JPH0415255B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a thermoplastic resin composition that has excellent weather resistance, impact resistance, and appearance. [Prior Art] As an impact-resistant resin, there is an ABS resin consisting of a resin-rubber two-phase system. However, this ABS resin
The butadiene-based polymer, which is a rubber component that provides impact resistance, has many chemically unstable double bonds in its main chain, so it is easily degraded by UV rays and has poor weather resistance. It is well known that it is inferior to As a way to improve the weather resistance of this ABS resin,
A method using a saturated rubber-like polymer having almost no double bonds in the main chain has been proposed, and a typical method using an acrylic ester rubber is known. The so-called ASA resin, which is made by graft polymerizing styrene and acrylonitrile to this acrylic ester rubber, has excellent weather resistance and, like ABS resin, has a good balance of physical properties such as mechanical strength, impact strength, and heat resistance. Because it is easy to mold and process, it is widely used both indoors and outdoors in the fields of vehicles, home appliances, industrial parts, etc. However, in these application fields or in the development of new applications, the following problems have occurred with ASA resins. In other words, although acrylic ester rubber is stable against ultraviolet rays, it does not have crosslinking or grafting active sites, so it is difficult to form rubber crosslinking or graft structures, which are essential conditions for resin-rubber two-phase resins. Compared to those using diene rubber, it has the drawbacks of being soft, having a low elastic modulus, and slowing elastic recovery. Therefore, ABS using acrylic ester rubber
When injection molding is performed using a resin composition similar to resin as a molding material, the orientation of the rubber particles is significant.
Pearl-like luster appears over the entire surface area of the molded product or in a certain direction of flow. Furthermore, when colored with pigments or the like, this tendency is further accentuated, resulting in a reduction in commercial value. In order to improve this drawback, methods include copolymerization by selecting the type of crosslinking agent, methods using peroxide crosslinking, and Japanese Patent Publication No. 47-47863 using multi-structure crosslinked acrylic rubber containing diene rubber inside the particles. Publication, Japanese Unexamined Patent Publication No. 1983-
Publication No. 86918, Japanese Patent Application Publication No. 133311/1983, Japanese Patent Application Publication No. 1986-133311, Japanese Patent Application Publication No.
Methods disclosed in JP-A No. 57-167308, Japanese Patent Application Laid-Open No. 120663-1980, etc. have been proposed. [Problems to be Solved by the Invention] However, regarding the resin compositions described in the above-mentioned publications, etc., 1. Although the resin compositions are better than ABS resins in weather resistance, they do not reach the level of an original weather-resistant resin. 2. Moldability During injection molding, the deformation and orientation of rubber particles is significant.
Pearl-like luster still appears over the entire surface area of the molded product or in a certain direction of flow. 3 Regarding the relationship between molded product gloss and impact resistance, the balance between gloss and impact resistance is at a low level,
In particular, low-temperature impact resistance is at a low level. Problems that should be improved have been pointed out, and the current situation is that a thermoplastic resin having the desired excellent impact resistance, weather resistance, and moldability has not yet been obtained. [Means for Solving the Problems] In view of the current situation, the inventors of the present invention have made extensive studies with the aim of improving these, and as a result, they have developed a method for converting small-particle-diameter diene rubber latex produced by a specific method into a copolymer containing acid groups. The particles contain diene rubber enlarged with polymer latex, and the outer layer is a crosslinked acrylic ester polymer formed using a combination of a grafting agent and a crosslinking agent, with acrylic ester as the main component. A graft copolymer resin is produced by copolymerizing at least one aromatic vinyl compound and at least one ethylenically unsaturated compound in the presence of a latex containing a multilayered acrylic rubber comprising By blending with AES resin and other hard thermoplastic resins, the above problems can be solved at once, resulting in a thermoplastic resin composition that has excellent impact resistance, weather resistance, and molded appearance at room and low temperatures. The present invention was achieved by discovering that the following can be obtained. That is, the thermoplastic resin composition of the present invention contains 2 to 80% by weight of diene rubber (i) enlarged with an acid group-containing copolymer latex inside the particles, contains an acrylic ester as a main component, and contains a graft cross-agent. Latex 5 of a multi-layered crosslinked acrylic rubber (1) whose outer layer is composed of 20 to 98% by weight of a crosslinked acrylic ester polymer (ii) formed using a combination of a crosslinking agent and a crosslinking agent. 10-90% by weight of at least one aromatic vinyl compound in the presence of ~90 parts by weight (as solids)
