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WO2018180493A1 - Composition de résine de polycarbonate et article moulé - Google Patents

Composition de résine de polycarbonate et article moulé Download PDF

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Publication number
WO2018180493A1
WO2018180493A1 PCT/JP2018/009942 JP2018009942W WO2018180493A1 WO 2018180493 A1 WO2018180493 A1 WO 2018180493A1 JP 2018009942 W JP2018009942 W JP 2018009942W WO 2018180493 A1 WO2018180493 A1 WO 2018180493A1
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Prior art keywords
polycarbonate resin
mass
resin composition
styrene
polycarbonate
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PCT/JP2018/009942
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English (en)
Japanese (ja)
Inventor
和幸 ▲高▼橋
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三菱エンジニアリングプラスチックス株式会社
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Priority to CN201880005576.3A priority Critical patent/CN110139899B/zh
Publication of WO2018180493A1 publication Critical patent/WO2018180493A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a polycarbonate resin composition and a molded article, and more specifically, a polycarbonate resin composition having a high impact resistance, a high pencil hardness, excellent color developability, and a good nail scratch preventing performance, and a molded article thereof. About.
  • Polycarbonate resin is excellent in mechanical strength, electrical characteristics, transparency, etc., and is widely used as an engineering plastic in various fields such as electrical and electronic equipment and automobile fields.
  • the bisphenol A type polycarbonate resin has a problem that it has a high melt viscosity and is inferior in molding processability, and a polymer alloy with acrylonitrile-butadiene-styrene resin (hereinafter also referred to as ABS resin) is a single component of the polycarbonate resin. Since the moldability is improved compared to the case, and the impact resistance and heat resistance can be improved compared to the case of the ABS resin alone, the materials having strength, heat resistance and moldability are included in the fields of automobiles, electrical and electronic equipment, etc. Widely used in various fields.
  • ABS resin polymer alloy with acrylonitrile-butadiene-styrene resin
  • the polycarbonate-ABS resin composition has inferior scratch resistance due to the low surface hardness of the molded product, and has a defect that the surface is easily scratched. For example, in applications where a high-class feeling is required, such as housings for home appliances and portable terminal devices and automobile interior parts, it has become a particularly serious problem.
  • Patent Document 1 proposes a polycarbonate resin composition containing at least a polycarbonate resin portion derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane.
  • Patent Document 2 proposes a polycarbonate resin composition excellent in jetness using an organic black dye.
  • the resin composition has the same surface hardness as that of a normal polycarbonate resin and uses an organic dye, there is a problem that the light resistance is inferior to that of the pigment system.
  • An object (problem) of the present invention is to provide a polycarbonate resin composition exhibiting impact resistance, high surface hardness, color developability (particularly jet black), and good nail scratch prevention performance, and a molded product thereof.
  • the present inventor has obtained 2,2-bis (3-methyl-4) into a composition comprising a bisphenol A-type polycarbonate resin and a styrene resin not containing a butadiene skeleton. It has been found that a polycarbonate resin composition containing a specific amount of a polycarbonate resin derived from an aromatic dihydroxy compound having a specific structure such as -hydroxyphenyl) propane, that is, bisphenol C, solves the above-mentioned problems. It came to be completed.
  • the present invention relates to the following polycarbonate resin composition and molded article.
  • a polycarbonate resin composition comprising: The content ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is 0 to 80/20 to 100 in terms of mass ratio of (A) / (B), The content of the styrene-based resin (C) not containing a structural unit derived from butadiene is 1 to 30 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B). Polycarbonate resin composition.
  • R 1 is a methyl group
  • R 2 and R 3 are each independently a hydrogen atom or a methyl group
  • X is R 4 and R 5 each independently represent a hydrogen atom or a methyl group
  • Z represents an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent bonded to C. The group to be formed is shown.
  • the graft copolymer (D) having a polyethylene-based segment and a vinyl-based polymer segment is contained in an amount of 1 to 10 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resins (A) and (B).
  • the polycarbonate resin composition of the present invention has excellent impact resistance, high surface hardness, excellent scratch resistance with nails, and excellent color developability, particularly when it is colored black. Jetness can be expressed. For this reason, the polycarbonate resin composition of the present invention can be suitably used particularly for vehicle interior parts, electronic electrical equipment, OA equipment, housing members for information terminal equipment, and the like.
  • the polycarbonate resin composition of the present invention includes a bisphenol A-type polycarbonate resin (A), a polycarbonate resin (B) having a structural unit represented by the general formula (1), and a styrene-based resin that does not contain a structural unit derived from butadiene.
  • a polycarbonate resin composition containing a resin (C) The content ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is 0 to 80/20 to 100 in terms of mass ratio of (A) / (B),
  • the content of the styrene-based resin (C) not containing a structural unit derived from butadiene is 1 to 30 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B). .
  • the polycarbonate resin contained in the polycarbonate resin composition of the present invention is a bisphenol A type polycarbonate resin (A).
