JPH0632961A - Preparation of thermoplastic resin composition excellent in impact resistance, weatherability, moldability and appearance - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in impact resistance, weatherability, moldability and appearance by mixing a specified polymer with a rigid thermoplastic resin at a specified ratio. CONSTITUTION:A graft copolymer resin latex is obtained by polymerizing an aromatic vinyl compound and at least one monomer selected from among ethylenically unsaturated compounds represented by the formula CH2=CRX [wherein H or CH3; and X is CN or COOR<1> (wherein R<1> is 1-8C alkyl)] each in a specified amount in the presence of a specified amount of a latex of a crosslinked acrylic rubber of a multiple structure, which contains within the particles a prescribed amount of a diene rubber having the mean particle diameter enlarged to a given value by a latex of a copolymer containing an acid radical and which has an outer layer part formed from a specified amount of a crosslinked acrylic ester polymer composed mainly of an acrylic ester and obtained by using a grafting agent together with a crosslinking agent. A polymer is deposited from the obtained latex by using an inorganic salt and then mixed with a rigid thermoplastic resin in such a manner that the content of the acrylic rubber in the whole resin composition has a given value.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a thermoplastic resin composition having excellent impact resistance, weather resistance, moldability and appearance.

[0002]

2. Description of the Related Art As an impact resistant resin, there is an ABS resin composed of a resin-rubber two-phase system. However, this ABS resin is deteriorated by ultraviolet rays because the butadiene-based polymer, which is a rubber component for imparting impact resistance, has many chemically unstable double bonds in its main chain. Easy to do,
It is well known that it has poor weather resistance.

As a method of improving the weather resistance of this ABS resin, a method of using a saturated rubber-like polymer having almost no double bond in the main chain has been proposed, of which acrylic acid is a typical one. It is known to use ester rubber. Although this saturated rubber is stable against ultraviolet rays, it does not have cross-linking or graft active sites, so the resin-
It is difficult to take the rubber cross-linking or graft structure which is an essential condition in the rubber two-phase resin, and it has the drawbacks that it is softer, has a lower elastic modulus, and has a slower elastic recovery than the one using the diene rubber. Therefore, when injection molding is performed using a resin composition similar to an ABS resin using such a saturated rubber as a molding material, the orientation of the rubber particles is remarkable, and pearls are formed in the entire region of the surface of the molded product or in a constant flow direction. The luster appears. Further, when colored with a pigment or the like, this tendency is further emphasized, so that there is a drawback that the commercial value is reduced. In order to remedy this drawback, a method of copolymerizing by selecting the type of a crosslinking agent, a method by peroxide crosslinking, etc., and Japanese Patent Publication No. 47-47863 using a multi-structured crosslinked acrylic rubber containing a diene rubber inside the particles. Publication, JP-A-56
-86918, JP-A-56-13311, JP-A-57-167308, and JP-A-58-1.
The method disclosed in Japanese Patent No. 20663 is proposed.

However, these proposed thermoplastic resins are not always satisfactory in terms of the balance between gloss and impact resistance of the molded product when it is molded at high temperature.
That is, when molded in a wide range of molding temperature from low temperature to high temperature, there is a drawback that the high gloss of the molded product cannot be maintained, and a desired thermoplastic resin having excellent impact resistance, weather resistance and moldability has been obtained. The reality was that there was nothing.

As a result of the improvement, the present inventors have studied for the purpose of improving the impact resistance-gloss balance under molding conditions from low temperature to high temperature, and as a result, have found that the diene system having a small particle size produced by a specific method. A cross-linked acrylic acid ester-based polymer containing a diene-based rubber obtained by expanding a rubber latex with an acid group-containing copolymer latex inside the particles, and having an acrylic acid ester as a main component obtained by using a graft crossing agent and a cross-linking agent together. Polymerization of at least one monomer selected from the group consisting of an aromatic vinyl compound and an ethylenically unsaturated compound in the presence of a latex containing a multi-structured crosslinked acrylic rubber in which the coalescence constitutes the outer layer portion thereof By producing a graft copolymer resin by using the above method, the above problems can be solved and a thermoplastic resin composition excellent in impact resistance, weather resistance and moldability can be obtained. Japanese Patent Application No. Sho found Rukoto 61-2
No. 4533 and Japanese Patent Application No. 3-1951.