and the general formula CH ₂ = CRX (wherein, R is H or CH ₃ and X is CN or
Represents COOR ¹ . However, R ¹ is an alkyl group having 1 to 8 carbon atoms. ) Monomer mixture (2)95 consisting of 90 to 10% by weight of at least one type of ethylenically unsaturated compound represented by (2)95
~10 parts by weight (total amount of (1) and (2) 100 parts by weight) Graft copolymer resin () 5-95% by weight, AES resin 5-95% by weight () and other hard materials Consisting of 0 to 80% by weight of thermoplastic resin (),
This is a thermoplastic resin composition in which the total amount of (), (), and () is 100% by weight. In the present invention, multi-structure cross-linked acrylic rubber
Enlarged diene rubber (i) constituting the inner layer of particles in (1)
contains 100 to 50% by weight of 1,3-butadiene and 0 monomers having a CH ₂ =C group copolymerizable therewith.
~50% by weight (total 100% by weight), and is a 1,3-polybutadiene homopolymer or a copolymer composed of 50% by weight or more of 1,3-butadiene units. Examples of the copolymer include butadiene-styrene copolymer,
Butadiene-aromatic vinyl compound copolymers such as butadiene-vinyltoluene copolymers; butadiene-acrylonitrile copolymers; butadiene-methacrylonitrile copolymers; butadiene-
Butadiene-acrylic acid alkyl ester copolymers such as methyl acrylate copolymer, butadiene-ethyl acrylate copolymer, butadiene-butyl acrylate copolymer, butadiene-2-ethylhexyl acrylate copolymer; butadiene - butadiene-methacrylic acid alkyl ester copolymers, such as methyl methacrylate copolymers, butadiene-ethyl methacrylate copolymers, etc., further comprising 50% by weight of 1,3-butadiene units;
It also includes ternary copolymers composed of the above. These can usually be easily produced by known emulsion polymerization. In addition, various types of catalysts, emulsifiers, etc. can be used without particular restrictions in the production of this diene rubber, but the particle size of this rubber is 0.04~
Preferably, the thickness is 0.2 μm. In the present invention, an acid group-containing copolymer latex is used to enlarge the diene rubber latex. It is essential that this acid group-containing copolymer latex contains an acid group-containing monomer and an acrylic acid alkyl ester as constituent components. Examples of acid group-containing monomers include 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;
If it exceeds the weight percentage, on the contrary, the enlargement ability is too strong,
This is not very preferable since it tends to produce particles that are larger than 1 μm. 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 thickening effect is exhibited in areas where the amount of acid group-containing monomer is small, but when the amount of acid group-containing monomer increases, the latex is destroyed. This is not desirable because it causes Conversely, when the hydrophilicity of the acrylic acid alkyl ester is low, the enlargement effect is small in the region where the amount of the acid group-containing monomer is low, and the effect is exerted only when the amount of the acid group-containing monomer exceeds a certain level. Can not. For example, in the case of methyl acrylate and ethyl acrylate, which are highly hydrophilic acrylic acid alkyl esters, the optimum amount of acid group-containing monomer is 5 to 10% by weight; In the case of butyl acrylate and 2-ethylhexyl acrylate, which are hydrophobic acrylic acid alkyl esters having 4 or more carbon atoms, the optimum amount is 13 to 20% by weight of the acid group-containing monomer. Note that when a highly hydrophilic acrylic acid alkyl ester is used, the system tends to become unstable even when the amount of acid group-containing monomer is 5 to 10% by weight, resulting in the formation of cullets (coarse particles). However, when a hydrophobic acrylic acid alkyl ester is used, the system does not become unstable and uniform enlarged particles can often be obtained. In addition to the above monomers, the acid group-containing monomers include:
There are cinnamic acid, 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, and its particle size has a great effect on its enlargement ability, with the preferred average particle size being 0.05 to 0.2μ.