  • the bisphenol A type polycarbonate resin (A) is produced from bisphenol A, that is, 2,2-bis (4-hydroxyphenyl) propane, and a carbonate precursor as a raw material dihydroxy compound.
  • carbonyl halides carbonic acid diesters and the like are used as examples of the carbonate precursor.
  • 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.
  • carbonyl halide examples include phosgene; haloformates such as a bischloroformate of a dihydroxy compound and a monochloroformate of a dihydroxy compound.
  • carbonic acid diester examples include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and cyclic carbonates And carbonate bodies of dihydroxy compounds such as
  • the polycarbonate resin (A) may be a copolymer polycarbonate resin in which another dihydroxy compound other than bisphenol A is used in combination.
  • dihydroxy compounds other than bisphenol A include the following aromatic dihydroxy compounds.
  • the component derived from bisphenol A is preferably 50 mol% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, especially 90 mass% or more, particularly 95. It is preferable that it is mass% or more.
  • the polycarbonate resin (A) may be linear or branched.
  • the manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
  • Arbitrary methods include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
  • a polycarbonate resin is produced by an interfacial polymerization method.
  • a dihydroxy compound and a carbonate precursor preferably phosgene
  • an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher.
  • Polycarbonate resin is obtained by interfacial polymerization in the presence.
  • a molecular weight adjusting agent may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.
  • the dihydroxy compound and the carbonate precursor are as described above.
  • phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.
  • organic solvent inert to the reaction examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done.
  • 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.
  • alkali compound contained in the alkaline aqueous solution examples include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred.
  • 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the concentration of the alkali compound in the alkaline aqueous solution is not limited, but it is usually used at 5 to 10% by mass in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12.
  • the molar ratio of the bisphenol compound to the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11.
  • the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.
  • polymerization catalyst examples include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanidine salt; and the like.
  • 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the molecular weight regulator examples include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like, among which aromatic phenols are preferred.
  • aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol.
  • a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the amount used of the molecular weight regulator is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the dihydroxy compound.
  • the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set.
  • the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
  • the reaction temperature is usually 0 to 40 ° C.
  • the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).
  • melt transesterification method for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.
  • the dihydroxy compound is as described above.
  • examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable.
  • carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and above all, 1.01 mol or more is used. It is more preferable.
  • the upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.
  • the amount of terminal hydroxyl groups tends to have a large effect on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method.
  • a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like.
  • the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.
  • the mixing ratio is as described above.
  • a more aggressive adjustment method there may be mentioned a method in which a terminal terminator is mixed separately during the reaction.
  • the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like.
  • 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.
  • a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the reaction temperature is usually 100 to 320 ° C.
  • the pressure at the time of reaction is normally performed under reduced pressure below normal pressure, the reduced pressure state is adjusted according to the progress of the reaction, and finally the condition is 2 mmHg or less.
  • a melt polycondensation reaction may be performed under the above conditions while removing by-products such as aromatic hydroxy compounds.
  • the melt polycondensation reaction can be performed by either a batch method or a continuous method.
  • the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily.
  • the melt polycondensation reaction is preferably carried out continuously.
  • a catalyst deactivator may be used as necessary.
  • a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof.
  • 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.
  • the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 12,000 to 30,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be easily obtained. When the viscosity average molecular weight is less than 12,000, the surface impact resistance is remarkably deteriorated and exceeds 30,000. The melt viscosity increases and injection molding tends to be difficult.
  • the lower limit of the molecular weight of the polycarbonate resin (A) is more preferably 15,000, still more preferably 16,000, particularly preferably 17,000, and the upper limit is more preferably 28,000.
  • the terminal hydroxyl group concentration of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but is usually 1,200 ppm or less, preferably 1,000 ppm or less, more preferably 800 ppm or less. Thereby, the residence heat stability and color tone of polycarbonate resin can be improved more.
  • the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a resin composition can be improved more.
  • the unit of the terminal hydroxyl group concentration represents the mass of the terminal hydroxyl group with respect to the mass of the polycarbonate resin in ppm.
  • the measuring method is a colorimetric determination by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88 215 (1965)).
  • the polycarbonate resin (B) is a polycarbonate resin having a structural unit represented by the following general formula (1).
  • R 1 is a methyl group
  • R 2 and R 3 are each independently a hydrogen atom or a methyl group
  • X is R 4 and R 5 each independently represent a hydrogen atom or a methyl group
  • Z represents an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent bonded to C. The group to be formed is shown.
  • R 1 is a methyl group
  • R 2 and R 3 are each independently a hydrogen atom or a methyl group, but R 2 and R 3 are particularly preferably a hydrogen atom.
  • X is Is preferably an isopropylidene group in which both R 4 and R 5 are methyl groups, and X is In this case, Z is bonded to carbon C bonded to the two phenyl groups in the above formula (1) to form a bivalent alicyclic hydrocarbon group having 6 to 12 carbon atoms.
  • Examples of the alicyclic hydrocarbon group include cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group.
  • Examples of the substituted ones include those having these methyl substituents and ethyl substituents.