However, among the above-mentioned graft rubbers, those in which the average particle size of the enlarged diene rubber is smaller than 0.3 μm, the coagulant used when coagulating the graft copolymer polymer from the latex may be an inorganic acid or an inorganic acid. Even if the salt has a high level of gloss at the time of high-temperature molding, when the average particle size of the enlarged diene rubber is 0.3 μm or more, the gloss level of high-temperature molding is high when the coagulant is an inorganic acid. It was found that it decreases with increasing diameter. On the other hand, the use of high impact type is increasing in the market, and in order to obtain the high impact type, it is necessary to increase the particle size of the graft copolymer enlarged diene rubber, and the average particle size is 0. .3μ
There is a need for a graft copolymer of an enlarged diene-based rubber that exhibits excellent balanced physical properties such as a high gloss at the time of high temperature molding and a high level of gloss at the same time.

[0007]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive investigations by the present inventors, a specific method was obtained as a result of the purpose of obtaining a graft copolymer having almost no deterioration in gloss in high temperature molding even in a place where impact resistance is considerably high. The diene rubber latex produced by the above method is used to contain the diene rubber enlarged by the acid group-containing copolymer latex so that the average particle diameter is 0.3 μm or more. By using the graft crosslinker and the crosslinking agent together, Aromatic vinyl compounds and ethylenically unsaturated compounds were obtained in the presence of a latex containing a multi-structured crosslinked acrylic rubber in which the crosslinked acrylic acid ester-based polymer having the obtained acrylic acid alkyl ester as a main component constitutes the outer layer portion thereof. Using a specific inorganic salt from the graft copolymer resin latex obtained by polymerizing at least one monomer selected from the group consisting of compounds By specifying the amount of analysis polymer and the rigid thermoplastic resin, impact resistance, has reached the weather resistance, moldability and found good that the thermoplastic resin composition is obtained in the appearance present invention.

[0008]

Means for Solving the Problems The present invention comprises 2 to 80% by weight of a diene rubber (i), which is an acid group-containing copolymer latex and has an average particle size of 0.3 μm or more, in the inside of a particle. A crosslinked acrylic rubber (20) to 98% by weight of a crosslinked acrylic acid ester-based polymer (ii) containing an acrylic acid ester as a main component, which is obtained by using a crosslinker and a crosslinker together, constitutes the outer layer portion thereof ( I) latex 5
In the presence of 90 parts by weight (as solid content), an aromatic vinyl compound and the general formula CH ₂ = CRX (wherein R represents H or CH ₃ , X represents CN or COOR ¹ , and R ¹ represents R ¹ ). 95 to 10 parts by weight of at least one monomer (II) ((I) and (II) selected from the group consisting of ethylenically unsaturated compounds represented by an alkyl group having 1 to 8 carbon atoms). (100 parts by weight in total) of the graft copolymer resin latex obtained by polymerizing the polymer (A) coagulated using an inorganic salt, and a hard thermoplastic resin (B) as a whole resin composition ( Impact resistance, weather resistance, characterized in that the multi-structured crosslinked acrylic rubber (I) in (A) and (B) is mixed in a ratio such that the ratio is 5 to 80% by weight. A method for producing a thermoplastic resin composition having excellent moldability and appearance.

In the present invention, the enlarged diene rubber (i) constituting the particle inner layer of the multi-structured crosslinked acrylic rubber (I) is 100 to 50% by weight of 1,3-butadiene and CH copolymerizable therewith. ₂ = C <group-containing monomer 0-
50% by weight (total 100% by weight), 1,3-polybutadiene homopolymer or 1,
It is a copolymer composed of 50% by weight or more of 3-butadiene unit. Examples of the copolymer include butadiene-aromatic vinyl compound copolymers such as butadiene-styrene copolymer, butadiene-vinyltoluene copolymer, butadiene-acrylonitrile copolymer, butadiene-methacrylonitrile. Copolymer; butadiene-methyl acrylate copolymer, butadiene-acrylic acid 2-
Butadiene-acrylic acid alkyl ester copolymer such as ethylhexyl copolymer; butadiene-methacrylic acid alkyl ester copolymer such as butadiene-methyl methacrylate copolymer, butadiene-ethyl methacrylate copolymer and the like; In addition, it also includes a terpolymer composed of 50% by weight or more of 1,3-butadiene unit. These can usually be easily produced by known emulsion polymerization. Various kinds of catalysts, emulsifiers and the like can be used without particular limitation in the production of the diene rubber, but the particle diameter of the rubber is 0.04 to 0.
It is preferably 2 μm.