m range. If it is smaller than 0.05 μm, the enlargement ability will be significantly reduced, and if it is larger than 0.2 μm, the rubber particle size after enlargement will become too large, which may cause problems in subsequent graft polymerization. It becomes stable and tends to aggregate. 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 to 10 parts by weight (as solid content) per 100 parts by weight (as solid content) of the base diene rubber latex.
The amount is particularly preferably 0.5 to 5 parts by weight.
With such an amount added, the particle size of the latex of the enlarged diene rubber (i) is adjusted to 0.15 to 1 μm, and the particle size of the latex of the crosslinked acrylic ester polymer containing this rubber inside is adjusted to 0.15 to 1 μm. The range is 0.18 to 3 μm, which is preferable in terms of appearance. In the present invention, when the diene rubber is enlarged, the pH of the base diene rubber latex is 7.
It is preferable to keep it at a level higher than that. When the PH value is on the acidic side, even if an acid group-containing copolymer latex is added, the enlargement effect is low, and it is difficult to advantageously produce the composition targeted by the present invention. The pH of the base diene rubber latex may be adjusted to 7 or higher during the polymerization of the base diene rubber, or may be adjusted separately before the enlargement treatment. The acrylic ester that is the main component (50% by weight or more) of the crosslinked acrylic ester polymer (ii) in the present invention includes, for example, ester moieties such as methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl. , alkyl esters having 1 to 12 carbon atoms such as n-lauryl; haloalkyl esters such as chloroethyl acrylate; aromatic esters such as benzyl acrylate or phenethyl; and the like. Monomers that can be copolymerized with these acrylic esters include methacrylic esters such as methyl methacrylate and butyl methacrylate; acrylonitrile; and styrene. , these may be used in an amount of 50% by weight or less as a structural unit, if desired. In order to form a cross-linked structure in this acrylic ester polymer, a polyfunctional grafting agent or a polyfunctional crosslinking agent is added to the monomer or monomer mixture containing the acrylic ester as a main component. A common method is to use it alone and polymerize it. However, in the present invention, by using a combination of a polyfunctional graft cross-linking agent and a polyfunctional cross-linking agent, the problems such as moldability and gloss of molded products that occurred in the above-mentioned single-use system were solved. It is a polymerization method. The graft cross-agent used here refers to a compound that has 2 to 3 unsaturated groups having addition polymerizability, and each unsaturated group has a large difference in polymerization reactivity.Specific examples include: Examples include allyl esters of unsaturated acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, cyanuric acid, and isocyanuric acid. In addition, a polyfunctional crosslinking agent refers to a compound that has a plurality of unsaturated groups having addition polymerizability, and the polymerization reactivity of each unsaturated group is approximately the same or has a small difference, and specific examples include: Examples include diacrylic acid ester, dimethacrylic acid ester, and divinylbenzene of polyalkylene glycol. When producing the thermoplastic resin composition of the present invention, the following method can 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 copolymer latex. Next, this enlarged diene rubber latex 2~
In the presence of 80% by weight, preferably 5 to 50% by weight (as solid content), 20 to 98% by weight, preferably 50% by weight, of the crosslinked acrylic ester polymer constituent monomer mixture
A so-called seed polymerization is carried out in which ~95% by weight is polymerized. The swelling degree (the ratio of the swollen weight to the absolute dry weight after immersion in methyl ethyl ketone at 30°C for 24 hours) of the multi-structure crosslinked acrylic rubber (i) polymerized in this way is determined by the appearance of the molded product. Considering the balance of resin properties such as impact strength, it is 4 to 16, preferably 6.
