diameter determined by electron microscopy for the uncrosslinked resin latex of 2009 and the absorbance at a wavelength of 700 nm of a diluted solution of the latex (0.15 g/β), and the absorbance of the latex was measured. It was determined from the calibration curve.

Examples 1 to 7 (I) Synthesis of enlarged diene rubber (A) 1) Synthesis of synthetic base rubber (a-1) of enlarged diene rubber (A-1) 1.3-Butadiene 66 parts n- Butyl acrylate (BuA) 9 parts Styrene (
ST) 25 parts diisopropylbenzene hydroperoxide 0.2
Part potassium oleate 1.0 part Disproportionated potassium rosinate 1.0 part Sodium birophosphate 0.5 part Ferrous sulfate
0.005 parts dextrose 0
．． 3 parts anhydrous sodium sulfate 0.3
1 part ion-exchanged water 200 parts The above composition was polymerized at 50°C in a 100°C autoclave. 9
Polymerization was almost completed in a few hours, with a conversion rate of 97% and an average particle size of 0.
．． A rubber latex with a pH of 9.0 and a pH of 9.0 was obtained.

Next, an acid group-containing copolymer (B) latex for enlargement was prepared as follows.

n-Butyl acrylate (BuA) 85 parts Methacrylic acid (MAA) 15 parts Potassium oleate 2 parts Dioctylsulfur amber
Sodium acid 1 part Cumene hydroperoxide 0.4 part Sodium nelmaldehyde sulnexylate 0.3
1 part ion-exchanged water 200 parts The above composition was polymerized at 70° C. for 4 hours in a separate polymerization apparatus. The conversion rate was 98%, and a latex with an average particle size of 0.08 μm was obtained. Base rubber (a-1) 100 parts latex (
2 parts of the acid group-containing copolymer (B) latex (solid content) was added with stirring to the acid group-containing copolymer (B) latex (solid content), and stirring was continued for an additional 30 minutes to form an enlarged diene rubber latex (A) with an average particle size of 0.27 μm. -1) was obtained.

2) Synthetic base rubber (a) of enlarged diene rubber (A-2)
-2) Synthesis 1.3-butadiene 100 parts diisopropylbenzene hydroperoxide
0.2 parts t-dodecyl mercaptan 0.5
Part potassium oleate 1.0 part Disproportionated potassium rosinate 1.0 part Sodium birophosphate 0.5 part Ferrous sulfate
0.005 parts dextrose 0
．． 3 parts anhydrous sodium sulfate 0.4 parts ion-exchanged water 200 parts The above composition was polymerized in a 1004 autoclave at 50°C.

Polymerization was almost completed in 9 hours, with a conversion rate of 96%, an average particle size of 0.08 μm, and a base rubber latex (a
-2) was obtained. 2 parts (solid content) of the acid group-containing copolymer (B) latex were added to 100 parts (solid content) of this rubber latex with stirring, and stirring was continued for 30 minutes. A rubber latex (A-2) was obtained.

(II) Production of multi-structure crosslinked acrylic rubber (C) Enlarged diene rubber latex (A-1) 20 parts (solid content)
was transferred to a reaction vessel, 150 parts of ion-exchanged water was added, nitrogen substitution was performed, and the temperature was raised to 70°C (internal temperature). Add 0.12 parts of potassium persulfate (KPS) to 10 parts of ion-exchanged water.
was added thereto, and the following nitrogen-substituted monomer mixture was continuously added dropwise over 2 hours.

BuA 50 parts Allyl methacrylate (AMA) 0.20 parts Ethylene glycol dimecrylate (EDMA)
The internal temperature did not rise at the same time as the addition of 0.10 part was completed (but if the temperature was further raised to 80°C and the reaction was continued for 1 hour, the conversion rate reached 98.0% and the enlarged diene rubber was removed). A multi-structured crosslinked acrylic rubber (C-1) contained inside was obtained.The degree of swelling of this multi-structured crosslinked acrylic rubber was 6.
4. Gel content is 93.0%, average particle size is 0.35μ
It was m.

The following is exactly the same as above except that the type and amount of the enlarged diene rubber latex and the type and amount of monomer for the crosslinked acrylic ester polymer are changed as shown in Table 1. Multi-structure cross-linked acrylic rubber C
-2, C-3 and C-4 latexes were produced. The results are shown in Table 1.

