JP2017145318A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in surface impact resistance, impact resistance, scratch resistance, heat resistance, color development and weather resistance, and to provide a molded article obtained by molding the thermoplastic resin composition.SOLUTION: There are provided a thermoplastic resin composition which contains 45-75 pts.mass of a polycarbonate resin (A) including a structure derived from isosorbides, 20-50 pts.mass of a methacrylate ester resin (B) obtained by polymerization of a vinyl monomer mixture (b) containing methacrylate ester, and 4.9-25 pts.mass of a graft polymer (C) obtained by graft polymerizing a monomer (d) containing at least one selected from an aromatic vinyl monomer, a vinyl cyanide monomer and a methacrylate ester monomer with a rubbery polymer (c), in 100 pts.mass of a resin component, where a glass transition temperature of the methacrylate ester resin (B) is 100-150°C; and a molded article using the thermoplastic resin composition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermoplastic resin composition excellent in surface impact resistance, impact resistance, scratch resistance, heat resistance, color developability, and weather resistance, and a molded product formed by molding this thermoplastic resin composition About.

  Aromatic polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical properties, and is widely used in automotive parts, electrical and electronic equipment, housing materials, other industrial parts, and manufacturing materials. ing. However, the aromatic polycarbonate resin has a drawback that it has a low surface hardness and is easily scratched, and when used outdoors, it is yellowed by being exposed to ultraviolet rays for a long time, and its transparency is impaired.

  On the other hand, although acrylic resins mainly composed of methacrylic acid esters have problems in dimensional stability, surface impact resistance, etc., they are excellent in weather resistance, surface hardness, etc., and therefore are blended with aromatic polycarbonate resins. Thus, the surface hardness can be improved. However, the acrylic resin is not completely compatible with the aromatic polycarbonate resin, and has a different refractive index. Therefore, pearly luster is generated on the surface of the molded product, resulting in poor appearance. Moreover, heat resistance falls by mix | blending an acrylic resin.

  A polycarbonate resin having an isosorbite skeleton is known as a polycarbonate resin with improved weather resistance, but the problem of low surface hardness and poor scratch resistance has not been solved (Patent Document 1). Further, when used outdoors for a long time, the gloss is lowered.

JP 2012-214665 A

  The present invention relates to a thermoplastic resin composition excellent in surface impact resistance, impact resistance, scratch resistance, heat resistance, color developability, and weather resistance, and a molded product formed by molding this thermoplastic resin composition The purpose is to provide.

  As a result of repeated studies to solve the above problems, the present inventor has obtained a polycarbonate resin (A) containing a structure derived from isosorbides, a methacrylic ester resin (B) having a specific glass transition temperature, a rubber weight Graft weight obtained by graft polymerization of monomer (b) containing at least one selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and a methacrylic acid ester monomer on the polymer (c) It discovered that the said subject could be solved by mix | blending unification | combination (C) with a predetermined | prescribed ratio.

  That is, the gist of the present invention is as follows.

[1] Obtained by polymerizing 45 to 75 parts by mass of a polycarbonate resin (A) containing a structure derived from isosorbides and a vinyl monomer mixture (b) containing a methacrylic ester in 100 parts by mass of a resin component. From 20 to 50 parts by mass of the resulting methacrylic ester resin (B) and the rubbery polymer (c), from an aromatic vinyl monomer, a vinyl cyanide monomer, and a methacrylic ester monomer. A thermoplastic resin composition comprising 4.9 to 25 parts by mass of a graft polymer (C) obtained by graft polymerization of a monomer (d) containing at least one selected from the above-mentioned methacrylate resin (B) A thermoplastic resin composition having a glass transition temperature of 100 ° C. to 150 ° C.

[2] A polycarbonate resin (A) including a structure derived from isosorbides includes a structural unit derived from a dihydroxy compound represented by the following formula (1) and cyclohexanedimethanol, and includes a structure derived from isosorbides. Among the structural units derived from all dihydroxy compounds contained in the resin (A), 95 to 30 mol% of structural units derived from the dihydroxy compound represented by the following formula (1) and 5 structural units derived from cyclohexanedimethanol The thermoplastic resin composition according to [1], which is contained in an amount of ˜70 mol%.

[3] The methacrylic acid in the vinyl monomer mixture (b), wherein the vinyl monomer mixture (b) includes a methacrylic acid ester and another vinyl monomer copolymerizable with the methacrylic acid ester. Content of ester is 50-99.5 mass%, The thermoplastic resin composition as described in [1] or [2] characterized by the above-mentioned.

[4] The monomer (d) according to any one of [1] to [3], wherein the monomer (d) includes 70 to 82% by mass of an aromatic vinyl monomer and 18 to 30% by mass of a vinyl cyanide monomer. Thermoplastic resin composition.

[5] The rubbery polymer (c) is at least one selected from an ethylene / propylene copolymer, an ethylene / propylene / non-conjugated diene copolymer, and an ethylene / α-olefin copolymer [1]. Thru | or the thermoplastic resin composition in any one of [4].

[6] The volume average particle diameter of the rubber polymer (c) is 80 to 500 nm, the gel content of the rubber polymer (c) is 40 to 99% by mass, and the graft polymer (C) is grafted. The thermoplastic resin composition according to any one of [1] to [5], wherein the rate is 23 to 100%.

[7] The graft polymer (C) is obtained by graft polymerization of 40 to 80% by mass of the rubbery polymer (c) and 20 to 60% by mass of the monomer (d) [1. ] To the thermoplastic resin composition according to any one of [6].

[8] A molded article using the thermoplastic resin composition according to any one of [1] to [7].

  According to the present invention, there are provided a thermoplastic resin composition having excellent surface impact resistance, impact resistance, scratch resistance, heat resistance, color developability, and weather resistance, and a molded product thereof.

It is explanatory drawing of the evaluation method of scratch resistance (gauze abrasion resistance) in an Example.