-9 is desirable. In order to adjust the degree of swelling within this range, the above-mentioned grafting cross-agent and cross-linking agent should be used in combination so that the total amount thereof is 0.1 to 10% by weight based on the constituent monomers of the acrylic ester polymer. It is preferable to do so. If the total amount of the graft cross-linking agent and crosslinking agent is less than 0.1% by weight, the degree of swelling will be outside the above range, which is unfavorable for the appearance of the molded product, and if the amount added exceeds 10% by weight, the impact strength will tend to decrease. Become. Further, unless such seed polymerization is carried out so that the cross-linked acrylic rubber completely covers the enlarged diene rubber, the desired resin with excellent appearance and weather resistance cannot be obtained. Next, in the presence of 5 to 90 parts by weight (as solid content) of the latex of the multi-structure crosslinked acrylic rubber (1) thus obtained, 10 to 90 parts by weight of at least one aromatic vinyl monomer is added. and the general formula CH ₂ = CRX (wherein, R is H or CH ₃ and X is CN or
Represents COOR ¹ . However, R ¹ is an alkyl group having 1 to 8 carbon atoms. ) Monomer mixture (2)95 consisting of 90 to 10% by weight of at least one type of ethylenically unsaturated compound represented by (2)95
~10 parts by weight (total amount of (1) and (2) is 100 parts by weight),
Polymerization is carried out by adding the entire amount of the monomer mixture (2) to the latex all at once, in portions, or continuously in the presence of a radical initiator. When the amount of the monomer mixture to be added is large, a continuous injection method is desirable in order to maintain the melt fluidity of the resulting polymer and to promote the formation of the graft polymer. The aromatic vinyl compound includes styrene,
Representative examples include α-methylstyrene and vinyltoluene. Also, the general formula CH ₂ =
Representative examples of the ethylenically unsaturated compound represented by CRX include acrylonitrile, methacrylonitrile, and methyl, ethyl, propyl, and butyl esters of acrylic acid or methacrylic acid. In addition, the AES resin () used in the present invention is EPDM (ethylene-propylene-nonconjugated diene rubber elastic material) used in the production of AES resin.
However, the ethylene/propylene weight ratio is 80/20~30/
70, the amount of non-conjugated diene (dicyclopentadiene, alkylidenenorbornene, 1,4-hexadiene, etc.) is 0.1 to 10 mol%, and such
EPDM is mixed with an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, or nuclear halogenated styrene, preferably styrene, and a vinyl cyanide compound such as acrylonitrile or methacrylonitrile, preferably acrylonitrile, in the form of a lump. Any material that can be obtained by a well-known method of graft polymerization using suspension or emulsion polymerization can be used without particular limitation. The thermoplastic resin composition of the present invention mainly comprises 5 to 95% by weight of the above-mentioned graft copolymer resin () and
Consists of AES resin () 5-95% by weight,
If desired, add other hard thermoplastic resins ()
These (), () and () can be blended in an amount of 0 to 80% by weight based on the total resin composition.