In the present invention, an acid group-containing copolymer latex is used to enlarge the latex of the diene rubber. The acid group-containing copolymer latex must contain the acid group-containing monomer and the alkyl acrylate as constituents. Examples of the acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid and crotonic acid. As the acrylic acid alkyl ester, at least one kind of acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is selected.

Instead of alkyl acrylate,
For example, even if a monomer such as methacrylic acid ester, styrene, or acrylonitrile is used, no effect of enlarging the size is observed. However, it is possible to replace less than half of the acrylic acid alkyl ester with the above-mentioned other monomer or the like.

The acid group-containing monomer is used in the range of 3 to 10% 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, on the contrary, the enlargement ability is too strong, which tends to generate excessive particles exceeding 1 μm, which is not preferable.

The optimum amount of the acid group-containing monomer also changes depending on the degree of hydrophilicity of the alkyl acrylate used. When the hydrophilicity of alkyl acrylate is high, the effect of enlargement is exhibited in the region where the amount of acid group-containing monomer is small, but the latex is destroyed when the amount of acid group-containing monomer increases. Therefore, it is not preferable. Conversely, if the acrylic acid alkyl ester has low hydrophilicity,
In the region where the amount of the acid group-containing monomer is low, the effect of enlargement is small, and the effect cannot be exhibited unless the amount of the acid group-containing monomer becomes larger than a certain amount. For example, in the case of methyl acrylate or ethyl acrylate, which are highly hydrophilic alkyl acrylates, the amount of the acid group-containing monomer is 5 to 10% by weight.
In the case of butyl acrylate or 2-ethylhexyl acrylate, which is a hydrophobic alkyl acrylate ester whose alkyl group has 4 or more carbon atoms,
It is optimum when the amount of the acid group-containing monomer is 13 to 20% by weight. When an acrylic acid alkyl ester having high hydrophilicity is used, the system tends to become unstable even when the amount of the acid group-containing monomer is 5 to 10% by weight, which causes cullet (coarse particles) to occur. In contrast to the difficulty of being easy, when a hydrophobic alkyl acrylate is used, the system does not become unstable and uniform enlarged particles are often obtained.

Examples of the acid group-containing monomer include cinnamic acid, maleic anhydride, butenetricarboxylic acid and the like in addition to the above-mentioned monomers, but these are not practical because they have a large enlargement ability.

The acid group-containing copolymer is used in the form of a latex, and the particle size thereof has a great influence on the enlargement ability, and the preferable average particle size is 0.05 to 0.2 μm.
The range is m. If it is less than 0.05 μm, its bloat capacity is significantly reduced, and if it is more than 0.2 μm, the rubber particle size after bloat becomes too large, which is not suitable for subsequent graft polymerization. It is not preferable because it becomes stable and easily aggregates.

The enlargement of the diene rubber is 0.04 to 0.
It is carried out by adding an acid group-containing copolymer latex to a diene rubber latex having a small particle size such as 2 μm. The addition amount of the acid group-containing copolymer latex is 0.5 to 10 parts by weight (as solid content) with respect to 100 parts by weight (as solid content) of the base diene rubber latex, and particularly preferably 0.8 to 5 parts by weight. With such an addition amount, the particle size of the latex of the enlarged diene rubber (i) is
The particle size of the latex of the crosslinked acrylic acid ester-based polymer, which is adjusted to 0.30 to 1 μm and contains the rubber inside, is in the range of 0.32 to 3 μm, which is preferable in terms of appearance of the molded product.

In the present invention, when the diene rubber is enlarged, the substrate diene rubber latex has a pH of 7.
It is preferable to keep above. When the pH value is on the acidic side, the enlargement effect is low even if the acid group-containing copolymer latex is added, and it is difficult to advantageously produce the resin composition intended by the present invention.

The pH of the base diene rubber latex may be adjusted to 7 or higher during the polymerization of the diene rubber, or separately before the enlargement treatment.

