JP2002194034A - Graft copolymer, thermoplastic resin composition and molded product using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which has a mat property, impact resistance, moldability, surface hardness and weather resistance at high levels. SOLUTION: The graft copolymer (A) wherein a (meth)acrylate rubber polymer (G) contains two or more sorts of polyfunctional monomer units is obtained by grafting a vinyl polymer with the fattened rubber polymer using an acid group-containing copolymer latex (K).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition having excellent matting properties, impact resistance, moldability, surface hardness, and weather resistance.

[0002]

2. Description of the Related Art Improving the impact resistance of a resin material has great industrial utility, such as expanding the application of the material and making it possible to reduce the thickness and size of a molded product. . Therefore, various methods for improving the impact resistance of the resin material have been studied. Among these, ABS resin, high-impact polystyrene resin, modified PPE resin, MBS resin-reinforced polyvinyl chloride resin, and the like are already industrialized as materials whose impact resistance is enhanced by combining a rubber-like polymer with a hard resin. Is used regularly. Particularly, by using a saturated rubber component such as a (meth) acrylic acid alkyl ester rubber as a rubber-like polymer, as a resin material having good weather resistance, for example, an ASA resin which is a weather-resistant ABS resin has been proposed. It has been used for outdoor electrical equipment such as parts, vending machines and casing parts of radio wave measurement bases. In recent years, demand for so-called matting materials with significantly reduced gloss has been increasing, mainly in the fields of automobile interior parts such as dashboards and resinous building materials for houses.

[0003] Conventional matting methods are disclosed in JP-A-51-146398 and JP-A-58-034384.
JP, JP-A-63-86756, JP-A-63-86756
297449, JP-A-08-73686,
JP-A-08-253641, JP-A-08-1990
No. 27, Japanese Patent Application Laid-Open No. 2000-212293,
A method has been proposed in which a matting property is exhibited by blending a crosslinked hard polymer into a thermoplastic resin composition. Also, JP-A-60-18536 and JP-A-61-23
6850, JP-A-63-156847, JP-A-63-156851, JP-A-01-5676
No. 2, JP-A-01-101355, JP-A-1
Japanese Patent Application Laid-Open No. 0-219079 proposes a method of expressing a matting property by blending a polymer containing an epoxy group. Further, JP-A-60-44517, JP-A-60-104150, and JP-A-60-1
97713, JP-A-60-188452,
JP-A-60-202143, JP-A-01-121
No. 350 and Japanese Patent Application Laid-Open No. 06-57154 propose a method of expressing a matting property by blending a polymer containing an acid or a base group. Moreover,
JP-A-02-503322, JP-A-02-214
712, JP-A-11-508960, JP-A-09-194656, JP-A-2000-1989
No. 05 proposes a matte thermoplastic resin containing a rubbery polymer having a large dispersed particle diameter in a thermoplastic resin composition.

[0004]

However, the thermoplastic resin obtained by these prior arts can no longer satisfy the demands of strict material specifications in recent years. Specifically, the epoxy group and the acid group described above,
A thermoplastic resin containing a polymer having a reactive functional group such as a base group has a fluidity that is significantly reduced due to the progress of a crosslinking reaction, and its use is limited. Special publication 02-50332
Although the thermoplastic resin composition obtained in JP-A No. 2 is good in fluidity and impact resistance, it has a low gloss value, so-called matte level, which is insufficient for recent demands. JP 0
Although the thermoplastic resin composition obtained in Japanese Patent Application Laid-Open No. 2-214712 has good fluidity, the balance between surface gloss and impact resistance was low, and it was not possible to satisfy both performances at the same time. The thermoplastic resin composition obtained in Japanese Patent Publication No. 11-508960 has good weather resistance and matting properties, but lacks impact resistance and fluidity. Although the thermoplastic resin composition obtained in JP-A-09-194656 has good weather resistance and matting property, it has insufficient impact resistance represented by notched Izod impact strength. The thermoplastic resin composition obtained in Japanese Patent Application Laid-Open No. 2000-198905 has a poor balance between matting properties, impact resistance, and surface hardness, and cannot simultaneously satisfy all the objects of the present invention. An object of the present invention is to provide a thermoplastic resin composition having a high level of mattability, impact resistance, moldability, surface hardness, and weather resistance.

[0005]

That is, the gist of the present invention is as follows.
(G) (meth) acrylate-based rubbery polymer which has been enlarged by an acid group-containing copolymer latex (K)
(Meth) acrylate rubbery polymer is a graft copolymer comprising two or more types of polyfunctional monomer units (A )It is in. Further, the gist of the present invention is that the graft copolymer (A) described above is 5 to 95% by mass, the other thermoplastic resin (F) is 95 to 5% by mass, and the other graft copolymer (B) 0 to 0%. 50% by mass (however, (A), (F), (B)
Is 100% by mass). Further, the gist of the present invention resides in a molded article comprising the above-mentioned thermoplastic resin composition, particularly preferably in a sheet-like molded article thereof.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The (meth) acrylate rubber-based polymer (G) constituting the graft copolymer (A) of the present invention is a polymer having (meth) acrylate monomer units. Examples of the alkyl (meth) acrylate monomer used include, for example, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, alkyl methacrylate such as lauryl methacrylate, methyl acrylate,
Ethyl acrylate, propyl acrylate, n-acrylate
Alkyl acrylates such as -butyl and 2-ethylhexyl acrylate;
-Butyl and / or 2-ethylhexyl acrylate. In these (meth) acrylic acid alkyl ester monomers, it is preferable to use a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms as an essential component. Also, (meta)
The acrylate-based rubbery polymer (G) may contain 50% by mass or more of one or more of the above-mentioned (meth) acrylate monomer units in 100% by mass of the rubbery polymer. preferable. The content is preferably 60% by mass, more preferably 70% by mass or more, since the obtained thermoplastic resin composition has excellent impact resistance.