Let the total amount be 100% by weight. As the hard thermoplastic resin, any material that is hard at room temperature can be used without any particular restriction. Polymer, acrylonitrile-α
-Methylstyrene copolymer, α-methylstyrene-methylmethacrylate-acrylonitrile terpolymer, styrene-methylmethacrylate copolymer, styrene-acrylonitrile-methylmethacrylate terpolymer, styrene-maleic anhydride copolymer , acrylonitrile-styrene-maleic anhydride terpolymer, styrene-maleimide copolymer, acrylonitrile-maleimide copolymer, vinyl polymers such as polystyrene, polyvinyl chloride, chlorinated polyethylene, ABS resin and polycarbonate Examples include impact-resistant resins such as resins, and engineering plastics such as polyphenylene ether, polyethylene terephthalate, and polysulfone. The thermoplastic resin composition of the present invention is prepared by blending the graft copolymer resin (), AES resin (), and, if desired, other hard thermoplastic resin () in the above-mentioned range, and mixing it with a Henschel mixer or tumbler. After mechanically mixing with a melt extruder or a Banbury mixer, the mixture is kneaded into pellets. The thermoplastic resin composition of the present invention may optionally contain various coloring agents such as dyes and pigments, lubricants such as metal soap,
Hindered amine compounds, benzotriazole compounds, and benzophenone compounds are used alone or in combination as stabilizers against light, and hindered phenol compounds, thioether compounds, and phosphite compounds are used alone or in combination as stabilizers against heat. , inorganic or organic granular, powdery or fibrous fillers, foaming agents and the like can be added. In addition, this composition can be molded by various processing methods such as injection molding and 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 those exposed to sunlight. It can also be used as the outermost layer. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, % and parts represent weight % and parts by weight, respectively, and the particle size of each latex is methyl methacrylate/acrylonitrile/styrene = 20/20/
A calibration curve was created from the relationship between the particle diameter determined by electron microscopy for an uncrosslinked resin latex composed of 60% (weight ratio) and the absorbance at a wavelength of 700 μm of a diluted solution (0.5 g/) of that latex. The absorbance was measured and calculated from the calibration curve. Further, the gel content and degree of swelling of the multi-structure cross-linked acrylic rubber (1) were calculated using the following formula. Gel content = W ₂ /W ₀ ×100 (%) Swelling degree = W ₁ −W ₂ /W ₂ (where, W ₀ = initial sample weight, W ₁ = approx. 150
Soak the sample in twice the volume of methyl ethyl ketone and
℃, weight after standing for 24 hours, weight in absolute dry state of W ₂ = W ₁ ) Examples 1 to 5 () Synthesis of enlarged diene rubber (A) 1 Enlarged diene rubber (A-1 ) Synthesis of basic rubber (a-1) 1,3-butadiene (Bd) 66 parts n-butyl acrylate (BuA) 9 parts styrene (ST) 25 parts diisopropylbenzene hydroperoxide
0.2 parts Potassium oleate 1.0 parts Disproportionated potassium rosinate 1.0 parts Sodium pyrophosphate 0.5 parts Ferrous sulfate 0.005 parts Dextrose 0.3 parts Anhydrous sodium sulfate 0.3 parts Deionized water 200 parts The above composition was placed in an autoclave at 100 °C. 50
Polymerized at ℃. Polymerization was almost completed in 9 hours, and a rubber latex with a conversion rate of 97%, a particle size of 0.08 μm, and a pH of 9.0 was obtained. Next, an acid group-containing copolymer (B) latex for enlargement was synthesized as follows. BuA 85 parts Methacrylic acid 15 parts Potassium oleate 2 parts Sodium dioctyl sulfosuccinate 1 part Cumene hydroperoxide 0.4 parts Sodium formaldehyde sulfoxylate
0.3 parts ion-exchanged water 200 parts The above composition was polymerized at 70° C. for 4 hours in a separate polymerization apparatus. Conversion rate is 98%, average particle size
A latex of 0.08 μm was obtained. Base rubber (a
-1) Add 2 parts (solid content) of the above acid group-containing copolymer (B) latex to 100 parts (solid content) with stirring, and continue stirring for an additional 30 minutes to increase the particle size to an average particle size of 0.27 μm. A diene rubber (A-1) latex was obtained. 2 Synthesis of enlarged diene rubber (A-2) Synthesis of base rubber (a-2) Bd 100 parts diisopropylbenzene hydroperoxide
0.2 parts t-dodecyl mercaptan 0.5 parts Potassium oleate 1.0 parts Disproportionated potassium rosinate 1.0 parts Sodium pyrophosphate 0.5 parts Ferrous sulfate 0.005 parts Dextrose 0.3 parts Anhydrous sodium sulfate 0.4 parts Ion exchange water 200 parts The above composition in autoclay at 100 °C at 50 °C.
