JP2022158917A - Matte polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition which enables manufacture of a molded product excellent in a matte property without impairing impact resistance even by using a smooth mold.SOLUTION: A matte polycarbonate resin composition contains, with respect to 100 pts.mass of a polycarbonate resin (A), 0.5-40 pts.mass of a copolymer resin (B) including a constitutional unit derived from (meth)acrylate having olefin and an epoxy group, and 0.1-20 pts.mass of an acrylic core-shell elastomer (C), and has a total content ratio of the polycarbonate resin (A), the copolymer resin (B) and the acrylic core-shell elastomer (C) in 100 mass% of the composition of 80 mass% or more.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition having excellent matting properties.

Polycarbonate resin (PC) is excellent in impact resistance, heat resistance, and transparency, and is widely used in fields such as electrical/electronics, optics, building materials, medicine, food, and vehicles. On the other hand, when the surface is a mirror surface, the light transmittance is high, but the reflected light is strong at the position in the direction of specular reflection from the light source, which may cause glare. For example, in outdoor building materials, the reflected light may be too bright, which may impede practical use.

In recent years, in the fields of automobiles, furniture, home electric appliances, etc., there has been an increasing demand for a matte appearance in order to give a sense of luxury. In addition to the design aspect, for example, if the surface of the molded product around the gauge in automobile interior parts is glossy, the gauge may be difficult to see due to reflected light, and there is a concern that it may interfere with driving. appearance is required.

As a method for obtaining a matte appearance, a method of forming unevenness on the surface with an embossing roll and a method of providing fine unevenness on the inner surface of a mold for injection molding have been proposed. However, when switching to the molding of mirror-finished products, it is necessary to change the equipment such as replacement of rolls and molds, so there was a problem that the production efficiency as a whole deteriorated. It is also known to apply a coating to obtain a matte appearance. However, there is a problem that dust and the like are likely to be adsorbed during coating, and the cost is high.

Patent Document 1 proposes a method of dispersing fine particles in a thermoplastic resin as a technique for modifying the resin itself. However, although matte properties can be obtained, there is a problem that the mechanical strength is lowered.

Patent Literature 2 proposes a method in which a material in which fine particles are dispersed in a resin is used as a surface layer and this is integrally molded with a base material. However, there is a problem that additional equipment, for example, multi-layer extrusion equipment for extrusion molding and a two-color molding machine and two-color mold for injection molding, lead to an increase in cost.

JP-A-63-137911 JP-A-3-58840

An object of the present invention is to provide a polycarbonate resin composition from which a molded article having excellent mattness can be produced without impairing impact resistance even when a smooth mold is used.

The present inventors have made intensive studies to solve the above problems, and found that a copolymer resin containing structural units derived from a (meth)acrylic acid ester having an olefin and an epoxy group in a polycarbonate resin and an acrylic core-shell The inventors have found that by adding an elastomer, it is possible to obtain a polycarbonate resin composition capable of producing molded articles with excellent matte properties without impairing impact resistance, and thus completed the present invention.

That is, the present invention
Polycarbonate resin (A) 100 parts by mass, copolymer resin (B) 0.5 to 40 parts by mass containing structural units derived from (meth)acrylic acid ester having an olefin and an epoxy group, acrylic core-shell elastomer 0.1 to 20 parts by mass of (C), and the total content of polycarbonate resin (A), copolymer resin (B), and acrylic core-shell elastomer (C) in 100% by mass of the composition is 80% by mass. % or more, it relates to a matte polycarbonate resin composition.

The copolymer resin (B) containing a structural unit derived from an olefin and a (meth)acrylic acid ester having an epoxy group is an ethylene glycidyl (meth)acrylate copolymer or an ethylene glycidyl (meth)acrylate-vinyl acetate copolymer. , or ethylene glycidyl (meth) acrylate-methyl acrylate copolymer.

The acrylic core-shell elastomer (C) is preferably methyl methacrylate-butadiene-styrene copolymer (MBS) or methyl methacrylate-butadiene copolymer (MB).

It is preferable that the content of structural units derived from vinyl acetate is 4% by mass or less, and the content of structural units derived from methyl acrylate is 28% by mass or less, based on 100% by mass of the copolymer resin (B).