  Hereinafter, embodiments of the present invention will be described in detail.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) is derived from isosorbides as a resin component in the resin composition with respect to 100 parts by mass of the resin component. 45 to 75 parts by mass of a polycarbonate resin (A) containing a structure, and 20 to 50 parts by mass of a methacrylate ester resin (B) obtained by polymerizing a vinyl monomer mixture (b) containing a methacrylate ester, The rubber polymer (c) is graft-polymerized with a monomer (d) containing at least one selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and a methacrylic acid ester monomer. A thermoplastic resin composition containing 4.9 to 25 parts by mass of the graft polymer (C), wherein the glass transition temperature of the methacrylic ester resin (B) is 100 ° C. to 150 ° C. You .

[Polycarbonate resin (A) including a structure derived from isosorbides]
The polycarbonate resin (A) having a structure derived from isosorbides used in the present invention (hereinafter sometimes referred to as “isosorbide-based polycarbonate resin (A)”) is preferably represented by the following formula (1). A polycarbonate resin containing a structural unit derived from a dihydroxy compound, or a polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following formula (1) and cyclohexanedimethanol.

Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be.
Among them, isosorbide obtained by dehydrating and condensing sorbitol produced from various starches that are abundant as plant-derived resources is easy to obtain and manufacture, moldability, heat resistance, and impact resistance. Most preferable from the viewpoints of properties, surface hardness, and carbon neutral.

  On the other hand, examples of cyclohexanedimethanol include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol is preferable from the viewpoint of availability.

  The isosorbide-based polycarbonate resin (A) used in the present invention is derived from a dihydroxy compound represented by the formula (1) or a dihydroxy compound other than cyclohexanedimethanol (hereinafter sometimes referred to as “other dihydroxy compounds”). And other dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1, Aliphatic dihydroxy compounds such as 2-butanediol, 1,5-heptanediol, 1,6-hexanediol; tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5- Decalin dimethanol, 2,3-decalin dimethanol , 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol and other alicyclic hydrocarbon dihydroxy compounds; 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy) -(3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy -Diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1, -Bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4'- Dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-) And aromatic bisphenols such as 2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene.

When the isosorbide-based polycarbonate resin (A) includes a structural unit derived from the dihydroxy compound represented by the above formula (1) and a structural unit derived from cyclohexanedimethanol, the total dihydroxy contained in the isosorbide-based polycarbonate resin (A) In the structural unit derived from the compound, the proportion of the structural unit derived from cyclohexanedimethanol is preferably 70 mol% or less, for example, 5 to 70 mol%. When the isosorbide-based polycarbonate resin (A) contains a structural unit derived from cyclohexanedimethanol, coloring is unlikely to occur, and the effects of increasing the molecular weight, improving the impact strength, and improving the glass transition temperature are exhibited. When too much, such an effect by including the structural unit derived from the dihydroxy compound represented by Formula (1) will be impaired, and it is not preferable.
In particular, the isosorbide-based polycarbonate resin (A) includes 95 to 95 structural units derived from the dihydroxy compound represented by the formula (1) among structural units derived from all dihydroxy compounds contained in the isosorbide-based polycarbonate resin (A). 30 mol%, especially 60 to 40 mol%, 5 to 70 mol%, especially 40 to 60 mol% of structural units derived from cyclohexanedimethanol are less likely to cause coloring, increase the molecular weight, improve impact strength, It is preferable in terms of improving the glass transition temperature.

  When the isosorbide-based polycarbonate resin (A) contains structural units derived from other dihydroxy compounds, the structural units derived from other dihydroxy compounds are structures derived from all dihydroxy compounds in the isosorbide-based polycarbonate resin (A). It is preferably 10 mol% or less of the unit, more preferably 5 mol% or less. When the isosorbide-based polycarbonate resin (A) contains a structural unit derived from another dihydroxy compound, the impact resistance is improved, but if this ratio is excessively large, the heat resistance is lowered. Further, when the isosorbide-based polycarbonate resin (A) includes a structural unit derived from an aromatic bisphenol as a structural unit derived from another dihydroxy compound, the heat resistance is improved, but if this ratio is excessively large, the weather resistance Gets worse.

  The isosorbide-based polycarbonate resin (A) used in the present invention can be produced by a generally used production method, and the production method can be any of a solution polymerization method using phosgene and a melt polymerization method in which a carbonic acid diester is reacted. Although a method may be used, a melt polymerization method is preferred in which a dihydroxy compound containing the dihydroxy compound represented by the formula (1) is reacted with a carbon dioxide diester having lower toxicity to the environment in the presence of a polymerization catalyst.

  Examples of the carbonic acid diester used in the melt polymerization method include those represented by the following general formula (2). These carbonic acid diesters may be used alone or in combination of two or more.

(In the general formula ^{(2), A 1, A} 2 is an aromatic group which may have an aliphatic group or a substituent having 1 to 18 carbon atoms which may have a substituent, A ¹ and A ² may be the same or different.)

  Examples of the carbonic acid diester represented by the general formula (2) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate.

  Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.

In addition, as a polymerization catalyst (transesterification catalyst) in melt polymerization, a known alkali metal compound and / or alkaline earth metal compound is used. It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound together with an alkali metal compound and / or an alkaline earth metal compound.
As the polymerization reaction, a known method can be used, and any method of a batch method, a continuous method, or a combination of a batch method and a continuous method may be used.

  In the present invention, the weight average molecular weight (Mw) of the isosorbide-based polycarbonate resin (A) is preferably in the range of 25,000 to 60,000, more preferably 30,000 to 60,000, particularly preferably 35. 5,000 to 58,000 is preferable from the viewpoint of the appearance and impact resistance of the obtained molded product. If the weight average molecular weight of the isosorbide-based polycarbonate resin (A) is larger than this range, the fluidity is lowered, and if it is smaller, the impact resistance and heat resistance of the resulting molded product are lowered, and the appearance is deteriorated. .

  The blending amount of the isosorbide-based polycarbonate resin (A) in the resin composition of the present invention is excellent in the surface impact resistance and scratch resistance of the resulting resin composition and its molded product. It is 75 mass parts, Preferably it is 50-70 mass parts. If there is more isosorbite-based polycarbonate (A) than this range, impact resistance, weather resistance, and scratch resistance due to hard materials will decrease, and if it is less, surface impact resistance will decrease.

[Methacrylate resin (B)]
The methacrylic ester resin (B) in the present invention is sometimes referred to as methacrylic ester and other vinyl monomers copolymerizable with the methacrylic ester (hereinafter referred to as “other vinyl monomers”). )) And a vinyl monomer mixture (b).