(m) Graft copolymer (Dl) Production of latex Multi-structure crosslinked acrylic rubber (C-1) 30 parts latex (
Solid content) was placed in a reaction vessel, diluted by adding 140 parts of ion-exchanged water, and the temperature was raised to 70°C. +AI! 70 parts of a monomer mixture for graft polymerization consisting of acrylonitrile (AN)/ST=29/71% was prepared, 0.35 part of benzoyl peroxide (BPO) was dissolved therein, and the mixture was purged with nitrogen. This monomer mixture was added to the reaction system at a rate of 15 parts/hr using a metering pump. After the injection of the entire monomer mixture was completed, the system temperature was raised to 80°C, and stirring was continued for 30 minutes to form the graft copolymer latex (D-1).
I got it. The polymerization rate was 99%.

Dilute sulfuric acid was added to a portion of D-1 and the powder was coagulated and dried, and the powder was directly extracted under refluxing methyl ethyl ketone.
/c was measured at 25° C. using dimethylformaluminum 7d (DMF) as a solvent and found to be 0.67 dβ/g.

In addition, types of multi-structure cross-linked acrylic rubber latex,
Graft copolymers D-2 to D-4 were polymerized under exactly the same conditions as above, except that the amount used and the type and amount of monomer for graft polymerization were changed as shown in Table 2. went.

(IV) Method for producing crosslinked acrylic ester rubber (F) Charge the following components into a reaction vessel; Add 1 part of disproportionated potassium rosinate and 120 parts of ion-exchanged water, perform nitrogen purge, and heat at 70°C ( The temperature was raised to (internal temperature). A solution prepared by dissolving 0.10 parts of potassium persulfate (KPS) in 10 parts of ion-exchanged water was added to this, and the following nitrogen-substituted monomer mixture was continuously added dropwise over 2 hours.

BuA 100 parts Acrylic methacrylate (AMA) 0.4 parts Ethylene glycol dimecrylate (EDMA)
At the same time as the completion of dropping 0.2 part, the temperature was raised to 80°C and 1 part was added.
When the reaction was continued for a period of time, the polymerization rate reached 98.5%, and a crosslinked acrylic ester rubber (F-1) was obtained. The degree of swelling of this crosslinked acrylic ester rubber was 6.0, the gel content was 94.5%, and the particle size was 0.10 μm. Table 3 shows the results of polymerization in which the amounts of disproportionated potassium rosin acid and AMA were changed in the same manner.

(V) Production of graft copolymer (G) latex Charge the following components into a reaction vessel: Place 30 parts (solid content) of crosslinked acrylate rubber (F) latex in a reaction vessel, and add 140 parts of ion-exchanged water. After diluting the mixture by adding 50% of the mixture, the temperature was raised to 70°C. Separately, 70 parts of a monomer mixture for graft polymerization consisting of acrylonitrile (AN)/5T=29/71% was prepared, 0.35 part of benzoyl peroxide (BPO) was added and dissolved, and the mixture was purged with nitrogen. This monomer mixture was added to the reaction system at a rate of 15 parts/hr using a metering pump. After the injection of all the monomer mixtures was completed, the system temperature was raised to 80°C and stirring was continued for 30 minutes, and the graft copolymer latex (G
-1) The zero polymerization rate obtained was 9963%. Also (
When ηSP/C was measured in the same manner as in III), it was 0.65 dI2/g.

Similarly, each of F-2 to F-4 was graft-polymerized and G-2
~G-4 was obtained.

The results of G-1 and G-2 to G-4 are also shown in Table 3-2.

(Vl) Salting out and pelletizing the polymer Latex D-1 to D-5 and G-1 to G produced as above
-4 in an amount three times that of the total latex, aluminum chloride (A
ICl,・68! O) It was poured into a 0.15% aqueous solution (90°C) with stirring and solidified.

After the addition of all the latex was completed, the temperature inside the coagulation tank was raised to 93°C and left as it was for 5 minutes. After cooling, it was dehydrated and washed using a centrifugal dehydrator, and then dried. Dry powders of these graft copolymers D-1-D-4 and G-1
-G-4 in the proportions shown in Table 5, and added with 1 part of barium stearate and 0 phenolic antioxidant (trade name: ANTAGE W-300, manufactured by Kawaguchi Chemical Co., Ltd.)
．． 1 part, (trade name Tinuvin-P, manufactured by Ciba Kaigy Co., Ltd., ultraviolet absorber) 0.5 part, polydimethylsiloxane (lo
ocs, 25°C) was added and mixed for 5 minutes at 200 rpm using a Henschel mixer, and then mixed at 40 m
It was pelletized using a mψ extruder at a cylinder temperature of 220°C.

