JP2007308551A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in weather resistance, impact resistance, and flowability, and has a wide molding condition width giving a good matted appearance. <P>SOLUTION: This thermoplastic resin composition comprises a specific amount of a graft copolymer (A) obtained by grafting graft chains containing aromatic vinylic monomer units and vinyl cyanide-based monomer units to a (meth)acrylate-based rubbery polymer (G) and a specified amount of a vinylic copolymer (B) containing aromatic vinylic monomer units and vinyl cyanide-based monomer units, wherein the (meth)acrylate-based rubbery polymer (G) is obtained by expanding an un-expanded (meth)acrylate-based rubbery polymer (g) with an acid group-containing copolymer latex (K), and a difference (GA-BA) between the content (GA) of the vinyl cyanide monomer units and the content (BA) of the vinyl cyanide monomer units in the vinylic copolymer (B) is 8 to 25 pts.wt. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition for obtaining a molded article having a matte appearance, and a molded article having a matte appearance.

Improving the impact resistance of resin materials not only expands the applications of resin materials, but also makes it possible to respond to the reduction in thickness and size of molded products. Various techniques for improving the impact resistance of resin materials have been proposed.
Of the techniques for improving the impact resistance of resin materials, a technique for combining a rubbery polymer and a hard resin has been widely industrialized. Examples of the resin material combining the rubber-like polymer and the hard resin include acrylonitrile-butadiene-styrene (ABS) resin, high impact polystyrene (HIPS) resin, modified PPE resin, and MBS resin reinforced polyvinyl chloride resin. It is done.
These resin materials contain polybutadiene as a rubbery polymer. However, since polybutadiene has an unsaturated double bond, there is a problem that weather resistance is low.
Therefore, when weather resistance is required, instead of polybutadiene as a rubbery polymer, a saturated rubber such as a (meth) acrylate rubber polymer, a (meth) acrylate rubber polymer and a polybutadiene is used. A composite rubber with an organosiloxane and an ethylene-propylene rubber are used.

Recently, there has been an increasing demand for materials with significantly reduced gloss, so-called matte materials, mainly in the fields of automotive interior parts such as dashboards and instrument panels and resin-based building materials for housing.
As a method for matting, for example, a method of blending a crosslinked hard polymer in a thermoplastic resin composition has been proposed (see Patent Documents 1 to 3). According to the methods described in Patent Documents 1 to 3, although the weather resistance is improved, there is a problem that the impact resistance is remarkably lowered, and the application field of the obtained thermoplastic resin composition is limited.
Thus, as a method for matting while preventing a decrease in impact resistance, a method using a rubbery polymer having a large particle size has been proposed (see, for example, Patent Documents 4 to 6).
In the methods described in Patent Documents 4 to 6, it is possible to prevent a decrease in impact resistance, but the appearance of a matte appearance is likely to depend on molding conditions, and the molding condition width for obtaining a good matte appearance is narrowed. The gloss tends to vary depending on the part of the molded product, and glossy spots tend to occur.
As a method of widening the molding condition range for obtaining a good matte appearance and reducing the occurrence of spots, a method of blending a polymer containing a reactive functional group has been proposed (for example, patent document). 7-9).
However, the thermoplastic resin composition obtained by blending a polymer containing a reactive functional group has low fluidity, which may hinder molding processing.
JP-A 63-297449 Japanese Patent Laid-Open No. 08-199027 JP 2000-212293 A JP 09-194656 A JP 2000-198505 A JP 2002-194034 A JP-A-61-236850 JP-A 63-156847 Japanese Patent Laid-Open No. 10-219079

In view of the above, there has been a strong demand for a thermoplastic resin composition having a wide molding condition range in which all of weather resistance, impact resistance, and fluidity are excellent and a good matte appearance can be obtained.
The present invention has been made in view of the above circumstances, and is excellent in all of weather resistance, impact resistance, and fluidity, and has a wide molding condition range in which a good matte appearance can be obtained. The purpose is to provide. Another object of the present invention is to provide a molded article having excellent weather resistance, impact resistance, and fluidity and having a good matte appearance.

  The inventors of the present invention have used a (meth) acrylic ester-based rubbery polymer that has been subjected to an enlargement treatment with an acid group-containing copolymer latex, and the inclusion of vinyl cyanide copolymer units in the graft chain. And found that the above-mentioned problems can be solved by making the difference between the amount of vinyl cyanide monomer units in the vinyl copolymer within a specific range, and invented the following thermoplastic resin composition and molded article did.

That is, the thermoplastic resin composition of the present invention has a graft chain containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit on the (meth) acrylate rubber polymer (G). 20-80 parts by mass of grafted graft copolymer (A) and 80-20 parts by mass of vinyl copolymer (B) containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit Contains,
The (meth) acrylic acid ester rubbery polymer (G) was subjected to an enlargement treatment of the non-hypertrophic (meth) acrylic acid ester rubbery polymer (g) with the acid group-containing copolymer latex (K). Is,
Content (GA) of vinyl cyanide monomer units in the graft chain in the graft copolymer (A) and content (BA) of vinyl cyanide monomer units in the vinyl copolymer (B) The difference (GA-BA) is 8 to 25 parts by mass.
The molded article of the present invention is characterized in that the above-mentioned thermoplastic resin composition is molded.
In the molded article of the present invention, the effect of the present invention is exhibited particularly when the thermoplastic resin composition is extruded and is a sheet molded article or a deformed article.

