WO2023022139A1 - Resin composition for double molding and molded article of same - Google Patents

Resin composition for double molding and molded article of same Download PDF

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Publication number
WO2023022139A1
WO2023022139A1 PCT/JP2022/030924 JP2022030924W WO2023022139A1 WO 2023022139 A1 WO2023022139 A1 WO 2023022139A1 JP 2022030924 W JP2022030924 W JP 2022030924W WO 2023022139 A1 WO2023022139 A1 WO 2023022139A1
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Prior art keywords
mass
copolymer
resin composition
resin
parts
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PCT/JP2022/030924
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French (fr)
Japanese (ja)
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吉弘 浅井
博樹 深津
一也 五島
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ポリプラスチックス株式会社
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Publication of WO2023022139A1 publication Critical patent/WO2023022139A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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 resin composition for two-color molding and a molded article thereof.
  • Double molding is an injection molding method that can obtain a molded product in which multiple resins of different materials and colors are integrated in a small number of processes. , welding, or bonding, in that the process can be simplified.
  • Polybutylene terephthalate resin is excellent in mechanical properties, electrical properties, and other physical and chemical properties, and has good workability. Therefore, polybutylene terephthalate resin is used as an engineering plastic for a wide range of applications such as automobile parts and electric/electronic parts. Automobile parts are required to have a variety of properties, so resins suitable for each part are used, and they are often used as modules that combine multiple types of resins.
  • Patent Literature 1 proposes a polybutylene terephthalate resin composition capable of molding a molded article having excellent bonding strength in a double-molded article with a polycarbonate resin molded article in addition to alkali resistance.
  • each resin composition constituting the two-color molded product is excellent, if it is a two-color molded product with a resin with a different composition, it will The strength may decrease due to use in a hot and humid environment).
  • An object of the present invention is to solve the above-mentioned problems, and to provide a resin composition for two-color molding and a molded product thereof that can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member. do.
  • a resin composition for two-color molding with a polycarbonate resin member contains (A) a polybutylene terephthalate resin and (B) an olefin-based copolymer, (B) the olefin-based copolymer is (B1) a copolymer containing an ⁇ -olefin monomer unit and an ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester monomer unit; and (B2) an ⁇ -olefin monomer unit and ⁇ , ⁇ -unsaturation a graft copolymer containing as a main chain a copolymer containing a carboxylic acid alkyl ester monomer unit, and a polymer containing an ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester monomer unit as a side chain; including one or more selected from (B) A resin composition for two-color molding with a polycarbonate resin member, where
  • the molded article according to [7] which is an automobile part.
  • the present invention it is possible to provide a resin composition for two-color molding and a molded product thereof, which can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member.
  • the resin composition for two-color molding according to the present embodiment (hereinafter also simply referred to as "resin composition”) is a resin composition for two-color molding with a polycarbonate resin member, and (A) a polybutylene terephthalate resin and , and (B) an olefinic copolymer.
  • a "polycarbonate resin member” is a primary molded product containing a polycarbonate resin.
  • the polycarbonate resin member preferably contains 50% by mass or more of polycarbonate resin.
  • the shape and size of the polycarbonate resin member are not limited.
  • the shape of the primary molded product can be plate-like, columnar, or spherical.
  • "For two-color molding” means that it is used for producing a molded article by injection molding by a two-color molding method.
  • (A) polybutylene terephthalate resin) (A) Polybutylene terephthalate resin (PBT resin) is the first base material of the two-color molded product.
  • PBT resin comprises at least a dicarboxylic acid component containing terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) and at least It is a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing alkylene glycol (1,4-butanediol) or its ester-forming derivatives (acetylated products, etc.).
  • Polybutylene terephthalate resin is not limited to homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol % or more (especially 75 mol % or more and 95 mol % or less) of butylene terephthalate units.
  • a dicarboxylic acid component (comonomer component) other than terephthalic acid and its ester-forming derivative examples include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4 C 8-14 aromatic dicarboxylic acids such as ,4′-dicarboxydiphenyl ether; C 4-16 alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C 5-10 such as cyclohexanedicarboxylic acid and ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.).
  • dicarboxylic acid components can be used alone or in combination of two or more.
  • C 8-12 aromatic dicarboxylic acids such as isophthalic acid and C 6-12 alkane dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid are more preferred.
  • glycol component (comonomer component) other than 1,4-butanediol examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexa C2-10 alkylene glycols such as methylene glycol, neopentyl glycol and 1,3-octanediol; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol; lipids such as cyclohexane dimethanol and hydrogenated bisphenol A; Cyclic diols; aromatic diols such as bisphenol A and 4,4′-dihydroxybiphenyl; alkylene oxide adducts; or ester-forming derivatives of these glycols (acetylated products, etc.). These glycol components can be used individually or in combination of 2 or more types.
  • glycol components more preferred are C2-6 alkylene glycols such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycols such as diethylene glycol, and alicyclic diols such as cyclohexanedimethanol.
  • Comonomer components that can be used in addition to the dicarboxylic acid component and the glycol component include, for example, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4'-hydroxybiphenyl, and the like.
  • aromatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid
  • C3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone ( ⁇ -caprolactone, etc.); esters of these comonomer components formation derivatives (C 1-6 alkyl ester derivatives, acid halides, acetylates, etc.).
  • any of the polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as (A) the polybutylene terephthalate resin.
  • the polybutylene terephthalate resin (A) a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer may be used in combination.
  • the intrinsic viscosity of the polybutylene terephthalate resin is preferably 0.65 to 1.15 dL/g, more preferably 0.67 to 1.00, from the viewpoint of improving moldability.
  • Polybutylene terephthalate resins with different intrinsic viscosities can also be blended to adjust the intrinsic viscosity.
  • a polybutylene terephthalate resin with an intrinsic viscosity of 0.9 dL/g is prepared by blending a polybutylene terephthalate resin with an intrinsic viscosity of 1.0 dL/g and a polybutylene terephthalate resin with an intrinsic viscosity of 0.7 dL/g. can be done.
  • the intrinsic viscosity of the polybutylene terephthalate resin is a value measured in o-chlorophenol at a temperature of 35° C. using an Ubbelohde viscometer.
  • the amount of terminal carboxy groups in the polybutylene terephthalate resin is not particularly limited as long as it does not hinder the object of the present invention.
  • the terminal carboxy group content of (A) the polybutylene terephthalate resin used in the present embodiment is preferably 5 meq/kg or more and 30 meq/kg or less, more preferably 10 meq/kg or more and 25 meq/kg or less.
