JP6730028B2 - White resin composition and molded article - Google Patents

Description

The present invention relates to a white resin composition capable of improving whiteness without using a white pigment, and a molded product formed from this composition.

White is an achromatic color with high lightness, has a clean image, has high light reflectivity, and is excellent in printability and decorativeness. Therefore, white plastic moldings are used as various plastic moldings. In particular, since white polycarbonate is excellent in impact resistance and heat resistance, it is used as various molded articles for automobiles, electric and electronic parts and the like.

As the white polycarbonate, a polycarbonate resin composition in which a white pigment such as titanium oxide is blended is widely used, and in JP 2006-176567 A (Patent Document 1), titanium oxide is added to 100 parts by weight of the aromatic polycarbonate. 3 to 30 parts by weight, dye and pigment 0 to 0.1 part by weight, organic acid metal salt as a flame retardant 0.01 to 1 part by weight, fluoropolymer 0.01 to 1 part by weight, silicate compound 0.1 to 30 parts by weight A molded product having a white appearance is disclosed, which is made of a resin composition containing 0.001 to 5 parts by weight of an organic acidic compound.

However, when the concentration of the white pigment is increased in a molded body formed of white polycarbonate containing a white inorganic pigment such as titanium oxide, mechanical properties such as impact resistance are deteriorated.

In Japanese Patent Laid-Open No. 2014-188910 (Patent Document 2), a base layer portion and a surface layer portion are laminated and integrated by a coextrusion molding method, and the base layer portion includes 100 parts by weight of a polycarbonate resin and crosslinked acrylic beads or the like. A polycarbonate resin laminate containing 0.1 to 10 parts by weight of transparent fine particles and 0.01 to 1 part by weight of a white pigment such as titanium oxide is disclosed. In this laminate, since the polycarbonate has low weather resistance, the surface layer portion containing the ultraviolet absorber is formed on the surface layer portion to maintain the color tone of the white polycarbonate of the base layer.

However, the polycarbonate resin laminate has a multi-layered structure and a complicated structure, and further, coextrusion is required, and the manufacturing method is complicated.

Japanese Unexamined Patent Application Publication No. 2014-40556 (Patent Document 3) discloses that aromatic polycarbonate resin 40 to 95% by mass, styrene polymer 1 to 20% by mass, and flat glass fibers 5 to 99. 0.1 to 10 parts by mass of a mixture of 50 to 99.5% by mass of zinc sulfide and 0.5 to 50% by mass of barium sulfate based on 100 parts by mass of 5% by mass, an organic phosphate-based heat stabilizer. A polycarbonate resin composition containing 0.01 to 1 part by mass is disclosed. In this document, in a polycarbonate reinforced with glass fibers, a mixture of zinc sulfide and barium sulfate is used as a white pigment instead of titanium oxide in order to suppress crushing of the glass fibers by titanium oxide.

However, lead sulfide and barium sulfate are also inorganic white pigments, and increasing the concentration of the white pigment lowers mechanical properties such as impact resistance.

JP 2006-176567 A (claims, examples) JP, 2014-188910, A (claim, paragraph [0002], an example) JP, 2014-40556, A (claim 1, paragraph [0004] [0077]).

Therefore, an object of the present invention is to provide a resin composition having excellent mechanical properties such as impact resistance and high whiteness, and a molded product formed from this resin composition.

Another object of the present invention is to provide a resin composition having excellent light resistance and capable of suppressing yellowing even when exposed to light for a long period of time, and a molded product formed from this resin composition.

Still another object of the present invention is to provide a resin composition capable of improving heat resistance and flame retardancy, and a molded product formed from this resin composition.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination in order to achieve the said subject, this inventor combined the transparent resin (A) which does not contain an unsaturated bond, the rubber particle (B), and the ultraviolet absorber (C) which does not absorb visible light. As a result, they have found that the whiteness can be improved without lowering mechanical properties such as impact resistance, and have completed the present invention.

That is, the resin composition of the present invention contains a transparent resin (A) containing no unsaturated bond, rubber particles (B), and an ultraviolet absorber (C) that does not absorb visible light. The whiteness L value of the resin composition of the present invention may be 90 or more. The yellowness b value of the resin composition of the present invention may be 5 or less. The transparent resin (A) may be polycarbonate. The rubber particles (B) may contain a non-diene rubber, and particularly, a core-shell structure formed by a core portion containing a silicone rubber and/or an acrylic rubber and a shell portion containing a vinyl polymer. The particles may have. The average particle size of the rubber particles (B) is about 0.05 to 1 μm. The ultraviolet absorber (C) may be at least one selected from the group consisting of anilide oxalates, malonic acid esters, and cyanoacrylates. The weight ratio of the transparent resin (A) and the rubber particles (B) is about former/latter=95/5 to 80/20. The ratio of the ultraviolet absorber (C) is about 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the transparent resin (A) and the rubber particles (B). The resin composition of the present invention may further contain a phosphorus-based flame retardant (D). The phosphorus flame retardant (D) may be an aromatic condensed phosphoric acid ester. The ratio of the phosphorus-based flame retardant (D) is about 1 to 30 parts by weight based on 100 parts by weight of the total of the transparent resin (A) and the rubber particles (B). The resin composition of the present invention may further contain a fluororesin (E). Further, the resin composition of the present invention may further contain a white dye/pigment (F).