In this way, pellets E-1-E-7 were obtained from the graft copolymers D-1 to D-4 and G-1 to G-4, respectively. In addition, powder of graft copolymer D-5 and powder of G-
1 powder and polycarbonate (trade name: Kneepilon S-
20000, Mitsubishi Gas Chemical Co., Ltd. powder, commercially available AS resin powder (AT/ST = 26/74 (weight ratio), DMF
(25℃) solution ηSp/c=0.65 part℃/g) or commercially available acrylonitrile-〇-methylstyrene (α
MS) copolymer resin (AN/αMS= 20/80 (
weight ratio), DMF (25°C) solution y) sp/c=0
．． 45d12/g) at a weight ratio of 17:26:57 and extruded in the same manner to obtain pellets E-8, E-9 and E-10, respectively.

Comparative Examples 1 to 4 (II) Multi-structure crosslinked acrylic rubber (C) of Example 1
In the production of a multi-layered crosslinked acrylic resin obtained by polymerizing in the same manner as in Example 1, except for adding 1 part of disproportionated potassium rosin acid to the reaction system before the reaction and the conditions shown in Table 4. To 100 parts of each of the dry powders of the graft copolymers D°-1 to D-4, 1 part of nylium stearate was added.
Part, Antige W-3000, Part 1, Tinuvin P0.
5 parts, polydimethylsiloxane (100cs, 25°C)
Add 0.04 part and mix with Henschel mixer at 200 orp.
After combining for 5 minutes, the mixture was made into pellets using a 40-anφ extruder at a cylinder temperature of 220°C. In this way, pellets E'-1 to E'-4 were obtained from the graft copolymers D'-1 to D°-5, respectively.

Evaluation methods E-1 to E-10, E'-1 to E°-4 and commercially available AB
S resin, ASA resin, and AES resin pellets were molded using an injection molding machine (Model 5AV-30A screw type, manufactured by Yamaguchi Seiki Co., Ltd.) under the following three conditions.

Evaluation was carried out by the method shown below. The evaluation results are shown in Tables 5 and 6.

(1) Weather Resistance Changes in gloss were measured using a Weather Meter Model WE-DCH manufactured by Suga Test Instruments Co., Ltd. under the conditions of a black panel of 83° C. and a spray cycle of 18 minutes/120 minutes.

(2) Gloss Suga Test Machine Co., Ltd., digital variable angle glossy needle (measured with an incident thickness of 60°).

(3) Izotsu impact strength Measured according to ASTM D-256.

(4) Melt flow index (MFI) Manufactured by Toyo Baldwin Co., Ltd., AST with melt indexer
Measured using MD-1238 (200°C, 5 kg).

(5) Molding Appearance The change in color of the black colored molded plate is visually determined as the viewing angle with respect to the molded plate is changed.

○: Good General ABS level .

Claims (2)

[Claims] (1) Multi-structure crosslinked acrylic rubber [1] Particles contain 5 to 90% by weight of diene rubber (i) enlarged with acid group-containing copolymer latex, and crosslinked acrylic acid ester in the outer layer. 5 to 90 parts by weight of a latex having a structure containing 95 to 10% by weight of copolymer (ii), which is obtained by using a graft cross-linking agent and a cross-linking agent in combination, and whose main component is an acrylic ester. (as a solid content), an aromatic vinyl compound and the general formula CH_2=CRX (wherein R is -H or -CH_2, X is -CN or -
Represents COOR^1. Here R^1 is carbon atom 1-8
95 to 10 parts by weight of at least one monomer [2] selected from the group consisting of ethylenically unsaturated compounds represented by (100 parts by weight)) [3] 10
~90 parts by weight and graft copolymer resin [6]90~
A composition composed of 10 parts by weight (the total amount of [3] and [6] is 100 parts by weight), the resin [6]
is an aromatic vinyl compound and a general polymer in the presence of 5 to 90 parts by weight of a latex of a crosslinked acrylic ester polymer (iii) mainly composed of an acrylic ester obtained by using a grafting agent and a crosslinking agent. Formula CH_2=CRX (wherein, R is -H or -CH_2, X is -CN or -
Represents COOR^1. Here, R^1 is carbon atom 1~
It is an alkyl group containing 8 alkyl groups. ) 95 to 10 parts by weight of one or more monomers (iv) selected from the group consisting of ethylenically unsaturated compounds represented by
The total amount of iii) and (iv) is 100 parts by weight]
1. A thermoplastic resin composition having excellent impact resistance, weather resistance, and moldability, characterized in that it is obtained by subjecting it to polymerization. (2) The thermoplastic resin composition of claim 1 is blended with a hard thermoplastic resin [7], and the total resin composition ([3] +
[6] + [7]), the hard thermoplastic resin [7] is contained in a proportion such that the content of the former (the sum of [3] and [6]) is 5 to 80% by weight. A thermoplastic resin composition having excellent impact resistance, weather resistance and moldability.