Furthermore, acrylonitrile/butadiene/styrene copolymer (ABS) (D) is further added in an amount of 1 to 150 parts by mass to a total of 100 parts by mass of polycarbonate resin (A), copolymer resin (B) and acrylic core-shell elastomer (C). It is preferable to contain parts by mass.

The present invention also relates to a matte molded article containing the matte polycarbonate resin composition.

Furthermore, the present invention has a gloss measured at a measurement angle of 60 ° in accordance with JIS Z 8741 of 50% or less, and a notched Charpy impact strength measured in accordance with ISO 179-2 of 30 kJ / m ² or more. It relates to a certain matte molding.

By using the polycarbonate resin composition of the present invention, it is possible to obtain a molded article excellent in mattness without impairing the impact resistance even if a smooth mold is used.

The polycarbonate resin composition of the present invention is a copolymer resin (B) containing structural units derived from an olefin and an epoxy group-containing (meth)acrylic acid ester per 100 parts by mass of the polycarbonate resin (A). ~ 40 parts by mass, containing 0.1 to 20 parts by mass of acrylic core-shell elastomer (C), and in 100% by mass of the composition, polycarbonate resin (A), copolymer resin (B), and acrylic core-shell elastomer ( The total content of C) is 80% by mass or more. To obtain a matte appearance without impairing the original strength of a polycarbonate resin by using a copolymer resin containing a structural unit derived from an olefin and a (meth)acrylic acid ester having an epoxy group in combination with an acrylic core-shell elastomer. enable

<(A) polycarbonate resin>
Polycarbonate resin (A) is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate. A typical example is a polycarbonate resin made from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Polycarbonate resin (A) is used alone or in combination of two or more.

Examples of the dihydroxydiaryl compounds include bisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2, 2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3 -tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis( Bis(hydroxyaryl)alkanes such as 4-hydroxy-3,5-dichlorophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane bis(hydroxyaryl)cycloalkanes, dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, and 4,4'-dihydroxydiphenyl sulfide dihydroxydiarylsulfides, dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4 and dihydroxydiarylsulfones such as '-dihydroxy-3,3'-dimethyldiphenylsulfone. These are used singly or in combination of two or more. In addition to these, piperazine, dipiperidylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyl and the like may be mixed and used.

Furthermore, the above dihydroxyaryl compound and a trihydric or higher phenolic compound as shown below may be used in combination. Examples of trihydric or higher phenols include phloroglucin (1,3,5-trihydroxybenzene), 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene, 2,4,6- Dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzol, 1,1,1-tri-(4-hydroxyphenyl) -ethane and 2,2-bis-[4,4-(4,4'-dihydroxydiphenyl)-cyclohexyl]-propane. These are used singly or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin is usually 10,000 to 100,000, preferably 15,000 to 35,000, more preferably 17,000 to 28,000. The viscosity-average molecular weight can be adjusted by using, if necessary, a molecular weight modifier, a catalyst, etc. in producing the polycarbonate resin.
In addition, in this specification, the viscosity average molecular weight of the polycarbonate resin is measured by gel permeation chromatography (GPC).

<(B) Copolymer Resin Containing Structural Units Derived from Olefin and (Meth)Acrylic Acid Ester Having Epoxy Group>
The copolymer resin containing a structural unit derived from an olefin and a (meth)acrylic acid ester having an epoxy group (also simply referred to as a copolymer resin (B)) has a structural unit derived from an olefin and an epoxy group. It is not particularly limited as long as it is a copolymer resin containing a structural unit derived from (meth)acrylic acid ester. Copolymer resin (B) is used alone or in combination of two or more.

In this specification, the structural unit derived from olefin means a structural unit formed by using olefin as a monomer. Unless otherwise specified, the same applies to other structural units. Further, in the present specification, a structural unit derived from a (meth)acrylic acid ester having an epoxy group means a structural unit formed by using a (meth)acrylic acid ester having an epoxy group as a monomer, It is a structural unit derived from (meth)acrylic acid ester and is not particularly limited as long as it has a structure containing an epoxy group.

Olefins include, for example, ethylene, propylene, 1-butene, isobutylene, 2-butene, cyclobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, 4-methyl- 1-butene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene and the like. These are used singly or in combination of two or more. Among them, ethylene is preferred.