  • a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably 3,3,5-trimethyl-substituted), and a cyclododecylidene group are preferable.
  • polycarbonate resin (B) include the following polycarbonate resins (a) to (d).
  • polycarbonate resins are 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane, and 2,2-bis (3, respectively).
  • 5-Dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane can be prepared using the dihydroxy compound.
  • the polycarbonate resin (B) may be used alone or in combination of two or more in any combination and in any ratio.
  • the polycarbonate resin (B) can also have a carbonate structural unit other than the structural unit represented by the general formula (1).
  • the structural unit represented by the following general formula (2) It may have a structural unit derived from the dihydroxy compound.
  • the copolymerization amount of structural units other than the structural unit represented by the general formula (1) is usually less than 50 mol%, preferably 40 mol% or less, more preferably 30 mol% or less, and further 20 It is preferably at most 10 mol%, particularly at most 10 mol%. (Wherein X has the same meaning as X in formula (1)).
  • a preferred specific example of the polycarbonate structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol A.
  • the polycarbonate resin (B) is a component different from the polycarbonate resin (A)
  • the component derived from bisphenol A is 50 mol. %, Preferably 30% by mass or less, more preferably 20% by mass or less, especially 10% by mass or less, and particularly preferably 5% by mass or less.
  • dihydroxy compounds other than the structural unit represented by the general formula (2) include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, and 2,2-bis (4 -Hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) ) Cyclooctane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4, '- dihydroxyphenyl ether.
  • the viscosity average molecular weight (Mv) of the polycarbonate resin (B) is preferably 19,000 to 35,000. When the viscosity average molecular weight is in this range, a molded product having good moldability, high mechanical strength, and good scratch resistance can be easily obtained. When the viscosity average molecular weight is less than 19,000, the pencil hardness of the resin composition is lowered. Or impact resistance decreases, which is not preferable. On the other hand, if it exceeds 35,000, the melt viscosity increases and injection molding tends to be difficult.
  • the more preferable lower limit of the molecular weight of the polycarbonate resin (B) is 19,500, 20,000, 22,000, 23,000, 24,000, more preferably 25,000, and particularly preferably 26,000. Is more preferably 33,000, still more preferably 32,000.
  • the method for producing the polycarbonate resin (B) is not particularly limited, and is as described in the method for producing the polycarbonate resin.
  • the content of the polycarbonate resin (B) is such that the content ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is 0 to 80/20 to 100 in terms of the mass ratio of (A) / (B). If the mass ratio of the polycarbonate resin (B) is less than 20, it is not preferable because the pencil hardness is lowered or the nail scratch preventing performance is deteriorated.
  • the content of the polycarbonate resin (B) is preferably 1 to 80/20 to 99, more preferably 5 to 75/25 to 95, and still more preferably 10 to 70 in terms of mass ratio of (A) / (B). / 30 to 90.
  • Polycarbonate resins (A) and (B) are polycarbonate resins alone (polycarbonate resins alone are not limited to embodiments containing only one type of polycarbonate resin. For example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights are used. It may be used in the meaning including the embodiment including).
  • a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy
  • the polycarbonate resins (A) and (B) may contain a polycarbonate oligomer.
  • the viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less.
  • the polycarbonate ligomer contained is 30% by mass or less of the entire polycarbonate resin (including polycarbonate oligomer).
  • the polycarbonate resin composition of the present invention contains a styrene resin (C) that does not contain a structural unit derived from butadiene.
  • a styrene resin (C) that does not contain a structural unit derived from butadiene it not only facilitates the development of color development, particularly jetness, which has been hindered by the structural unit derived from butadiene, but also improves light resistance. In addition, it is easy to achieve improvement in heat and humidity resistance.
  • Styrenic resin (C) is not a resin containing a structural unit derived from butadiene such as ABS resin, but is an aromatic vinyl monomer alone or other copolymerizable with an aromatic vinyl monomer as required. It is a resin obtained by polymerizing one or more selected from vinyl monomers and rubbery polymers.
  • Examples of the aromatic vinyl monomer (c1) used in the styrene resin (C) include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert. -Styrene derivatives such as butyl styrene, vinyl naphthalene, methoxy styrene, monobromo styrene, dibromo styrene, fluorostyrene, tribromo styrene, etc. are mentioned, and styrene is particularly preferable. These may be used alone or in combination of two or more.
  • vinyl cyanide monomer (c2) is preferable, and examples thereof include acrylonitrile and methacrylonitrile.
  • aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate
  • Alkyl esters of acrylic acid such as cyclohexyl acrylate and dodecyl acrylate
  • aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl Methacrylate, cyclohexyl methacrylate Methacrylic acid alkyl esters
  • rubbery polymer (c3) copolymerizable with the aromatic vinyl monomer (c1) rubber having a glass transition temperature of 10 ° C. or lower is suitable.
  • Specific examples of such rubbery polymers include acrylic rubber, ethylene / propylene rubber, silicone rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component that are intertwined with each other so that they cannot be separated.