The crosslinked acrylic acid ester polymer (ii) constituting the rubber particle outer layer in the present invention is obtained by using a graft crosslinker and a crosslinking agent in combination.
Examples of the acrylic acid ester which is the main component (50% by weight or more) of i) include, for example, methyl, ethyl,
n-propyl, n-butyl, 2-ethylhexyl, n-
An alkyl ester having 1 to 12 carbon atoms such as lauryl; a haloalkyl ester such as chloroethyl acrylate; an aromatic ester such as benzyl alkylate or phenethyl; and the like are used.

Examples of monomers copolymerizable with these acrylic acid esters include methacrylic acid esters such as methyl methacrylate and butyl methacrylate; acrylonitrile; styrene and the like.
It is optionally used in an amount of 50% by weight or less of the structural unit of i).

By the way, in order to form a crosslinked structure in the acrylic ester type polymer, a graft crossing agent or a crosslinking agent is individually added to the monomer or monomer mixture containing the acrylic acid ester as a main component. A general method is to perform the polymerization. However, in the present invention,
By using a combination of a graft crossing agent and a cross-linking agent when forming a cross-linking structure in this acrylic ester-based polymer, the moldability which cannot be obtained by the conventional cross-linking agent or the cross-linking structure by using the cross-linking agent alone The biggest feature is that the problem of (1) has been solved.

Examples of the graft crossing 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 polyalkylene glycol diacrylate or dimethacrylate, and divinylbenzene.

In producing the thermoplastic resin composition of the present invention, there are the following methods for incorporating the enlarged diene rubber (i) inside the particles of the crosslinked acrylic acid 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 copolymer latex. Next, in the presence of 2 to 80% by weight, preferably 5 to 50% by weight (as solid content) of the enlarged diene rubber latex, the crosslinked acrylic acid ester polymer constituting monomer mixture 20 to
A so-called seed polymerization is carried out in which 98% by weight, preferably 95-50% by weight, is polymerized. The swelling degree (ratio of swelling weight after immersion and standing in methyl ethyl ketone at 30 ° C. for 24 hours and absolute dry weight) of the multi-structured crosslinked acrylic rubber (I) polymerized in this manner is the appearance impact of the molded product. Considering the balance of resin properties such as strength, it is preferably 4 to 16, and more preferably 6 to 9.

In order to adjust the swelling degree within this range, the total amount of the graft crossing agent and the cross-linking agent is added so as to be 0.1 to 10% by weight with respect to the acrylic acid ester polymer constituting monomer. It is preferable. If the total amount of the graft crossing agent and the cross-linking agent is less than 0.1% by weight, the degree of swelling will be outside the above range, which is not preferable in terms of appearance of the molded product, and if it exceeds 10% by weight, the impact strength will decrease with the addition amount. It becomes a tendency. Further, such seed polymerization cannot be performed to obtain a resin having a desired appearance and weather resistance unless the crosslinked acrylic rubber completely covers the enlarged diene rubber.

Then, in the presence of the latex of the thus obtained multi-structured crosslinked acrylic rubber (I), the aromatic vinyl compound and the general formula CH ₂ = CRX (wherein
R represents H or CH ₃ , and X represents CN or COOR ¹ . However, R ¹ is an alkyl group having 1 to 8 carbon atoms. ), At least one monomer (II) selected from the group consisting of ethylenically unsaturated compounds, in the presence of a radical initiator, the total amount of the monomer (II) at once or divided or Polymerization is carried out by continuously adding it to the latex. When the amount of the added monomer is large, the continuous injection method is desirable in order to maintain the melt fluidity of the produced polymer and promote the production of the graft polymer.

Typical examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like. Typical examples of the ethylenically unsaturated compound represented by the general formula CH ₂ = CRX include acrylonitrile, methacrylonitrile, acrylic acid or methyl methacrylate, ethyl, propyl, butyl ester and the like.

The compounding amount of the multi-structured crosslinked acrylic rubber (I) is 5 to 90 parts by weight (as solid content), preferably 10 to 80 parts by weight. If it is less than 5 parts by weight, the impact resistance is inferior, which is not preferable, and if it exceeds 90 parts by weight, the molding appearance is unfavorably deteriorated. The blending amount of the above-mentioned monomer (II) is 95 to 10 parts by weight, preferably 90 to 2 parts.
0 parts by weight. If it is less than 10 parts by weight, the impact resistance is inferior, which is not preferable, and if it exceeds 95 parts by weight, the molding appearance is unfavorably deteriorated.