  • the content of the polybutylene terephthalate resin is 50% by mass or more based on the total resin components, from the viewpoint of further expressing the mechanical properties and chemical properties of the polybutylene terephthalate resin in the two-color molded product. , and more preferably 55% by mass or more.
  • the resin composition contains (B) an olefin copolymer having a predetermined structure in an amount of 2 to 35 parts by mass based on 100 parts by mass of (A) polybutylene terephthalate resin.
  • the olefin-based copolymer is (B1) a copolymer containing an ⁇ -olefin monomer unit and an ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester monomer unit (hereinafter also referred to as "copolymer B1"); and (B2) a main chain containing a copolymer containing an ⁇ -olefin monomer unit and an ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester monomer unit, and an ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester monomer unit;
  • a graft copolymer having a side chain containing a copolymer containing hereinafter also referred to as "graft copolymer B2"); including one or more selected from
  • Copolymer B1 is a copolymer using an ⁇ -olefin and a glycidyl ester of an ⁇ , ⁇ -unsaturated carboxylic acid as copolymerization components, and the ⁇ -olefin monomer unit and the ⁇ , ⁇ -unsaturated carboxylic acid and a glycidyl ester monomer unit of
  • ⁇ -olefins include, but are not limited to, linear or branched ⁇ -olefins having 1 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1 -heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
  • ⁇ -olefins selected from the above can be used. Among them, it is preferable to contain ethylene.
  • the content of ⁇ -olefin monomer units is preferably 50 to 98% by mass, more preferably 60 to 96% by mass, and 65 to 94% by mass relative to copolymer B1. is more preferred.
  • Glycidyl esters of ⁇ , ⁇ -unsaturated acids include, for example, the following general formula (I): (However, R 1 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.) and those having the structure shown in
  • Examples of the compound represented by the general formula (I) include glycidyl acrylate, glycidyl methacrylate (GMA), and glycidyl ethyl acrylate.
  • Glycidyl esters of ⁇ , ⁇ -unsaturated carboxylic acids can be used singly or in combination of two or more. Among them, it is preferable to contain glycidyl methacrylate.
  • the content of the ⁇ , ⁇ -unsaturated acid glycidyl ester monomer unit in the copolymer B1 is preferably 2 to 20% by mass in the copolymer B1, and is 2 to 15% by mass. is more preferable, and 3 to 12% by mass is even more preferable.
  • the method for measuring the content of glycidyl ester monomer units in the resin composition is to dissolve or disperse the copolymer B1 in a 0.2 mol/L hydrochloric acid-dioxane solution and add ethylene glycol monomethyl ether to the solution. It can be measured and calculated using a 0.1 M potassium hydroxide-ethanol solution as a liquid and a 0.1% cresol red-ethanol solution as an indicator.
  • the copolymer B1 can further contain structural units derived from (meth)acrylic acid esters.
  • the (meth)acrylic acid ester is also referred to as (meth)acrylate.
  • glycidyl (meth)acrylate is also referred to as glycidyl (meth)acrylate.
  • (meth)acrylic acid” means both acrylic acid and methacrylic acid
  • (meth)acrylate means both acrylate and methacrylate.
  • the (meth)acrylic acid ester is not particularly limited, but examples thereof include acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic acid -n-hexyl, -n-octyl acrylate), methacrylates (e.g., methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid-n-amyl, methacrylate-n-octyl) and the like.
  • acrylic acid esters e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic
  • the (meth)acrylic acid esters may be used singly or in combination of two or more.
  • the content of the (meth)acrylic acid ester monomer units is not particularly limited, but can be, for example, 0% by mass or more and 30% by mass or less in the copolymer B1.
  • copolymer B1 examples include, for example, a copolymer containing 80 to 95% by mass of ethylene and 5 to 20% by mass of glycidyl methacrylate; a copolymer containing 8% by mass and 15 to 30% by mass of methyl acrylate;
  • Copolymer B1 can be produced by copolymerization by a conventionally known method.
  • the above-mentioned copolymer B1 can be obtained by carrying out copolymerization by a generally well-known radical polymerization reaction.
  • the type of copolymer B1 is not particularly limited, and may be, for example, a random copolymer or a block copolymer.
  • the olefinic copolymer used in the present embodiment can contain structural units derived from other copolymer components within a range that does not impair the effects of the present invention.
  • Graft copolymer B2 contains as a main chain a copolymer containing ⁇ -olefin monomer units and ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester monomer units, and ⁇ , ⁇ -unsaturated carboxylic acid It is a graft copolymer containing a copolymer of acid alkyl ester monomer units as a side chain.
  • the copolymer constituting the main chain is a copolymer containing ⁇ -olefin monomer units and ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester monomer units, and is a random copolymer or a block copolymer. and the copolymer may be modified with one or more selected from the group consisting of unsaturated carboxylic acids, acid anhydrides thereof, and derivatives thereof.
  • ⁇ -olefins examples include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1 - includes hexene and the like.
  • ethylene is preferred.
  • One or more ⁇ -olefins selected from the above can be used.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acid alkyl esters include acrylic acid esters (methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, , n-hexyl acrylate, n-amyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate), methacrylate esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate , isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-amyl methacrylate, n-octyl
  • Unsaturated carboxylic acids or acid anhydrides thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, and glutaconic acid. , monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methyl maleic anhydride, maleic anhydride, methyl maleic anhydride, citraconic anhydride, etc., which may be used alone or in combination of two or more. can be used
  • the copolymer constituting the main chain examples include copolymers of ethylene and (meth)acrylic acid ester such as ethylene ethyl acrylate copolymer (EEA) and ethylene methyl methacrylate copolymer. be done.
  • ESA ethylene ethyl acrylate copolymer
  • ethylene methyl methacrylate copolymer be done.
  • the copolymer itself constituting the main chain is used as the (B) olefin-based copolymer (when it does not have a side chain)
  • the wet heat environment of the two-color molded product It was not possible to suppress the decrease in strength due to use under.
  • the content of the copolymer constituting the main chain is preferably 50 to 90% by mass, more preferably 65 to 80% by mass, in the copolymer B2.
  • the method for producing the copolymer that constitutes the main chain is not limited, and it can be produced by carrying out copolymerization by a conventionally known method.
  • a copolymer that constitutes the main chain can be obtained by performing copolymerization by a generally well-known radical polymerization reaction.
  • the side chain contains ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester monomer units, and may be a random copolymer or a block copolymer.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acid alkyl esters include acrylic acid esters (methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, , n-hexyl acrylate, n-amyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate), methacrylate esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate , isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-amyl methacrylate, n-octyl
  • It preferably contains two or more ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester monomer units with different compositions selected from these.