Polymerized with Polymerization was almost completed in 9 hours, and the conversion rate was
Base rubber (a-
2) Latex was obtained. This rubber latex
Add 2 parts (solid content) of the acid group-containing copolymer (B) latex to 100 parts (solid content) with stirring,
Stirring was continued for a minute to obtain enlarged diene rubber (A-2) latex with an average particle size of 0.28 μm. () Production of multi-structure cross-linked acrylic rubber (C) Transfer 20 parts (solid content) of enlarged diene-based (A-1) rubber latex to a reaction vessel, add 1 part of disproportionated potassium rosinate, and 150 parts of ion-exchanged water. was added, the mixture was replaced with nitrogen, 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 80 parts Allyl methacrylate (AMA) 0.32 parts Ethylene glycol dimethacrylate 0.16 parts As soon as the dropwise addition was completed, the internal temperature stopped rising, but if the temperature was further raised to 80°C and the reaction continued for 1 hour, the polymerization rate decreased.
98.8%, and a multi-structured cross-linked acrylic rubber (C-1) containing enlarged diene rubber therein was obtained.
The degree of swelling of this multi-structure cross-linked acrylic rubber is 6.4.
The gel content was 93.0% and the particle size was 0.28 μm. The type of enlarged diene rubber latex is A-2.
A latex of multi-structured cross-linked acrylic rubber (C-2) was produced under the same conditions as above except that . () Production of graft copolymer (D) latex Put 50 parts (solid content) of multi-structure crosslinked acrylic rubber (C-1) latex into a reaction vessel, dilute with 140 parts of ion-exchanged water, and heat to 70°C. It was warm. Separately, acrylonitrile (AN)/styrene (ST) = 29/
50 parts of a monomer mixture for graft polymerization consisting of 71 (weight ratio) was prepared, and after dissolving 0.35 part of benzoyl peroxide (BPO), the mixture was purged with nitrogen. This monomer mixture was added to the reaction system at a rate of 15 parts/hour using a metering pump. After the injection of all the monomers was completed, the temperature inside the system was raised to 80°C, and stirring was continued for 30 minutes to obtain a graft copolymer (D-1) latex. The polymerization rate was 99%. Dilute sulfuric acid was added to a portion of Latex D-1, and the powder was coagulated and dried. Direct extraction was performed under refluxing methyl ethyl ketone, and the ηsp/C of the extracted portion was measured at 25°C using dimethylformalide as a solvent, and it was found to be 0.67.
It was hot. In addition, a graft copolymer (D-2) was polymerized under exactly the same conditions as above except that the type of multi-structure crosslinked acrylic rubber latex was changed to C-2. () Salting out and pelletizing the polymer Latexes D-1 and D-2 produced as described above were each treated with a 0.15% aqueous solution of aluminum chloride (AlCl ₃ 6H ₂ O) (90% ℃) with stirring, and solidified. After all the latex has been added, the temperature inside the coagulation tank is
The temperature was raised to 93°C and left as it was for 5 minutes. After cooling, it was dehydrated using a centrifugal dehydrator, washed, and dried. Dry powder of these graft copolymers D-
1. D-2, AES resin JSR110 (trade name, manufactured by Japan Synthetic Rubber Co., Ltd.), and commercially available AS resin powder (AN/ST=
26/74 (weight ratio), ηsp/C=0.65), commercially available AN-
α-methylstyrene (αMS) copolymer resin (αSAN) (AN/αMS=20/80 (weight ratio), ηsp/
C=0.45) or polycarbonate powder (Iupilon S-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the proportions shown in Table 1, 1 part of barium stearate and ANTAGE W-300 ( Product name, manufactured by Kawaguchi Chemical Co., Ltd., phenolic antioxidant)
After adding 0.1 part of Tinuvin-P (trade name, manufactured by Ciba Kaigy Co., Ltd., ultraviolet absorber) and 0.5 parts of Tinuvin-P (trade name, manufactured by Ciba Kaigy Co., Ltd., ultraviolet absorber), the mixture was mixed for 5 minutes at 2000 rpm using a Henschel mixer, and then pelletized using a 40 mmφ extruder at a cylinder temperature of 200°C. In this way, pellets E-1, E-2, E-3, E-4, and E-5 were obtained from the graft copolymers D-1 and D-2, respectively. Comparative Example 1 Example using cross-linked acrylic rubber containing normal diene rubber inside KPS 0.3 parts t-dodecyl mercaptan 0.4 parts Potassium oleate 0.5 parts Disproportionated potassium rosinate 0.5 parts Ion-exchanged water 50 parts Above composition The material was placed in a 100° autoclave, and polymerization was started at 60°C with stirring at 80 rpm. When the polymerization conversion rate reaches 30%, increase the stirring speed.