The graft copolymer resin (A) thus obtained contains 5 to 80% by weight of the multi-structured crosslinked acrylic rubber (I) in the total resin composition (total of (A) and (B)).
It is used as a resin composition by mixing with a separately manufactured hard thermoplastic resin (B) in such a ratio. If the compounding amount of the multi-structured crosslinked acrylic rubber (I) in the whole resin composition is less than 5% by weight, the impact resistance is inferior, and if it exceeds 80% by weight, the molding appearance is inferior and it is not preferable.

As the above-mentioned hard thermoplastic resin (B),
It can be used without particular limitation as long as it is hard at normal temperature, but it is an aromatic vinyl compound-acrylonitrile copolymer, an aromatic vinyl compound-acrylonitrile-methyl methacrylate terpolymer, an aromatic vinyl compound-acrylonitrile. -Lower alkyl acrylate terpolymer, acrylonitrile-lower alkyl acrylate copolymer and polycarbonate, polymethyl methacrylate, acrylonitrile-styrene-maleimide copolymer, ABS resin and the like are exemplified as preferable ones.

In the present invention, examples of the coagulant used for coagulating the polymer from the graft copolymer resin latex include inorganic salts such as magnesium sulfate, calcium sulfate, calcium chloride, aluminum chloride and magnesium chloride. These may be used alone or in combination of two or more.

The thermoplastic resin composition excellent in impact resistance, weather resistance and moldability obtained by the method of the present invention comprises various colorants such as dyes and pigments, stabilizers against light or heat, and inorganic materials, if necessary. Or an organic granular, powdery or fibrous filler,
A foaming agent or the like can be added. Further, this composition is molded by various processing methods such as injection molding and extrusion molding,
It can be used as various molded articles having excellent impact resistance and weather resistance, and also as a constituent element of a laminated structure, for example, an outermost layer exposed to sunlight.

[0033]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. In addition, "%" in Examples and Comparative Examples,
"Part" means "% by weight" and "part by weight", respectively. The "particle size" is the particle size of the resin latex obtained by electron microscopy and a diluted solution of the latex (0.15 g /
A calibration curve was prepared from the relationship with l) the absorbance at a wavelength of 700 nm, and the absorbance of the latex was measured to obtain the calibration curve.

The pellets obtained in the following Examples and Comparative Examples, and the commercially available ABS resin, ASA resin and AES resin pellets were injection-molded by a machine (Yamashiro Seiki Co., Ltd., SAV-30A).
Molded under the following two conditions.

Molding conditions 1: Cylinder temperature 200 ° C., mold temperature 60 ° C., as test pieces for evaluation (a) notched Izod test, (b) flat plate for appearance evaluation (50 × 80 × 3)
mm) Molding condition 2: cylinder temperature 270 ° C., mold temperature 60
℃, Appearance evaluation flat plate (50 × 80 × 3)
mm) The evaluation method was performed as follows.

1. Weather resistance A change in gloss was measured by a weather meter WE-DCH manufactured by Suga Test Instruments Co., Ltd. under the conditions of a black panel 83 ° C. and a spray cycle of 18 minutes / 120 minutes.

2. Gloss Suga Test Instruments Co., Ltd. digital variable angle gloss meter (incident angle: 6
0 °).

3. Izod impact strength Measured according to ASTM D-256.

4. Melt Flow Index (MI) Measured by ASTM D-1238 (200 ° C., 5 Kg) using a melt indexer manufactured by Toyo Baldwin Co., Ltd.

Examples 1 to 6 and Comparative Examples 1 to 9 1) Synthesis of base rubber (1) a-1 1.3-butadiene (Bd) 66 parts 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 pyrophosphate 0.5 part Ferrous sulfate 0.005 part Dextrose 0.3 part Anhydrous sodium sulfate 0.3 part Ion-exchanged water 200 parts The above composition was polymerized at 100C in a 100 l autoclave. Polymerization was almost completed in 9 hours, the conversion rate was 97%,
A rubber latex having a particle size of 0.08 μm and a pH of 9.0 was obtained.