The thermoplastic resin composition of the present invention is excellent in all of weather resistance, impact resistance, and fluidity, and has a wide range of molding conditions for obtaining a good matte appearance. In addition, the balance of weather resistance, impact resistance, and fluidity is excellent. Such a thermoplastic resin composition has extremely high utility value as various industrial materials.
The molded article of the present invention is excellent in weather resistance, impact resistance and fluidity, and has a good matte appearance.

(Thermoplastic resin composition)
The thermoplastic resin composition of the present invention contains a graft copolymer (A) in which a graft chain is grafted to a (meth) acrylic ester rubber-like polymer (G), and a vinyl copolymer (B). To do.

<Graft copolymer (A)>
[(Meth) acrylic ester rubbery polymer (G)]
The (meth) acrylic acid ester rubbery polymer (G) constituting the graft copolymer (A) is a polymer containing a (meth) acrylic acid ester monomer unit.
As the (meth) acrylic acid ester monomer, it is preferable to use a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms. Examples of the (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, methacryl Examples include methacrylic acid alkyl esters such as lauryl acid, and acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These (meth) acrylic acid ester monomers may be used individually by 1 type, and may use 2 or more types together.
Among these, n-butyl acrylate and / or 2-ethylhexyl acrylate are preferable because the resulting thermoplastic resin composition has higher impact resistance.

  The content of the (meth) acrylic acid ester monomer unit in the (meth) acrylic acid ester-based rubbery polymer (G) is more excellent in impact resistance of the resulting thermoplastic resin composition. ) It is preferably 50 parts by weight, more preferably 60 parts by weight, and particularly preferably 70 parts by weight or more based on 100 parts by weight of the acrylate-based rubbery polymer (G).

  In the (meth) acrylate rubber-based polymer (G), other monomer units may be contained in addition to the (meth) acrylate monomer units. Other monomers include, for example, aromatic alkenyl compounds such as styrene, α-methylstyrene, vinyl toluene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacryl Other (meth) acrylic acid esters having a functional group such as acid N and N-dimethylaminoethyl, diene compounds such as butadiene, chloroprene and isoprene, acrylamide, methacrylamide, maleic anhydride, N-substituted maleimide and the like It is done. These may be used individually by 1 type according to the objective, and may use 2 or more types together.

In addition, the (meth) acrylic ester rubber-like polymer (G) tends to improve the balance between the impact resistance and the matte property of the resulting thermoplastic resin composition. It is preferable to contain one or more kinds of crossing agent units.
Examples of the crosslinking agent and the graft crossing agent include allyl compounds such as allyl methacrylate, triallyl cyanurate and triallyl isocyanurate, divinyl compounds such as divinylbenzene, dimethacrylic acid ethylene glycol diester, dimethacrylic acid propylene glycol diester, and dimethacrylic acid. Examples thereof include di (meth) acrylic acid ester compounds such as acid 1,3-butylene glycol diester and dimethacrylic acid 1,4-butylene glycol diester. Two or more of these are used in combination, one is used as a crosslinking agent, and one is used as a graft crossing agent.
A preferred combination is a combination using an allyl compound as a graft crossing agent and a di (meth) acrylate compound as a cross-linking agent, and a more preferable combination is using allyl methacrylate or triallyl cyanurate as a cross-linking agent and crosslinking. It is a combination using dimethacrylic acid 1,3-butylene glycol diester as an agent.
The total content of the crosslinking agent unit and the graft crossing agent unit is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the (meth) acrylic ester rubber-like polymer. More preferably, it is part by mass.

This (meth) acrylic acid ester monomer is a non-hypertrophic (meth) acrylic acid ester-based rubbery polymer (g) subjected to an enlargement treatment with an acid group-containing copolymer latex (K).
The non-hypertrophic (meth) acrylate rubber-like polymer (g) is obtained, for example, by emulsion polymerization of the above-described (meth) acrylate monomer, a crosslinking agent, and a graft crossing agent. .

Various emulsifiers such as sodium sarcosine, fatty acid potassium, fatty acid sodium, alkenyl succinate dipotassium, rosin acid soap, etc., as the emulsifier used at the time of emulsion polymerization are excellent in latex stability and can increase the polymerization rate Anionic emulsifiers such as alkyl sulfate, sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate are preferable.
Examples of the radical polymerization initiator used during emulsion polymerization include organic or inorganic peroxides, azo initiators, and the like.

  In the latex of the non-hypertrophic (meth) acrylic ester rubber polymer (g) obtained by emulsion polymerization, the mass average particle diameter of the non-hypertrophic (meth) acrylic ester rubber polymer (g) Is preferably 30 to 250 nm, more preferably 40 to 200 nm, and particularly preferably 50 to 150 nm. If the mass average particle diameter of the non-hypertrophic (meth) acrylic ester rubber polymer (g) is 250 nm or less, it is easily enlarged by the acid group-containing copolymer latex (K), and is obtained as a result. In the thermoplastic resin composition, a good matte appearance is more easily obtained. On the other hand, if the mass average particle diameter of the non-hypertrophic (meth) acrylic ester rubber polymer (g) is 30 nm or more, it can be efficiently enlarged.

  Further, in the latex of the non-hypertrophic (meth) acrylic ester rubber polymer (g), the pH is preferably 7 or more, more preferably 8 or more, and particularly preferably 9 or more. preferable. Examples of the method of adjusting the pH to 7 or more include a method of adding an alkaline substance such as sodium carbonate, potassium carbonate, sodium hydroxide to the latex.