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, Examples include isoamyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and phenyl methacrylate, and one of these may be used alone. Two or more kinds may be mixed and used.

  50-99.5 mass% is preferable and, as for content of the methacrylic acid ester in a vinyl-type monomer mixture (b), 60-99.5 mass% is more preferable. When the content of the methacrylic acid ester is less than 50% by mass, the color developability of the resulting resin composition and the molded product thereof is inferior, and furthermore, the scratch resistance tends to be inferior. On the other hand, when the content of the methacrylic ester exceeds 99.5% by mass, the methacrylic ester resin (B) is likely to be decomposed during melt-kneading or molding, which may cause discoloration or poor appearance (silver). is there.

  Other vinyl monomers contained in the vinyl monomer mixture (b) include aromatic vinyl monomers, vinyl cyanide monomers, acrylic acid esters, maleimides and maleic anhydride. These may be used, and one kind may be used alone, or two or more kinds may be mixed and used.

  Examples of the aromatic vinyl monomer include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, etc. One or more of these can be used. Of these, styrene and α-methylstyrene are preferable.

  Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl acrylate, 2-ethylhexyl acrylate, and the like, and one or more of these can be used.

  Examples of maleimides include N-cyclohexylmaleimide and N-phenylmaleimide, and one or more of these can be used. Of these, N-phenylmaleimide is particularly preferable from the viewpoint of heat resistance and the like.

  It does not restrict | limit especially as a manufacturing method of methacrylic ester resin (B), Well-known methods, such as emulsion polymerization, suspension polymerization, block polymerization, and solution polymerization, are mentioned. From the viewpoint of the heat resistance of the resulting resin composition and molded product, suspension polymerization and bulk polymerization are preferred.

  The weight average molecular weight of the methacrylic ester resin (B) is preferably 50,000 to 300,000, and more preferably 65,000 to 200,000. When the weight average molecular weight of the methacrylic ester resin (B) is within the above range, the resulting resin composition or molded product tends to have good impact resistance, heat resistance, and scratch resistance.

  In the present invention, it is an essential requirement that the glass transition temperature of the methacrylic ester resin (B) to be used is 100 to 150 ° C. If the glass transition temperature of the methacrylic ester resin (B) is lower than the lower limit, the resulting resin composition or molded product tends to be inferior in heat resistance. If the glass transition temperature is higher than the upper limit, surface impact resistance, impact resistance Tend to be inferior in color and color development. The glass transition temperature of the methacrylic ester resin (B) is preferably 130 to 145 ° C.

  The compounding amount of the methacrylic ester resin (B) in the resin composition of the present invention is excellent in the color developability of the obtained resin composition and its molded product, and is hard to be damaged by a hard pointed resin component 100. It is 20-50 mass parts in a mass part, Preferably it is 25-45 mass parts. If the amount of the methacrylic ester resin (B) is less than the above lower limit, the scratch resistance and weather resistance tend to be inferior to hard scratches, and if it exceeds the above upper limit, the scratch resistance against soft scratches is likely. Tend to be inferior.

[Graft polymer (C)]
The graft polymer (C) contained in the thermoplastic resin composition of the present invention comprises a rubbery polymer (c), an aromatic vinyl monomer, a vinyl cyanide monomer, and a methacrylate ester monomer. A monomer (d) containing at least one selected from monomers is graft-polymerized.

Examples of the rubber polymer (c) forming the graft polymer (C) include polybutadiene, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, acrylate / butadiene copolymer, and styrene / isoprene copolymer. Polymers, diene rubbers such as natural rubber, acrylic rubbers such as polybutyl acrylate, ethylene / propylene copolymers, ethylene / propylene / non-conjugated diene copolymers, olefins such as ethylene / α-olefin copolymers Examples thereof include silicone rubbers such as polyrubbers and polyorganosiloxanes, and these can be used alone or in admixture of two or more. The rubbery polymer (c) may have a composite structure, for example, a polybutadiene polymerized with an acrylate ester or a polyorganosiloxane polymerized with an acrylate ester. Among these rubbery polymers (c), acrylic rubber, silicon rubber and olefin rubber are preferred because the resulting resin composition is excellent in weather resistance, and moreover, in the molded product of the resin composition obtained. Olefin rubbers are preferred because they are less likely to be scratched. For example, ethylene / propylene copolymers, ethylene / propylene / non-conjugated diene copolymers, and ethylene / α-olefin copolymer rubbers are more preferred. Here, the ethylene / α-olefin copolymer is a copolymer of ethylene and α-olefin. As the α-olefin, one or more of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like, and copolymers thereof can be used.
The ethylene / α-olefin copolymer is an ethylene / α-containing copolymer containing at least one unit composed of a non-conjugated diene component such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, and dicyclopentadiene. It may be an olefin / non-conjugated diene copolymer.

  The volume average particle diameter of the rubber polymer (c) is preferably 80 to 500 nm, more preferably 80 to 400 nm, and further preferably 80 to 260 nm. When the volume average particle diameter of the rubbery polymer (c) is within the above range, the resulting resin composition or molded article has good impact resistance and color developability.

  The method for controlling the particle size of the rubbery polymer (c) is not particularly limited, and known methods can be used. In particular, the method of adjusting the type or amount of the emulsifier used during the production of the emulsified latex of the rubber polymer (c), the shearing force applied at the time of kneading, the temperature condition, the moisture content, etc. can easily control the particle size. Preferably, the particle size of the rubbery polymer (c) tends to be reduced by increasing the amount of the emulsifier used, increasing the shearing force applied during kneading, increasing the temperature, or increasing the moisture content.