  • a composite rubber (IPN type rubber) or the like having an acid content is preferable, and an acrylic rubber or the like is preferable.
  • acrylic rubber examples include acrylic acid alkyl ester rubber, and the carbon number of the alkyl group is preferably 1-8.
  • alkyl acrylate examples include ethyl acrylate, butyl acrylate, hexyl acrylate and the like.
  • An ethylenically unsaturated monomer may optionally be used in the acrylic acid alkyl ester rubber.
  • Specific examples of such compounds include di (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, and the like.
  • These rubbery polymers (c3) may be used alone or in combination of two or more.
  • the styrenic resin (C) is composed of the aromatic vinyl monomer component (c1) 50 to 100% by mass, the vinyl cyanide monomer component (c2) 0 to 30% by mass, the rubbery polymer component (c3). It is preferably composed of 0 to 30% by mass and other monomer component (c4) 0 to 30% by mass, aromatic vinyl monomer component (c1) 45 to 80% by mass, vinyl cyanide monomer component ( c2) 10 to 30% by mass, rubbery polymer component (c3) 10 to 25% by mass, and other monomer component (c4) 0 to 40% by mass, more preferably an aromatic vinyl monomer component (C1) 55 to 70% by mass, vinyl cyanide monomer component (c2) 15 to 25% by mass, rubbery polymer component (c3) 15 to 20% by mass, other monomer components (c4) 0 to More preferably, it consists of 5% by mass.
  • styrene resin (C) used in the present invention include, for example, a styrene homopolymer, a copolymer of styrene and (meth) acrylonitrile, and a copolymer of styrene and an alkyl (meth) acrylate.
  • Preferable examples include graft copolymers obtained by graft polymerization with acrylonitrile.
  • AS resin acrylonitrile-styrene copolymer
  • MS resin methacrylic acid alkyl ester-styrene copolymer
  • SMA resin styrene-maleic anhydride copolymer
  • ASA resin acrylonitrile- Styrene-acrylic rubber copoly
  • acrylonitrile-styrene copolymer AS resin
  • methacrylic acid alkyl ester-styrene copolymer MS resin
  • ASA resin acrylonitrile-styrene-acrylic rubber copolymer
  • AES resin acrylonitrile-ethylenepropylene rubber
  • AS resin acrylonitrile-styrene copolymer
  • AS resin acrylonitrile-styrene copolymer
  • MS resin methacrylic acid alkyl ester-styrene copolymer
  • ASA resin acrylonitrile-styrene-acrylic rubber copolymer
  • AES resin styrene copolymer
  • AS resin acrylonitrile-styrene copolymer
  • MS resin methacrylic acid alkyl ester-styrene copolymer
  • These styrene resins (C) may be used alone or in combination of two or more.
  • the content of the styrene resin (C) not containing a structural unit derived from butadiene is 1 to 30 parts by mass, preferably 3 to 100 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B).
  • the amount is 25 parts by mass, more preferably 5 to 20 parts by mass.
  • the polycarbonate resin composition of the present invention preferably further contains a graft copolymer (D) having a polyethylene segment and a vinyl polymer segment.
  • a graft copolymer (D) having a polyethylene segment and a vinyl polymer segment.
  • a polyethylene-based segment is a main chain of the graft copolymer, and a segment obtained by polymerizing a vinyl-based monomer is a side chain of the graft copolymer.
  • the polyethylene segment may be either a homopolymer of ethylene or a copolymer with other ⁇ -olefin other than ethylene which is mainly composed of ethylene and copolymerizable therewith.
  • Other ⁇ -olefins other than ethylene are ⁇ -olefins having usually 3 to 20 carbon atoms, preferably 3 to 12, and include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1 Preferred are -pentene, 1-octene, 1-decene, 1-dodecene and the like.
  • the amount of the ⁇ -olefin unit is usually 0 to 50% by mass, preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further 0 to 10% by mass. It is preferable that
  • the molecular weight of the polyethylene segment is usually about 10,000 to 600,000 in terms of number average molecular weight (Mn).
  • Mn number average molecular weight
  • the number average molecular weight means what is calculated
  • polyethylene-based segment examples include commercially available high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), or high pressure obtained by a high-pressure radical method.
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • VLDPE very low-density polyethylene
  • high-pressure radical method any of low-density polyethylene (HPLD) and the like may be used, but low-density polyethylene, linear low-density polyethylene, very low-density polyethylene, and high-pressure low-density polyethylene are preferable, and very low-density polyethylene (VLDPE) is particularly preferable. More preferred.
  • Low density polyethylene usually has a density of 0.91 to 0.94 g / cm 3 , preferably 0.912 to 0.935 g / cm 3 .
  • the linear low density polyethylene preferably has a density of 0.91 to 0.94 g / cm 3 .
  • Ultra-low density polyethylene is a copolymer of ethylene and ⁇ -olefin, and usually has a density in the range of 0.86 to 0.91 g / cm 3 .
  • the high-pressure low-density polyethylene by the high-pressure method preferably has a density of 0.91 to 0.94 g / cm 3 .