The present invention also includes a molded body formed of the resin composition.

In the present invention, the transparent resin (A) containing no unsaturated bond, the rubber particles (B), and the ultraviolet absorber (C) that does not absorb visible light are combined, so that mechanical properties such as impact resistance are improved. Whiteness can also be improved without lowering. Further, it has excellent light resistance and can suppress yellowing even when exposed to light for a long time. Further, it has high heat resistance, and when it is combined with a phosphorus-based flame retardant (D), flame retardancy and whiteness can be improved. Especially, when it is combined with an aromatic condensed phosphoric acid ester, it does not use halogen, which has a large impact on the environment. The flame retardancy can be improved.

[Transparent resin (A)]
The resin composition of the present invention contains a transparent resin (A). From the viewpoint of light resistance, the transparent resin may be a transparent resin containing no unsaturated bond (ethylenically unsaturated bond), and may be a thermosetting resin. Resins are preferred.

As the thermoplastic resin, for example, polyolefin (polyethylene resin, polypropylene resin, cyclic polyolefin, etc.), halogen-containing resin (vinyl chloride resin, vinylidene chloride resin, etc.), (meth)acrylic resin (polymethyl methacrylate) -Based resins), styrene-based resins (polystyrene, acrylonitrile-styrene-based resins, etc.), polyesters (polyalkylene terephthalates, polybutylene terephthalates, and other polyalkylene arylates), polycarbonates (bisphenol A-type polycarbonates, etc.), polyamides (polyamide 6, polyamide) And aliphatic derivatives such as 66) and cellulose derivatives (such as cellulose acetate such as cellulose triacetate and cellulose diacetate). These thermoplastic resins can be used alone or in combination of two or more kinds. Among these thermoplastic resins, polyester, polycarbonate, and polyamide are preferable, and polycarbonate is particularly preferable, from the viewpoint of excellent balance between transparency and mechanical strength.

As the polycarbonate, an aromatic polycarbonate-based resin (polycarbonate-based resin having an aromatic dihydroxy compound as a polymerization component), particularly a bisphenol-type polycarbonate-based resin (polycarbonate-based resin having a bisphenol as a polymerization component) is preferable.

Examples of bisphenols include bis(hydroxyphenyl)alkanes [eg, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)]. Propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3- Bis(hydroxyphenyl)C _1-6 alkanes such as methylbutane], bis(hydroxyaryl)cycloalkanes [eg, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxy) Bis(hydroxyphenyl)C _4-10 cycloalkane etc. such as phenyl)cyclohexane], bis(hydroxyphenyl)ethers [eg bis(4-hydroxyphenyl)ether], bis(hydroxyphenyl)sulfones [eg, Examples thereof include bis(4-hydroxyphenyl)sulfone] and bis(hydroxyphenyl)sulfides [eg, bis(4-hydroxyphenyl)sulfide]. These bisphenols can be used alone or in combination of two or more.

Further, from the viewpoint of improving flame retardancy, the bisphenols may be halogenated with bromine or the like.

Of these bisphenols, bis(hydroxyaryl)C _1-6 alkanes such as bisphenol A are preferred.

The viscosity average molecular weight of the polycarbonate can be selected from the range of 10000 or more (for example, 15000 to 50000) when measured at 20° C. using methylene chloride, and from the viewpoint of impact resistance, 16000 or more is preferable, and for example, 16000 to 50000. (For example, 16000 to 45000), preferably 18000 to 40000 (for example, 18000 to 35000), and more preferably 20000 to 30000 (particularly 20000 to 25000). When the molecular weight is in this range, the balance between fluidity and impact resistance is excellent.

The glass transition temperature (Tg) of the polycarbonate may be, for example, 110 to 160°C, preferably 115 to 155°C, more preferably 120 to 150°C.

Polycarbonate can be obtained by a conventional method (eg, phosgene method, transesterification method, etc.).

[Rubber particles (B)]
The resin composition of the present invention further contains rubber particles (B) in order to improve mechanical strength such as impact resistance and develop white color.

The rubber particles may include rubber components such as natural rubber and synthetic rubber, and various thermoplastic elastomers, but from the viewpoint of improving light resistance, non-diene rubbers (saturated rubbers) having no unsaturated bond can be used. ) Is preferred. Examples of such rubber include butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, chlorosulfonated polyethylene, chlorinated polyethylene, acrylic rubber, epichlorohydrin rubber, fluororubber and polysulfide rubber. These rubbers can be used alone or in combination of two or more.

Among these rubbers, silicone rubber and/or acrylic rubber are preferable, and a combination of silicone rubber and acrylic rubber (composite rubber) is particularly preferable, from the viewpoint of excellent impact resistance and light resistance.