The acid group-containing copolymer latex (K) used as a thickening agent is an acid group-containing copolymer latex having an acid group-containing monomer unit and a (meth) acrylic acid ester monomer unit. .
Examples of the acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, and crotonic acid.
The (meth) acrylic acid ester is preferably a (meth) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms. The (meth) acrylic acid ester can be the same as that used for the production of the (meth) acrylic acid ester-based rubbery polymer (G). Among them, an acrylic acid ester monomer is preferable. An acrylic acid ester monomer having a large number of carbon atoms is more preferred. If the acid group-containing copolymer contains an acrylate monomer unit, the glass transition temperature (Tg) of the acid group-containing copolymer is lowered, and as a result, the resulting thermoplastic resin composition has a resistance to resistance. The impact and fluidity can be further increased, and a molded article having a better matte appearance can be obtained.

  The content of the (meth) acrylic acid ester in the acid group-containing copolymer is preferably 0.1 to 30 parts by mass when the acid group-containing copolymer is 100 parts by mass, and 10 to 25 parts by mass. More preferably, it is a part. If the content of the (meth) acrylic acid ester in the acid group-containing copolymer is in the above range, it is easy to control the mass average particle diameter of the resulting (meth) acrylic acid ester-based rubbery polymer (G), The matte appearance of the resulting thermoplastic resin composition can be made better.

  The mass average particle size of the acid group-containing polymer in the acid group-containing polymer latex is preferably 50 to 250 nm. If the mass average particle diameter of the acid group-containing polymer in the acid group-containing polymer latex is within the above range, the latex of the latex when the non-hypertrophic (meth) acrylate rubber polymer (g) is enlarged is used. Stability can be increased. Moreover, the mass average particle diameter of the (meth) acrylic ester rubber (G) obtained by enlargement can be easily controlled, and the matte appearance of the resulting thermoplastic resin composition can be improved.

For example, JP-A-50-25655 and JP-A-58 show a method for subjecting an unexpanded (meth) acrylic ester rubber polymer (g) to an enlargement treatment with an acid group-containing copolymer latex (K). Known methods described in JP-A-61102 and JP-A-59-149902 can be applied.
The amount of the acid group-containing copolymer latex (K) used in the enlargement treatment includes the properties of the non-hypertrophic (meth) acrylic ester rubber polymer (g) and the acid group-containing copolymer latex (K). Depending on the composition and properties of the above, it is 0.1 to 10 parts by mass (in terms of solid content) with respect to 100 parts by mass (in terms of solid content) of the non-hypertrophic (meth) acrylic acid ester rubber polymer (g). It is preferable that it is 0.3 to 5 parts by mass. When the amount of the acid group-containing copolymer latex (K) used is less than 0.1 parts by mass, not only the enlargement does not progress, but also the matte property of the resulting thermoplastic resin composition is lowered, and the impact resistance is increased. Tend to decrease. Moreover, even when it exceeds 10 mass parts, it exists in the tendency for the matte property of the thermoplastic resin composition obtained to fall.

In the case of the enlargement process, it is preferable to use a small amount of an inorganic electrolyte because enlargement is more likely to proceed.
As the inorganic electrolyte, for example, neutral or alkaline inorganic electrolytes such as sodium sulfate, sodium chloride, potassium chloride, and potassium carbonate are preferable.
The inorganic electrolyte may be contained in advance before polymerization of the non-hypertrophic (meth) acrylic ester rubber-like polymer, or may be added before the enlargement treatment.

  Further, in the enlargement treatment, the remaining amount of the unexpanded (meth) acrylate rubber (g) in the (meth) acrylate rubber (G) is enlarged to 15 parts by mass or less. It is preferable. In order to make the remaining amount of unhypertrophic (meth) acrylic acid ester rubber (g) 15 parts by mass or less, for example, the amount of acid group-containing copolymer latex (K) used or the amount of inorganic electrolyte used Many ways are taken.

The mass average particle diameter of the (meth) acrylic ester rubber polymer (G) obtained by such enlargement treatment is such that the balance between the impact resistance and the matte property of the resulting thermoplastic resin composition is obtained. Since it is excellent, it is preferably 1000 nm or less, more preferably 800 nm or less, and particularly preferably 600 nm or less.
The mass average particle diameter of the (meth) acrylic acid ester-based rubbery polymer (G) is within a range that does not fall below the particle diameter of the used non-hypertrophic (meth) acrylic acid ester-based rubbery polymer (g). Specifically, it is preferably 200 nm or more, more preferably 250 nm or more, and particularly preferably 300 nm or more.

[Graft chain]
The graft chain grafted onto the (meth) acrylic ester rubber polymer (G) described above contains an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.
Here, examples of the aromatic vinyl monomer include vinyl toluenes such as styrene, α-methyl styrene and p-methyl styrene, halogenated styrenes such as p-chlorostyrene, pt-butyl styrene, Examples thereof include dimethyl styrene and vinyl naphthalenes. Among these, styrene or α-methylstyrene is preferable.
Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, vinylidene cyanide, and among these, acrylonitrile is preferable.

The ratio of the vinyl cyanide monomer unit and the aromatic vinyl monomer unit in the graft chain is 10 to 50% by mass of the vinyl cyanide monomer unit and 50 to 50% of the aromatic vinyl monomer unit. It is preferably 90% by mass, more preferably 15 to 45% by mass of vinyl cyanide monomer units and 55 to 85% by mass of aromatic vinyl monomer units.
If the ratio of the vinyl cyanide monomer unit and the aromatic vinyl monomer unit in the graft chain is within the above range, the impact resistance and fluidity of the resulting thermoplastic resin composition will be higher.