(Meth)acrylic acid esters having an epoxy group include, for example, glycidyl (meth)acrylate, epoxy (meth)acrylate, epoxycyclohexyl (meth)acrylate, hydroxybutyl acrylate glycidyl ether, and the like. These are used singly or in combination of two or more. Among them, glycidyl (meth)acrylate is preferred.
In this specification, (meth)acrylic acid means one or both of acrylic acid and methacrylic acid, and (meth)acrylate means one or both of acrylate and methacrylate.

The number of carbon atoms in the (meth)acrylic acid ester having an epoxy group is preferably 10 or less, more preferably 9 or less, still more preferably 8 or less, and preferably 6 or more. As a result, the function as a compatibilizer tends to be exhibited more effectively, and the effect can be obtained more favorably.

The content of structural units derived from olefins in 100% by mass of the copolymer resin (B) is preferably 75% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more, and preferably It is 99% by mass or less, more preferably 97% by mass or less, still more preferably 93% by mass or less, and particularly preferably 90% by mass or less. Within the above range, the effect tends to be obtained more favorably.

In 100% by mass of the copolymer resin (B), the content of structural units derived from a (meth)acrylic acid ester having an epoxy group is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably It is 7% by mass or more, particularly preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. Within the above range, the effect tends to be obtained more favorably.

The copolymer resin (B) may have a structural unit other than the structural unit derived from an olefin and the structural unit derived from a (meth)acrylic acid ester having an epoxy group. The structural units include, for example, structural units derived from (meth)acrylic acid esters having no epoxy group, structural units derived from allylic acid esters, and structural units derived from vinyl compounds such as vinyl acetate, acrylonitrile, and styrene. etc. These are used singly or in combination of two or more.

In 100% by mass of the copolymer resin (B), the total content of structural units derived from an olefin and a structural unit derived from a (meth)acrylic acid ester having an epoxy group is preferably at least 80% by mass, more preferably It is 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass. Within the above range, the effect tends to be obtained more favorably.

The content of structural units derived from vinyl acetate in 100% by mass of the copolymer resin (B) is preferably 6% by mass or less, more preferably 4% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less, most preferably 0% by mass. Within the above range, the effect tends to be obtained more favorably.

The content of structural units derived from methyl acrylate in 100% by mass of the copolymer resin (B) is preferably 28% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably It is 5% by mass or less, most preferably 2% by mass or less, more preferably 1% by mass or less, and most preferably 0% by mass. Within the above range, the effect tends to be obtained more favorably.

In this specification, the content ratio of each structural unit in the copolymer is a value measured by NMR.

As the copolymer resin (B), the copolymer resin (B) containing a structural unit derived from an olefin and a (meth)acrylic acid ester having an epoxy group is not particularly limited. polymers, ethylene glycidyl (meth) acrylate-vinyl acetate copolymers, ethylene glycidyl (meth) acrylate-methyl acrylate copolymers, and the like. Specific products include Sumitomo Chemical Co., Ltd. "Bondfast-E" (ethylene glycidyl (meth) acrylate copolymer), "Bondfast-2C" (ethylene glycidyl (meth) acrylate copolymer), "Bondfast-2B ” (ethylene glycidyl (meth) acrylate-vinyl acetate copolymer), “Bondfast-7B” (ethylene glycidyl (meth) acrylate-vinyl acetate copolymer), “Bondfast-7L” (ethylene glycidyl (meth) acrylate-methyl acrylate copolymer), "Bondfast-7M" (ethylene glycidyl (meth) acrylate-methyl acrylate copolymer), NOF Corporation "Modiper A4400" (ethylene glycidyl (meth) acrylate-styrene-acrylonitrile copolymer ) and the like. Among them, an ethylene glycidyl methacrylate copolymer is preferred.

The copolymer resin (B) may be a commercially available product, or may be synthesized by copolymerizing an olefin and a (meth)acrylic acid ester having an epoxy group. The polymerization method may be, for example, known emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, or a combination of these polymerization methods.

The content of the copolymer resin (B) is 0.5 to 40 parts by mass, preferably 1 to 40 parts by mass, per 100 parts by mass of the polycarbonate resin (A). When the ABS resin (D) is not included, it is preferably 0.5 to 20 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 8 parts by mass, relative to 100 parts by mass of the polycarbonate resin (A). When the ABS resin (D) is included, it is preferably 0.5 to 20 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 4 to 16 parts by mass, relative to 100 parts by mass of the polycarbonate resin (A). If the amount added is less than 0.5 parts by mass, a sufficient matting effect cannot be obtained, and if the amount exceeds 40 parts by mass, the appearance tends to be poor.