(2) a-2 Bd 100 parts Diisopropylbenzene hydroperoxide 0.2 parts t-dodecyl mercaptan 0.5 parts potassium oleate 1.0 part disproportionated potassium rosinate 1.0 part sodium pyrophosphate 0 0.5 parts Ferrous sulfate 0.005 parts Dextrose 0.3 parts Anhydrous sodium sulfate 0.4 parts Deionized water 200 parts The above composition was polymerized at 50 ° C. in a 100 l autoclave. Polymerization was almost completed in 9 hours, the conversion rate was 96%,
A rubber latex having a particle size of 0.08 μm and a pH of 8.8 was obtained.

(3) a-3 Bd 100 parts potassium persulfate 0.4 parts t-dodecyl mercaptan 0.4 parts potassium oleate 0.3 parts disproportionated potassium rosinate 0.3 parts ion-exchanged water 50 parts above Into a 100 l autoclave, the composition of
Polymerization was initiated at 60 ° C. with stirring at 80 rpm. When the polymerization conversion rate reached 30%, the stirring speed was changed to 140 rpm.
Until the polymerization conversion rate exceeds 50%, the stirring rotation speed is reduced to 100 rpm, and potassium oleate,
A mixture of 1 part each of disproportionated potassium rosinate and 15 parts water was added intermittently to the polymerization system. Polymerization is almost complete in 80 hours,
A rubber latex having a conversion rate of 98.0%, a particle size of 0.32 μm and a pH of 8.9 was obtained.

2) Synthesis of acid group-containing copolymer for enlargement (1) b-1 BuA 85 parts Methacrylic acid (MAA) 15 parts Potassium oleate 2.0 parts Sodium dioctylsulfosuccinate 1.0 part Cumene hydroper Oxide 0.4 part Sodium formaldehyde sulfoxylate 0.3 part Ion-exchanged water 200 parts The above composition was polymerized in another polymerization apparatus at 70 ° C. for 4 hours. A rubber latex having a conversion rate of 98% and a particle diameter of 0.08 μm was obtained.

(2) b-2 In b-1, the amounts of BuA and MAA are set to 80
The polymerization was carried out in the same manner as in the polymerization of b-1 except that the amount was changed to 20 parts. The conversion rate was 97% and the particle size was 0.09 μm.

(3) b-3 In b-1, the amounts of BuA and MAA are each 75
The polymerization was carried out in the same manner as in b-1 except that the amount was changed to 25 parts. The conversion rate was 98% and the particle size was 0.09 μm.

3) Synthesis of Enlarged Diene-Based Rubber Base rubber latex 10 synthesized in 1) shown in Table 1
To 0 parts (as solid content), 2 parts (as solid content) of the acid group-containing copolymer latex for enlargement synthesized in 2) was added with stirring, and the mixture was further stirred for 30 minutes, and the enlargement diene rubber latex was added. Got Table 1 shows the average particle size after the enlargement.

[0047]

[Table 1]

4) Manufacture of cross-linked acrylic rubber having multiple structures Enlarged diene rubber latex (c-1 to c-6) 20
Parts (as solid content) were transferred to a reaction kettle, 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 (KPS) in 10 parts of ion-exchanged water was added thereto, and the following nitrogen-substituted monomer mixture was continuously added dropwise over 2 hours.

BuA 80 parts Allyl methacrylate (AMA) 0.32 parts Ethylene glycol dimethacrylate (EDMA) 0.16 parts The internal temperature does not rise at the same time as the dropping is completed, but further 80
The temperature was raised to 0 ° C. and the reaction was continued for 1 hour to obtain a multi-structured acrylic rubber (d-1 to d-6) containing the enlarged diene rubber inside. Polymerization rate, degree of swelling of crosslinked acrylic rubber with multiple structure,
The results of gel content and average particle size are shown in Table 2.