  There is no restriction | limiting in particular as a manufacturing method of the emulsion latex of a rubbery polymer (c), A well-known method can be used. For example, the rubber polymer (c) and the emulsifier are melt kneaded by a known melt kneading means such as an emulsion polymerization method in an aqueous medium, a kneader, a Banbury mixer, a multi-screw extruder, etc., and mechanical shearing force is given. The rubbery polymer (c) is dissolved in a hydrocarbon solvent such as pentane, hexane, heptane, benzene, toluene and xylene together with an emulsifier and emulsified by adding to the aqueous medium. Thereafter, a method of sufficiently stirring and distilling off the hydrocarbon solvent may be mentioned. From the viewpoint of easy control of the particle diameter, diene rubber, acrylic rubber, silicon rubber, and rubber having a composite form thereof are preferably emulsion polymerization methods in an aqueous medium. Silicon rubber, olefin rubber, and these In the case of rubber having a composite form, a rubber polymer (c) and an emulsifier are melt-kneaded by a known melt-kneading means such as a kneader, a Banbury mixer, or a multi-screw extruder, and dispersed by applying a mechanical shearing force. A method of adding to an aqueous medium is preferable. At the time of melt kneading, a wax component such as maleic anhydride-modified polyethylene may be used together with an emulsifier from the viewpoint of kneading properties.

  The emulsifier that can be used for emulsifying the rubbery polymer (c) may be any emulsifier that is usually used. For example, a long-chain alkyl carboxylate, a sulfosuccinic acid alkyl ester salt, an alkylbenzene sulfonate, etc. The well-known thing is mentioned.

The presence or absence of crosslinking of the rubbery polymer (c) is not particularly limited, but is preferably crosslinked because of excellent impact resistance and color developability. The gel content of the rubbery polymer (c) is 40 to 40. It is preferable that it is 99 mass%, and it is more preferable that it is 50-88 mass%.
The gel content of the rubbery polymer (c) indicates the degree of crosslinking of the rubbery polymer (c). Specifically, the measured amount of the rubbery polymer (c) in an appropriate solvent over 40 hours. Dissolved, then separated with a 200 mesh wire mesh, dried insoluble matter remaining in the wire mesh, weighed, and ratio of dried insoluble matter to the rubbery polymer (c) before being dissolved in the solvent (mass) %). As the solvent used for dissolving the rubber polymer (c), for example, toluene is used for diene rubber and olefin rubber, and acetone is used for acrylic rubber.

  There is no restriction | limiting in particular as a method of bridge | crosslinking rubbery polymer (c), A well-known thing can be used. For example, a method of adjusting the addition amount of an organic peroxide or a chain transfer agent used at the time of emulsion polymerization of a diene rubber, a method of copolymerizing with a polyfunctional compound at the time of polymerization of a diene rubber or an acrylic rubber, a diene rubber, A method of heating by adding an organic peroxide and, if necessary, a polyfunctional compound to silicon rubber or olefin rubber is preferable because the degree of crosslinking can be easily adjusted.

  Although there is no restriction | limiting in particular in an organic peroxide, For example, a peroxyester compound, a peroxyketal compound, a dialkyl peroxide compound etc. are mentioned, 1 or more types of these can be used.

  Specific examples of the peroxyester compound include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecano Eight, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylper Oxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1- Cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-hexyl Ruhexanoate, t-butylperoxy-2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3, 5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butyl Peroxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m -Toluoyl benzoate, t-butyl peroxy Nzoeito, bis (t-butylperoxy) Isofutareito the like.

  Specific examples of the peroxyketal compound include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis. (T-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (T-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, etc. It is done.

  Specific examples of the dialkyl peroxide compound include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane. , T-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, and the like.

  The polyfunctional compound is not particularly limited as long as it has 2 to 4 radical polymerizable sites in the molecule. For example, divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene Examples include glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate, and the like. One or more of these can be used.

  The addition amount of the organic peroxide and the polyfunctional compound is easy to adjust the gel content of the rubbery polymer (c) in the range of 40 to 99% by mass and easily develop impact resistance and color development. The organic peroxide is 0.01 to 5 parts by mass with respect to 100 parts by mass of the rubbery polymer (c), and the polyfunctional compound is 10 parts by mass or less with respect to 100 parts by mass of the rubbery polymer (c). It is preferable to use in a range.

  The graft polymer (C) is obtained by graft polymerization of the monomer (d) to the rubber polymer (c). The monomer (d) includes at least one selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and a methacrylic acid ester monomer.

  Examples of the aromatic vinyl monomer include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, etc. One or more of these can be used. Of these, styrene and α-methylstyrene are preferable.

  Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and one or more of these can be used.

  Examples of the methacrylic acid ester monomer include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, Examples include amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and phenyl methacrylate. Can be used.

The monomer (d) includes, in addition to the above aromatic vinyl monomer, vinyl cyanide monomer and methacrylic acid ester monomer, other monomers copolymerizable therewith, You may include in the range which does not impair the effect of this invention.
As other monomers, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl acrylate, 2-ethylhexyl acrylate, N-cyclohexylmaleimide, N-phenyl Maleimides such as maleimide can be used, and one or more of these can be used. Of these, methyl acrylate is preferable from the viewpoint of heat resistance and the like.

  When using an aromatic vinyl monomer and a vinyl cyanide monomer as the monomer (d), the aromatic vinyl monomer is 70 to 82% by mass in 100% by mass of the monomer (d). The vinyl cyanide monomer is preferably 18 to 30% by mass. If the content of the aromatic vinyl monomer and the vinyl cyanide monomer in the monomer (d) is within the above range, the color developability and impact resistance of the resulting resin composition and its molded product Will be improved.

  When a methacrylic acid ester monomer is used as the monomer (d), decomposition during melt kneading can be suppressed, so that an aromatic vinyl monomer, cyanide in 100% by mass of the monomer (d). 0.1 to 50% by mass, preferably 0.1 to 30% by mass, and more preferably 1 to 5% of one or more of the vinyl halide monomers and the other copolymerizable monomers described above It is preferable to contain the mass%.

  The graft polymer (C) is obtained by graft polymerization of the monomer (d) in the presence of the rubbery polymer (c). The ratio of the rubbery polymer (c) at the time of graft polymerization is preferably 40 to 80% by mass, and the ratio of the monomer (d) is preferably 20 to 60% by mass (however, the rubbery polymer ( The sum of c) and monomer (d) is 100% by mass). In general, when the ratio of the rubbery polymer (c) is within the above range, the productivity of the graft polymer (C) is good, and the color developability and resistance of the resulting resin composition and molded product thereof are improved. Improves impact.

  The graft polymer (C) preferably has a graft ratio of 23 to 100%, more preferably 25 to 35, since the resulting resin composition and the molded product thereof have good color developability and impact resistance. %.