<(C) Acrylic core-shell elastomer>
The polycarbonate resin composition of the present invention preferably further contains an acrylic core-shell elastomer (C). The acrylic core-shell elastomer (C) may be used alone or in combination of two or more. The acrylic core-shell elastomer (C) comprises acrylic acid ester and/or methacrylic acid ester as an essential component, and optionally aromatic vinyl such as styrene, unsaturated hydrocarbon such as butadiene, and other copolymerizable monomers. It is a polymer composed of Its morphology is not critical, but it may be a core-shell type in which the hard segment is a continuous layer and the soft segment is a dispersed layer, or vice versa.

The acrylic core-shell elastomer (C) preferably has a core layer formed of a rubber component and a shell layer formed by polymerizing a (meth)acrylic acid ester. It is preferable to have a shell layer formed by polymerizing a (meth)acrylic acid ester around the core layer.

Examples of rubber components include polybutadiene-containing rubbers such as polybutadiene rubber and styrene-butadiene rubber, silicone-based rubbers such as polyorganosiloxane rubber, polyisoprene rubber, polyalkylacrylate-containing rubber, polyorganosiloxane rubber and polyalkylacrylate rubber. and IPN type composite rubber, butyl rubber, fluororubber, and the like. These are used singly or in combination of two or more. Among them, polybutadiene-containing rubber is preferable, and polybutadiene rubber and styrene-butadiene rubber are more preferable.

Examples of (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, (Meth)acrylic acid esters of linear aliphatic alcohols such as acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, or (meth)acrylic acid of cycloaliphatic alcohols such as cyclohexyl (meth)acrylate (Meth)acrylic acid esters of aromatic alcohols such as esters, phenyl (meth)acrylate and benzyl (meth)acrylate. These are used singly or in combination of two or more. Among them, methyl methacrylate is more preferable.

The number of carbon atoms in the (meth)acrylic acid ester is preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and preferably 4 or more. As a result, the effect tends to be obtained more favorably.

The shell layer is also preferably formed by polymerizing an aromatic vinyl together with a (meth)acrylate. Examples of aromatic vinyl include styrene, α-methylstyrene, α-ethylstyrene, vinyltoluene, vinylnaphthalene, vinylanthracene, 3-methylstyrene, 4-methylstyrene, 4-isopropylstyrene, 2,4-dimethylstyrene. , chlorostyrene, bromostyrene, 2,4-dichlorostyrene, 2-chloro-4-methylstyrene, 2,6-dichloro-4-methylstyrene and the like. These are used singly or in combination of two or more. Among them, styrene is preferred.

The content of the rubber component in 100% by mass of the acrylic core-shell elastomer (C) is preferably 8% by mass or more, more preferably 20% by mass or more, still more preferably 40% by mass or more, and preferably 80% by mass or less. , more preferably 60% by mass or less. Within the above range, the effect tends to be obtained more favorably.

The content of the (meth)acrylic acid ester-derived component in 100% by mass of the acrylic core-shell elastomer (C) is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 92% by mass or less. It is preferably 70% by mass or less, more preferably 50% by mass or less. Within the above range, the effect tends to be obtained more favorably.

As used herein, the content of each component in the acrylic core-shell elastomer is a value measured by NMR.

Specific examples of the acrylic core-shell elastomer (C) include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymers, methyl methacrylate-(acrylic/silicone IPN rubber) copolymers, and the like. These are used singly or in combination of two or more. Among them, methyl methacrylate-butadiene-styrene copolymer (MBS) and methyl methacrylate-butadiene copolymer (MB) are preferred.

Preferably, core-shell type MBS (methyl methacrylate-butadiene-styrene copolymer) can be used. Examples of commercially available products include "Paraloid EXL2603", "Paraloid EXL2678", and "Paraloid EXL2314" manufactured by Rohm and Haas Japan, "E-870A" and "E-860A" manufactured by Mitsubishi Chemical Corporation, Core-shell type graft copolymers such as “Kane Ace M722”, “Kane Ace M732” and “Kane Ace M711” manufactured by Kaneka Corporation can be mentioned.