  • vinyl monomers for forming vinyl polymer segments include styrene monomers, ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acid esters, unsaturated nitrile monomers A body etc. are mentioned preferably.
  • styrene monomer examples include styrene, methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, chlorostyrene, and the like, and styrene is particularly preferable.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid include (meth) acrylic acid esters such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate, acrylic acid, and methacrylic acid. Preference is given to fumaric acid, maleic anhydride, itaconic acid and the like.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester include methyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and n methacrylate.
  • Preferred examples include -butyl and isobutyl methacrylate.
  • As the unsaturated nitrile monomer acrylonitrile is preferably exemplified.
  • styrene monomers particularly styrene, are preferred because they are highly compatible with the polycarbonate resin (A) and have excellent scratch resistance effects.
  • Styrene alone or styrene It is preferable to copolymerize with OH group-containing (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or acrylonitrile.
  • the molecular weight of the graft copolymer (D) is preferably 5,000 to 500,000 in terms of mass average molecular weight (Mw).
  • Mw mass average molecular weight
  • a mass average molecular weight means what is calculated
  • the graft copolymer (D) preferably further contains a polyorganosiloxane.
  • the polyorganosiloxane When the polyorganosiloxane is contained, it may have as a main chain or a side chain of the graft copolymer (D), and may be one of the graft copolymers that form a core / shell type multilayer structure. It may be contained as a part.
  • the polyorganosiloxane is not particularly limited, but representative examples thereof include polydimethylsiloxane and polymethylphenylsiloxane, and examples thereof include polydimethyldiphenylsiloxane copolymer, polydimethylphenylmethylsiloxane copolymer, and polymethylphenyldiphenylsiloxane copolymer. Among them, a polymer containing a dialkylsiloxane unit, particularly a dimethylsiloxane unit as a constituent unit is preferable. Moreover, as polyorganosiloxane, what contains the siloxane containing a vinyl group as a structural component is preferable. Siloxanes containing vinyl groups are well known and contain vinyl groups to which organosiloxanes are bonded via siloxane bonds.
  • the proportion of the polyethylene polymer segment in the graft copolymer (D) is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 80% by mass. is there.
  • the proportion of the vinyl polymer segment is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 20 to 35% by mass.
  • the content is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 2 to 10% by mass. .
  • the content in the case of containing a polyorganosiloxane segment is mass% based on a total of 100 mass% of the polyethylene polymer segment, the vinyl polymer segment, and the polyorganosiloxane segment.
  • the graft copolymer (D) preferably has an endothermic peak measured at 100 ° C. or lower according to JIS K7121 by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the graft copolymer (D) may have a plurality of endothermic peaks. Even when there are a plurality of endothermic peaks, the graft copolymer (D) preferably has an endothermic peak at 100 ° C. or lower.
  • the endothermic peak temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and its lower limit is usually 60 ° C. or higher.
  • the endothermic peak of the graft copolymer (D) is measured according to JIS K7121, using a differential scanning calorimeter DSC7020 manufactured by Seiko Instruments Inc. It is performed by observing a 10 mg sample by raising the temperature from 30 ° C. to 300 ° C. at a rate of 10 ° C./min.
  • the temperature of the endothermic peak at the lowest temperature side is measured.
  • any of various known graft copolymerization methods may be used, and examples thereof include the following methods.
  • the polyethylene polymer is suspended in water, and the vinyl monomer, radical polymerizable organic peroxide (for example, t-butyl peroxymethacryloyloxyethyl carbonate, etc.), polymerization initiator (for example, a mixed solution in which 3,5,5-trimethylhexanoyl peroxide or the like is dissolved is added and then heated to copolymerize to produce a graft copolymer.
  • radical polymerizable organic peroxide for example, t-butyl peroxymethacryloyloxyethyl carbonate, etc.
  • polymerization initiator for example, a mixed solution in which 3,5,5-trimethylhexanoyl peroxide or the like is dissolved is added and then heated to copolymerize to produce a graft copolymer.
  • the graft copolymer (D) is commercially available and can be used.
  • it is sold as “Nofalloy (registered trademark) KA series” by NOF Corporation, for example, “Nofalloy KA147”. Etc. are available.
  • the preferred content of the graft copolymer (D) is 1 to 10 parts by weight, more preferably 1.5 to 9 parts by weight, based on a total of 100 parts by weight of the polycarbonate resins (A) and (B). More preferably, it is 2 to 8 parts by mass.
  • the amount is less than 1 part by mass, the scratch resistance at the nail and the effect of improving slight scratches at low hardness in the pencil hardness test tend to be small, and when the amount exceeds 10 parts by mass, the hue deteriorates, the mechanical strength and It tends to cause a decrease in heat resistance.
  • the polycarbonate resin composition of the present invention preferably contains an impact resistance improver (E).
  • the impact resistance improver (E) is preferably an elastomer, and the elastomer is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith.
  • the graft copolymer here is defined as different from the above-mentioned styrene resin (C).