The graft ratio (G) in this specification is calculated | required from a following formula.
G = 100 (PE) / E
P: Mass of acetone-insoluble matter (graft polymer (C) or resin composition was washed with methanol, extracted with acetone, and separated into acetone-soluble and acetone-insoluble matter with a centrifuge, and obtained acetone Mass (g) after vacuum drying insoluble matter
E: Mass (g) of the rubbery polymer (c) used in the production of the graft polymer (C)

  The graft polymer (C) is produced by a known method such as a bulk polymerization method, a solution polymerization method, a bulk suspension polymerization method, a suspension polymerization method, or an emulsion polymerization method. In view of easy control of the particle size and easy polymerization, the emulsion polymerization method is preferred.

  The blending amount of the graft polymer (C) in the resin composition of the present invention is 4 in 100 parts by mass of the resin component because the color developability, impact resistance and scratch resistance of the resulting resin composition and its molded product are excellent. .9 to 25 parts by mass, preferably 8 to 13 parts by mass. If the graft polymer (C) is less than the above lower limit, the surface impact resistance, impact resistance, and scratch resistance tend to be inferior with a soft one, and if it exceeds the upper limit, the molded appearance and hard one are attached. Scratch resistance and weather resistance tend to be inferior.

[Other resins]
In the resin composition of this invention, you may contain other resins other than said isosorbide type polycarbonate resin (A), methacrylic ester resin (B), and a graft polymer (C).

  Examples of other resins include AS resins, polystyrene resins, polyacetal resins, nylon resins, polyvinyl chloride resins, polyphenylene ether resins, and polyesters such as polylactic acid resins. Also, a blend of two or more of these may be used, and the above resin modified with a compatibilizer or a functional group may be blended.

  However, when the resin composition of the present invention contains these other resins, the effect by including the above-mentioned isosorbide-based polycarbonate resin (A), methacrylic ester resin (B), and graft polymer (C) is surely obtained. In order to obtain, other resin is 20 mass parts in 100 mass parts of resin components (namely, total of isosorbide-type polycarbonate resin (A), methacrylic ester resin (B), graft polymer (C), and other resin)). The following is preferable.

[Additive]
In addition to isosorbide-based polycarbonate resin (A), methacrylic acid ester resin (B) and graft polymer (C), the resin composition of the present invention is a resin that does not impair the physical properties of the resin composition or molded product. Other conventional additives such as lubricants, pigments (carbon black, titanium oxide, etc.), dyes, fillers (silica, mica, wollastonite, talc, glass, during production (mixing) and molding of the composition Fibers, carbon fibers, etc.), heat-resistant agents, oxidative degradation inhibitors, weathering agents, mold release agents, plasticizers, antistatic agents, flame retardants, and the like.

[Method for producing resin composition]
The resin composition of the present invention can be produced by a known method using a known device. For example, there is a melt mixing method as a general method, and examples of an apparatus used in this method include an extruder, a Banbury mixer, a roller, and a kneader. Either a batch type or a continuous type may be employed for mixing. Moreover, there is no restriction | limiting in particular in the mixing order of each component, etc., All the components should just be mixed uniformly.

〔Molding〕
The molded product of the present invention is formed by molding the above-described resin composition of the present invention. Examples of the molding method include an injection molding method, an injection compression molding method, an extrusion method, a blow molding method, a vacuum molding method, a pressure forming method, a calendar molding method, and an inflation molding method. Among these, the injection molding method and the injection compression molding method are preferable because they are excellent in mass productivity and a molded product with high dimensional accuracy can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples, and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

<Measuring method of glass transition temperature of methacrylate ester resin (B)>
The glass transition temperature of the methacrylic acid ester resin (B) was measured by differential scanning calorimetry (DSC), the sample was heated from 35 ° C. to 250 ° C. at 10 ° C./min in a nitrogen atmosphere, and then cooled to 35 ° C. The glass transition temperature observed when the temperature was raised again to 250 ° C. was measured.

<Measurement Method of Mass Average Molecular Weight (Mw), Molecular Weight Distribution (Mw / Mn)>
Mass average molecular weight in terms of polystyrene using GPC (GPC: “GPC / V2000” manufactured by Waters, column: “Shodex AT-G + AT-806MS” manufactured by Showa Denko KK) and o-dichlorobenzene (145 ° C.) as a solvent. (Mw), number average molecular weight (Mn) were measured, and molecular weight distribution (Mw / Mn) was calculated.

[Production Example 1: Isosorbide-based polycarbonate resin (A1)]
In a polymerization reactor equipped with a stirring blade, a reflux condenser controlled at 100 ° C., and a jacket type heater, isosorbide (ISB), 1,4-cyclohexanedimethanol (CHDM), and chloride ion concentration after purification by distillation Of diphenyl carbonate (DPC) and calcium acetate monohydrate with a molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.5 / 0.5 / 1.00 / 1.3 The mixture was charged to × 10 ⁻⁶ and sufficiently substituted with nitrogen (oxygen concentration 0.0005 vol% to 0.001 vol%). Subsequently, the contents were heated with a heating medium.
Stirring was started when the internal temperature reached 100 ° C, and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. Thereafter, the temperature increase was started, and the internal temperature was brought to 210 ° C. in 40 minutes.
When the internal temperature reaches 210 ° C., control is performed to maintain this temperature, and at the same time, pressure reduction is started, and after reaching 210 ° C., 13.3 kPa (absolute pressure, the same applies hereinafter) is reached in 90 minutes. The pressure was held for an additional 60 minutes. The phenol vapor produced as a by-product with the polymerization reaction was led to a reflux condenser. The components condensed in the reflux condenser were returned to the polymerization reaction apparatus, and the phenol vapor that was not condensed was subsequently recovered by guiding it to a condenser using 45 ° C. hot water as a refrigerant.

  The content oligomerized in the polymerization reactor is once restored to atmospheric pressure, and then transferred to another polymerization reactor equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. Depressurization was started, and an internal temperature of 220 ° C. and a pressure of 200 Pa were achieved in 60 minutes. Thereafter, the internal temperature was set to 228 ° C. and the pressure was set to 133 Pa or less over 20 minutes. When the predetermined stirring power was reached, the pressure was restored, and a molten polycarbonate copolymer was obtained from the outlet of the polymerization reactor.