The graft chain contains other monomer units (hereinafter abbreviated as other monomers) other than the aromatic vinyl monomer and the vinyl cyanide monomer depending on the purpose. Also good.
Examples of other monomers include unsaturated acrylates such as methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, acrylic acid-n-hexyl, methyl methacrylate, and ethyl methacrylate. Carboxylic acid ester monomers, unsaturated dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide And an imide compound of an unsaturated dicarboxylic acid. These may be used individually by 1 type and may use 2 or more types together.

  When other monomer units are contained in the graft chain, the content is preferably 40% by mass or less, and more preferably 20% by mass or less.

The graft copolymer (A) can be obtained, for example, by subjecting a (meth) acrylic ester rubber-like polymer (G) to emulsion graft polymerization of a monomer component.
When emulsion graft polymerization is performed, the (meth) acrylic acid ester-based rubbery polymer (G) is used in an amount of 10 to 80 parts by mass, and the monomer component is 90 to 20 parts by mass (the rubbery polymer and the monomer component). Is preferably 100 parts by mass), 30 to 70 parts by mass of the (meth) acrylic ester rubber polymer (G), and 70 to 30 parts by mass of the monomer component (rubber-like weight). More preferably, the total amount of the coalescence and the monomer component is 100 parts by mass). When the amount of the monomer component is 10 parts by mass or more, the resulting thermoplastic resin composition has higher impact resistance and fluidity, and when it is 80 parts by mass or less, the impact resistance becomes higher. Also, the matte appearance can be improved.

As an emulsifier used for emulsion graft polymerization, as in the case of obtaining an unhypertrophic (meth) acrylate rubber polymer (g), the stability of the latex is excellent, and the polymerization rate can be increased. Use anionic emulsifiers such as sodium carboxylate, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, rosin acid soap, alkyl sulfate, sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate Is preferred. The emulsifier may not be newly added at the time of emulsion graft polymerization, and the emulsifier used at the time of polymerization of the non-hypertrophic (meth) acrylic ester rubber polymer (g) may be used as it is.
As the radical polymerization initiator, for example, a peroxide, an azo compound, or a redox initiator obtained by combining these with an oxidizing agent / reducing agent can be used. Among these, a redox initiator is preferable, and a combination of ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, a combination of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, hydroperoxide is particularly preferable. preferable.
In emulsion graft polymerization, a chain transfer agent may be added in order to control the graft rate and the weight average molecular weight of the graft chain.

In the emulsion graft polymerization, the graft copolymer (A) is obtained in a latex state. As a method for recovering the graft copolymer (A) from the latex of the graft copolymer (A), for example, the latex of the graft copolymer (A) is added to hot water containing a coagulant and grafted. Examples thereof include a method of coagulating the copolymer (A) and separating and recovering the coagulated product.
As the coagulant, 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 can be used. Here, the type of coagulant is preferably selected according to the type of emulsifier used in the polymerization. For example, when only a carboxylic acid soap such as fatty acid soap or rosin acid soap is used at the time of polymerization, the graft copolymer (A) can be recovered using any coagulant, but an acid such as sodium alkylbenzene sulfonate can be recovered. When an emulsifier exhibiting stable emulsifying power in the region is used, it is preferable to use a metal salt.
The separated and recovered graft copolymer (A) is re-dispersed again 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. preferable. After washing, the slurry is dehydrated with a dehydrator or the like, and the obtained solid is dried with an air dryer or the like, whereby the powdery or particulate graft copolymer (A) can be obtained.

<Vinyl copolymer (B)>
The vinyl copolymer (B) contains an aromatic vinyl monomer unit and a vinyl cyanide monomer. The vinyl copolymer (B) may contain other monomer units other than the aromatic vinyl monomer unit and the vinyl cyanide monomer unit.
Other vinyl monomers other than aromatic vinyl monomer units, vinyl cyanide monomer units, aromatic vinyl monomer units and vinyl cyanide monomer units in vinyl copolymer (B) As the body unit, the same units as those constituting the graft chain of the graft copolymer (A) can be used. Among these, from the viewpoint of impact resistance and fluidity of the resulting thermoplastic resin composition, the aromatic vinyl monomer unit is preferably a styrene unit and the vinyl cyanide monomer unit is preferably an acrylonitrile unit.

The proportion of the aromatic vinyl monomer unit and the vinyl cyanide monomer unit in the vinyl copolymer (B) is 40 to 90% by mass of the aromatic vinyl monomer unit, and the vinyl cyanide monomer unit. The monomer unit is preferably 10 to 60% by mass, the aromatic vinyl monomer unit is preferably 45 to 85% by mass, and the vinyl cyanide monomer unit is preferably 15 to 55% by mass.
If the ratio of the aromatic vinyl monomer unit and the vinyl cyanide monomer unit in the graft chain is within the above range, the impact resistance and fluidity of the resulting thermoplastic resin composition will be higher.
Moreover, when another monomer unit is contained in a vinyl-type copolymer (B), it is preferable that the content is 50 mass% or less, and it is more preferable that it is 20 mass% or less.

[Formulation of thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains 20 to 80 parts by mass of the graft copolymer (A) and 80 to 20 parts by mass of the vinyl copolymer (B). When the content of the graft copolymer (A) in the thermoplastic resin composition is 20 parts by mass or more, impact resistance can be increased, and the content of the graft copolymer (A) is 80 parts by mass or less. By being, fluidity can be increased.