  • one or more selected from acrylic acid esters and one or more selected from methacrylic acid esters are preferably used, and butyl acrylate and methyl methacrylate are more preferably used.
  • the method for producing the side chain is not limited and can be produced by a conventionally known method.
  • a copolymer that constitutes the side chain can be obtained by performing copolymerization by a generally well-known radical polymerization reaction.
  • a specific example of the graft copolymer B2 is a graft copolymer containing an ethylene ethyl acrylate copolymer as a main chain and a butyl acrylate-methyl methacrylate copolymer as a side chain.
  • Graft copolymer B2 can be produced by conventionally known methods such as chain transfer method and ionizing radiation irradiation method. For example, an olefinic polymer formed from ethylene and a polar monomer suspended in water, a vinylic monomer containing at least a vinylic monomer having an acrylic acid alkyl ester, a radically polymerizable organic peroxide, and a radical polymerization initiator, and a vinyl monomer and a radically polymerizable organic peroxide in an olefin polymer formed from ethylene and a polar monomer.
  • the graft copolymer B2 may be obtained by melt-kneading the grafted precursor obtained by copolymerization.
  • the content of the olefin copolymer (B) is 2 to 35 parts by mass, preferably 2.5 to 33 parts by mass, more preferably 2.5 to 33 parts by mass, based on 100 parts by mass of the polybutylene terephthalate resin (A). It is 8 to 33 parts by mass, more preferably 3 to 32 parts by mass.
  • the content of the olefin copolymer is 2 parts by mass or more with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, so that the strength of the two-color molded product decreases when used in a hot and humid environment. The effect of suppressing is sufficiently obtained.
  • the content of the (B) olefinic copolymer is 35 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, it is possible to prevent the moldability from deteriorating.
  • the resin composition may further contain (C) a polycarbonate resin, if necessary.
  • a polycarbonate resin By including (C) a polycarbonate resin, the initial adhesion to the polycarbonate resin member can be further enhanced.
  • the (C) polycarbonate resin includes a polymer obtained by reacting a dihydroxy compound with a carbonate ester such as phosgene or diphenyl carbonate.
  • dihydroxy compounds examples include alicyclic compounds (eg, alicyclic diols) and bisphenol compounds, but bisphenol compounds are preferred.
  • Bisphenol compounds include bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy- 3-methylphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methyl phenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-ethylphenyl)propane, 2,2-bis(4-hydroxy- 3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl) -3-methylbutane, 2,2-bis(4-hydroxyphenyl)pent
  • a preferred (C) polycarbonate resin includes bisphenol A type polycarbonate.
  • the polycarbonate resin may be a homopolycarbonate or a copolycarbonate. Moreover, polycarbonate resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the melt viscosity of the polycarbonate resin is 0.40 kPa s as the melt viscosity at 300 ° C. and 1000 sec -1 in accordance with ISO 11443 from the viewpoint of further improving the adhesion during two-color molding with the polycarbonate resin member. It is preferably 0.35 kPa ⁇ s or less, more preferably 0.30 kPa ⁇ s or less.
  • the melt viscosity is a value measured using a capillograph manufactured by Toyo Seiki Seisakusho, using a capillary of 1 mm ⁇ 20 mmL/flat die, a barrel temperature of 300° C., and a shear rate of 1000 sec ⁇ 1 .
  • the content of the polycarbonate resin (C) is preferably 1 to 90 parts by mass, preferably 1.5 to 90 parts by mass, preferably 1.5 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). It is more preferably from 1.6 to 87 parts by mass, more preferably from 1.6 to 87 parts by mass. (C) By containing 1 to 90 parts by mass of the polycarbonate resin with respect to 100 parts by mass of the polybutylene terephthalate resin, it is possible to further improve the adhesion with the polycarbonate resin member during two-color molding, and two-color molding It is possible to further suppress the decrease in the strength of the product after wet heat treatment.
  • the resin composition may further contain (D) an inorganic filler, if necessary.
  • an inorganic filler By further including (D) an inorganic filler, the rigidity of the portion containing the resin composition for two-color molding in the two-color molded article can be further improved.
  • Inorganic fillers include, for example, fibrous inorganic fillers [e.g., glass fiber, asbestos fiber, carbon fiber, silica fiber, alumina fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, Boron fiber, potassium titanate fiber, silicon carbide fiber, whiskers (whiskers of silicon carbide, alumina, silicon nitride, etc.)], plate-like inorganic fillers [e.g., talc, mica, glass flakes, graphite, etc.], powdery inorganic fillers agents [eg, glass beads, glass powder, milled fiber (milled fiber such as glass), wollastonite, etc.].
  • fibrous inorganic fillers e.g., glass fiber, asbestos fiber, carbon fiber, silica fiber, alumina fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, Boron fiber
  • glass-based inorganic fillers glass fibers, glass flakes, glass beads, etc.
  • talc talc
  • mica wollastonite
  • plate-like or powdery inorganic fillers can be preferably used from the viewpoint of suppressing the anisotropy of the molding shrinkage and linear expansion coefficient of the polybutylene terephthalate resin composition.
  • a known surface treatment agent can be used as necessary.
  • a fibrous inorganic filler When a fibrous inorganic filler is used as the inorganic filler, its shape is not particularly limited. For example, it can be about 1 to 50 ⁇ m, more preferably about 3 to 30 ⁇ m. When plate-like inorganic fillers or powdery inorganic fillers are used, the average particle size is not particularly limited, but can be, for example, about 0.1 to 100 ⁇ m, more preferably about 0.1 to 50 ⁇ m. These (D) inorganic fillers can be used individually by 1 type or in combination of 2 or more types. "Average length", "average fiber diameter", and “average particle diameter” are obtained by heating the resin composition at 600 ° C.
  • ashing residue for 2 hours to obtain an ashing residue, and viewing this ashing residue with a CCD camera (for example, Seishin Enterprise Co., Ltd., dynamic image analysis method/particle (state) analyzer PITA-3) can be analyzed and calculated by weighted average.
  • a CCD camera for example, Seishin Enterprise Co., Ltd., dynamic image analysis method/particle (state) analyzer PITA-3
  • the content of the inorganic filler (D) is preferably 0 to 80 parts by mass, more preferably 0 to 75 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). 70 parts by mass, more preferably 1 to 65 parts by mass.
  • (D) By containing 80 parts by mass or less of the inorganic filler with respect to 100 parts by mass of the polybutylene terephthalate resin composition (A), the effect of suppressing the decrease in strength after wet heat treatment of the two-color molded product is maintained. The mechanical properties of the portion containing the polybutylene terephthalate resin of the two-color molded product can be further improved.