The rubber particles may contain the rubber, but from the viewpoint of compatibility with the transparent resin (dispersibility in the transparent resin) and the like, the rubber-containing core portion and the vinyl polymer-containing shell portion are included. It may be a particle having a core-shell structure formed by

The vinyl polymer constituting the shell portion may be, for example, a homopolymer or a copolymer of vinyl monomers. Examples of vinyl-based monomers include aromatic vinyl-based monomers (eg, styrene, vinyltoluene, α-methylstyrene, etc.), vinyl cyanide-based monomers (eg, (meth)acrylonitrile, etc.), acrylic System monomers (for example, (meth)acrylic acid C _1-4 alkyl ester such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate) Can be mentioned. These vinyl monomers can be used alone or in combination of two or more. Among these vinyl-based monomers, (meth)acrylic acid C _1-4 alkyl ester is preferable, and (meth)acrylic acid C _1-2 alkyl ester such as methyl (meth)acrylate (particularly methacrylic acid such as methyl methacrylate) is used. Acid C _1-2 alkyl esters) are particularly preferred.

The vinyl-based polymer is preferably a polymer containing a (meth)acrylic acid C _1-2 alkyl ester such as methyl (meth)acrylate as a polymerization component, and contains methyl (meth)acrylate such as methyl methacrylate. Copolymers are particularly preferred. As the copolymer containing methyl (meth)acrylate, C _2-4 alkyl ester of (meth)acrylic acid, styrene, acrylonitrile and the like can be preferably used as other copolymerizable monomers. In this copolymer, the molar ratio of methyl (meth)acrylate and the other copolymerizable monomer is such that the former/the latter=99/1 to 10/90, preferably 95/5 to 30/70, More preferably, it is about 90/10 to 50/50. The vinyl-based polymer may be further modified depending on the type of the transparent resin, for example, may be epoxy-modified by introducing an epoxy group.

In the particles having a core-shell structure, the weight ratio of the core part to the shell part is former/latter=99/1 to 10/90, preferably 95/5 to 20/80, and more preferably 90/10 to 30/70. (Especially 80/20 to 50/50). If the proportion of the core portion is too small, mechanical properties such as impact resistance may deteriorate, and if it is too large, the effect of improving the compatibility may deteriorate.

In the particles having a core-shell structure, the core part and the shell part may or may not be copolymerized with each other by graft polymerization or the like.

The shape of the rubber particles (B) is not particularly limited, and isotropic (for example, spherical or substantially spherical, rectangular parallelepiped, etc.), anisotropic shape (for example, ellipsoidal, fibrous, acicular, irregular shape, etc.). It may be either. Among these shapes, a spherical shape or a substantially spherical shape is preferable from the viewpoint of dispersibility.

The average particle size of the rubber particles (B) is, for example, about 0.01 to 3 μm, preferably about 0.03 to 2 μm, and more preferably about 0.05 to 1 μm (particularly 0.08 to 0.6 μm). If the average particle size of the rubber particles (B) is too small, the impact resistance and whiteness of the resin composition may decrease, and if it is too large, the mechanical properties such as rigidity of the resin composition deteriorate. There is a risk. In the present invention, the average particle size of the rubber particles can be measured based on the photograph taken with a transmission electron microscope. Specifically, the average particle diameter of the rubber particles is the number average particle diameter of 300 rubber particles, and the particle diameter of each rubber particle is obtained by measuring the major axis and the minor axis and calculating the average value of both diameters. It is a value multiplied by 4/π.

The weight ratio of the transparent resin (A) and the rubber particles (B) is, for example, former/latter=98/2 to 70/30 (e.g. 97/3 to 75/25), preferably 95/5 to 80/20. (For example, 89.5/10.5 to 80/20), more preferably about 95/5 to 82/18 (particularly 89/11 to 85/15). When the resin composition contains inorganic particles such as talc or titanium oxide or an inorganic pigment, the weight ratio of the transparent resin (A) and the rubber particles (B) may be, for example, the former/the latter from the viewpoint of improving impact resistance. =90/10, for example, the former/the latter=89/11 to 70/30, preferably 88/12 to 80/20, and more preferably about 90/10 to 85/15. .. If the proportion of the rubber particles (B) is too small, mechanical properties such as impact resistance may be deteriorated. On the contrary, if the proportion is too large, rigidity (elastic modulus) and economical efficiency may be deteriorated.

[Ultraviolet absorber (C)]
The resin composition of the present invention further contains an ultraviolet absorber (C) that does not absorb visible light in order to improve light resistance and develop white.

The ultraviolet absorber (C) may be any ultraviolet absorber that does not absorb visible light, and specifically, an ultraviolet absorber that does not have an absorption peak in the ultraviolet region near visible light (for example, 350 to 400 nm) is preferable. .. The absorption peak of such an ultraviolet absorber (C) may be 350 nm or less (for example, 1 to 350 nm), for example, 100 to 340 nm, preferably 150 to 330 nm, and more preferably about 200 to 320 nm. ..

Examples of the ultraviolet absorber (C) having such an absorption property include anilide oxalates, malonic acid esters, cyanoacrylates and the like. These ultraviolet absorbers can be used alone or in combination of two or more kinds.