The stirring speed was increased to 140 rpm, and when the polymerization conversion rate exceeded 50%, the stirring speed was lowered to 100 rpm, and a mixture of 1 part each of potassium oleate and disproportionated potassium rosinate and 15 parts of water was intermittently added to the polymerization system. added. Polymerization was almost completed in 70 hours, and a rubber latex with a polymerization conversion rate of 98.0%, a particle size of 0.28 μm, and a pH of 8.9 was obtained. C-1, D-1, and E of Example 1 except that the above rubber was used instead of the enlarged diene rubber (A-1).
Pellet E-6 was obtained in exactly the same manner as in the production of Pellet-1. Comparative Example 2 Example using a crosslinked acrylic rubber containing a small particle size diene rubber inside The base rubber (a-
2) was used as it was without any enlargement treatment.
Pellet E-7 was obtained in exactly the same manner as in the production of C-1, D-1, and E-1 in Example 1. Comparative Example 3 Example using a crosslinked acrylic rubber containing no enlarged diene rubber inside 200 parts of ion-exchanged water containing 0.15 parts of KPS substituted with nitrogen was placed in a polymerization vessel, and the temperature was raised to 70°C. Separately, a monomer mixture having the following composition was prepared and replaced with nitrogen. BuA 100 parts AMA 0.6 parts Sodium dioctyl sulfosuccinate 2 parts 15 parts were taken from this monomer mixture, added to a polymerization vessel, and polymerized in about 20 minutes. The remaining monomer mixture was continuously added to the polymerization system over about 2 hours, and after the addition was completed, the temperature of the system was raised to 80°C and the reaction was continued for 30 minutes. To 100 parts (solid content) of the obtained rubber latex, 2 parts (solid content) of the aforementioned acid group-containing copolymer (B) latex for enlargement was added with stirring, and stirring was continued for 30 minutes to form a rubber latex with a particle size of 0.28 μm. A swollen rubber latex was obtained. C-1, D-2, and E of Example 1 except that the above rubber was used instead of the enlarged diene rubber (A-1).
Pellet E-8 was obtained in exactly the same manner as in the production of Pellet-1. Comparative Example 4 An example using cross-linked acrylic rubber containing diene rubber enlarged with salt. 1.5 parts of Glauber's salt was added to 100 parts of the base rubber (a-2) latex with stirring, and the stirring was continued for 30 minutes.