  • the content of the (D) inorganic filler can be 30 to 75 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, and 34.5 to 72.5 parts by mass. can do.
  • the resin composition may contain other additives than those mentioned above.
  • Other additives include antioxidants, stabilizers, molecular weight modifiers, ultraviolet absorbers, antistatic agents, colorants, lubricants, release agents, crystallization accelerators, crystal nucleating agents, infrared absorbers, flame retardants, Retardants, flame retardant auxiliaries, hydrolysis resistance improvers, fluidity improvers and the like can be mentioned.
  • the content of the additive can be 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.
  • a phosphorus-based stabilizer primary calcium phosphate, etc. (such as metal phosphate of ) is preferably added.
  • the amount of the other additives added can be 0.01 to 2 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.
  • the melt viscosity of the resin composition for two-color molding according to the present embodiment is 0.6 KPa s or less from the viewpoint of moldability as a melt viscosity at 260 ° C. and 1000 sec -1 in accordance with ISO 11443. It is preferably 0.5 KPa ⁇ s or less, and more preferably 0.5 KPa ⁇ s or less.
  • the melt viscosity is a value measured using a capilograph manufactured by Toyo Seiki Seisakusho, using a capillary of 1 mm ⁇ 20 mmL/flat die, a barrel temperature of 260° C., and a shear rate of 1000 sec ⁇ 1 .
  • the method for producing the resin composition is not particularly limited, and it can be prepared by a conventionally known method.
  • the resin composition is prepared by blending each component and melt-kneading them using a single-screw or twin-screw extruder.
  • the resin composition for two-color molding according to the present embodiment can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member when used in a moist and hot environment.
  • the resin composition for two-color molding can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member after wet heat treatment.
  • “Wet heat treatment” means a process of treating for 24 hours in a steam environment of 203 kPa under an environment of 121° C. temperature and 100% humidity, and leaving it for 24 hours under an environment of 23° C. temperature and 50% humidity.
  • the resin composition for two-color molding can be used when manufacturing automobile parts, electric/electronic parts, etc.
  • the resin composition for two-color molding can suppress the decrease in strength when used in a hot and humid environment, it can be preferably used for manufacturing automobile parts.
  • the molded article according to the present embodiment has a portion containing a polycarbonate resin and a portion containing the resin composition (for two-color molding), and the portion containing the polycarbonate resin and the portion containing the resin composition are At least a part of it touches and is integrated. Description of the resin composition for two-color molding is omitted here because it is as described above.
  • integral means that the portion containing the polycarbonate resin and the portion containing the resin composition are integrally formed in direct contact at least partially without an adhesive or the like. means.
  • the portion containing polycarbonate resin can be obtained by injection molding polycarbonate resin.
  • the portion containing polycarbonate resin may be a primary molded article of polycarbonate resin that is molded prior to two-color molding.
  • the portion containing the polycarbonate resin may be an insert member.
  • the content of the polycarbonate resin in the portion containing the polycarbonate resin is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and 95% by mass. is even more preferable.
  • Polycarbonate resins include polymers obtained by reacting dihydroxy compounds with phosgene or carbonic acid esters such as diphenyl carbonate.
  • the dihydroxy compound and the carbonate ester such as phosgene or diphenyl carbonate are not particularly limited, and can be added to the two-color molding resin composition described above. can be used.
  • the polycarbonate resin may have the same composition as (C) the polycarbonate resin that can be added to the resin composition for two-color molding, or may have a different composition.
  • the viscosity-average molecular weight and melt viscosity of the polycarbonate resin (melt viscosity at 300° C. and 1000 sec ⁇ 1 in accordance with ISO 11443) are not particularly limited, and for example, (C) polycarbonate resin can be added to the resin composition described above. can be similar to that described in
  • the polycarbonate resin may contain inorganic fillers and elastomers, and may further contain antioxidants, stabilizers, molecular weight modifiers, ultraviolet absorbers, antistatic agents, colorants, lubricants, and release agents.
  • Additives such as a crystallization accelerator, a crystal nucleating agent, an infrared absorber, a flame retardant, a flame retardant auxiliary, a hydrolysis resistance improver, and a fluidity improver may be contained.
  • the amount of the additive added can be 0.1 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin.
  • the portion containing the polycarbonate resin preferably has an anchor structure on at least a part of the surface in order to further enhance the adhesion to the resin composition for two-color molding during two-color molding.
  • the anchor structure can be formed by undercuts such as protrusions, holes, and depressions on the surface of the polycarbonate resin molded product.
  • the size and shape of the portion containing the polycarbonate resin, the portion containing the resin composition for two-color molding, and the entire two-color molded article are not limited, and can be set according to the application.
  • the portion containing the polycarbonate resin and the portion containing the resin composition are plate-shaped, one side of the portion containing the polycarbonate resin may be in contact with one side of the portion containing the resin composition.
  • the portion containing the resin composition may surround at least a portion (or the entirety) of the portion containing the polycarbonate.
  • the molded article is a two-color molded article.
  • the term "two-color molded article” as used herein means a molded article obtained by injection-molding a polycarbonate resin and the above-described resin composition for two-color molding by a two-color molding method.
  • Being a two-color molded product means that the part containing the resin composition and the part containing the polycarbonate resin in the two-color molded product are integrally molded so that at least a part is in contact without an adhesive layer, screws, etc.
  • a two-color molded product can be distinguished by having no traces of sliding, wear powder, or burrs due to ultrasonic welding, vibration welding, or the like on the joint surface, or traces of molten pools due to laser welding, or the like.
  • the molded product is preferably manufactured by two-color molding.
  • a primary molded product (polycarbonate resin molded product) obtained by injection molding polycarbonate resin in advance is placed in a mold cavity, and the polycarbonate resin is molded.
  • a molded article can be obtained by injection-molding the resin composition for two-color molding so as to be in contact with at least a part of the molded article.
  • the molded product can also be an insert molded product obtained by injection molding together with an insert member made of a metal (alloy) and/or an inorganic solid.
  • the material of the metal (alloy) and/or inorganic solid is not limited.
  • the manufacturing method of the insert-molded product is not particularly limited.
  • a primary molded product (polycarbonate resin member) obtained by injection molding a polycarbonate resin in advance is placed in a mold cavity together with an insert member made of a metal and / or an inorganic solid, and the polycarbonate resin molded product and the insert are placed in the mold cavity.
  • a two-color molded article can be obtained by injection-molding the polybutylene terephthalate resin composition onto the member.