Examples of the oxalic acid anilides include oxalic acid dianilide (oxanilide or oxalanilide); N-(2-ethylphenyl)-N'-(2-ethoxyphenyl)oxalic acid diamide, N-[4-(1- N-C _1-18 alkylphenyl-N′-C _1-4 alkoxyphenyl oxalic acid diamide such as methyl)undecylphenyl]-N′-(2-ethoxyphenyl)oxalic acid diamide; N-(2-ethylphenyl ) -N '- (2-ethoxy--5-t-butylphenyl) such as oxalic acid diamide _{N-C 1-18 alkylphenyl-N'-C 1-4} alkoxy _{C 1-18} alkyl phenyl oxamide; N N-diC _1-18 alkylphenyl-N′-C ₁ − such as -(2-ethyl-4-t-butylphenyl)-N′-(2-ethoxy-5-t-butylphenyl)oxalic acid diamide. ₄ an alkoxy _{C 1-18} alkyl phenyl oxamide and the like. These oxalic acid anilides can be used alone or in combination of two or more kinds.

Examples of malonic acid esters include 2-C _1-4 alkoxyphenyl methylene malonate _{diC 1-4} alkyl such as dimethyl 2-[(4-methoxyphenyl)-methylene]malonate; 2-(p-methoxy 2-C _1-4 alkoxybenzylidene malonic acid di-C _1-4 alkyl ester such as dimethylidene malonate; 2-(p-methoxybenzylidene)-bis(1,2,2,6,6-pentamethyl-4-) _{2-C 1-4} alkoxy benzylidene such as piperidinyl) malonate - bis _{(C 1-4} alkyl piperidinylmethyl) malonate; tetraethyl-2,2 '- (1,4-phenylene methylidene) bismalonate such as tetra _{C 1- 4-} alkyl-2,2'-(1,4-phenylene methylidene) bismalonate and the like can be mentioned. These malonic acid esters can be used alone or in combination of two or more.

Examples of cyanoacrylates include 2-cyano-3,3-diphenylacrylic acid C ₁ such as 2-cyano-3,3-diphenylacrylic acid ethyl and 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl. _-10 alkyl ester etc. are mentioned. These cyanoacrylates can be used alone or in combination of two or more.

Among these ultraviolet absorbers, oxalic acid anilides are preferable because they have high light resistance and can highly improve whiteness, and N-(2-ethylphenyl)-N'-(2-ethoxyphenyl)oxalic acid is preferable. _{N-C 1-4 alkylphenyl-N'-C 1-4} alkoxyphenyl oxamide such diamide is particularly preferred.

The proportion of the ultraviolet absorber (C) is, for example, 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight (for example, 0.1 to 4 parts by weight, based on 100 parts by weight of the total of the transparent resin (A) and the rubber particles (B). 0.2 to 3 parts by weight), more preferably 0.3 to 1 part by weight (particularly 0.35 to 0.8 part by weight). If the proportion of (C) in the ultraviolet absorber is too small, the light resistance may decrease, and if it is too large, the mechanical properties may deteriorate.

[Phosphorus flame retardant (D)]
The resin composition of the present invention may further contain a phosphorus-based flame retardant (D) from the viewpoint that the flame retardancy of the resin composition can be improved and the whiteness can also be improved.

The phosphorus-based flame retardant (D) includes an organic phosphorus-based flame retardant, an inorganic phosphorus-based flame retardant (red phosphorus-based flame retardant, for example, red phosphorus, stabilization obtained by coating the surface of red phosphorus with a thermosetting resin and/or an inorganic compound. Red phosphorus etc.) etc. are included. Among these phosphorus-based flame retardants, organic phosphorus-based flame retardants are preferable, and aromatic condensed phosphoric acid esters are particularly preferable because the flame retardancy can be improved with a small load on the environment.

Aromatic condensed phosphoric acid esters are usually formed by reacting phosphorus components such as phosphorus oxychloride, polyols composed of at least aromatic polyols, and monoalcohols (particularly monohydroxyarenes such as phenols). It is a product (particularly, an aromatic condensed phosphoric acid ester) and a compound having at least two (particularly two) phosphoric acid units in the molecule.

The polyols may be composed of at least an aromatic polyol (generally, a polyhydric phenol, a bisphenol, etc.), and may contain a non-aromatic polyol (eg, an aliphatic polyol, etc.). Usually, the polyols may be composed of the aromatic polyol alone.

Representative polyhydric phenols (polyhydroxybenzenes) include, for example, dihydroxybenzene (resorcinol, hydroquinone, etc.), dihydroxybenzene having a substituent (alkyl-dihydroxybenzene [dihydroxytoluene, 5-t-butylresorcinol, dihydroxyxylene). (2,6-dihydroxy-p-xylene and the like) or mono or di C _1-10 alkyl-dihydroxybenzene and the like], aryl-dihydroxybenzene (C _6-10 aryl-dihydroxybenzene and the like such as 2,4-dihydroxybiphenyl and the like ), mono- or dihalo-dihydroxybenzene (such as 2,4-difluorohydroquinone), etc.; and trihydroxybenzenes corresponding to these dihydroxybenzenes.