Further, in this thermoplastic resin composition, the content (GA) of the vinyl cyanide monomer unit in the graft chain in the graft copolymer (A) and the cyanation in the vinyl copolymer (B). The difference (GA-BA) from the vinyl monomer unit content (BA) is 8 to 25 parts by mass, preferably 10 to 20 parts by mass.
When (GA-BA) is 8 parts by mass or more, the obtained thermoplastic resin composition can widen the molding conditions for obtaining a good matte appearance, and as a result, a stable matte appearance can be obtained. Moreover, when (GA-BA) is 25 parts by mass or less, glossy spots can be suppressed, and impact resistance can be improved.

In the thermoplastic resin composition of the present invention, other thermoplastic resins (C) other than the graft copolymer (A) and the vinyl copolymer (B) may be contained within a range not impairing the performance. .
Examples of the other thermoplastic resin (C) include polymethyl methacrylate, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyolefins such as polyvinyl chloride, polyethylene, and polypropylene, styrene-butadiene-styrene ( SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene elastomers such as styrene-isoprene-styrene (SIS), various olefin elastomers, various polyester elastomers, polystyrene, methyl methacrylate-styrene copolymer (MS Resin), polyacetal, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymer, polyphenylene sulfide (PPS), polyether sulfone (PES) Polyetheretherketone (PEEK), polyarylate, liquid crystal polyester resins, polyamide (nylon) and the like. These thermoplastic resins may be used individually by 1 type, and may use 2 or more types together.
Among these, from the viewpoint of improving weather resistance, methyl methacrylate-styrene copolymer (MS resin) and polymethyl methacrylate are preferable. From the viewpoint of improving impact resistance, polycarbonate is preferable, and chemical resistance is improved. From the viewpoint, polybutylene terephthalate (PBT) is preferable. From the viewpoint of improving moldability, polyethylene terephthalate (PET) and polystyrene are preferable. From the viewpoint of improving heat resistance, modified polyphenylene ether (modified PPE) and polyamide are preferable. .
When these other thermoplastic resins (C) are included, the content is preferably 0 to 60 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition.

  In addition, if necessary, the thermoplastic resin composition may include a colorant such as a pigment or a dye, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a foaming agent, a lubricant, a plasticizer, or an antistatic agent. Agents, processing aids and the like may be included.

  The thermoplastic resin composition of the present invention includes, for example, a graft copolymer (A), a vinyl copolymer (B), and if necessary, another thermoplastic resin (C), a V-type blender or a Henschel mixer. It mixes with mixing apparatuses, such as, and it manufactures by melt-kneading the mixture obtained with the mixing apparatus. In the melt-kneading, a single-screw or twin-screw extruder, a Banbury mixer, a heating kneader, a kneader such as a roll, or the like is used.

  As described above, in the thermoplastic resin composition of the present invention, the (meth) acrylic ester rubber-like polymer (G) constituting the graft copolymer (A) is not enlarged (meth) acrylic ester. System rubber-like polymer is enlarged by acid group-containing copolymer latex (K). The difference between the content of the vinyl cyanide copolymer unit in the graft chain and the content of the vinyl cyanide monomer unit in the vinyl copolymer is within a specific range. Such a thermoplastic resin composition is excellent in all of weather resistance, impact resistance, and fluidity, and has a wide range of molding conditions for obtaining a good matte appearance.

(Molding)
The molded product of the present invention is formed by molding the above-described thermoplastic resin composition.
Examples of the molding method of the thermoplastic resin composition include an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method. Among these, since the effect exhibited by the thermoplastic resin composition is particularly useful, the extrusion molding method is preferable, and the molded product obtained by the extrusion molding method is preferably a sheet molded product or a deformed product.

  The molded product of the present invention may be coated with other resins, metals, and the like. Here, as other resin used for coating, for example, other thermoplastic resins (C) described above, rubber-modified thermoplastic resins such as ABS resin and high impact polystyrene resin (HIPS), phenol resin, and melamine are used. Examples thereof include thermosetting resins such as resins.

Since the molded article of the present invention is formed by molding the above-described thermoplastic resin composition, it has excellent weather resistance, impact resistance and fluidity, and also has a good matte appearance.
Such a molded article can be used for various purposes. For example, for industrial use, automobile parts, especially various exterior / interior parts used without painting, wall materials, building material parts such as window frames, tableware, toys, vacuum cleaner housings, television housings, air conditioner housings, etc. It is suitably used for parts, interior members, ship members, communication equipment housings, notebook computer housings, PDA housings, electrical equipment housings such as liquid crystal projector housings, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to the following examples. In the following examples, “%” and “part” are based on mass unless otherwise specified.

[Production Example 1] Production of non-hypertrophic (meth) acrylic ester rubber polymer (g-1) In a 10 liter stainless steel autoclave with a stirrer and a temperature control jacket, deionized water (hereinafter abbreviated as water) .) 400 parts, 1.0 part of dipotassium alkenyl succinate (Latemul ASK manufactured by Kao Corporation), 0.3 part of sodium sulfate, 97 parts of n-butyl acrylate, 3 parts of acrylonitrile, 0.8 part of triallyl cyanurate, 0.3 parts of 1,3-butylene glycol diester dimethacrylic acid was charged with stirring. Subsequently, after the inside of the autoclave was replaced with nitrogen, the temperature inside the autoclave was raised to 55 ° C. by a temperature control jacket.
Next, at an internal temperature of 55 ° C., an initiator aqueous solution containing 0.2 part of potassium persulfate and 5 parts of water was added to initiate polymerization. After the polymerization exotherm was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until no polymerization exotherm was confirmed. And it cooled after 3 hours from superposition | polymerization, solid content density | concentration is 19.9%, a mass mean particle diameter is 75 nm, pH is 8.6 non-hypertrophic (meth) acrylic acid ester rubber-like polymer (g -1) A latex was obtained.