  • a polycarbonate resin molded product is injection molded, an insert member made of a metal and/or an inorganic solid is placed in the mold cavity and the polycarbonate resin is injection molded on the insert member to obtain a polycarbonate resin having an insert member.
  • a two-color molded article can be obtained by injection molding a polybutylene terephthalate resin composition in a state in which the polycarbonate resin molded article having the insert member is placed in the mold cavity.
  • the joint strength (initial strength) of the two-color molded product preferably exceeds 20 MPa, more preferably 20.6 MPa or more.
  • the initial strength exceeds 20 MPa, a two-color molded article having excellent bonding strength can be obtained.
  • the two-color molded product is treated for 24 hours in a water vapor environment at a temperature of 121 ° C., a humidity of 100%, and 203 kPa, and the bonding strength after the wet heat treatment is left for 24 hours at a temperature of 23 ° C. and a humidity of 50%. It is preferably more than 20%, more preferably 40% or more, even more preferably 50% or more, and even more preferably 70% or more of the bonding strength before the wet heat treatment.
  • the molded product has a ratio of tensile strength after wet heat treatment to tensile strength before wet heat treatment (tensile strength retention rate) exceeds 20%, so it suppresses a decrease in strength when used in a hot and humid environment. be able to.
  • the molded product according to this embodiment can be used in various applications such as automobile parts, electric/electronic parts, and the like.
  • this two-color molded article can be preferably used as an automobile part because it can suppress a decrease in strength even when used in a hot and humid environment.
  • B-ii “Bond First (registered trademark) 2C” manufactured by Sumitomo Chemical Co., Ltd., containing 94% by mass of ethylene and 6% by mass of glycidyl methacrylate as copolymer components.
  • B-iii “Bond First (registered trademark) E” manufactured by Sumitomo Chemical Co., Ltd., containing 88% by mass of ethylene and 12% by mass of glycidyl methacrylate as copolymer components.
  • B-iv NOF Corporation, ethylene ethyl acrylate (main chain) and butyl acrylate-methyl methacrylate (side chain) graft copolymer
  • B-v ENEOS NUC Co., ethylene ethyl acrylate copolymer, "NUC (Registered Trademark)-6570”
  • C Polycarbonate resin (manufactured by Teijin Limited, melt viscosity: 0.27 kPa s)
  • D Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-127)
  • E Bisphenol A type epoxy resin (1004K manufactured by Mitsubishi Chemical Corporation)
  • Examples 1 to 11, Comparative Examples 1 to 5 Preparation of resin composition for two-color molding
  • the raw materials were mixed at the ratios shown in Tables 1 and 2, and melt-kneaded and extruded using a twin-screw extruder (TEX30, manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 260 ° C. and a screw rotation of 130 rpm.
  • Resin compositions of Examples 1 to 5 (resin compositions for two-color molding) were prepared.
  • test piece 10 (Preparation of test piece of two-color molded product)
  • the strip-shaped test piece (polycarbonate resin member) of the polycarbonate resin obtained above was placed in the mold as an insert member, and the resin composition for two-color molding obtained above was used at a cylinder temperature of 285 ° C. and the mold Insert molding was performed at a temperature of 90° C. to prepare a test piece of a two-color molded product having the shape shown in FIG. 1 .
  • the test piece 10 has a portion 1 containing polycarbonate resin with a size of 50 mm ⁇ 10 mm ⁇ thickness 2 mm, and a portion 2 containing the resin composition for two-color molding with a size of 50 mm ⁇ 10 mm.
  • test piece 10 is 100 mm x 10 mm x 2 mm thick.
  • test piece of the two-color molded product obtained above is subjected to a tensile test using a universal testing machine at a distance between grips of 50 mm and a speed of 5 mm / min. and
  • test piece was subjected to wet heat treatment in a steam environment of 121° C., 100% RH, and 203 kPa for 24 hours, and left at a temperature of 23° C. and a humidity of 50% for 24 hours (wet heat treatment). Thereafter, using a universal testing machine, a tensile test was performed at a gripper distance of 50 mm and a speed of 5 mm/min, and the maximum stress at breakage was measured as the bonding strength. The ratio of the bonding strength to the initial strength was calculated and used as the strength retention rate (%) after wet heat treatment.
  • the resin composition of Comparative Example 1 which does not contain an olefin copolymer, has an initial strength of two-color molded article exceeding 20 MPa, but the retention rate of strength after wet heat treatment relative to the initial strength. is 0% (meaning that the two-color molded product after wet heat treatment has already peeled, or peeled during chucking in a tensile test, or the bonding strength is 0 MPa), suppressing the decrease in strength after wet heat treatment. Can not do it.
  • Comparative Examples 2 and 4 in which an ethylene ethyl acrylate copolymer was used as the olefin-based copolymer, the initial strength of the two-color molded article was less than 20 MPa, and the retention of strength after wet heat treatment relative to the initial strength was 0%. Therefore, the decrease in strength after wet heat treatment cannot be suppressed. Even if epoxy resin E, which is effective in suppressing hydrolysis of polyester resin, was added, this tendency could not be improved (Comparative Example 4). (B) The resin composition of Comparative Example 3, in which an epoxy resin was used instead of the olefin-based copolymer, had an initial strength of more than 20 MPa, but the retention of strength after wet heat treatment relative to the initial strength was 0%.
  • the resin composition for two-color molding according to the present embodiment can suppress a decrease in the strength of a two-color molded product with a polycarbonate resin member, it can be used for various applications such as automobile parts, electric and electronic parts. and has industrial applicability.
  • Test piece 1 Portion containing polycarbonate resin 2

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Abstract

The present invention provides a resin composition for double molding and a molded article of the same that make it possible to suppress a reduction in strength of a double molded article with a polycarbonate resin member.　Provided is a resin composition for double molding with a polycarbonate resin member comprising (A) a polybutylene terephthalate resin and (B) an olefinic copolymer, wherein the olefinic copolymer (B) includes at least one selected from: (B1) a copolymer which contains α-olefin monomeric units and α,β-unsaturated carboxylic acid glycidyl ester monomeric units; and (B2) a graft copolymer which contains, as the main chain thereof, a copolymer containing α-olefin monomeric units and α,β-unsaturated carboxylic acid alkyl ester monomeric units and which contains, as a side chain thereof, a polymer containing α,β-unsaturated carboxylic acid alkyl ester monomeric units, and the content of the olefinic copolymer (B) is 2-35 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A).