The acrylic core-shell elastomer (C) may be a commercially available product, or may be synthesized by polymerizing a (meth)acrylic acid ester, for example, by graft-polymerizing a (meth)acrylic acid ester to a rubber component. The polymerization method may be, for example, known emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, or a combination of these polymerization methods.

The content of the acrylic core-shell elastomer (C) is 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 2 to 8 parts by mass, with respect to 100 parts by mass of the polycarbonate resin (A). is more preferred. If the amount added is less than 0.1 parts by mass, a sufficient matting effect cannot be obtained.

The total content of polycarbonate resin (A), copolymer resin (B), and acrylic core-shell elastomer (C) in 100% by mass of the polycarbonate resin composition is preferably 80% by mass or more, more preferably 90% by mass. Above, more preferably 95% by mass or more, and may be 100% by mass. Within the above range, the effect tends to be obtained more favorably. Here, as described in paragraph [0052], when using an acrylonitrile/butadiene/styrene copolymer (ABS resin) (D) instead of a part of the polycarbonate resin (A), the polycarbonate The content of resin (A) is the total content of polycarbonate resin (A) and acrylonitrile/butadiene/styrene copolymer (ABS resin) (D).

In the resin composition of the present invention, an acrylonitrile/butadiene/styrene copolymer (ABS resin) (D) is used in place of a part of the polycarbonate resin (A) within the range in which the effect of the present invention is exhibited. can also By containing the component (D), the melt viscosity is lowered, and it becomes possible to apply molded products with complicated shapes and large-sized molded products that are difficult to mold with polycarbonate resin alone. The copolymer may be produced by any polymerization method of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage grafting or multi-stage grafting. good. Alternatively, it may be a mixture with a copolymer containing only a graft component, which is a by-product of production. Among them, those obtained by emulsion polymerization are preferable because they have a high matting effect. Commercially available products include Clarastic SXH330 (trade name) (manufactured by Japan A&L Co., Ltd. ABS resin, butadiene rubber component of about 18% by mass, emulsion polymerization product). In addition, those obtained by bulk polymerization can also be used. Commercially available products include SANTAC AT-05 (trade name) manufactured by Japan A&L Co., Ltd. (ABS resin), bulk polymerization product), and the like.

The content of the ABS resin (D) is preferably 1 to 150 parts by mass, preferably 5 to 80 parts by mass, with respect to a total of 100 parts by mass of the polycarbonate resin (A), copolymer resin (B) and acrylic core-shell elastomer (C). More preferably 10 to 70 parts by mass, particularly preferably 40 to 60 parts by mass. The content of the ABS resin (D) is preferably 1 to 100 parts by mass, more preferably 50 to 100 parts by mass, per 100 parts by mass of the polycarbonate resin (A).

The ABS resin (D) can be used by mixing emulsion-polymerized ones and bulk-polymerized ones. By using a mixture of both, the fluidity of the resin composition is improved. The mixing ratio of the two is preferably 20 to 70 mass %, more preferably 30 to 50 mass %, of the emulsion polymerized ABS resin in a total of 100 parts by mass of the emulsion polymerized ABS resin and bulk polymerized ABS resin.

The total content of the polycarbonate resin (A), the copolymer resin (B), the acrylic core-shell elastomer (C), and the ABS resin (D) in 100% by mass of the polycarbonate resin composition is preferably 80% by mass or more, It is more preferably 90% by mass or more, still more preferably 95% by mass or more, and may be 100% by mass. Within the above range, the effect tends to be obtained more favorably.

Regardless of the presence or absence of the ABS resin (D), the total content of the copolymer resin (B) and the acrylic core-shell elastomer (C) in 100% by mass of the polycarbonate resin composition is preferably 3% by mass or more, more preferably. is 5% by mass or more, more preferably 8% by mass or more. On the other hand, although the upper limit is not limited, it is preferably 30% by mass or less, more preferably 20% by mass or less. Within the above range, the effect tends to be obtained more favorably.

Various known additives, polymers, and the like can be added to the polycarbonate resin composition of the present invention, if necessary. For example, a hindered amine light stabilizer can be added to suppress discoloration of the resin molded product when exposed to light for a long period of time, and a benzoxazole fluorescent brightener can be added to obtain a vivid color tone. good. Furthermore, these may be used in combination.