  • the production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.
  • the rubber component generally has a glass transition temperature of 0 ° C. or lower, preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower.
  • Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber.
  • Silicone rubber butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene- ⁇ -olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more.
  • IPN Interpenetrating Polymer Network
  • polybutadiene rubber polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .
  • monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like.
  • These monomer components may be used alone or in combination of two or more.
  • aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable.
  • Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.
  • the graft copolymer obtained by copolymerizing the rubber component is preferably a core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance.
  • a rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it.
  • a core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred.
  • the core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.
  • the core / shell type does not necessarily have to be clearly distinguishable between the core layer and the shell layer, and widely includes compounds obtained by graft polymerization of a rubber component around the core portion. is there.
  • these core / shell type graft copolymers include butadiene-methyl acrylate copolymer, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-acrylic / butadiene rubber copolymer.
  • examples thereof include a polymer, a methyl methacrylate-acrylic butadiene rubber-styrene copolymer, and a methyl methacrylate- (acrylic silicone IPN rubber) copolymer.
  • Such rubbery polymers may be used alone or in combination of two or more.
  • the content of the impact resistance improver (E) is 7 to 7 parts per 100 parts by mass in total of the polycarbonate resins (A) and (B). 20 parts by mass is preferable, 8 to 18 parts by mass is more preferable, and 10 to 15 parts by mass is further preferable.
  • the content of the impact modifier (E) is less than 7 parts by mass, the impact resistance tends to decrease, and when the content of the impact modifier (E) exceeds 20 parts by mass, the fluidity tends to decrease.
  • the impact resistance improver (E) may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the polycarbonate resin composition of the present invention preferably contains a stabilizer (F).
  • a stabilizer examples include an antioxidant and a heat stabilizer.
  • an antioxidant or a heat stabilizer may be used alone, but it is preferable to use both an antioxidant and a heat stabilizer in combination.
  • antioxidant examples include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl).
  • the content of the antioxidant is usually from 0.001 to 1 part by weight, preferably from 0.01 to 0.000 parts per 100 parts by weight in total of the polycarbonate resins (A) and (B) and the styrene resin (C). 5 parts by mass.
  • the content of the antioxidant is less than 0.001 part by mass, the effect as an antioxidant is insufficient, and when it exceeds 1 part by mass, the effect reaches a peak and is not economical.
  • heat stabilizer examples include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.
  • Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylene bis (4,6-di- tert-butylphenyl) octyl phosphite, 3,9-bis ⁇ 1,1-dimethyl-2- [ ⁇ - (3-tert-butyl-4-hydroxy
  • an organic phosphite compound examples include, for example, “ADEKA STAB (registered trademark, the same applies hereinafter) PEP-36”, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADK STAB HP-” manufactured by ADEKA Corporation. 10 ”,“ JP-351 ”,“ JP-360 ”,“ JP-3CP ”manufactured by Johoku Chemical Industry Co., Ltd.,“ Irgaphos (registered trademark) 168 ”manufactured by BASF Japan Ltd., and the like.
  • the heat stabilizer may be contained only by 1 type and 2 or more types may be contained by arbitrary combinations and ratios.
  • Content of a heat stabilizer is 0.001 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (A), (B) and styrene resin (C), Preferably it is 0.005 mass part or more, More preferably, it is 0.01 mass part or more, and is 1 mass part or less normally, Preferably it is 0.5 mass part or less, More preferably, it is 0.3 mass part or less.
  • the content of the heat stabilizer is less than the lower limit of the above range, the heat stability effect may be insufficient, and when the content of the heat stabilizer exceeds the upper limit of the above range, the effect reaches a peak. It becomes less economical.
  • the polycarbonate resin composition of the present invention preferably contains a release agent (G).
  • the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.
  • the aliphatic carboxylic acid examples include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids.
  • the aliphatic carboxylic acid includes alicyclic carboxylic acid.
  • preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred.
  • aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.
  • an aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol for example, the same one as the aliphatic carboxylic acid can be used.
  • the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable.
  • an aliphatic includes an alicyclic compound here.
  • alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.
  • said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity.
  • said ester may be a pure substance, it may be a mixture of a plurality of compounds.
  • the aliphatic carboxylic acid and alcohol which combine and comprise one ester may each be used 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
  • examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastea
  • Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and ⁇ -olefin oligomer having 3 to 12 carbon atoms.
  • the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized. The number average molecular weight is preferably 5,000 or less.
  • the aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.
  • paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable
  • paraffin wax and polyethylene wax are more preferable
  • polyethylene wax is particularly preferable.
  • 1 type may contain the mold release agent (G) and 2 or more types may contain it by arbitrary combinations and a ratio.
  • the content of the release agent (G) is usually 0.001 parts by mass or more, preferably 0.01 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A), (B) and the styrene resin (C). It is usually 2 parts by mass or less, preferably 1 part by mass or less.
  • the content of the release agent is less than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.