The (meth) acrylate-based rubbery polymer (G) may contain other monomer units in addition to the above-mentioned (meth) acrylate alkyl ester monomer units. Other monomers that can be used include:
For example, styrene, α-methylstyrene, aromatic alkenyl compounds such as vinyl toluene, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile, 2-hydroxyethyl methacrylate and glycidyl methacrylate, N-methacrylic acid, N-dimethylaminoethyl and the like And other diene compounds such as butadiene, chloroprene and isoprene, acrylamide and methacrylamide, maleic anhydride, and N-substituted maleimide. These can be used alone or in combination of two or more depending on the purpose.

In the present invention, the monomer units constituting the (meth) acrylate-based rubbery polymer (G) include:
It comprises two or more different polyfunctional monomer units.
The two or more polyfunctional monomers to be used are not particularly limited as long as the structures are not very similar, but it is preferable to use a cross-linking agent and a graft cross-linking agent in combination. If two or more polyfunctional monomer units are not used, the balance between the impact resistance and the matting property is low, and as a result, the ratio of the rubbery polymer in the thermoplastic resin composition must be increased. As a result, the surface hardness tends to decrease. Examples of the cross-linking agent or graft cross-linking agent that can be used include allyl compounds such as allyl methacrylate, triallyl cyanurate and triallyl isocyanurate, divinylbenzene, ethylene glycol diester dimethacrylate, propylene glycol diester dimethacrylate, and dimethacrylyl. Acid 1,3
-Butylene glycol diester, dimethacrylic acid 1,
Examples thereof include di (meth) acrylate compounds such as 4-butylene glycol diester. Two or more of these compounds are used in combination. Preferably, a combination of an allyl compound as a graft-crossing agent and a di (meth) acrylate compound as a cross-linking agent is used. More preferably, allyl methacrylate as a graft-crossing agent and dimethacrylic acid 1,3 as a cross-linking agent are used. -In combination with butylene glycol diester. The polyfunctional monomer unit contained was (meth) acrylate rubber-based polymer 1
The content is preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass in 00% by mass.

[0009] A mixture of a monomer mixture containing a (meth) acrylic acid ester monomer as an essential component and two or more polyfunctional monomers is emulsion-polymerized to form a mixture having a small particle diameter. A (meth) acrylate-based rubbery polymer (g) can be prepared. The weight-average particle diameter of the (meth) acrylic ester-based rubbery polymer (g) having a small particle diameter is not particularly limited. However, since the enlargement by the acid group-containing copolymer latex (K) is easy to proceed, It is preferably from 30 to 250 nm, more preferably from 40 to 200 nm.
nm, more preferably 50 to 150 nm. 25
If it exceeds 0 nm, enlargement by the acid group-containing copolymer latex (K) becomes difficult to progress, and the matting properties of the resulting thermoplastic resin composition deteriorate, which is not preferable.

The acid group-containing copolymer latex (K) used as a thickening agent contains a copolymer having an acid group-containing monomer unit and a (meth) acrylic acid alkyl ester monomer unit. Latex. Examples of the acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and examples of the alkyl (meth) acrylate include (meth) acrylic acid having an alkyl group having 1 to 12 carbon atoms. Alkyl esters are preferred.
Regarding this, the same ones as used in the production of the (meth) acrylate-based rubbery polymer (G) can be used. However, the impact resistance and matting properties, which are the objects of the present invention,
For the purpose of obtaining a thermoplastic resin composition having excellent moldability, it is preferable that the glass transition temperature (Tg) of the acid group-containing copolymer is low, and it is preferable to use an acrylate monomer. In this case, it is more preferable to use an alkyl acrylate monomer having a large number of carbon atoms in the alkyl group. The mass ratio of the alkyl (meth) acrylate in the acid group-containing copolymer is such that the weight-average particle diameter of the (meth) acrylic ester-based rubbery polymer (G) obtained by enlargement is easily controlled, Since the matting property of the obtained thermoplastic resin composition is excellent, the
It is 30% by mass, more preferably 10 to 25% by mass. The weight-average particle size of the acid group-containing polymer in the acid group-containing polymer latex is such that the stability of the latex when the small particle size (meth) acrylate rubber-based polymer (g) is enlarged is enlarged. From 50 to 250 nm because it is easy to control the weight average particle size of the (meth) acrylate rubber (G) obtained by enlarging and enlarging, and the resulting thermoplastic resin composition has excellent matting properties. Is preferred.

The (meth) acrylic ester rubbery polymer (G) of the present invention is characterized in that the (meth) acrylic ester rubbery polymer (g) having a small particle diameter comprises the acid group-containing copolymer latex (G). K). The enlargement treatment is performed by adding an acid group-containing copolymer latex (K) to the small particle size (meth) acrylate-based rubbery polymer (g) latex obtained by emulsion polymerization as described above. The method of enlargement is described in JP-A-50-25655 and JP-A-58-61102.
The method can be carried out according to the method described in Kisa in Japanese Patent Laid-Open Publication No. Sho 59-149902. The appropriate amount of the acid group-containing copolymer latex (K) to be used includes the properties of the small particle size (meth) acrylate rubber-based polymer (g) and the acid group-containing copolymer latex (K). Although it depends on the composition and properties, the amount is 0.1 to 10 parts by mass (solid content) based on 100 parts by mass (solid content) of the small particle size (meth) acrylate-based rubbery polymer (g). Preferably, it is 0.3 to 5 parts by mass. If this amount is less than 0.1 parts by mass,
Not only the enlargement does not progress, but also the matting property of the obtained thermoplastic resin composition deteriorates, and the impact resistance tends to decrease. If the amount exceeds 10 parts by mass, the matting property of the obtained thermoplastic resin composition tends to decrease again.