The polycarbonate resin composition of the present invention may contain known additives other than those described above, such as phenol-based or phosphorus-based heat stabilizers [2,6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl), )-4,6-dimethylphenol, 4,4′-thiobis-(6-t-butyl-3-methylphenol), 2,2-methylenebis-(4-ethyl-6-t-methylphenol), n- Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-t-butylphenyl)phosphite, 4,4′-biphenylenediphosphinic acid tetrakis-(2 , 4-di-t-butylphenyl), etc.], lubricants [paraffin wax, n-butyl stearate, synthetic beeswax, natural beeswax, glycerin monoester, montanic acid wax, polyethylene wax, pentaerythritol tetrastearate, etc.], coloring agents [e.g., titanium oxide, carbon black, dyes], fillers [calcium carbonate, clay, silica, glass fibers, glass spheres, glass flakes, carbon fibers, talc, mica, various whiskers, etc.], fluidity improvers, expanders, Adhesives [epoxidized soybean oil, liquid paraffin, etc.] can be added as needed.

The content of calcium carbonate with respect to 100 parts by mass of the polycarbonate resin (A) is preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, and still more preferably, for the reason that better impact resistance is obtained. is 0 parts by mass. Within the above range, the effect tends to be obtained more favorably.

The method for producing the polycarbonate resin composition of the present invention is not particularly limited. For example, the polycarbonate resin (A), the copolymer resin (B), and the acrylic core-shell elastomer (C) are weighed and collectively mixed with a tumbler, ribbon blender, high-speed mixer, etc., and then the mixture is extruded by a normal single-screw extruder or A method of melt-kneading and pelletizing using a twin-screw extruder, or a method of separately weighing a part or all of the individual components, feeding them into the extruder from a plurality of feeding devices, and melt-mixing them. , The acrylic core-shell elastomer (C) and the polycarbonate resin (A) and / or copolymer resin (B) are blended at a high concentration, melt-mixed once and pelletized to form a masterbatch, and then the masterbatch and Polycarbonate resin (A) and/or copolymer resin (B) can also be mixed in a desired ratio. Then, when these components are melt-mixed, arbitrary conditions such as the position of introduction into the extruder, extrusion temperature, screw rotation speed, supply amount, etc. can be selected according to the situation, and pelletization can be performed.

The method for producing a molded article from the polycarbonate resin composition is also not particularly limited. Examples include a method in which the material is directly charged into a molding device or a sheet extruder device to form a molded product.

Further, the matte molded article of the present invention is characterized by being obtained from the polycarbonate resin composition. The molded article has high mattness.

Furthermore, the matte molded article of the present invention has a gloss measured at a measurement angle of 60 ° in accordance with JIS Z 8741 of 50% or less, and a notched Charpy impact strength measured in accordance with ISO 179-2 of 30 kJ. /m ² or more. The gloss value is preferably 30% or less, and the Charpy impact strength is preferably 40 kJ/m ² or more.

<Application>
Molded articles obtained from the polycarbonate resin composition of the present invention are used for members that impair their functions due to specular reflection, housings for electric and electronic products that require matting as a design, exteriors for game and amusement related equipment, It can be suitably used in the construction field such as partitions and the interior and exterior of furniture. In addition, it can also be suitably used for vehicle interior parts that require matte properties from the standpoint of safety, such as vehicle dashboards, door mirrors, housings for measuring instruments for automatic driving, and camera covers.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. "%" and "parts" in the examples are based on mass unless otherwise specified.

Raw materials used in the examples are as follows.
Polycarbonate resin (A)
Polycarbonate resin synthesized from bisphenol A and phosgene (SD polycarbonate 200-20 manufactured by Sumika Polycarbonate Co., Ltd., viscosity average molecular weight 18800)