Representative bisphenols include 4,4′-dihydroxybiphenyl, bis(hydroxyphenyl)alkanes [eg, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1, 1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis (4-Hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis( It has a substituent such as 4-hydroxyphenyl)octane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, and 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane. Bis(hydroxyphenyl)C _1-10 alkane], bis(hydroxyphenyl)cycloalkane [eg, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)] Bis(hydroxyphenyl)C _5-10 cycloalkane which may have a substituent such as -3,3,5-trimethylcyclohexane and 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane], Corresponding bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl-alkyl)arenes [4,4′] -(M-phenylenediisopropylidene)diphenol and the like], and alkylene oxide adducts thereof (for example, C _2-4 alkylene oxide such as ethylene oxide) and the like.

Among these, preferable polyols include dihydroxybenzenes [dihydroxybenzene (resorcinol, hydroquinone, etc.), alkyl-dihydroxybenzene, halo-dihydroxybenzene, and other optionally substituted dihydroxybenzenes (particularly, Resorcinol which may be contained], bisphenols and the like, and particularly dihydroxybenzenes and bisphenols are preferable.

Examples of monoalcohols (monohydroxy compounds) include non-aromatic monoalcohols (such as aliphatic alcohols) and monohydroxyarenes. The monoalcohols may usually be monohydroxyarenes. Typical monohydroxyarenes include, for example, phenols {for example, phenol, phenols having a substituent [alkylphenol (o-, m-, p-cresol, 2,3-dimethylphenol, 2,5-dimethyl Mono- or di-C _1-10 alkylphenols such as phenol, 2,6-dimethylphenol and 2,6-di-t-butylphenol, preferably mono- or di-C _1-6 alkylphenols, more preferably di-C _1-4 alkylphenols) , Arylphenols (such as o-phenylphenol), cycloalkylphenols and other hydrocarbon-containing phenols, alkoxyphenols (such as o-methoxyphenol), halophenols (such as chlorophenol), and acylphenols] And optionally monohydroxy C _6-10 arenes are included.

Among these monoalcohols, phenol and phenols having a hydrocarbon group are preferable, and alkylphenol is particularly preferable. The monoalcohols to be reacted with the phosphorus component and the polyols may be used alone or in combination of two or more.

Preferred aromatic condensed phosphoric acid esters include aromatic condensed phosphoric acid esters in which monoalcohols are monohydroxyarenes, for example, dihydroxybenzene bis(diaryl phosphate)s {for example, resorcinol bis(diaryl phosphate)s [for example, Resorcinol bis(diphenyl phosphate); resorcinol bis(dicresyl phosphate), resorcinol bis(dixylyl phosphate) (eg, resorcinol bis(di-2,6-xylyl phosphate), etc.) C _1-4 alkyl)phenyl phosphate] and the like], hydroquinone bisaryl phosphates [eg, hydroquinone bis(diphenyl phosphate); hydroquinone bis(dicresyl phosphate), hydroquinone bis(dixylyl phosphate) (eg, hydroquinone bis(di- 2,6-xylyl phosphate) etc.) and other hydroquinone bis[di(mono to tri C _1-4 alkyl)phenyl phosphate] etc.] polyols are dihydroxybenzenes and monoalcohols monohydroxyarene Condensed aromatic phosphates which are compounds}, bisphenol bis(diaryl phosphates) {for example, bisphenol A-bis(diaryl phosphate)s [for example, bisphenol A-bis(diphenyl phosphate); bisphenol A-bis(dicresyl phosphate) ), bisphenol A-bis(dixylyl phosphate) and other bisphenol A-bis [di(mono to tri C _1-4 alkyl)phenyl phosphate] and other polyols are bisphenols, and monoalcohols are monoalcohols. Aromatic condensed phosphoric acid esters, which are hydroxyarenes, and the like.

The proportion of the phosphorus-based flame retardant (D) is, for example, 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 with respect to 100 parts by weight of the total of the transparent resin (A) and the rubber particles (B). It is about 20 to 20 parts by weight (particularly 10 to 18 parts by weight). If the proportion of the phosphorus-based flame retardant (D) is too small, the effect of improving the flame retardancy may decrease, and if it is too large, the mechanical properties of the resin composition may deteriorate.

[Fluororesin (E)]
The resin composition of the present invention may further contain a fluororesin (E) from the viewpoint of improving the flame retardancy of the resin composition.

Examples of the fluororesin (E) include homopolymers of polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene, polyvinylidene fluoride (PVDF), etc.; tetrafluoroethylene-ethylene copolymer (ETFE), tetrapolymer Fluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer Examples thereof include polymers and copolymers such as ethylene-chlorotrifluoroethylene copolymers. These fluororesins can be used alone or in combination of two or more. Among these fluororesins, PTFE, PFA, FEP, etc. (particularly PTFE) are widely used.