In the case of performing the enlargement treatment, Japanese Patent Application Laid-Open No. 56-16 / 1981
As proposed in JP-A-6201, it is preferable to use a small amount of an inorganic electrolyte in combination from the viewpoint of facilitating the enlargement. Although any inorganic electrolyte may be used, neutral or alkaline inorganic electrolytes such as sodium sulfate, sodium chloride, potassium chloride, and potassium carbonate are preferable. It is not limited to the method of using the inorganic electrolyte,
It may be contained before the polymerization of the rubbery polymer in advance or added before the enlargement treatment. Further, as proposed in JP-A-50-25655, it is preferable to adjust the pH of the rubbery polymer latex (g) having a small particle diameter to be enlarged to be 7 or more, more preferably. Is 8 or more, more preferably 9 or more. Although any method may be used for adjusting the pH, a method of adding an alkaline substance such as sodium carbonate, potassium carbonate, or sodium hydroxide is exemplified. The range of the weight average particle diameter of the enlarged (meth) acrylate rubber-based polymer (G) is excellent in the balance between the impact resistance and the matting property of the obtained thermoplastic resin composition.
The upper limit is 1000 nm, preferably 800 nm, more preferably 600 nm, and the lower limit is 200 nm, preferably 250 n, so long as it does not fall below the particle size of the small particle size (meth) acrylate rubber polymer (g) used.
m, more preferably 300 nm. In the enlargement treatment, the proportion of the non-enlarged small particle (meth) acrylate rubber (g) in the (meth) acrylate rubber (G) is 15% by mass or less. It is preferable to enlarge it.

The graft copolymer (A) of the present invention is a (meth) acrylate-based rubbery polymer (G) enlarged by the aforementioned acid group-containing copolymer latex (K).
By graft polymerization of a vinyl monomer. The vinyl monomer used for the graft polymerization is not particularly limited, but preferably at least one monomer component selected from an aromatic alkenyl compound, an alkyl (meth) acrylate and a vinyl cyanide compound is used. Among the monomer components, examples of the aromatic alkenyl compound include styrene, α-methylstyrene, and vinyl toluene. Examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, and n-methacrylic acid. Examples thereof include butyl, 2-ethylhexyl acrylate, methyl acrylate, ethyl acrylate, and n-butyl acrylate. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, the use of a mixture of styrene and acrylonitrile is preferable because the resulting thermoplastic resin composition has excellent impact resistance.

The graft copolymer (A) is preferably obtained by subjecting a monomer component to emulsion graft polymerization of an enlarged (meth) acrylate rubber-based polymer, and further comprises (meth) acrylic acid. Acid ester rubbery polymer (G) 10 to 80% by mass and monomer component 90 to 20% by mass
(Total amount of rubbery polymer and monomer component is 100% by mass)
It is preferable to use a graft copolymer consisting of
When the emulsion graft polymerization is performed at such a mass ratio, the thermoplastic resin composition finally obtained is excellent in impact resistance, fluidity, and matting property. When the amount of the monomer component is less than 10% by mass, the impact resistance of the finally obtained thermoplastic resin composition tends to decrease, and when it exceeds 80% by mass, the impact resistance decreases again. Matting properties tend to deteriorate. More preferably, in the graft copolymer (A), the rubbery polymer (G) is 30 to 70% by mass, and the monomer component is 70 to 70% by mass.
30% by mass. In such a case, the thermoplastic resin composition finally obtained is preferable because it expresses impact resistance, moldability, and matting at a high level in a well-balanced manner. Emulsion polymerization at the time of producing the (meth) acrylate-based rubbery polymer (G) and the graft copolymer (A) can be performed by a radical polymerization technique using an emulsifier. In addition, various chain transfer agents for controlling the graft ratio and the molecular weight of the graft component can be added to the monomers to be graft-polymerized.

As the radical polymerization initiator used for the graft polymerization, a peroxide, an azo initiator or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferable, and in particular, a redox initiator obtained by combining ferrous sulfate, sodium pyrophosphate, glucose, and hydroperoxide, and a combination of ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide. Agents are preferred.

The emulsifier used in the graft polymerization is not particularly limited. However, since the latex has excellent stability during the emulsion polymerization and can increase the polymerization rate, sodium sarcosinate, fatty acid potassium, fatty acid sodium, dipotassium alkenylsuccinate are used. Anionic emulsifiers selected from various carboxylate salts such as rosin acid soaps, alkyl sulfates, sodium alkyl benzene sulfonates, sodium polyoxyethylene nonyl phenyl ether sulfate and the like are preferably used. These can be used properly depending on the purpose. Needless to say, the emulsifier used for preparing the rubbery polymer is used as it is, and it is not necessary to add the emulsifier at the time of emulsion graft polymerization.