Description

二色成形用樹脂組成物及びその成形品Resin composition for two-color molding and molded article thereof
　本発明は、二色成形用樹脂組成物及びその成形品に関する。 The present invention relates to a resin composition for two-color molding and a molded article thereof.
　二色成形（Ｄｏｕｂｌｅ　ｍｏｌｄｉｎｇ）は、材質や色が異なる複数の樹脂が一体化された成形品を少ない工程で得ることができる射出成形方法であり、それぞれの樹脂の成形品を作製した後にネジ止め、溶着、又は接着させる方法よりも、工程を簡略化できる点で優れた方法である。
　ポリブチレンテレフタレート樹脂は、機械的性質、電気的性質、並びにその他の物理的特性及び化学的特性に優れ、かつ加工性が良好である。そのため、ポリブチレンテレフタレート樹脂は、エンジニアリングプラスチックとして自動車部品、電気・電子部品などの広汎な用途に使用されている。自動車部品には多様な特性が求められていることから、部品毎に適した樹脂が使用されており、複数種類の樹脂を組み合わせたモジュールとして使用されることも多い。
　特許文献１には、耐アルカリ性に加え、ポリカーボネート樹脂成形品との二重成形品における接合強度にも優れる成形品を成形することが可能なポリブチレンテレフタレート樹脂組成物が提案されている。 Double molding is an injection molding method that can obtain a molded product in which multiple resins of different materials and colors are integrated in a small number of processes. , welding, or bonding, in that the process can be simplified.
Polybutylene terephthalate resin is excellent in mechanical properties, electrical properties, and other physical and chemical properties, and has good workability. Therefore, polybutylene terephthalate resin is used as an engineering plastic for a wide range of applications such as automobile parts and electric/electronic parts. Automobile parts are required to have a variety of properties, so resins suitable for each part are used, and they are often used as modules that combine multiple types of resins.
Patent Literature 1 proposes a polybutylene terephthalate resin composition capable of molding a molded article having excellent bonding strength in a double-molded article with a polycarbonate resin molded article in addition to alkali resistance.
国際公開第２０２０／１１６６２９号WO2020/116629
　母材（二色成形品を構成する各樹脂組成物）の成形品の強度が優れている場合であっても、組成が異なる樹脂との二色成形品とした場合は湿熱環境下（つまり、高温多湿の環境下）での使用により強度が低下してしまうことがある。 Even if the strength of the molded product of the base material (each resin composition constituting the two-color molded product) is excellent, if it is a two-color molded product with a resin with a different composition, it will The strength may decrease due to use in a hot and humid environment).
　本発明は、上記問題点を解決するものであり、ポリカーボネート樹脂部材との二色成形品の強度低下を抑制することができる二色成形用樹脂組成物及びその成形品を提供することを課題とする。 An object of the present invention is to solve the above-mentioned problems, and to provide a resin composition for two-color molding and a molded product thereof that can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member. do.
　本発明は以下の態様を有する。
［１］ポリカーボネート樹脂部材との二色成形用樹脂組成物であり、
　樹脂組成物が、（Ａ）ポリブチレンテレフタレート樹脂と、（Ｂ）オレフィン系共重合体と、を含み、
　（Ｂ）オレフィン系共重合体が、
　（Ｂ１）α－オレフィン単量体単位とα，β－不飽和カルボン酸グリシジルエステル単量体単位とを含む共重合体；及び
　（Ｂ２）α－オレフィン単量体単位とα，β－不飽和カルボン酸アルキルエステル単量体単位とを含む共重合体を主鎖として含み、及び、α，β－不飽和カルボン酸アルキルエステル単量体単位を含む重合体を側鎖として含むグラフト共重合体；
から選択される１以上を含み、
　（Ｂ）オレフィン系共重合体の含有量が、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対し２～３５質量部である、ポリカーボネート樹脂部材との二色成形用樹脂組成物。
［２］（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して１～９０質量部の（Ｃ）ポリカーボネート樹脂をさらに含む、［１］に記載の樹脂組成物。
［３］（Ｂ１）α－オレフィン単量体単位とα，β－不飽和カルボン酸のグリシジルエステル単量体単位とを含む共重合体中のグリシジルエステル単量体単位の含有量が、２～１５質量％である、［１］又は［２］に記載の樹脂組成物。
［４］（Ａ）ポリブチレンテレフタレート樹脂の、ｏ－クロロフェノール中、温度３５℃で測定した固有粘度が０．６５～１．１５ｄＬ／ｇである、［１］から［３］のいずれかに記載の樹脂組成物。
［５］（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して０～８０質量部の（Ｄ）無機充填剤をさらに含む、［１］から［４］のいずれかに記載の樹脂組成物。
［６］溶融粘度が０．６ＫＰａ・ｓ以下である、［１］から［５］のいずれかに記載の樹脂組成物。
［７］ポリカーボネート樹脂を含む部分と、［１］から［６］のいずれかに記載の樹脂組成物を含む部分とを有し、ポリカーボネート樹脂を含む部分と前記樹脂組成物を含む部分とが少なくとも一部で接して一体化されている、成形品。
［８］自動車部品である、［７］に記載の成形品。 The present invention has the following aspects.
[1] A resin composition for two-color molding with a polycarbonate resin member,
The resin composition contains (A) a polybutylene terephthalate resin and (B) an olefin-based copolymer,
(B) the olefin-based copolymer is
(B1) a copolymer containing an α-olefin monomer unit and an α,β-unsaturated carboxylic acid glycidyl ester monomer unit; and (B2) an α-olefin monomer unit and α,β-unsaturation a graft copolymer containing as a main chain a copolymer containing a carboxylic acid alkyl ester monomer unit, and a polymer containing an α,β-unsaturated carboxylic acid alkyl ester monomer unit as a side chain;
including one or more selected from
(B) A resin composition for two-color molding with a polycarbonate resin member, wherein the content of the olefin copolymer is 2 to 35 parts by mass based on 100 parts by mass of the (A) polybutylene terephthalate resin.
[2] The resin composition according to [1], further comprising 1 to 90 parts by mass of (C) a polycarbonate resin per 100 parts by mass of (A) polybutylene terephthalate resin.
[3] (B1) The content of glycidyl ester monomer units in the copolymer containing α-olefin monomer units and α,β-unsaturated carboxylic acid glycidyl ester monomer units is 2 to The resin composition according to [1] or [2], which is 15% by mass.
[4] (A) Any one of [1] to [3], wherein the polybutylene terephthalate resin has an intrinsic viscosity of 0.65 to 1.15 dL/g measured in o-chlorophenol at a temperature of 35°C. The described resin composition.