Copolymer resin (B) containing a structural unit derived from an olefin and a (meth)acrylic acid ester having an epoxy group
Ethylene glycidyl methacrylate copolymer (B-1): (Sumitomo Chemical Co., Ltd. Bondfast E (ethylene glycidyl methacrylate copolymer, content ratio of structural units derived from ethylene: 88% by mass, structural units derived from glycidyl methacrylate Content ratio: 12% by mass))
Ethylene glycidyl methacrylate copolymer (B-2): (Sumitomo Chemical Co., Ltd. Bondfast 2C (ethylene glycidyl methacrylate copolymer, content of structural units derived from ethylene: 94% by mass, structural units derived from glycidyl methacrylate content ratio: 6% by mass, content ratio of structural units derived from vinyl acetate: 0% by mass, content ratio of structural units derived from methyl acrylate: 0% by mass)
Ethylene glycidyl methacrylate vinyl acetate copolymer (B-3): (Sumitomo Chemical Co., Ltd. Bondfast 2B (ethylene glycidyl methacrylate-vinyl acetate copolymer, content ratio of constituent units derived from ethylene: 83% by mass, glycidyl methacrylate Content ratio of structural units derived from: 12% by mass, Content ratio of structural units derived from vinyl acetate: 5% by mass, Content ratio of structural units derived from methyl acrylate: 0% by mass)
Ethylene glycidyl methacrylate vinyl acetate copolymer (B-4): (Sumitomo Chemical Co., Ltd. Bondfast 7B (ethylene glycidyl methacrylate-vinyl acetate copolymer, content ratio of structural units derived from ethylene: 83% by mass, glycidyl methacrylate Content ratio of structural units derived from: 12% by mass, Content ratio of structural units derived from vinyl acetate: 5% by mass, Content ratio of structural units derived from methyl acrylate: 0% by mass)
Ethylene glycidyl methacrylate methyl acrylate copolymer (B-5): (Sumitomo Chemical Co., Ltd. Bondfast 7L (ethylene glycidyl methacrylate-methyl acrylate copolymer, content of constituent units derived from ethylene: 70% by mass, glycidyl methacrylate Content ratio of structural units derived from: 3 mass%, Content ratio of structural units derived from methyl acrylate: 27 mass%, Content ratio of structural units derived from vinyl acetate: 0 mass%)
Ethylene glycidyl methacrylate methyl acrylate copolymer (B-6): (Sumitomo Chemical Co., Ltd. Bondfast 7M (ethylene glycidyl methacrylate-methyl acrylate copolymer, content of constituent units derived from ethylene: 67% by mass, glycidyl methacrylate Content ratio of structural units derived from: 6 mass%, Content ratio of structural units derived from methyl acrylate: 27 mass%, Content ratio of structural units derived from vinyl acetate: 0 mass%)

Acrylic core-shell elastomer (C)
Acrylic core-shell elastomer (C-1): Rohm and Haas Japan Co., Ltd. EXL-2678 (methyl methacrylate-butadiene-styrene copolymer (MBS resin, core: polybutadiene, shell: styrene and methyl methacrylate), Content of butadiene component (rubber component): 50% by mass)
Acrylic core-shell elastomer (C-2): M-711 manufactured by Kaneka Corporation (methyl methacrylate-butadiene copolymer (MB resin, core: polybutadiene, shell: methyl methacrylate))

Acrylonitrile/butadiene/styrene copolymer (D)
ABS resin (D-1): Clarastic SXH-330 manufactured by Nippon A&L Co., Ltd., emulsion polymerized product ABS resin (D-2): Santac AT-05 manufactured by Nippon A&L Co., Ltd., bulk polymerized product

Examples 1-16 and Comparative Examples 1-4
After dry-wet mixing each component in a tumbler at the blending ratio shown in Tables 1 to 4, a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX30α) was used to melt at a temperature of 280 ° C. (including component (D) The mixture was melt-kneaded at 260° C. in some cases) to obtain pellets of the polycarbonate resin compositions of Examples 1-16 and Comparative Examples 1-4. Using the obtained pellets, the following various evaluations were performed. The evaluation results are shown in Tables 1-4.

<gross>
After drying the pellets of the resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 4 at 120° C. (100° C. when component D is included) for 4 hours or more, an injection molding machine (manufactured by Fanuc Corporation, Using ROBOSHOT S2000i100B), a molding temperature of 300°C (260°C when component D is included) and a mold temperature of 80°C, flat test pieces (thickness of 80 mm x 50 mm x 2 mm) were produced. Using the obtained test piece, the gloss at a measurement angle of 60° was measured according to JIS Z 8741. 50% or less was set as the pass.

<Appearance>
The external appearance of the molded article was visually checked, and the case where there was an appearance defect such as delamination, silver, jetting, or flow marks was evaluated as x, and the case where there was no appearance defect was evaluated as ◯.