The graft copolymer (A) latex obtained by the emulsion graft polymerization is then poured into hot water in which a coagulant is dissolved, and coagulated and solidified. Examples of the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate. The choice of coagulant is chosen in pairs with the emulsifier used in the polymerization. In other words, when only a carboxylic acid soap such as a fatty acid soap or a rosin acid soap is used, it can be recovered using any coagulant,
When an emulsifier that shows stable emulsifying power even in an acidic region such as sodium alkylbenzene sulfonate is contained, the above inorganic acid is not sufficient, and a metal salt must be used. Next, the graft copolymer (A) solidified using the coagulant as described above is redispersed in water or warm water to form a slurry, and the emulsifier residue remaining in the graft copolymer (A) Is eluted in water and washed. After washing
When the slurry is dehydrated with a dehydrator or the like and the obtained solid is dried with a flash dryer or the like, the graft copolymer (A) is obtained in the form of powder or particles.

The thermoplastic resin composition of the present invention comprises the above graft copolymer (A) and another thermoplastic resin (F).
Is blended. The other thermoplastic resin (F) is not particularly limited, and may be, for example, polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene- Maleic anhydride copolymer,
Styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyolefin such as polyvinyl chloride, polyethylene, polypropylene, styrene-butadiene-styrene (SBS), styrene-butadiene (SB
R), hydrogenated SBS, styrene-based elastomers such as styrene-isoprene-styrene (SIS), various olefin-based elastomers, various polyester-based elastomers, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene- Methyl methacrylate copolymer, polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene-
Vinyl acetate copolymer, PPS resin, PES resin, PEE
Examples include K resin, polyarylate, liquid crystal polyester resin, and polyamide resin (nylon). Preferably, polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-styrene-N-substituted maleimide terpolymer are used. Polymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT
Resin), polyethylene terephthalate (PET resin),
Polyvinyl chloride, polystyrene, methyl methacrylate
Styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer, modified polyphenylene ether (modified PPE resin), and polyamide resin. These may be used alone or in combination according to the purpose. Can be used. These other thermoplastic resins (F) are 15% by weight in 100% by mass of the thermoplastic resin composition.
It can be used in the range of up to 95% by mass.

The thermoplastic resin composition of the present invention may contain one or more other graft copolymers (B), if necessary, with respect to the graft copolymer (A). As the other graft copolymer (B), known resins such as ABS resin and MBS resin can be used. At this time, the content of the other graft copolymer (B) is 5 to 95% by mass of the graft copolymer (A), 95 to 15% by mass of the other thermoplastic resin (F), and the other graft copolymer. (B)
0 to 50% by mass ((A), (F), (B)
0% by mass). These mixtures are mixed and dispersed using a V-type blender or Henschel mixer, etc.
The mixture can be produced by melt-kneading using an extruder or a kneader such as a Banbury mixer, a pressure kneader, or a roll. The obtained thermoplastic resin composition is as it is, or, if necessary, a dye, a pigment, a stabilizer,
After compounding additives such as a reinforcing agent, a filler, a flame retardant, a foaming agent, a lubricant, and a plasticizer, it can be used as a raw material for producing a molded article. This thermoplastic resin composition is prepared by an injection molding method,
The desired molded product is obtained by various molding methods such as an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method. Further, depending on the case, it is also possible to use it by coating it with another resin or metal. The other resin that can be coated here is not particularly limited, but those described in the above-mentioned other thermoplastic resin (F), a thermoplastic rubber-modified resin such as ABS resin, high-impact polystyrene, and chloride resin. Thermosetting resins such as vinyl resins, phenol resins and melamine resins can be widely used. The thermoplastic resin composition of the present invention can obtain a molded product which has been subjected to primary processing by profile extrusion molding, sheet molding, or multilayer sheet molding with the above-mentioned other materials by the above-mentioned molding method. The molded article subjected to the primary processing in this way can be a material that can be used in a wide range of industrial fields by thermoforming, vacuum forming, or the like, depending on the application. Examples of industrial applications of such thermoplastic resin compositions and sheet-like molded products,
Vehicle parts, especially exterior parts used without painting, interior parts around dashboards, building materials parts such as wall materials, window frames, rain gutters, various hose covers, miscellaneous goods such as tableware and toys, vacuum cleaner housings, televisions Home appliance parts such as housing, air conditioner housing, OA equipment housing, interior materials,
Ship members, communication equipment housings, etc.

[0020]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. The percentages and parts in the following examples are based on mass unless otherwise specified. [Production Example 1] Production of small particle size (meth) acrylate-based rubbery polymer (g-1) In a 10-liter stainless steel autoclave equipped with a stirrer and a temperature control jacket, deionized water (hereinafter simply referred to as water) Abbreviation) 400 parts Dipotassium alkenyl succinate (Latemul ASK manufactured by Kao Corporation) 1.0 part Sodium sulfate 0.3 part n-butyl acrylate 80 parts Acrylonitrile 3 parts Styrene 7 parts Triallyl cyanurate 0.8 parts Dimethacrylic acid 0.3 parts of ethylene glycol ester was charged under stirring, and the inside of the reactor was purged with nitrogen. Thereafter, 10 parts of 1,3-butadiene was charged and the content was heated. At an internal temperature of 55 ° C., an aqueous solution consisting of 0.2 parts of potassium persulfate and 5 parts of water was added to initiate polymerization. When the heat of polymerization was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until the heat of polymerization was not confirmed. After 3 hours from the start of the polymerization, the mixture was cooled to obtain a small particle size acrylate rubber-like polymer (g-1) latex having a solid content of 19.9%, a weight average particle size of 75 nm and a pH of 8.7. Was.