The average particle diameter of the fluororesin (E) is preferably invisible to the naked eye, and is, for example, 1 mm or less (for example, 0.001 to 1 mm), preferably 0.5 mm or less, and more preferably 0.1 mm or less. If the average particle size of the fluororesin (E) is too large, the appearance characteristics and the like may deteriorate. In the present invention, the average particle size of the fluororesin can be measured by the same method as the average particle size of the rubber particles described above.

The proportion of the fluororesin (E) is 3 parts by weight or less (particularly 1 part by weight or less), for example, 0.01 to 3 parts by weight, based on 100 parts by weight of the total of the transparent resin (A) and the rubber particles (B). The amount is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight (particularly 0.3 to 0.8 part by weight). If the proportion of the fluororesin (E) is too large, the mechanical properties of the resin composition may deteriorate.

The fluororesin (E) may be combined with talc from the viewpoint of improving dispersibility in the resin composition and flame retardancy of the resin composition. Further, from the viewpoint that the dispersibility can be improved, talc and fluororesin may be mixed at the raw material stage, and the fluororesin may be dispersed in the talc for use. The proportion of talc is, for example, 10 to 100 parts by weight, preferably 30 to 80 parts by weight, and more preferably 40 to 60 parts by weight, relative to 100 parts by weight of the fluororesin (E). The resin composition of the present invention does not need to contain talc because mechanical properties such as impact resistance can be improved.

The fluororesin (E) may be used by dispersing it in water at the raw material stage from the viewpoint that the dispersibility in the resin composition can be improved. The proportion of water is, for example, 10 to 200 parts by weight, preferably 30 to 150 parts by weight, and more preferably about 50 to 100 parts by weight with respect to 100 parts by weight of the fluororesin (E). Water is usually lost by volatilization during the process of preparing the resin composition.

[White dye (F)]
The resin composition of the present invention can improve whiteness without containing a white dye/pigment (F), but may further contain a white dye/pigment (F), if necessary.

Examples of the white dye/pigment (F) include titanium-based white pigments [titanium oxide (titanium white) and the like], zinc-based white pigments (zinc oxide, zinc sulfide and the like), complex white pigments (lithopone and the like), extender pigments [Kay. Magnesium oxide, magnesium oxide, calcium carbonate, barium sulfate, aluminum-based extender pigments (alumina, aluminum hydroxide, aluminum silicate, etc.), silica, mica, bentonite, etc.] and the like. These white dyes and pigments can be used alone or in combination of two or more. Among these white dyes and pigments, titanium-based white pigments, particularly titanium oxide, are preferable.

The crystal form of titanium oxide may be the anatase type, but the rutile type is preferable because it has a large refractive index and excellent hiding power.

Further, the titanium oxide is particularly preferably titanium oxide obtained by a chlorination method, since the whiteness can be improved.

The average particle diameter of the white dye/pigment (particularly white inorganic pigment such as titanium oxide) is preferably 3 μm or less, for example, 0.01 to 3 μm, preferably 0.05 to 2 μm (eg, 0.05 to 1 μm), and more preferably 0. 0.1 to 1 μm (particularly 0.1 to 0.5 μm). If the average particle size of the white dye/pigment is too small, the effect of improving the whiteness may be reduced, and the appearance characteristics may be reduced. In the present invention, the average particle size of the white dye/pigment can be measured by the same method as the average particle size of the rubber particles described above.

The ratio of the white dye/pigment (F) is 10 parts by weight or less, for example 0.1 to 10 parts by weight, preferably 0.3, based on 100 parts by weight of the total of the transparent resin (A) and the rubber particles (B). -8 parts by weight, more preferably 0.5-5 parts by weight (particularly 1-3 parts by weight). If the proportion of the white dye/pigment (F) is too large, the mechanical properties of the resin composition may deteriorate. From the viewpoint that mechanical properties such as impact resistance can be improved, the resin composition of the present invention may contain a small amount of a white dye/pigment (particularly a white inorganic pigment) (for example, 1 part based on 100 parts by weight in total). It may be less than or equal to parts by weight) and may not contain a white dye/pigment (particularly a white inorganic pigment).

[Other additives]
The resin composition of the present invention contains other UV absorbers (benzo and lyazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, etc.) as long as the effects of the present invention are not impaired. However, it is possible to use these UV absorbers (UV absorbers that absorb visible light or UV absorbers that have an absorption peak in the UV region close to the visible light region) from the viewpoint of improving whiteness and light resistance. Compositions not included in are preferred. The proportion of the other ultraviolet absorber is, for example, 5% by weight or less (for example, 0.01 to 5% by weight), preferably 3% by weight or less, and more preferably 1% by weight or less, based on the entire resin composition. Good.

The resin composition of the present invention contains other flame retardants (halogen flame retardants, organic acid metal salt flame retardants, silicone flame retardants, phosphazene flame retardants, metal oxides, as long as the effects of the present invention are not impaired. Thing etc.) may be included. The proportion of the other flame retardant may be, for example, 10% by weight or less (for example, 0.01 to 10% by weight), preferably 5% by weight or less, and more preferably 1% by weight or less, based on the entire resin composition. Good.