  • Black pigment (H) Since the polycarbonate resin composition of the present invention is excellent in color developability, particularly jet black, it is preferable to contain a black pigment (H).
  • a black pigment (H) carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc. can be used, but carbon black is preferred from the viewpoint of jet blackness and light resistance (weather), and carbon black Preferred examples of black include acetylene black, lamp black, thermal black, furnace black, channel black, and ketjen black.
  • the content of the black pigment (H) is preferably 0.5 to 1.8 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B) and the styrene resin (C). If it is less than 0.5 parts by mass, jet blackness tends to be insufficient, and if it exceeds 1.8 parts by mass, the mechanical properties may decrease.
  • the content of the black pigment (H) is more preferably 0.7 to 1.6 parts by mass, still more preferably 0.9 to 1.4 parts by mass.
  • the polycarbonate resin composition of the present invention may contain an ultraviolet absorber.
  • ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds Examples include ultraviolet absorbers. Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting an organic ultraviolet absorber, transparency and mechanical properties are improved.
  • benzotriazole compound examples include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole 2,2′-methylenebis [4- (1,
  • the content in the case of containing the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0 with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B) and the styrene resin (C).
  • the upper limit is preferably 1 part by mass or less, more preferably 0.5 part by mass or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, the mold Debogit etc. may occur and cause mold contamination.
  • 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.
  • the polycarbonate resin composition of the present invention may contain other components other than the above, if necessary, as long as the desired physical properties are not significantly impaired.
  • examples of other components include resins other than those described above and various resin additives other than those described above.
  • 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.
  • content in the case of containing other resins other than those described above should be 20 parts by mass or less with respect to a total of 100 parts by mass of the polycarbonate resins (A), (B) and the styrene resin (C). More preferably, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.
  • resin additive examples include flame retardants, anti-dripping agents, fillers, dyes and pigments, antistatic agents, antifogging agents, lubricants, antiblocking agents, plasticizers, dispersants, antibacterial agents, and the like.
  • 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
  • various mixers such as a tumbler and Henschel mixer, after pre-mixing, such as Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader
  • the method of melt-kneading with a mixer is mentioned.
  • the temperature for melt kneading is not particularly limited, but is preferably in the range of 240 to 320 ° C, particularly preferably 240 to 300 ° C.
  • the above-mentioned polycarbonate resin composition (pellet) is molded by various molding methods into a molded product.
  • the shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product.
  • a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape.
  • the method for molding a molded product is not particularly limited, and a conventionally known molding method can be employed.
  • a conventionally known molding method can be employed.
  • the molding is preferably performed by an injection molding method.
  • the molding is performed using a known injection molding machine such as an injection molding machine, an ultra-high speed injection molding machine, or an injection compression molding machine.
  • the cylinder temperature of the injection molding machine at the time of injection molding is preferably 240 to 320 ° C, more preferably 250 to 300 ° C, and further preferably 260 to 280 ° C.
  • the injection speed during injection molding is preferably 10 to 1,000 mm / sec, more preferably 10 to 500 mm / sec.
  • the pencil hardness of the molded body made of the polycarbonate resin composition of the present invention is preferably HB or higher, more preferably F or higher, and still more preferably H or higher. If the pencil hardness is less than HB, the surface of the resin molding tends to be damaged.
  • the pencil hardness of HB or higher can be achieved by blending the polycarbonate resin (A), the polycarbonate resin (B), and the styrene resin (C) at a specific ratio.
  • the pencil hardness is measured under a load of 750 g using a pencil hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with ISO 15184.
  • the polycarbonate resin composition of the present invention preferably conforms to ISO 6603-2, has a striker diameter of 10 mm, a sample support diameter of 40 mm, a punching speed of 4.4 m / sec, a collision energy of 50.1 J, and a sample thickness of 3 mm.
  • the fracture mode shows YD.
  • FIG. 1 there are YD, YS, YU, and NY as fracture modes, and the fracture mode YD refers to the yield caused by deep drawing, and the polycarbonate resin composition of the present invention can achieve the fracture mode YD.
  • the impact fracture mode is YS (yield caused by stable crack growth), YU (yield caused by unstable crack growth), and NY (non-breaking).
  • the characteristics of puncture impact are achieved by adjusting the blending ratio of polycarbonate resin (A), polycarbonate resin (B), and styrene resin (C), and adding impact modifier (D) as necessary. Is done.
  • the polycarbonate resin composition of the present invention has a notched Charpy impact value measured in accordance with ISO 179-2 at room temperature (23 ° C.), preferably 20 kJ / m 2 or more, more preferably 23 kJ / m 2 or more. More preferably, it is 25 kJ / m 2 .
  • the room temperature impact resistance value is obtained by adjusting the blending ratio of the polycarbonate resin (A), the polycarbonate resin (B), and the styrene resin (C), and adding an impact resistance improver (E) as necessary. Achieved.
  • nylon scratched In order to confirm the damage property by the nail
  • the nylon scratch test in the present invention is based on ISO 15184, using a pencil hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), attaching a nylon round bar instead of a pencil, and applying a load of 50, 100, 300, While changing to 500 and 750 g, the load that damages the molded bag is obtained.