[Production Example 2] Production of non-hypertrophic (meth) acrylic acid ester rubber polymer (g-2) Production in Production Example 1 except that dimethacrylic acid 1,3-butylene glycol diester was not used. Polymerization was carried out in the same manner as in Example 1, and a non-hypertrophic (meth) acrylate rubber polymer (g-) having a solid content concentration of 19.9%, a mass average particle size of 80 nm and a pH of 8.4. 2) A latex was obtained.

[Production Example 3] Production of unhypertrophic (meth) acrylic ester rubber polymer (g-3) In Production Example 1, the same method as in Production Example 1 except that triallyl cyanurate was not used. Polymerization was performed to obtain a non-hypertrophic (meth) acrylic ester rubber polymer (g-3) latex having a solid content concentration of 20.0%, a mass average particle diameter of 75 nm, and a pH of 8.5.

[Production Example 4] Preparation of acid group-containing copolymer latex (K) In a reactor equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 2.5 parts of sodium, sodium formaldehyde sulfoxylate Hydrate 0.3 part, water 200 part, potassium oleate 2.2 part, dioctylsulfosuccinic acid, ferrous sulfate heptahydrate 0.003 part, ethylenediaminetetraacetic acid disodium 0.009 part under nitrogen stream After charging, the temperature in the reactor 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 into the reactor over 120 minutes. . After completion of the dropwise addition, the mixture was kept at 60 ° C. for 2 hours to obtain an acid group-containing copolymer latex (K) having a solid content concentration of 33.0%, a polymerization conversion rate of 99%, and a mass average particle diameter of 145 nm. It was.

[Production Example 5] Production of (meth) acrylic acid ester-based rubbery polymers (G-1a to 1c, G-2, G-3) Each non-hypertrophic (meth) acrylic acid obtained in Production Examples 1 to 3 A 1% aqueous sodium hydroxide solution was added to the ester rubber-like polymers (g-1) to (g-3) to adjust the pH of the latex to 9-10.
Next, the acid group-containing copolymer latex in the amount shown in Table 1 was added to the (meth) acrylic ester rubber-like polymers (g-1) to (g-3) whose pH was adjusted at a temperature of 65 ° C. (K) was added all at once, and the stirring was continued for 30 minutes while maintaining the temperature, and the enlarged (meth) acrylic acid ester rubbery polymers (G-1a) to (G-1c), ( G-2) and (G-3) latex were obtained.
The mass average particle diameter of the obtained (meth) acrylic acid ester rubbery polymer (G-1a to 1c, G-2, G-3) was measured. The results are shown in Table 1.
The mass average particle diameter was measured using a submicron particle size distribution analyzer CHDF-2000 manufactured by Matec Applied Science.

[Production Example 6] Production of large particle size (meth) acrylic acid ester-based rubbery polymer (Z-1) In Production Example 1, the amount of dipotassium alkenyl succinate was 0.2 parts, and after the completion of polymerization, the amount was further reduced to 0. Polymerization was carried out in the same manner as in Production Example 1 except that 8 parts were additionally added, and a (meth) acryl with a large particle size having a solid content concentration of 19.4%, a mass average particle size of 370 nm and a pH of 8.7. An acid ester rubbery polymer (Z-1) latex was obtained.

[Production Example 7] Production of graft copolymer (A-1) A reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer was charged with a (meth) acrylate rubber polymer (G- 1a) 50 parts of latex (in terms of solid content), 170 parts of water (including water in the (meth) acrylate rubber-based polymer latex), 0.15 part of Rongalite, 0.5 part of dipotassium alkenyl succinate are charged. While stirring, the temperature in the reactor was raised to 75 ° C. under a nitrogen stream.
Next, a mixed solution of 5 parts of acrylonitrile (indicated as AN in Table 2), 15 parts of styrene (indicated as St in Table 2), and 0.08 part of t-butyl hydroperoxide was reacted for 1 hour. The solution was dropped into the vessel and polymerized. After completion of dropping, the temperature is maintained at 75 ° C. for 1 hour, and then ferrous sulfate heptahydrate 0.001 part, ethylenediaminetetraacetic acid disodium salt 0.003 part, Rongalite 0.15 part, ion-exchanged water 10 parts An aqueous oxidizing / reducing agent solution consisting of
Next, a mixture of 7.5 parts of acrylonitrile, 22.5 parts of styrene, and 0.2 parts of t-butyl hydroperoxide was dropped into the reactor over 1.5 hours, and the temperature in the reactor exceeded 80 ° C. Polymerization was carried out in such a way that
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.
Subsequently, 150 parts of a 1.2% sulfuric acid aqueous solution was heated to 75 ° C., and 100 parts of the graft copolymer (A-1) latex was gradually dropped and solidified while stirring the heated aqueous sulfuric acid solution. The temperature was raised to ° C. and held for 5 minutes to obtain a coagulated product. Subsequently, the obtained solidified product was dehydrated, washed and dried to obtain a white powdery graft copolymer (A-1).