[Production Example 2] Production of Small Particle Diameter Acrylic Ester Rubber Polymer (g-2) In a 10-liter stainless steel autoclave equipped with a stirrer and a temperature control jacket, deionized water (hereinafter simply referred to as water) Abbreviation) 400 parts Dipotassium alkenyl succinate (Latemul ASK manufactured by Kao Corporation) 1.0 part 0.3 parts sodium sulfate 0.3 part sodium formaldehyde sulfoxylate dihydrate 0.3 parts, and separately n-butyl acrylate 95 parts Acrylonitrile 5 parts Allyl methacrylate 0.3 parts Dimethacrylic acid 1,3-butylene glycol ester 0.15 parts Tert-butyl hydroperoxide 0.2 parts Was replaced with nitrogen and heated. At an internal temperature of 50 ° C., an aqueous solution consisting of 0.0005 parts of ferrous sulfate heptahydrate, 0.0015 parts of disodium ethylenediaminetetraacetate, and 5 parts of water was added to initiate polymerization. When the heat of polymerization was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until the heat of polymerization was not confirmed. After 2 hours from the start of the polymerization, the mixture was cooled to obtain a small particle size acrylate rubber-based polymer (g-2) latex having a solid content of 20.1%, a weight average particle size of 100 nm and a pH of 8.6. Was.

[Production Example 3] Production of Small Particle Diameter Acrylic Ester Rubber Polymer (g-3) A 10-liter stainless steel autoclave equipped with a stirrer and a temperature control jacket was charged with deionized water (hereinafter simply referred to as water). Abbreviation) 400 parts Dipotassium alkenyl succinate (Latemul ASK manufactured by Kao Corporation) 1.0 part Sodium sulfate 0.3 part Sodium formaldehyde sulfoxylate dihydrate 0.3 part Acrylamide 2 parts Another acrylic acid n-butyl 65 parts 2-ethylhexyl acrylate 33 parts allyl methacrylate 0.3 parts dimethacrylic acid 1,3-butylene glycol ester 0.15 parts tert-butyl hydroperoxide 0.2 parts The reactor was charged and replaced with nitrogen, and the temperature was raised after stirring. At an internal temperature of 50 ° C., an aqueous solution consisting of 0.0005 parts of ferrous sulfate heptahydrate, 0.0015 parts of disodium ethylenediaminetetraacetate, and 5 parts of water was added to initiate polymerization. When the heat of polymerization was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until the heat of polymerization was not confirmed. After 2 hours from the start of the polymerization, the mixture was cooled to obtain a small particle size acrylate rubber-based polymer (g-3) latex having a solid content of 19.7%, a weight average particle size of 95 nm and a pH of 8.9. Was.

Production Example 4 Production of Small Particle Diameter Acrylic Ester Rubber Polymer (g-4) Polymerization was carried out in the same manner as in Production Example 1 except that ethylene glycol dimethacrylate was not used. The solid content was 19.9% and the weight average particle size was 80 nm.
And a small particle size acrylate rubber-based polymer (g-4) latex having a pH of 8.4 was obtained.

Production Example 5 Production of Small Particle Diameter Acrylic Ester Rubber Polymer (g-5) Polymerization was carried out in the same manner as in Production Example 1 except that triallyl cyanurate was not used. 20 minutes.
0%, a small particle size acrylic acid ester rubbery polymer having a weight average particle size of 75 nm and a pH of 8.5 (g-
5) A latex was obtained.

[Production Example 6] Production of Large Particle Diameter Acrylic Ester Rubber Polymer (Z-1) In the example described in Production Example 1, the amount of dipotassium alkenylsuccinate used was changed to 0.2 part, and after polymerization, Further 0.8
Polymerization was carried out in the same manner except that part was additionally added, and a large particle diameter acrylate rubbery polymer (Z) having a solid content of 19.4%, a weight average particle diameter of 370 nm and a pH of 8.7 was used. -1) A latex was obtained.

[Production Example 7] Preparation of acid group-containing copolymer latex (K-1) In a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 200 parts of water and potassium oleate 2 .2 parts Dioctyl sodium sulfosuccinate 2.5 parts Sodium formaldehyde sulfoxylate dihydrate 0.3 parts Ferrous sulfate heptahydrate 0.003 parts Disodium ethylenediaminetetraacetate 0.009 parts charged under nitrogen flow The temperature was raised to 60 ° C. When the temperature reached 60 ° C., a mixture consisting of 81.5 parts of n-butyl acrylate, 18.5 parts of methacrylic acid, and 0.5 part of cumene hydroperoxide was continuously dropped over 120 minutes. After completion of the dropwise addition, aging was further performed at 60 ° C. for 2 hours, and an acid group-containing copolymer latex (K-1) having a solid content of 33.0%, a polymerization conversion of 99%, and a weight average particle size of 145 nm. I got

[Production Example 8] Preparation of acid group-containing copolymer latex (K-2) 200 parts of water and 200 parts of potassium oleate 2 were placed in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer. 1 part Sodium dioctylsulfosuccinate 2.5 parts Sodium formaldehyde sulfoxylate dihydrate 0.3 parts Ferrous sulfate heptahydrate 0.003 parts Disodium ethylenediaminetetraacetate 0.009 parts 0.001 part under nitrogen flow The temperature was raised to 70 ° C. After the temperature reached 70 ° C., a mixture consisting of 24 parts of n-butyl methacrylate, 1 part of methacrylic acid, 0.1 part of tert-dodecyl mercaptan, 0.1 part of cumene hydroperoxide was continuously supplied dropwise over 75 minutes to carry out polymerization. I let it. After holding for 30 minutes, n-butyl acrylate 25 parts n-butyl methacrylate 37 parts methacrylic acid 13 parts tert-dodecyl mercaptan 0.3 parts cumene hydroperoxide 0.08 parts 33.1% solids,
An acid group-containing copolymer latex (K-2) having a polymerization conversion of 99% and a weight average particle size of 90 nm was obtained.