  Furthermore, the melted polycarbonate copolymer is continuously supplied to a twin-screw extruder provided with three vent ports and water injection equipment, and an antioxidant and a release agent are continuously added. After low-molecular-weight substances such as phenol were devolatilized under reduced pressure at each vent portion provided in the above, pelletization was performed with a pelletizer to obtain an isosorbide-based polycarbonate resin (A1).

[Production Example 2: Isosorbide-based polycarbonate resin (A2)]
In Production Example 1, except that the molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate was changed to 0.7 / 0.3 / 1.00 / 1.3 × 10 ⁻⁶ , By reacting under the same conditions, an isosorbide-based polycarbonate resin (A2) was obtained.

[Production Example 3: Isosorbide-based polycarbonate resin (A3)]
In Production Example 1, 1,4-cyclohexanedimethanol (CHDM) was not used, and the molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate was 1.00 / 0.0 / 1.00 / 1.3. except for using × 10 ^-6 was obtained was reacted under the same conditions as in production example 1 with isosorbide-based polycarbonate resin (A3).

[Production Example 4: Methacrylate resin (B1)]
In a pressure-resistant reaction vessel, 150 parts by mass of distilled water, 99 parts by mass of methyl methacrylate, 1 part by mass of methyl acrylate, 0.2 part by mass of 2,2′-azobis (isobutyronitrile), 0.2% by mass of n-octyl mercaptan. 25 parts by mass, 0.47 parts by mass of calcium hydroxyapatite and 0.003 parts by mass of potassium alkenyl succinate were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. Then, it heated up to 90 degreeC and reaction was completed by hold | maintaining for 60 minutes. The contents were washed with a centrifugal dehydrator, dehydrated repeatedly, and dried to obtain a methacrylic ester resin (B1). The glass transition temperature of the resulting methacrylic ester resin (B1) was 105 ° C. The molecular weight was 77,000.

[Production Example 5: Methacrylate resin (B2)]
In a pressure resistant reactor, 150 parts by mass of distilled water, 15 parts by mass of N-phenylmaleimide, 5 parts by mass of styrene, 5 parts by mass of α-methylstyrene, 75 parts by mass of methyl methacrylate, and 2,2′-azobis (iso Butyronitrile) 0.2 parts by mass, n-octyl mercaptan 0.25 parts by mass, polyvinyl alcohol 0.7 parts by mass were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. Then, it heated up to 90 degreeC and reaction was completed by hold | maintaining for 60 minutes. The contents were washed with a centrifugal dehydrator, dehydrated repeatedly, and dried to obtain a methacrylic ester resin (B2). The resulting methacrylic ester resin (B2) had a glass transition temperature of 131 ° C. The molecular weight was 135,000.

[Production Example 6: Methacrylate resin (B3)]
A methacrylic ester resin (B3) is reacted under the same conditions as in Production Example 5 except that 25 parts by mass of N-phenylmaleimide, 10 parts by mass of styrene, 10 parts by mass of α-methylstyrene, and 55 parts by mass of methyl methacrylate are used. Got. The glass transition temperature of the resulting methacrylic ester resin (B3) was 147 ° C. The molecular weight was 130,000.

[Production Example 7: Methacrylate resin (B4)]
A methacrylic ester resin (B4) was obtained by reacting under the same conditions as in Production Example 4 except that 90 parts by mass of methyl methacrylate and 10 parts by mass of methyl acrylate were used. The glass transition temperature of the obtained methacrylic ester resin (B4) was 90 ° C. The molecular weight was 70,000.

[Production Example 8: Graft polymer (C1)]
<Production of emulsion latex of ethylene / propylene copolymer (c1)>
100 parts by weight of EPDM (“TP3180” manufactured by Mitsui Chemicals, Inc.), 9 parts by weight of low molecular weight modified polyethylene (“High Wax 2203A” manufactured by Mitsui Chemicals, Inc.), and 3.1 parts by weight of potassium oleate were mixed. . Subsequently, these mixtures were supplied at a rate of 6 kg / hour from the hopper of a twin screw extruder (“PCM-30 type” manufactured by Ikekai Steel Co., Ltd., L / D = 40), and 110 g of a 15% by weight potassium hydroxide aqueous solution was supplied. The melt was extruded by melting and kneading at a heating temperature of 200 ° C. while continuously feeding at a time of / hour. Subsequently, the melt was continuously supplied to a cooling single screw extruder attached to the tip of the extruder and cooled to 90 ° C. The taken-out solid was poured into warm water at 80 ° C. and continuously dispersed to obtain a rubber polymer latex having a volume average particle diameter of 250 nm.

An ethylene / propylene copolymer is prepared by adding 1.2 parts by mass of t-butylcumyl peroxide and 1.0 part by mass of divinylbenzene to 100 parts by mass of the solid content of the latex and reacting at 135 ° C. for 5 hours. A latex (c1) was prepared.
The gel content of this ethylene / propylene copolymer (c1) was 72% by mass. The gel content was determined by coagulating the copolymer latex with dilute sulfuric acid, washing with water and drying, collecting 1 g of this, immersing it in 200 ml of toluene for 40 hours, and then filtering through a 200-mesh wire mesh. Was dried and measured for its mass.

<Production of graft polymer (C1)>
To 70 parts by mass (in terms of solid content) of an emulsified latex of an ethylene / propylene copolymer (c1) having a gel content of 72% by mass and a volume average particle size of 250 nm, 0.15 parts by mass of sodium pyrophosphate and seven ferrous sulfates 0.006 part by mass of water salt and 0.35 part by mass of fructose were charged, and the internal temperature was kept at 80 ° C. To this, a monomer mixture composed of 25.2 parts by mass of styrene and 4.8 parts by mass of acrylonitrile and 0.6 parts by mass of cumene hydroperoxide were simultaneously added dropwise from another supply port over 140 minutes. Polymerization was performed. During this time, the internal temperature was controlled to be constant at 80 ° C. After completion of dropping, the mixture was kept at 80 ° C. for 100 minutes and then cooled to complete graft polymerization. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft polymer (C1). The graft ratio of the graft polymer (C1) was 29%.