The resin composition of the present invention may further contain a conventional additive. Examples of conventional additives include flame retardant aids, anti-dripping agents, other dyes and pigments, stabilizers (antioxidants, light stabilizers, heat stabilizers, etc.), reinforcing agents (fillers such as talc, glass, etc.). Fiber, carbon fiber, polyamide fiber, reinforcing fiber such as polyester fiber), lubricant, antistatic agent, release agent, plasticizer and the like. These additives may be used alone or in combination of two or more. Even if the ratio of these additives is, for example, 10% by weight or less (for example, 0.01 to 10% by weight), preferably 5% by weight or less, and more preferably 1% by weight or less, based on the entire resin composition. Good.

[Resin composition and molded product]
The resin composition of the present invention comprises a transparent resin (A), rubber particles (B), an ultraviolet absorber (C) (and optionally a phosphorus-based flame retardant (D), a fluororesin (E) and a white dye/pigment ( It may be a composition in which F)) is premixed by using a mixer such as a V-type blender, a super mixer, a super floater or a Henschel mixer, but usually, it is a mixture obtained by uniformly melt-mixing the premix. There are many. Such a mixture can be obtained by melt-kneading the preliminary mixture at a temperature of, for example, 200 to 300° C., preferably 220 to 280° C. using a kneading means, and pelletizing. As the kneading means, various melt mixers, for example, a kneader, a single-screw or twin-screw extruder can be used, but when the resin composition is melted and extruded using a twin-screw extruder or the like and pelletized by a pelletizer. There are many.

The resin composition of the present invention has a high whiteness and may have a whiteness L value of 90 or more, for example, 90 to 99.9, preferably 91 to 99 (for example, 92 to 98), more preferably 93 to. It is about 97 (particularly 94 to 96). In the present invention, the whiteness L value can be measured by a method using a spectrophotometer, and more specifically, it can be measured by a method described in Examples described later.

The resin composition of the present invention may have a low yellowness and a yellowness b value of 5 or less, for example, 0.1 to 5, preferably 0.3 to 3, and more preferably 0.5 to 2 (particularly It is about 0.8 to 1.5). In addition, in the present invention, the yellowness b value can be measured by a method using a spectrocolorimeter, and specifically, can be measured by a method described in Examples described later.

The resin composition of the present invention has excellent light resistance and may have a hue of 5 or less (for example, 0.1 to 5) when irradiated with a 63° C. xenon lamp for 300 hours, for example, 0.1 to 4, and preferably Is about 0.1 to 3, more preferably about 0.1 to 2 (especially 0.1 to 1.5). In addition, in the present invention, the light resistance can be measured by a method using a xenon weatherometer, and specifically, can be measured by a method described in Examples described later.

The resin composition of the present invention is excellent in heat resistance, and has a deflection temperature under load HDT (°C) under high load (1.80 MPa) of 70°C or higher (for example, 70 to 150°C), preferably 75 to 120°C, and further It is preferably about 80 to 100°C. In addition, in the present invention, the heat resistance can be measured by a method according to ISO75, and more specifically, it can be measured by a method described in Examples described later.

The resin composition of the present invention has excellent impact resistance, and may have a Charpy impact strength of 15 kJ/m ² or more (for example, 15 to 100 kJ/m ² ), and particularly, particles of rubber particles (B). By adjusting the diameter and the ratio, a high impact resistance can be realized, and for example, 30 to 90 kJ/m ² , preferably 35 to 80 kJ/m ² , and more preferably 40 to 70 kJ/m ² (particularly 45 to 60 kJ/m ² ). m ² ) or so. In the present invention, the impact resistance can be measured according to ISO179, and more specifically, it can be measured by the method described in Examples described later.

The molded product of the present invention is formed of the resin composition, and the system resin composition is molded by a conventional method, for example, a molding method such as injection molding, extrusion molding, blow molding, press molding, or vacuum molding. It is obtained by

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The details of the raw materials used in Examples and Comparative Examples are as follows, and the resin compositions obtained in Examples and Comparative Examples were evaluated in the following items.

[material]
(Transparent resin)
PC: Polycarbonate resin, "S-2000F" manufactured by Mitsubishi Engineering Plastics Co., Ltd.
ABS: ABS resin, "S-2601" manufactured by A&L Co., Ltd.

(Rubber particles)
Rubber particles A: Rubber particles having a core portion formed of a composite rubber of silicone rubber and acrylic rubber and a shell portion formed of a methyl methacrylate-based copolymer, manufactured by Mitsubishi Rayon Co., Ltd. 2001"
Rubber particle B: a rubber particle having a core portion formed of a composite rubber of silicone rubber and acrylic rubber and a shell portion formed of a methyl methacrylate-based copolymer, "Metablen SX- manufactured by Mitsubishi Rayon Co., Ltd."005".

(UV absorber)
Anilide oxalate: "VSU-P" manufactured by Clariant Co., Ltd.
Benzotriazole: "EVERSORB 73" manufactured by Everlight Chemical Industrial Corporation.