[Production Example 9] Production of (meth) acrylic ester rubbery polymer (G) The acrylic ester rubbery polymers (g-1) to (g-5) produced in Reference Examples 1 to 8 Using an acid group-containing copolymer latex (K-1) or (K-2), the acrylic acid ester-based rubbery polymer (g) was stirred at an internal temperature of 65 ° C. and under stirring.
A predetermined amount shown in Table 1 was added all at once, and stirring was continued for 30 minutes while maintaining the temperature, and the acrylate-based rubbery polymers (G-1a) to (G-1d) to (G-1d), (G-
2) to (g-5) latex were obtained. At this time, before the enlargement treatment, the pH of the acrylate-based rubbery polymer (g) was adjusted to 9.0 with a 1% aqueous sodium hydroxide solution.
Adjusted between 100.

[0029]

[Table 1]

Example 1 Graft Copolymer (A-1)
In a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer, an acrylate rubber-based polymer (G-1a) latex (as solid content) 50 parts water (acrylate rubber) Rongalit 0.15 part Dipotassium alkenyl succinate 0.5 part was added, and the internal temperature was raised to 75 ° C. under a nitrogen stream while stirring. Then, a mixed solution of 5 parts of acrylonitrile, 15 parts of styrene, and 0.08 part of t-butyl hydroperoxide was dropped and polymerized over 1 hour. After completion of the dropping, the temperature of 75 ° C. was maintained for 1 hour, and an aqueous solution comprising ferrous sulfate heptahydrate 0.001 part ethylenediaminetetraacetic acid disodium salt 0.003 part Rongalit 0.15 part ion-exchanged water 10 parts Then, a mixture consisting of 7.5 parts of acrylonitrile, 22.5 parts of styrene, and 0.2 parts of t-butyl hydroperoxide was added dropwise over 1.5 hours, during which polymerization was carried out so that the internal temperature did not exceed 80 ° C. I was sorry. After completion of the dropping, the temperature of 80 ° C. was maintained for 30 minutes and then cooled to obtain a graft copolymer (A-1) latex. Next, 150 parts of a 1.2% sulfuric acid aqueous solution was heated to 75 ° C., and the graft copolymer (A-1) latex 1 was added thereto with stirring.
00 parts were gradually dropped and solidified, and the temperature was further raised to 90 ° C. and maintained for 5 minutes. The precipitate is then dehydrated, washed and dried,
A powdery graft copolymer (A-1) having an acetone-insoluble content of 70% and ηsp / C of 0.76 dl / g was obtained.

[Examples 2 to 6, Comparative Examples 1 and 2] Production of Graft Copolymers (A-2) to (A-8) Acrylic ester rubbery polymer used in the production example of Example 1 (G-1a) is replaced with (G-1b) to (G-1)
d), polymerization was carried out in the same manner except that (G-2) to (G-5) were changed, and graft copolymers (A-2) to (A-
8) was obtained. The production results are shown in Table 2.

Comparative Example 3 Graft Copolymer (A-9)
The polymerization was carried out in the same manner as in the production example of Example 1 except that the acrylate-based rubbery polymer (G-1a) used was changed to (Z-1), and a graft copolymer (A-
9) was obtained. The production results are shown in Table 2.

Comparative Example 4 Graft Copolymer (A-1)
Production of 0) Except that the acrylate rubber polymer (G-1a) used in the production example of Example 1 was changed to a small particle acrylate rubber polymer (g-1) which was not enlarged. Performs polymerization in the same manner, and the graft copolymer (A
-10) was obtained. The production results are shown in Table 2.

[0034]

[Table 2]

Example 7 Graft copolymer (A-1)
Production of 1) Acrylic ester-based rubbery polymer (G-1a) latex (as solid content) 60 parts Water (acrylic ester) Rongalit 0.15 part N-lauroyl sarcosinate sodium 0.5 part was added, and the internal temperature was raised to 75 ° C under a nitrogen stream while stirring. Subsequently, a mixed solution of 30 parts of methyl methacrylate, 3 parts of acrylonitrile, 7 parts of styrene, and 0.16 part of t-butyl hydroperoxide was dropped and polymerized over 2 hours. After completion of the dropwise addition, the temperature was maintained at 75 ° C. for 1 hour and then cooled to obtain a graft copolymer (A-11) latex. Next, 150 parts of a 1.2% sulfuric acid aqueous solution was heated to 75 ° C., and 100 parts of this graft copolymer (A-11) latex was gradually dropped into the mixture with stirring to coagulate, and further heated to 90 ° C. Hold for 5 minutes. Next, the precipitate is dehydrated, washed and dried, and the acetone insoluble content is 80%, ηsp / C is 0.54 dl / g.
Was obtained as a powdery graft copolymer (A-11).