[5] The resin composition according to any one of [1] to [4], further comprising 0 to 80 parts by mass of (D) an inorganic filler with respect to 100 parts by mass of (A) polybutylene terephthalate resin.
[6] The resin composition according to any one of [1] to [5], which has a melt viscosity of 0.6 KPa·s or less.
[7] A portion containing a polycarbonate resin and a portion containing the resin composition according to any one of [1] to [6], wherein the portion containing the polycarbonate resin and the portion containing the resin composition are at least A molded product that is partially connected and integrated.
[8] The molded article according to [7], which is an automobile part.
　本発明によれば、ポリカーボネート樹脂部材との二色成形品の強度低下を抑制することができる二色成形用樹脂組成物及びその成形品を提供することができる。 According to the present invention, it is possible to provide a resin composition for two-color molding and a molded product thereof, which can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member.
実施例及び比較例の二色成形品の評価に使用した試験片の概略説明図である。BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic explanatory drawing of the test piece used for evaluation of the two-color molding of an Example and a comparative example.
　以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。 An embodiment of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope that does not impair the effects of the present invention.
［二色成形用樹脂組成物］
　本実施形態に係る二色成形用樹脂組成物（以下、単に「樹脂組成物」ともいう。）は、ポリカーボネート樹脂部材との二色成形用樹脂組成物であり、（Ａ）ポリブチレンテレフタレート樹脂と、（Ｂ）オレフィン系共重合体と、を含む。
　「ポリカーボネート樹脂部材」は、ポリカーボネート樹脂を含む一次成形品である。ポリカーボネート樹脂部材は、ポリカーボネート樹脂を５０質量％以上含むことが好ましい。ポリカーボネート樹脂部材の形状及び大きさは限定されない。例えば、一次成形品の形状は、板状、柱状、又は球状であり得る。
　「二色成形用」とは、二色成形法による射出成形により成形品を製造するために用いられることを意味している。 [Resin composition for two-color molding]
The resin composition for two-color molding according to the present embodiment (hereinafter also simply referred to as "resin composition") is a resin composition for two-color molding with a polycarbonate resin member, and (A) a polybutylene terephthalate resin and , and (B) an olefinic copolymer.
A "polycarbonate resin member" is a primary molded product containing a polycarbonate resin. The polycarbonate resin member preferably contains 50% by mass or more of polycarbonate resin. The shape and size of the polycarbonate resin member are not limited. For example, the shape of the primary molded product can be plate-like, columnar, or spherical.
"For two-color molding" means that it is used for producing a molded article by injection molding by a two-color molding method.
（（Ａ）ポリブチレンテレフタレート樹脂）
　（Ａ）ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、二色成形品の第１の母材である。（Ａ）ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１－６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも、炭素原子数４のアルキレングリコール（１，４－ブタンジオール）又はそのエステル形成性誘導体（アセチル化物等）を含むグリコール成分とを重縮合して得られるポリブチレンテレフタレート樹脂である。（Ａ）ポリブチレンテレフタレート樹脂はホモポリブチレンテレフタレート樹脂に限らず、ブチレンテレフタレート単位を６０モル％以上（特に７５モル％以上９５モル％以下）含有する共重合体であってもよい。 ((A) polybutylene terephthalate resin)
(A) Polybutylene terephthalate resin (PBT resin) is the first base material of the two-color molded product. (A) Polybutylene terephthalate resin (PBT resin) comprises at least a dicarboxylic acid component containing terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) and at least It is a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing alkylene glycol (1,4-butanediol) or its ester-forming derivatives (acetylated products, etc.). (A) Polybutylene terephthalate resin is not limited to homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol % or more (especially 75 mol % or more and 95 mol % or less) of butylene terephthalate units.
　（Ａ）ポリブチレンテレフタレート樹脂において、コモノマー成分としてテレフタル酸及びそのエステル形成性誘導体以外のジカルボン酸成分（コモノマー成分）を用いる場合、例えば、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジカルボキシジフェニルエーテル等のＣ８－１４の芳香族ジカルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸等のＣ４－１６のアルカンジカルボン酸；シクロヘキサンジカルボン酸等のＣ５－１０のシクロアルカンジカルボン酸；これらのジカルボン酸成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体や酸ハロゲン化物等）が挙げられる。これらのジカルボン酸成分は、単独で又は２種以上を組み合わせて使用できる。 (A) In the polybutylene terephthalate resin, when a dicarboxylic acid component (comonomer component) other than terephthalic acid and its ester-forming derivative is used as a comonomer component, examples include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4 C 8-14 aromatic dicarboxylic acids such as ,4′-dicarboxydiphenyl ether; C 4-16 alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C 5-10 such as cyclohexanedicarboxylic acid and ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components can be used alone or in combination of two or more.
　これらのジカルボン酸成分の中では、イソフタル酸等のＣ８－１２の芳香族ジカルボン酸、及び、アジピン酸、アゼライン酸、セバシン酸等のＣ６－１２のアルカンジカルボン酸がより好ましい。 Among these dicarboxylic acid components, C 8-12 aromatic dicarboxylic acids such as isophthalic acid and C 6-12 alkane dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid are more preferred.
　（Ａ）ポリブチレンテレフタレート樹脂において、コモノマー成分として１，４－ブタンジオール以外のグリコール成分（コモノマー成分）を用いる場合、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、１，３－オクタンジオール等のＣ２－１０のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等のポリオキシアルキレングリコール；シクロヘキサンジメタノール、水素化ビスフェノールＡ等の脂環式ジオール；ビスフェノールＡ、４，４’－ジヒドロキシビフェニル等の芳香族ジオール；ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等の、ビスフェノールＡのＣ２－４のアルキレンオキサイド付加体；又はこれらのグリコールのエステル形成性誘導体（アセチル化物等）が挙げられる。これらのグリコール成分は、単独で又は２種以上を組み合わせて使用できる。 (A) In the polybutylene terephthalate resin, when a glycol component (comonomer component) other than 1,4-butanediol is used as a comonomer component, examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexa C2-10 alkylene glycols such as methylene glycol, neopentyl glycol and 1,3-octanediol; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol; lipids such as cyclohexane dimethanol and hydrogenated bisphenol A; Cyclic diols; aromatic diols such as bisphenol A and 4,4′-dihydroxybiphenyl; alkylene oxide adducts; or ester-forming derivatives of these glycols (acetylated products, etc.). These glycol components can be used individually or in combination of 2 or more types.