(Phosphorus flame retardant)
Phosphorus flame retardant A: Liquid bisphenol aromatic condensed phosphate ester, manufactured by Daihachi Chemical Industry Co., Ltd., trade name "CR-741"
Phosphorus flame retardant B: resorcinol bis[di(2,6-xylyl) phosphate], trade name “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.

(White pigment)
Titanium oxide: "Ti-Pure R-103 (registered trademark)" manufactured by DuPont.

(Fluorine resin)
Fluorine resin A: tetrafluoroethylene (Mitsui DuPont Fluorochemical Co., Ltd. "PTFE 6-J") and talc (Hayashi Kasei Co., Ltd. "Micron White 5000S") tetrafluoroethylene/talc=65/ Mixture mixed at a ratio of 35 (weight ratio) Fluororesin B: Water-dispersed tetrafluoroethylene ("Polyflon PTFE D-210C" manufactured by Daikin Industries, Ltd.), solid content concentration 60% by weight.

[White value L value and yellowness b value]
The whiteness L value and the yellowness b value were measured using a spectrocolorimeter (“CM-3600d” manufactured by Konica Minolta Co., Ltd.) with the light source set to D65.

[Light resistance]
The light resistance was measured by using a xenon weatherometer (ATLAS ELECTRIC DEVICES CO.'s "Ci35A type") as a test device, light source: xenon arc lamp, black panel temperature: 63°C, irradiation energy: 0.35 W/m ² (340 nm ) The color resistance was measured under the test conditions.

[Flame retardance]
The flame retardancy (combustibility) was evaluated based on UL94 with the thickness of the test piece being 1.5 mm.

[Heat resistance (HDT high load)]
The deflection temperature under load HDT (° C.) under high load (1.80 MPa) was measured by a method based on ISO75.

[Impact resistance]
According to ISO179, the impact strength (Charpy impact strength, kJ/m ² ) was measured in a 1 mm-thick test piece in an atmosphere of 23°C.

Examples 1-7 and Comparative Examples 1-7
Each raw material was weighed at the ratio shown in Table 1, mixed for 4 minutes with a Henschel mixer, and then shaped into pellets at a cylinder temperature of 260° C. using a 30 mmφ twin-screw extruder. The obtained pellets are dried, various test pieces for measuring physical properties are prepared at an injection molding machine at a cylinder temperature of 260° C. and a mold temperature of 60° C., and evaluation results are shown in Table 1.

As is clear from the results in Table 1, the resin compositions of the examples have high whiteness and high light resistance, heat resistance, and impact resistance.

INDUSTRIAL APPLICABILITY The resin composition of the present invention is used in various white plastic moldings such as household appliances, outlets, routers, housings and enclosures for office automation (OA) equipment, housings and casings for mobile phones, terminal boxes, and the like. It is useful as a material for molding white molded articles of, and has excellent light resistance, so it is used for plastic moldings used outdoors, such as security devices and intercoms, switchboards, distribution boards, solar monitors, gas and water supplies. It is also useful as a casing (housing) for measuring instruments.

Claims (12)

A resin composition comprising a transparent resin (A) containing no unsaturated bond, rubber particles (B), and an ultraviolet absorber (C) which does not absorb visible light,
The transparent resin (A) is at least one selected from the group consisting of polyester, polycarbonate and polyamide,
Particles in which the rubber particles (B) have a core-shell structure formed of a core portion containing a non-diene rubber and a shell portion containing a vinyl polymer, and have an average particle diameter of 0.05 to 3 μm. And
The ultraviolet absorber (C) is at least one selected from the group consisting of anilide oxalates, malonates and cyanoacrylates,
The weight ratio of the transparent resin (A) and the rubber particles (B) is the former/the latter=95/5 to 80/20, and the ratio of the ultraviolet absorber (C) is the transparent resin (A). ) And 100 parts by weight of the rubber particles (B) in total, 0.1 to 4 parts by weight. The resin composition according to claim 1, which has a whiteness L value of 90 or more. The resin composition according to claim 1 or 2, which has a yellowness b value of 5 or less. The resin composition according to claim 1, wherein the transparent resin (A) is polycarbonate. Rubber particles (B) is, according to a core portion comprising a silicone rubber and / or acrylic rubbers, claim 1-4 is a particle having a core-shell structure formed by a shell portion comprising a vinyl polymer Resin composition. The resin composition according to any one of claims 1 to 5 mean particle size of the rubber particles (B) is 0.05 to 1 [mu] m. The resin composition according to any one of claims 1 to 6 further comprising a phosphorus-based flame retardant (D). The resin composition according to claim 7, wherein the phosphorus-based flame retardant (D) is an aromatic condensed phosphoric acid ester. The resin composition according to claim 7 or 8 , wherein the proportion of the phosphorus-based flame retardant (D) is 1 to 30 parts by weight based on 100 parts by weight of the total of the transparent resin (A) and the rubber particles (B). The resin composition according to any one of claims 1-9 further containing a fluorine resin (E). Further resin composition according to any one of claims 1 to 10 including a white dye or pigment (F). Shaped article formed with a resin composition according to any one of claims 1 to 11.