  • the damage property of the molded body made of the polycarbonate resin composition of the present invention is preferably 300 g load or more, more preferably 500 g load or more, and particularly preferably 750 g load.
  • the L * value measured with a D65 / 10 ° light source in a molded product having a thickness of 3 mm is preferably 5.5 or less, more preferably 5. 2 or less, more preferably 5.1 or less, particularly preferably 5.0 or less can be achieved.
  • the molded article of the polycarbonate resin composition of the present invention can be used in a wide range of fields, such as electronic and electrical equipment and parts thereof, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building members, and various types. It is useful for various applications such as containers, leisure goods / miscellaneous goods, and lighting equipment, and is expected to be applied particularly to housing parts and vehicle interior parts of electronic and electrical equipment, OA equipment, and information terminal equipment.
  • housing members for electronic electrical equipment, office automation equipment, and information terminal equipment display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, cameras, video cameras, mobile phones, recordings
  • Examples of the housing member include a medium drive and a reading device.
  • Examples of vehicle interior parts include a center panel, an instrument panel, a console box, a luggage floor board, a door pocket, and a display housing such as a car navigation system.
  • polycarbonate resins (B1) and (B2) used as the polycarbonate resin (B) were produced by the following production examples.
  • the reaction solution in the reactor is stirred, and cesium carbonate (Cs 2 CO 3 ) is used as a transesterification catalyst in the molten reaction solution so that the amount becomes 1.5 ⁇ 10 ⁇ 6 mol per 1 mol of BPC.
  • the reaction solution was stirred and brewed at 220 ° C. for 30 minutes in a nitrogen gas atmosphere.
  • the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.
  • the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled.
  • the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 60 minutes to complete the polycondensation reaction.
  • the stirring rotation speed of the stirrer was 38 rotations / minute
  • the reaction liquid temperature just before the completion of the reaction was 289 ° C.
  • the stirring power was 1.00 kW.
  • the molten reaction solution was fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate with respect to cesium carbonate was supplied from the first supply port of the twin screw extruder. After kneading with the reaction solution, the reaction solution was extruded in a strand shape through a die of a twin screw extruder and cut with a cutter to obtain carbonate resin pellets.
  • the physical properties of the obtained polycarbonate resin (B1) were as follows. Pencil hardness: 2H Viscosity average molecular weight (Mv): 26,000
  • reaction solution was stirred and brewed at 220 ° C. for 30 minutes in a nitrogen gas atmosphere.
  • pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.
  • the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled.
  • the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 60 minutes to complete the polycondensation reaction.
  • the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature immediately before the completion of the reaction was 289 ° C., and the stirring power was 0.60 kW.
  • the molten reaction solution was fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate with respect to cesium carbonate was supplied from the first supply port of the twin screw extruder. After kneading with the reaction solution, the reaction solution was extruded into a strand shape through a die of a twin screw extruder and cut with a cutter to obtain polycarbonate resin pellets.
  • the physical properties of the obtained polycarbonate resin (B2) were as follows. Pencil hardness: 2H Viscosity average molecular weight (Mv): 20,000
  • Examples 1 to 17, Comparative Examples 1 to 10 The respective components listed in Table 1 above are shown in the following Tables 2 to 5 (expressed in parts by mass. However, the amounts of the stabilizer, the release agent and the black pigment are the polycarbonate resins A and B and the styrene resin C.
  • Fracture form YD is a yield caused by deep drawing
  • Fracture form YS is a yield caused by stable crack growth
  • Fracture form YU is a yield caused by unstable crack growth
  • Fracture form NY is caused by unstable crack growth Indicates destruction that does not yield.
  • the polycarbonate resin composition of the present invention is excellent in impact resistance, has high surface hardness, excellent scratch resistance on nails, and excellent color developability (particularly jet blackness). It can be suitably used for parts such as a housing member of an information terminal device and application to a vehicle interior part, and there is a very high industrial utility.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine de polycarbonate qui comprend une résine de polycarbonate (A) de type bisphénol A, une résine de polycarbonate (B) ayant un motif structural représenté par la formule générale (1), et une résine à base de styrène (C) ne contenant pas de motif constitutif dérivé du butadiène, caractérisée en ce que le rapport de la teneur en résine de polycarbonate (A) à la teneur en résine de polycarbonate (B), (A)/(B), est (0 à 80)/(20 à 100) en masse et la teneur en résine à base de styrène (C) ne contenant pas de motif constitutif dérivé du butadiène est de 1 à 30 parties en masse pour 100 parties en masse de la somme des résines de polycarbonate (A) et (B).
PCT/JP2018/009942 2017-03-31 2018-03-14 Composition de résine de polycarbonate et article moulé WO2018180493A1 (fr)

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WO2024038853A1 (fr) * 2022-08-18 2024-02-22 三菱ケミカル株式会社 Composition de résine, granulés et article moulé

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