In the obtained graft copolymer (A-1), the content (GA) of vinyl cyanide monomer units in the graft chain, acetone insoluble matter, and reduced viscosity (η _sp / C) were measured. The results are shown in Table 2.
In addition, content (it describes with GA in Table 2) of the vinyl cyanide monomer unit in a graft chain was measured using the pyrolysis gas chromatography (The Shimadzu Corporation make, GC-14A).
Further, the reduced viscosity is obtained by first dissolving 0.2 g of acetone-soluble matter in 100 cm ³ of N, N-dimethylformamide, and measuring the viscosity of the solution using an automatic viscometer (manufactured by Sun Electronics Co., Ltd.). The viscosity of the solvent was measured at 0 ° C. and measured under the same conditions. And the reduced viscosity of acetone soluble part was calculated | required from the viscosity of the solution, and the viscosity of the solvent.

[Production Examples 8 to 14] Production of Graft Copolymers (A-2) to (A-8) In the example described in Production Example 7, (meth) acrylate rubber polymer (G-1a) is ( G-1b), (G-1c), (G-2), and (G-3) were each changed, and the monomer composition ratio used for graft polymerization was changed as shown in Table 2. Polymerization was performed in the same manner as in Production Example 7 to obtain graft copolymers (A-2) to (A-8).
For the graft copolymers (A-2) to (A-8), in the same manner as in Production Example 7, the content (GA) of vinyl cyanide monomer units in the graft chain, the acetone insoluble content, and the reduced viscosity were determined. It was measured. The results are shown in Table 2.

[Production Example 8] Production of graft copolymer (A-9) In Production Example 7, the (meth) acrylic ester rubber-like polymer (G-1a) is enlarged by an acid group-containing copolymer (K). Polymerization was carried out in the same manner as in Production Example 7 except that it was changed to (Z-1) which was not carried out to obtain a graft copolymer (A-9).
For the graft copolymer (A-9), in the same manner as in Production Example 7, the content (GA) of vinyl cyanide monomer units in the graft chain, acetone insoluble matter, and reduced viscosity were measured. The results are shown in Table 2.

[Production Example 9] Vinyl-based copolymer (B-1)
27 parts of acrylonitrile and 73 parts of styrene are subjected to suspension polymerization to obtain an acrylonitrile-styrene copolymer (B-1) having a reduced viscosity (measured at 25 ° C.) of 0.61 dl / g in an N, N-dimethylformamide solution. It was.
The content of vinyl cyanide monomer units (indicated as BA in Table 3) in the obtained vinyl copolymer (B-1) was measured in the same manner as the graft chain of the graft copolymer. The results are shown in Table 3.

[Production Example 10] Vinyl copolymers (B-2) to (B-4)
Polymerization was carried out in the same manner as in Production Example 9 except that the charged composition ratios of acrylonitrile and styrene were changed as shown in Table 3, and vinyl copolymers (B-2) to (B-4) were obtained.
The vinyl cyanide monomer unit content (BA) in the obtained vinyl copolymers (B-2) to (B-4) was measured in the same manner as in Production Example 9. The results are shown in Table 3.

[Production Example 11] Vinyl copolymer (B-5)
26 parts of acrylonitrile and 74 parts of α-methylstyrene were subjected to suspension polymerization, and an acrylonitrile-α-methylstyrene copolymer having a reduced viscosity (measured at 25 ° C.) in an N, N-dimethylformamide solution of 0.51 dl / g ( B-5) was obtained.
The vinyl cyanide monomer unit content (BA) in the obtained vinyl copolymer (B-5) was measured in the same manner as in Production Example 9. The results are shown in Table 3.

[Production Example 12] Vinyl copolymer (B-6)
27 parts of acrylonitrile, 30 parts of styrene and 43 parts of methyl methacrylate are subjected to suspension polymerization, and acrylonitrile-styrene-methyl methacrylate having a reduced viscosity (measured at 25 ° C.) in an N, N-dimethylformamide solution of 0.52 dl / g. A ternary copolymer (B-6) was obtained.
The vinyl cyanide monomer unit content (BA) in the obtained vinyl copolymer (B-6) was measured in the same manner as in Production Example 9. The results are shown in Table 3.

[Production Example 13] Vinyl-based copolymer (B-7)
99 parts of methyl methacrylate and 1 part of methyl acrylate are subjected to suspension polymerization to obtain an acrylic resin (B-7) having a reduced viscosity (measured at 25 ° C.) of 0.25 dl / g in an N, N-dimethylformamide solution. It was.
The vinyl cyanide monomer unit content (BA) in the obtained vinyl copolymer (B-7) was measured in the same manner as in Production Example 9. The results are shown in Table 3.

[Example 1 to Example 14, Comparative Example 1 to Comparative Example 7] Production of Thermoplastic Resin Composition Graft Copolymers (A-1) to (A-9), Vinyl Copolymer (B-1) To (B-7) in the proportions shown in Tables 4 to 6, and 0.4 parts of ethylene bisstearylamide, a light stabilizer ("ADK STAB LA-63P" 0.2 by Asahi Denka Kogyo Co., Ltd.) Part, 0.2 part of an ultraviolet absorber (Asahi Denka Kogyo Co., Ltd., “Adeka Stub LA-36”), 3 parts of titanium oxide (“CR60-2” manufactured by Ishihara Sangyo Co., Ltd.) as a colorant were added. After the mixture thus obtained was mixed with a Henschel mixer, it was shaped with a degassing twin-screw extruder (“PCM-30” manufactured by Ikekai Tekko Co., Ltd.) heated to a barrel temperature of 230 ° C. to produce pellets. .
The obtained pellets were extruded using a 40 mmφ single-screw extruder manufactured by Chuo Kikai Co., Ltd., to which a T-die with a width of 60 mm was attached, under the conditions of a barrel temperature of 190 ° C. or 250 ° C. and a cooling roll temperature of 55 ° C. A 200 mm sheet was obtained. At that time, the thickness was adjusted to about 1.0 mm by adjusting the winding speed.