The measurement was performed by the following method. (i) Weight average particle diameter of rubber-like polymer latex and ratio of unexpanded rubber-like polymer particles Measured using a submicron particle size distribution analyzer CHDF-2000 manufactured by MATEC APPLIED SCIENCES. (ii) Acetone insoluble content ratio About 2.5 g (weighed) of the graft copolymer and 80 ml of acetone were placed in a flask equipped with a cooling tube and a heater, and subjected to heat extraction at 55 ° C. for 3 hours using a heater.
After cooling, the inner liquid was treated with a centrifugal separator of Hitachi Koki Co., Ltd. at 14,000 rpm for 60 minutes to separate acetone-insoluble components, and then the precipitate after removing the supernatant was removed. After drying, the mass was measured and calculated by the following equation. Acetone insoluble matter (mass%) = dry mass of precipitate after separation / mass of graft copolymer before acetone extraction × 100 (iii) Reduced viscosity of acetone-soluble matter (ηsp / C) Acetone of the above graft copolymer The acetone-soluble component is precipitated and recovered by evaporating the acetone solvent in the supernatant obtained by extraction with a solvent and then separating the acetone-insoluble component by centrifugation under reduced pressure. Then, 0.2 g of the acetone-soluble component is added to 100 cc. Of the solution dissolved in N, N-dimethylformamide was measured at 25 ° C. using an automatic viscometer (manufactured by Sun Electronics Industry Co., Ltd.). The reduced viscosity was determined.

[Production Example 10] Another thermoplastic resin (F-
Preparation of 1) Consisting of 7 parts of acrylonitrile, 23 parts of styrene, and 70 parts of methyl methacrylate. The reduced viscosity measured at 25 ° C. from an N, N-dimethylformamide solution is 0.38 dl / g.
(F-1), an acrylonitrile-styrene-methyl methacrylate terpolymer, was produced by known suspension polymerization. [Production Example 11] Production of another thermoplastic resin (F-2) Consisting of 99 parts of methyl methacrylate and 1 part of methyl acrylate, 25 parts of N, N-dimethylformamide solution
An acrylic resin (F-2) having a reduced viscosity of 0.25 dl / g measured at ° C. was produced by known suspension polymerization.

[Production Example 13] Another thermoplastic resin (F-
Preparation of 3) Acrylonitrile-styrene copolymer (F-3) comprising 29 parts of acrylonitrile and 71 parts of styrene and having a reduced viscosity of 0.60 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution is known. Prepared by suspension polymerization of [Production Example 14] Production of another thermoplastic resin (F-4) Consists of 20 parts of acrylonitrile, 53 parts of styrene and 27 parts of N-phenylmaleimide, and has a reduced viscosity measured at 25 ° C from a N, N-dimethylformamide solution. 0.6
An acrylonitrile-styrene-N-phenylmaleimide terpolymer (F-4) at 5 dl / g was produced by a known continuous solution polymerization.

[Production Example 15] Another graft copolymer (B
Production of -1) In Production Example 9 and Production Example of Example 1, the small particle rubbery polymer latex used was polybutadiene rubber latex (particle diameter: 80 nm, gel content: 85%, solid content: 33).
%), And a diene-based graft copolymer (B-1) containing 50% by mass of a diene-based rubbery polymer was prepared. This graft copolymer is known from Japanese Patent Application Laid-Open No. 50-121387. [Production Example 16] Production of another graft copolymer (B-2) Production was carried out in the same manner as in the example described in Japanese Patent Publication No. 02-503322, Production C method, and a crosslinked acrylic ester-based rubbery polymer was produced. A known graft copolymer (B-2) containing 50% by mass of was prepared.

[Production Example 17] Another graft copolymer (B
Production of -3) A known graft containing 13% by mass of a crosslinked acrylate-based rubbery polymer, produced in the same manner as described in JP-A-02-214712 (graft copolymer (A-1)). A copolymer (B-3) was prepared. [Production Example 18] Production of another graft copolymer (B-4) Production was carried out in the same manner as in the example described in Japanese Patent Publication No. 11-508960 (Example 2), and a crosslinked acrylate-based rubbery polymer was produced. A known graft copolymer (B-4) containing 30% by mass of was prepared.

[Production Example 19] Another graft copolymer (B
-5) Production of JP-A-09-194656 (graft copolymer C)
Production was carried out in the same manner as in the example of -IV) to prepare a known graft copolymer (B-5) containing 60% by mass of a crosslinked acrylate-based rubbery polymer. [Production Example 20] Production of other graft copolymer (B-6) Production was carried out in the same manner as in the example of JP-A-2000-198905 (graft copolymer A-2), and a crosslinked acrylic ester rubber was produced. A known graft copolymer (B-6) containing 60% by mass of the polymer was prepared.

Examples 8 to 21 and Comparative Examples 1 to 10
Graft copolymers (A-1) to (A-
11), other thermoplastic resins (F-1) to (F-4), other graft copolymers (B-1) to (B-6), and ethylene bisstearylamide to 100 parts of resin component. And, if necessary, in the proportions shown in Table 1, and then mixed using a Henschel mixer. The mixture was heated to a barrel temperature of 230 ° C. in a degassing extruder (Nippon Steel Works ( The product was supplied to TEX-30) and kneaded to obtain pellets. Table 1 shows the Izod impact strength, molded gloss, appearance evaluation, thermal colorability, and weather resistance evaluation results measured using the obtained pellets.