[0050]

[Table 2]

5) Preparation of Graft Copolymer Resin Latex 30 parts (as solid content) of multi-structured crosslinked acrylic rubber (d-1 to d-6) latex is placed in a reaction kettle and diluted with 140 parts of ion-exchanged water. The temperature was raised to 70 ° C. Separately, 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, and then the atmosphere was replaced with nitrogen. This monomer mixture was added into the above reaction system at a rate of 15 parts / hr using a metering pump. After the injection of all the monomer mixture was completed, the system temperature was raised to 80 ° C.
Stirring is continued for 0 minutes, and the graft copolymer resin latex (e
-1 to e-6) were obtained. The polymerization rate was 99%.

A powder obtained by adding dilute sulfuric acid to a part of the latex and coagulating and drying was directly extracted under reflux of methyl ethyl ketone, and ηsp / C in the extraction portion was adjusted to dimethylformamide (DM
The measurement was performed at 25 ° C. using F) as a solvent. The results are shown in Table 3.

[0053]

[Table 3]

6) Polymer Coagulation and Pelletization Latexes e-1 to e-6 produced as described above
0.1% of the coagulant shown in Table 4 in an amount 3 times the total latex.
The mixture was poured into a 5% aqueous solution (90 ° C.) with stirring to solidify.

After the addition of all the latexes was completed, the temperature inside the coagulation tank was raised to 93 ° C. and left as it was for 5 minutes. After cooling this, it was drained and washed with a centrifugal dehydrator and dried. Dry powders of these graft copolymers e-1 to e-6
100 parts of each, barium stearate 1 part, Antage W-300 (trade name, manufactured by Kawaguchi Chemical Co., Ltd., phenolic antioxidant) 0.1 part, Tinuvin-P (trade name, manufactured by Ciba Geigy, UV rays) (Absorbent) 0.5 part was added, and the mixture was mixed at 2000 rpm for 5 minutes with a Henschel mixer, and then the cylinder temperature was 220 by a 40 mmφ extruder.
Pelleted at ° C.

Thus, the graft copolymers e-1 to e-1
e-6 to pellets f-1 to f-5 and f-7 to
f-14 was obtained. Further, the powder of the graft copolymer e-6 and the commercially available AS resin powder (AN / ST = 26/74 (weight ratio), ηsp / C = 0.65) were blended at 70:30 (weight ratio), respectively. And extruded in the same manner to obtain pellets f-6 and f-15, respectively. The evaluation results are shown in Table 4.

Comparative Example 10 Evaluation was carried out in the same manner as in Comparative Example 1 except that the base rubber (a-1) was used without enlargement (f-1).
6). The evaluation results are shown in Table 4.

Comparative Example 11 Evaluation was carried out in the same manner as in Comparative Example 1 except that the base rubber (a-3) was used without enlargement (f-1).
7). The evaluation results are shown in Table 4.

[0059]

[Table 4]

[0060]

From the above results, even if the average particle size of the diene rubber is set to 0.3 μm or more in order to make the impact resistance of the graft copolymer considerably high, the polymer of the graft copolymer can be obtained. It is clear that the use of a specific inorganic salt as the coagulant used for coagulation suppresses the gloss reduction at high temperatures.

Claims (1)

[Claims] 1. A diene rubber (i) 2 enlarged by an acid group-containing copolymer latex to have an average particle diameter of 0.3 μm or more.
20 to 98% by weight of a crosslinked acrylic acid ester-based polymer (ii) containing 80% by weight in the interior of the particles and containing acrylic acid ester as a main component obtained by using a graft crossing agent and a crosslinking agent in combination.
5 to 90 parts by weight (as solid content) of a latex of a multi-structured crosslinked acrylic rubber (I) having the outer layer part
In the presence of an aromatic vinyl compound and the general formula CH ₂ =
CRX (wherein R is H or CH ₃ and X is CN or CO
Represents OR ¹ . However, R ¹ is an alkyl group having 1 to 8 carbon atoms. ) At least one monomer (II) 95 to 10 selected from the group consisting of ethylenically unsaturated compounds represented by
Polymer (A) coagulated by using an inorganic salt from a graft copolymer resin latex obtained by polymerizing 100 parts by weight (total amount of (I) and (II) 100 parts by weight), and a hard thermoplastic resin The proportion of the multi-structured crosslinked acrylic rubber (I) in the total resin composition (the total of (A) and (B)) is 5 to 8 (B).
A method for producing a thermoplastic resin composition, which is excellent in impact resistance, weather resistance, moldability and appearance, characterized by mixing in a proportion of 0% by weight.