[Production Example 9: Graft polymer (C2)]
A graft polymer (C2) was obtained by reacting under the same conditions as in Production Example 8, except that the monomer mixture was 24 parts by mass of styrene and 6 parts by mass of acrylonitrile. The graft ratio of the graft polymer (C2) was 30%.

[Production Example 10: Graft polymer (C3)]
A graft polymer (C3) was obtained by reacting under the same conditions as in Production Example 8 except that the monomer mixture was changed to 21.6 parts by mass of styrene and 8.4 parts by mass of acrylonitrile. The graft ratio of the graft polymer (C2) was 29%.

[Production Example 11: Graft polymer (C4)]
A graft polymer (C4) was obtained by reacting under the same conditions as in Production Example 8 except that the monomer mixture was changed to 20.4 parts by mass of styrene and 9.6 parts by mass of acrylonitrile. The graft ratio of the graft polymer (C4) was 30%.

[Production Example 12: Graft polymer (C5)]
To 70 parts by mass (in terms of solid content) of emulsified latex of polybutyl acrylate rubber (c2) having a gel content of 84% by mass and a volume average particle size of 170 nm, 1 part by mass of disproportionated potassium rosinate, 0 parts of potassium hydroxide 0.03 part by mass, heated to 60 ° C., charged with 0.1 part by mass of sodium pyrophosphate, 0.007 part by mass of ferrous sulfate heptahydrate, and 0.3 part by mass of fructose, the internal temperature was 60 ° C. Kept. To this, a monomer mixture consisting of 23 parts by mass of styrene and 7 parts by mass of acrylonitrile and 0.5 parts by mass of cumene hydroperoxide were simultaneously added dropwise from another supply port over 120 minutes for polymerization. . After completion of dropping, the mixture was kept at 70 ° C. for 100 minutes and then cooled to complete graft polymerization. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft polymer (C5). The graft ratio of the graft polymer (C5) was 32%.

[Production Example 13: Graft polymer (C6)]
70 parts by mass (in terms of solid content) of an emulsified latex of polybutadiene rubber (c3) having a gel content of 95% and a volume average particle diameter of 320 nm, 23 parts by mass of styrene, 7 parts by mass of acrylonitrile, and disproportionated potassium rosinate 1 Parts by weight, sodium hydroxide 0.01 parts by weight, sodium pyrophosphate 0.45 parts by weight, ferrous sulfate heptahydrate 0.01 parts by weight, dextrose 0.57 parts by weight, t-dodecyl mercaptan 0.08 parts by weight And 1.0 part by mass of cumene hydroperoxide were charged, the reaction was started at 60 ° C., the temperature was raised to 75 ° C., held for 120 minutes, and cooled to complete the graft polymerization. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft polymer (C6). The graft ratio of the graft polymer (C6) was 31%.

[Production Example 14: Graft polymer (C7)]
A graft polymer (C7) was obtained by reacting under the same conditions as in Production Example 8, except that the monomer mixture was 29 parts by mass of methyl methacrylate and 1 part by mass of methyl acrylate. The graft ratio of the graft polymer (C7) was 30%.

[Production Example 15: Graft polymer (C8)]
Production Example 9 except that an ethylene / α-olefin copolymer (α-olefin is 1-butene) (c4) having a gel content of 74 mass% and a volume average particle diameter of 420 nm is used as the rubber polymer. The reaction was conducted under the same conditions to obtain a graft polymer (C8). The graft ratio of the graft polymer (C8) was 34%.

[Production Example 16: Graft polymer (C9)]
Production Example 9 except that an ethylene / α-olefin copolymer (α-olefin is 1-butene) (c5) having a gel content of 48 mass% and a volume average particle diameter of 250 nm was used as the rubber polymer. The reaction was conducted under the same conditions to obtain a graft polymer (C9). The graft ratio of the graft polymer (C9) was 36%.

[Production Example 17: Graft polymer (C10)]
60 mass parts (in terms of solid content) of an emulsified latex of an ethylene / propylene copolymer (c1) having a gel content of 72 mass% and a volume average particle diameter of 250 nm, 33.6 parts by mass of styrene and acrylonitrile as a monomer mixture Except having used 6.4 mass parts, it was made to react on the conditions similar to manufacture example 8, and the graft polymer (C10) was obtained. The graft ratio of the graft polymer (C10) was 41%.

[Reference Examples 1-12, Examples 1-20, Comparative Examples 1-6]
Each component was mixed by the mixing | blending shown in Tables 1-4, and it knead | mixed and kneaded at 260 degreeC using the 28 mm twin-screw extruder ("TEX-28V" by Nippon Steel Works), and obtained the pellet-shaped resin composition.

<Injection molding 1>
The pellets of the resin composition obtained by melt-kneading were subjected to an injection molding machine (Toshiba Machine Co., Ltd., “IS55FP-1.5A”) at a cylinder temperature of 200 to 270 ° C. and a mold temperature of 60 ° C., with a length of 80 mm, A molded product having a width of 10 mm and a thickness of 4 mm was molded and used as a molded product for impact resistance evaluation and a molded product for heat resistance evaluation (measurement of deflection temperature under load) (molded product (1)).

<Injection molding 2>
The pellets of the resin composition obtained by melt kneading were subjected to an injection molding machine (Toshiba Machine Co., Ltd., “IS55FP-1.5A”) at a cylinder temperature of 200 to 270 ° C. and a mold temperature of 80 ° C., with a length of 100 mm, Molded products with a width of 100 mm and a thickness of 3 mm, molded products for evaluation of surface impact resistance, molded products for evaluation of scratch resistance (pencil hardness measurement, gauze wear resistance measurement), molded products for transparency evaluation (molded products) Used as (2)).

<Injection molding 3>
Molded under the same conditions as injection molding 2 except that 0.8 parts by mass of carbon black was added during melt-kneading, molded product for scratch resistance evaluation (gauze abrasion resistance measurement), molded product for color development evaluation, weather resistance Used as a molded product for property evaluation (molded product (3)).

<Surface impact resistance>
The falling ball impact strength was measured using the molded product (2). A 230 g hard sphere was dropped from a predetermined height onto the center of the molded product, and the presence or absence of cracks or cracks was confirmed. After performing the test on 10 sheets, the height was changed by 10 cm, the same test was performed, and the height at which 5 or more molded articles were broken was obtained. The thing of 150 cm or more is described as 150. 100 cm or more was regarded as acceptable.