The thermoplastic resin compositions and molded articles obtained in each Example and each Comparative Example were evaluated by the following evaluation methods. The evaluation results are shown in Tables 7-9.
(i) Charpy impact strength (impact resistance)
In accordance with ISO 179, measurement was performed using a test piece with a notch that was allowed to stand for 12 hours or more in an environment of 23 ° C.
(ii) Melt volume rate (fluidity)
In accordance with ISO 1133, measurement was performed under conditions of a barrel temperature of 220 ° C. and a load of 98N.
(iii) Gloss of molded product and its dependency on molding temperature Gloss was measured as a reflectance of incident light of 60 °.
Further, the gloss difference was obtained by substituting the glossiness of the sheet obtained under the barrel temperature condition of 190 ° C. and the glossiness of the sheet obtained under the barrel temperature condition of 250 ° C. into the following formula (1). The larger the gloss difference, the more easily the gloss depends on the molding temperature, and the narrower the molding condition width for obtaining a matte appearance.
(Gloss difference (%)) = (Glossiness of sheet at barrel temperature 250 ° C.) − (Glossiness of sheet at barrel temperature 190 ° C.) Formula (1)
(Iv) Visual Evaluation of Appearance of Molded Product The molded product was visually observed, and the appearance was evaluated as follows from the matteness, the appearance of fish eyes and die lines, and the fineness of the surface texture.
○: There was no defect in appearance.
Δ: Slightly poor appearance was observed, but there is no practical problem.
X: Many defects are seen in the appearance and cannot be practically used.
(v) Weather resistance (accelerated exposure test)
The obtained sheet was treated with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 1,000 hours at a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12 minutes). Then, the hue of the treated sheet and the untreated sheet was measured with a color difference meter, and the color change degree ΔE before and after the treatment was obtained. It shows that it is excellent in a weather resistance, so that (DELTA) E is small.

From the examples and comparative examples, the following became clear.
(1) The thermoplastic resin compositions of Examples 1 to 14 containing a specific graft copolymer (A) and a vinyl copolymer (B) under specific conditions have Charpy impact strength and melt volume rate. Both were high and showed good matting properties at molding temperatures of 190 ° C and 250 ° C. Furthermore, discoloration was small in a weather resistance test using a sunshine weather meter. That is, these thermoplastic resin compositions were excellent in all of weather resistance, impact resistance, and fluidity, and had a wide range of molding conditions for obtaining a good matte appearance. Such a thermoplastic resin composition has a high utility value as an industrial material.
(2) The thermoplastic resin compositions of Comparative Examples 1 to 4 in which (GA-BA) was less than the lower limit of the specific range have relatively good matte properties at a molding temperature of 190 ° C, but a molding temperature of 250. The gloss was remarkably improved at 0 ° C. and the matte property was insufficient. In other words, these thermoplastic resin compositions had a narrow range of molding conditions for obtaining a good matte appearance. Such a thermoplastic resin composition has low utility value as an industrial material.
(3) In the thermoplastic resin composition of Comparative Example 5 in which (GA-BA) exceeded the upper limit of the specific range, the appearance of the molded product was remarkably poor, and gloss spots were generated depending on the site of the molded product. Such a thermoplastic resin composition has low utility value as an industrial material.
(3) The thermoplastic resin composition of Comparative Example 6 in which the vinyl copolymer (B) does not contain a vinyl cyanide monomer unit has good weather resistance, and has a matte property at a molding temperature of 190 ° C. Was relatively good, but the matte property was insufficient at a molding temperature of 250 ° C. In other words, these thermoplastic resin compositions had a narrow range of molding conditions for obtaining a good matte appearance. Such a thermoplastic resin composition has low utility value as an industrial material.
(4) The thermoplastic resin composition of Comparative Example 7 in which the (meth) acrylic ester rubber-like polymer (G) of the graft copolymer is not enlarged by the acid group-containing copolymer latex (K) No matte property was obtained at any of molding temperatures of 190 ° C. and 250 ° C. Such a thermoplastic resin composition has low utility value as an industrial material.

Claims (3)

Graft copolymer (A) 20-80 in which a graft chain containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit is grafted to the (meth) acrylic ester rubber polymer (G). Containing 80 to 20 parts by mass of a vinyl copolymer (B) containing a mass part and an aromatic vinyl monomer unit and a vinyl cyanide monomer unit;
The (meth) acrylic acid ester rubbery polymer (G) was subjected to an enlargement treatment of the non-hypertrophic (meth) acrylic acid ester rubbery polymer (g) with the acid group-containing copolymer latex (K). Is,
Content (GA) of vinyl cyanide monomer units in the graft chain in the graft copolymer (A) and content (BA) of vinyl cyanide monomer units in the vinyl copolymer (B) The thermoplastic resin composition, wherein the difference (GA-BA) is 8 to 25 parts by mass.   A molded article, wherein the thermoplastic resin composition according to claim 1 is molded.   The molded article according to claim 2, wherein the thermoplastic resin composition is extruded and is a sheet molded article or a deformed article.