A rubber latex enlarged with salt and having an average particle diameter of 0.25 μm was obtained. Grafting was carried out according to C-1 and D-2 of Example 1, except that the above enlarged rubber was used instead of the diene rubber (A-1) enlarged with acid group-containing copolymer (B) latex. Polymerization was carried out. However, during the polymerization, the system became unstable and the polymer coagulated, so that the polymerization was not completed. In this way, the graft polymerization of a thickened rubber system using salt is more susceptible to the effects of the emulsifier added, the type and amount of salt, temperature, etc., compared to the thickening system using acid group-containing copolymer (B) latex. It has been difficult to stably obtain graft polymers. Comparative Example 5 Example where the resin composition does not contain AES resin Pellets E-9 were produced in exactly the same manner as in Example 1, except that no AES resin was added. Obtained. Comparative Example 6 Example where the resin composition does not contain the graft copolymer resin () Without using the graft copolymer resin (),
Pellet E is made by blending AES resin and AS resin.
I got -10. Evaluation Example Pellets of resin compositions E-1 to E-10, commercially available ABS resin (Comparative Example 7), and ASA resin (Comparative Example 8) were each molded using an injection molding machine (manufactured by Yamashiro Seiki Co., Ltd.,
SAV-30A type screw type), the cylinder temperature is 220℃ and the mold temperature is 60℃.
A flat plate and a notched Izot impact measurement test piece were prepared for weather resistance and appearance evaluation, each measuring 3 mm in size. Evaluation was carried out by the method shown below. The evaluation results are shown in Table 1. (1) Weather resistance Black panel 83℃, spray cycle using weather meter model WE-DCH manufactured by Suga Test Instruments Co., Ltd.
Changes in gloss were measured under conditions of 18 minutes/120 minutes. (2) Glossiness Measured using a digital angle gloss meter (incident angle: 60°) manufactured by Suga Test Instruments Co., Ltd. (3) Izot impact strength Measured according to ASTMD-256. (4) Melt flow index (MI) Measured according to ASTMD-1238 (200°C, load 5 kg) using a melt indexer manufactured by Toyo Baldwin Co., Ltd. (5) Vikat Softening Temperature (VST) Measured according to ISO R-306 (unit: °C). (Load 5Kg)

【table】

[Table] *〓○ Good △ Bad × Extremely Bad [Effects of the Invention] The resin composition of the present invention not only has excellent heat resistance, but also excellent impact resistance and molded appearance, and can be used for injection molding, A molded article having the above-mentioned excellent properties can be obtained by various molding methods such as vacuum forming. For example, in Comparative Example 1, a crosslinked acrylic rubber containing normal diene rubber was used inside, but in this case, the molded appearance and weather resistance were inferior to those using enlarged diene rubber inside. It's on. Also,
When no diene rubber is contained inside (Comparative Example 3)
, the deformation orientation of the bridged acrylic rubber is large;
Poor molded appearance and weather resistance. When a crosslinked acrylic rubber containing a small particle size diene rubber inside was used (Comparative Example 2), the molded appearance and gloss were good, but the isot strength was low. Furthermore, AES
When no resin is contained (Comparative Example 5), the impact strength at low temperatures is low.

Claims (1)

[Scope of Claims] 1. Contains 2 to 80% by weight of diene rubber (i) enlarged with acid group-containing copolymer latex inside the particles, contains acrylic ester as the main component, and contains a grafting agent and a crosslinking agent. The latex of the multilayer crosslinked acrylic rubber (1) whose outer layer is composed of 20 to 98% by weight of the crosslinked acrylic ester polymer (ii) formed in combination with 5 to 90 parts by weight (solid at least one aromatic vinyl compound in the presence of 10 to 90
% by weight and the general formula CH ₂ = CRX (where R is H or CH ₃ and X is CN or
Represents COOR ¹ . However, R ₁ is an alkyl group having 1 to 8 carbon atoms. ) Monomer mixture (2)95 consisting of 90 to 10% by weight of at least one type of ethylenically unsaturated compound represented by (2)95
~10 parts by weight (total amount of (1) and (2): 100 parts by weight) Graft copolymer resin () 5-95% by weight, AES resin () 5-95% by weight and other hard materials Consisting of 0 to 80% by weight of thermoplastic resin (),
A thermoplastic resin composition in which the total amount of (), (), and () is 100% by weight.