<Impact resistance>
The molded product (1) was subjected to a Charpy impact test (notched) at 23 ° C. in accordance with ISO 179 standard, and the Charpy impact strength was measured.

<Pencil hardness>
Based on JIS K5600, the pencil hardness of the molded product (2) was measured at a load of 750 g. The higher the pencil hardness, the better the scratch resistance. HB or higher was accepted.

<Gauze wear resistance>
As shown in FIG. 1, a rod-shaped jig 2 having a tip 1 formed in a hemispherical shape was prepared, and the tip 1 was covered with a laminated sheet S in which eight sheets of gauze were stacked. The tip portion 1 covered with the laminated sheet S is brought into contact with the surface of the molded product (3) M so that the rod-shaped jig 2 is perpendicular to the surface of the molded product (3). It was slid in the horizontal direction (arrow direction in the figure) and reciprocated 100 times. At that time, the applied load was 1 kg. After reciprocating 100 times, scratches on the surface of the molded article (4) having scratches were visually observed and evaluated in the following four stages.
The better the gauze wear, the harder it is to scratch when the surface of the molded product is wiped with a work gloves, gauze or cloth, or when the clothing is rubbed, and the scratch resistance is better. ○ The above was accepted.
◎: Scratches are scarce ○: Scratches are inconspicuous △: Scratches are prominent ×: Scratched scratches are noticeable when touched by hand

<Heat resistance>
With respect to the molded article (1), the deflection temperature under load (° C.) was measured by a flatwise method in accordance with ISO test method 75, 1.83 MPa, 4 mm.

<Transparency>
With respect to the molded product (2), the total light transmittance was measured according to JIS K 7361.

<Color development>
For the molded product (3), the lightness L ^* was measured by the SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). The L ^* measured in this way is referred to as “L ^* (ma)”. The lower L ^* was, the more black the color was determined.
“Lightness (L ^* )” means a lightness value (L ^* ) among color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729.
The “SCE method” means a method of measuring a color by using a spectrocolorimeter in accordance with JIS Z 8722 and removing specularly reflected light with an optical trap.

<Weather resistance>
The molded product (3) was treated for 1500 hours under the conditions of a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall 12 minutes) using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). The 60 ° glossiness of the surface of the molded article (3) before and after the treatment was measured with a digital variable gloss meter (manufactured by Suga Test Instruments Co., Ltd.), and the 60 ° glossiness after the treatment relative to the 60 ° glossiness before the treatment was measured. The ratio (percentage) was calculated as the gloss retention after processing. 70% or more was accepted.

[result]
These evaluation results are shown in Tables 1-4.

[Discussion]
In Reference Examples 1 to 12 in Table 1, evaluation of molded products obtained from a thermoplastic resin composition comprising an isosorbite-based polycarbonate resin (A) and a methacrylic ester resin (B) was carried out. It was confirmed that impact resistance and gauze wear resistance were low, and the intended effect of the present invention could not be obtained.
As shown in Examples 1 to 20 of Tables 2 and 3, molded articles obtained from the thermoplastic resin composition of the present invention have surface impact resistance, impact resistance, scratch resistance, heat resistance, and color developability. In addition to being excellent, it was also excellent in weather resistance, and had all these characteristics in a well-balanced manner.
Since Comparative Examples 1-4 and 6 have the compounding quantity of any one of isosorbite-type polycarbonate resin (A), methacrylic acid ester resin (B), and a graft polymer (C) from the range of this invention, or more, The desired properties were not met. Since the glass transition temperature of the methacrylic ester resin (B) was lower than the range of this invention, the comparative example 5 was inferior to heat resistance.

  The molded article using the thermoplastic resin composition of the present invention is excellent in surface impact resistance, scratch resistance, heat resistance, transparency, and weather resistance. It is useful as a material for construction and housing.

1 Tip 2 Jig S Laminated Sheet M Molded Product

Claims (8)

  Methacrylic acid obtained by polymerizing 45 to 75 parts by mass of a polycarbonate resin (A) containing a structure derived from isosorbides and a vinyl monomer mixture (b) containing a methacrylate ester in 100 parts by mass of a resin component 20-50 parts by mass of the acid ester resin (B) and at least the rubber polymer (c) selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and a methacrylic acid ester monomer A thermoplastic resin composition comprising 4.9 to 25 parts by mass of a graft polymer (C) obtained by graft polymerization of a monomer (d) containing one kind, and a glass transition of the methacrylate resin (B) A thermoplastic resin composition having a temperature of 100 ° C to 150 ° C. The polycarbonate resin (A) including a structure derived from isosorbides includes a structural unit derived from a dihydroxy compound and cyclohexanedimethanol represented by the following formula (1), and includes a structure derived from isosorbides (A ), The structural unit derived from the dihydroxy compound represented by the following formula (1) is 95 to 30 mol%, and the structural unit derived from cyclohexanedimethanol is 5 to 70 mol. 2. The thermoplastic resin composition according to claim 1, comprising:

  The vinyl monomer mixture (b) contains a methacrylic acid ester and another vinyl monomer copolymerizable with the methacrylic acid ester, and contains the methacrylic acid ester in the vinyl monomer mixture (b). The thermoplastic resin composition according to claim 1 or 2, wherein the amount is 50 to 99.5 mass%.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the monomer (d) contains 70 to 82% by mass of an aromatic vinyl monomer and 18 to 30% by mass of a vinyl cyanide monomer. object.   The rubbery polymer (c) is at least one selected from an ethylene / propylene copolymer, an ethylene / propylene / non-conjugated diene copolymer, and an ethylene / α-olefin copolymer. The thermoplastic resin composition according to any one of the above.   The volume average particle diameter of the rubber polymer (c) is 80 to 500 nm, the gel content of the rubber polymer (c) is 40 to 99% by mass, and the graft ratio of the graft polymer (C) is 23. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin composition is -100%.   The graft polymer (C) is obtained by graft polymerization of 40 to 80% by mass of a rubbery polymer (c) and 20 to 60% by mass of a monomer (d). The thermoplastic resin composition according to any one of the above.   A molded article using the thermoplastic resin composition according to any one of claims 1 to 7.

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