The obtained thermoplastic resin composition was evaluated by the following method. (i) Izod impact strength Measured by a method in accordance with ASTM D256, after leaving the Izod test specimen in a 1/4 "thick specimen with a notch at 23 ° C for 12 hours or more. (ii) Melt flow rate (moldability) Measured according to ASTM D1238, barrel temperature 2
The measurement was performed under the conditions of 20 ° C. and a load of 98 N. (iii) Rockwell hardness (surface hardness) This was performed by a method based on ASTM D785. (iv) Molding gloss (matting property) Using a 25 mmφ single screw extruder manufactured by Thermoplastics Industry Co., Ltd., barrel temperature 220 ° C., cooling roll temperature 85 ° C.
Then, the resin is discharged in a sheet shape from a 60 mm width T die,
By adjusting the winding speed, the thickness can be adjusted to 200 to 2
A sheet having a width of 50 to 60 mm adjusted to 50 μm was formed, and measurement was performed using the obtained formed sheet. (v) Molding appearance For the obtained molded sheet, its matteness, occurrence state of fish eyes and die lines, fineness of the surface were determined by visual judgment, and those which were recognized as good sheets without any problem were determined. ○, those with many problems that do not stand practical use ×,
The middle was evaluated as △. (vi) Weather resistance A white colored plate of 100 mm × 100 mm × 3 mm was measured with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ° C. under cycle conditions of 60 minutes (rainfall: 12
Min) for 1,000 hours. In that case, evaluation was made based on the degree of discoloration (ΔE) measured by the color difference meter.

[0044]

[Table 3]

From the examples and comparative examples, the following has become clear. 1) Graft copolymers (A-1) of Examples 1 to 6 and 7
The thermoplastic resin compositions containing (A-6) and (A-11) all had good Izod impact strength, surface hardness, fluidity, mattability and appearance, and weather resistance. 2) The thermoplastic resin compositions of Comparative Examples 1 to 10 were inferior in any of the above items. 3) By using the thermoplastic resin composition of the present invention, a sheet-like molded product having a good matte appearance alone was obtained.

[0046]

The thermoplastic resin composition obtained by using the graft copolymer of the present invention has a particularly remarkable effect as follows, and its industrial utility value is extremely large. 1) It is excellent in impact resistance, surface hardness, moldability (flowability), matting properties, surface appearance such as fish eyes and rough skin, and weather resistance. 2) In particular, the balance among impact resistance, surface hardness, matting property, and weather resistance is a very high level that cannot be obtained with a conventionally known thermoplastic resin composition, and is useful as various industrial materials. Is extremely high. 3) The thermoplastic resin composition of the present invention is suitably used for a sheet-like molded product.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4F071 AA22 AA24 AA33 AA34 AA46 AA50 AA51 AA77 AF32 AH03 AH12 BA01 BB03 BB04 BB05 BB06 BB09 BC01 BC07 4J002 BC02X BC06X BC07X BD05X BG06X BH01X BH02 CG00 CG00 4J026 AA45 AC09 AC32 BA04 BA05 BA19 BA31 DA04 DB04 DB12 DB13 DB16 EA04 FA02 FA03 GA01 GA08

Claims (12)

[Claims] 1. A graft copolymer obtained by grafting a vinyl-based polymer onto a (meth) acrylate-based rubbery polymer (G) which has been subjected to an enlargement treatment with an acid group-containing copolymer latex (K). The (meth) acrylic ester rubbery polymer is a graft copolymer (A) comprising two or more types of polyfunctional monomer units. 2. The graft copolymer according to claim 1, wherein the (meth) acrylate-based rubbery polymer (G) is used.
Contains 50% by mass or more of a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 12 carbon atoms, the graft copolymer (A). 3. The graft copolymer according to claim 1, wherein two or more polyfunctional monomer units contained in the (meth) acrylate-based rubbery polymer (G) are graft-crosslinked. The graft copolymer (A), which is derived from at least one of an agent and a crosslinking agent. 4. The graft copolymer according to claim 3, wherein the (meth) acrylate-based rubbery polymer (G)
(A), wherein the graft-linking agent contained in (a) is an allyl compound and the crosslinking agent is a di (meth) acrylate compound. 5. The graft copolymer according to claim 1, wherein the acid group-containing copolymer latex (K) is a (meth) acrylic acid alkyl ester monomer unit in its solid content. The graft copolymer (A), which contains 0.1 to 30% by mass of 6. The graft copolymer according to any one of claims 1 to 5, wherein the weight average particle diameter is 200 to 100.
A graft copolymer (A) characterized by using a (meth) acrylate-based rubbery polymer (G) having a thickness of 0 nm. 7. The non-enlarged small particle size (meth) acrylic acid contained in the (meth) acrylate-based rubbery polymer in the graft copolymer according to any one of claims 1 to 6. A graft copolymer (A) characterized in that a (meth) acrylate rubber-based polymer (G) having an acid ester-based rubber-like polymer (g) content of 15% by mass or less is used. 8. The graft copolymer according to claim 1, wherein the grafted vinyl polymer is a (meth) acrylate compound monomer unit,
A graft copolymer (A) comprising at least one selected from vinyl cyanide-based compound monomer units and aromatic alkenyl-based compound monomer units. 9. The graft copolymer (A) according to claim 1, 5 to 95% by mass, another thermoplastic resin (F) 95 to 5% by mass, and another graft copolymer. Polymer (B)
A thermoplastic resin composition comprising 0 to 50% by mass (however, the total of (A), (F), and (B) is 100% by mass). 10. The thermoplastic resin composition according to claim 9, wherein the other thermoplastic resin (F) is a polymethyl methacrylate, an acrylonitrile-styrene copolymer (AS resin), or an acrylonitrile-styrene-N-substitution. Maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, methyl methacrylate -Styrene copolymer (M
S resin), acrylonitrile-styrene-methyl methacrylate copolymer, modified polyphenylene ether (modified P
A thermoplastic resin composition, which is at least one selected from the group consisting of PE resin) and polyamide. 11. A molded article comprising the thermoplastic resin composition according to claim 9 or 10. 12. A sheet-shaped molded article comprising the thermoplastic resin composition according to claim 9.