<Impact strength>
After drying the pellets of the resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 4 at 120° C. (100° C. when component D is included) for 4 hours or more, an injection molding machine (manufactured by Fanuc Corporation, Using ROBOSHOT S2000i100B), a test piece was prepared according to the ISO test method at a molding temperature of 280°C (260°C when component D is included) and a mold temperature of 80°C. Using the obtained test piece, the notched Charpy impact strength was measured according to ISO 179-2. A notched Charpy impact strength of 30 kJ/m ² or more was considered acceptable.

<Thermal stability>
After drying the pellets of the resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 4 at 120° C. (100° C. when component D is included) for 4 hours or more, an injection molding machine (manufactured by Fanuc Corporation, Using ROBOSHOT S2000i100B), a flat plate test piece (length 80 mm, width 50 mm, thickness 2 mm) was prepared before and after dwelling for 10 minutes at a molding temperature of 300 ° C (260 ° C if component D is included), and then measured with a spectrophotometer. (CMS-35SP manufactured by Murakami Color Laboratory Co., Ltd.) was used to measure the change in YI (ΔYI). ΔYI represents the difference in degree of yellowness before and after retention, and the smaller the ΔYI, the smaller the discoloration and the better the thermal stability. A ΔYI of less than 2.0 was considered acceptable.

<Liquidity>
After drying the resin composition pellets prepared in Examples 11 to 13 and 16 at 100 ° C. for 4 hours or more, a capillary rheometer (Rosnad RH-7 manufactured by NETZSCH) was used to set the temperature in the furnace to 260 ° C. and shear Melt viscosity was measured at a speed of 1000 s ⁻¹ .

<Spiral length>
After drying the pellets of the resin composition prepared in Examples 12, 14, and 15 at 100°C for 4 hours or more, an injection molding machine (Roboshot S2000i100B manufactured by Fanuc Corporation) was used at a set temperature of 250°C and an injection pressure of 160 MPa. , and a mold temperature of 50° C., the flow length of a resin with a thickness of 1 mm was measured.

From the evaluation results in Tables 1 to 4, a copolymer resin (B) containing structural units derived from a (meth)acrylic acid ester having an olefin and an epoxy group and an acrylic core-shell elastomer (C) are added to the polycarbonate resin (A). is added in a specific amount, a molded product with a low gloss value and high impact strength can be obtained. Further, from the evaluation results in Table 4, it can be seen that the fluidity is improved while maintaining the gloss value when the ABS resin is used in combination. Moreover, it is found that the combined use of an emulsion-polymerized ABS resin and a bulk-polymerized ABS resin further improves fluidity while maintaining other properties.

Claims (7)

Polycarbonate resin (A) 100 parts by mass, copolymer resin (B) 0.5 to 40 parts by mass containing structural units derived from (meth)acrylic acid ester having an olefin and an epoxy group, acrylic core-shell elastomer (C) containing 0.1 to 20 parts by mass,
A matte polycarbonate, wherein the total content of polycarbonate resin (A), copolymer resin (B), and acrylic core-shell elastomer (C) is 80% by mass or more in 100% by mass of the composition. Resin composition. The copolymer resin (B) containing a structural unit derived from an olefin and a (meth)acrylic acid ester having an epoxy group is an ethylene glycidyl (meth)acrylate copolymer or an ethylene glycidyl (meth)acrylate-vinyl acetate copolymer. , or an ethylene glycidyl (meth)acrylate-methyl acrylate copolymer, the matte polycarbonate resin composition according to claim 1. 3. The matte polycarbonate resin composition according to claim 1, wherein the acrylic core-shell elastomer (C) is a methyl methacrylate-butadiene-styrene copolymer or a methyl methacrylate-butadiene copolymer. Claims 1 to 3, wherein the content of structural units derived from vinyl acetate is 4% by mass or less, and the content of structural units derived from methyl acrylate is 28% by mass or less, based on 100% by mass of the copolymer resin (B). The matte polycarbonate resin composition according to any one of . 1 to 150 parts by mass of an acrylonitrile/butadiene/styrene copolymer (D) with respect to a total of 100 parts by mass of the polycarbonate resin (A), the copolymer resin (B) and the acrylic core-shell elastomer (C), The matte polycarbonate resin composition according to any one of claims 1 to 4. A matte molded article comprising the matte polycarbonate resin composition according to any one of claims 1 to 5. According to JIS Z 8741, the gloss measured at a measurement angle of 60 ° is 50% or less, and the notched Charpy impact strength measured according to ISO 179-2 is 30 kJ / m ² or more. matte molded product.