　これらのグリコール成分の中では、エチレングリコール、トリメチレングリコール等のＣ２－６のアルキレングリコール、ジエチレングリコール等のポリオキシアルキレングリコール、又は、シクロヘキサンジメタノール等の脂環式ジオール等がより好ましい。
　ジカルボン酸成分及びグリコール成分の他に使用できるコモノマー成分としては、例えば、４－ヒドロキシ安息香酸、３－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４－カルボキシ－４’－ヒドロキシビフェニル等の芳香族ヒドロキシカルボン酸；グリコール酸、ヒドロキシカプロン酸等の脂肪族ヒドロキシカルボン酸；プロピオラクトン、ブチロラクトン、バレロラクトン、カプロラクトン（ε－カプロラクトン等）等のＣ３－１２ラクトン；これらのコモノマー成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体、酸ハロゲン化物、アセチル化物等）が挙げられる。 Among these glycol components, more preferred are C2-6 alkylene glycols such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycols such as diethylene glycol, and alicyclic diols such as cyclohexanedimethanol.
Comonomer components that can be used in addition to the dicarboxylic acid component and the glycol component include, for example, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4'-hydroxybiphenyl, and the like. aromatic hydroxycarboxylic acids; aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (ε-caprolactone, etc.); esters of these comonomer components formation derivatives (C 1-6 alkyl ester derivatives, acid halides, acetylates, etc.).
　以上説明したコモノマー成分を共重合したポリブチレンテレフタレート共重合体は、いずれも（Ａ）ポリブチレンテレフタレート樹脂として好適に使用できる。また、（Ａ）ポリブチレンテレフタレート樹脂として、ホモポリブチレンテレフタレート重合体とポリブチレンテレフタレート共重合体とを組み合わせて使用してもよい。 Any of the polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as (A) the polybutylene terephthalate resin. Moreover, as the polybutylene terephthalate resin (A), a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer may be used in combination.
　（Ａ）ポリブチレンテレフタレート樹脂の固有粘度は、成形性を向上させる観点から、０．６５～１．１５ｄＬ／ｇであることが好ましく、０．６７～１．００であることがより好ましい。異なる固有粘度を有するポリブチレンテレフタレート樹脂をブレンドして、固有粘度を調整することもできる。例えば、固有粘度１．０ｄＬ／ｇのポリブチレンテレフタレート樹脂と固有粘度０．７ｄＬ／ｇのポリブチレンテレフタレート樹脂とをブレンドすることにより、固有粘度０．９ｄＬ／ｇのポリブチレンテレフタレート樹脂を調製することができる。（Ａ）ポリブチレンテレフタレート樹脂の固有粘度は、ウベローデ型粘度計を用いて、ｏ－クロロフェノール中で温度３５℃の条件で測定した値とする。 (A) The intrinsic viscosity of the polybutylene terephthalate resin is preferably 0.65 to 1.15 dL/g, more preferably 0.67 to 1.00, from the viewpoint of improving moldability. Polybutylene terephthalate resins with different intrinsic viscosities can also be blended to adjust the intrinsic viscosity. For example, a polybutylene terephthalate resin with an intrinsic viscosity of 0.9 dL/g is prepared by blending a polybutylene terephthalate resin with an intrinsic viscosity of 1.0 dL/g and a polybutylene terephthalate resin with an intrinsic viscosity of 0.7 dL/g. can be done. (A) The intrinsic viscosity of the polybutylene terephthalate resin is a value measured in o-chlorophenol at a temperature of 35° C. using an Ubbelohde viscometer.
　（Ａ）ポリブチレンテレフタレート樹脂の末端カルボキシ基量は、本発明の目的を阻害しない限り特に限定されない。本実施形態において用いる（Ａ）ポリブチレンテレフタレート樹脂の末端カルボキシ基量は、５ｍｅｑ／ｋｇ以上３０ｍｅｑ／ｋｇ以下が好ましく、１０ｍｅｑ／ｋｇ以上２５ｍｅｑ／ｋｇ以下がより好ましい。かかる範囲の末端カルボキシ基量のポリブチレンテレフタレート樹脂を用いることで、得られるポリブチレンテレフタレート樹脂組成物が湿熱環境下での強度低下をより抑制することができる。 (A) The amount of terminal carboxy groups in the polybutylene terephthalate resin is not particularly limited as long as it does not hinder the object of the present invention. The terminal carboxy group content of (A) the polybutylene terephthalate resin used in the present embodiment is preferably 5 meq/kg or more and 30 meq/kg or less, more preferably 10 meq/kg or more and 25 meq/kg or less. By using a polybutylene terephthalate resin having a terminal carboxyl group content within such a range, the resulting polybutylene terephthalate resin composition can further suppress a decrease in strength in a moist heat environment.
　（Ａ）ポリブチレンテレフタレート樹脂の含有量は、二色成形品においてポリブチレンテレフタレート樹脂が有する機械的性質及び化学的特性等をより発現する観点から、樹脂成分全体に対して５０質量％以上であることが好ましく、５５質量％以上であることがより好ましい。 (A) The content of the polybutylene terephthalate resin is 50% by mass or more based on the total resin components, from the viewpoint of further expressing the mechanical properties and chemical properties of the polybutylene terephthalate resin in the two-color molded product. , and more preferably 55% by mass or more.
（（Ｂ）オレフィン系共重合体）
　樹脂組成物は、所定の構造を有する（Ｂ）オレフィン系共重合体を、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対し２～３５質量部含む。
　本発明者の研究により、驚くべきことに、所定の構造を有する所定量の（Ｂ）オレフィン系共重合体を、二色成形品の一方の母材であるポリブチレンテレフタレート樹脂に添加することで、二色成形品の湿熱処理後の強度の低下を抑制できることが分かった。 ((B) Olefin-based copolymer)
The resin composition contains (B) an olefin copolymer having a predetermined structure in an amount of 2 to 35 parts by mass based on 100 parts by mass of (A) polybutylene terephthalate resin.
Surprisingly, according to the research of the present inventor, by adding a predetermined amount of (B) an olefin-based copolymer having a predetermined structure to a polybutylene terephthalate resin that is one base material of a two-color molded product, , It was found that the decrease in strength after wet heat treatment of two-color molded products can be suppressed.
　（Ｂ）オレフィン系共重合体は、
　（Ｂ１）α－オレフィン単量体単位とα，β－不飽和カルボン酸のグリシジルエステル単量体単位とを含む共重合体（以下、「共重合体Ｂ１」ともいう。）；及び
　（Ｂ２）α－オレフィン単量体単位とα，β－不飽和カルボン酸アルキルエステル単量体単位とを含む共重合体を含む主鎖、及び、α，β－不飽和カルボン酸アルキルエステル単量体単位を含む共重合体を含む側鎖、を有するグラフト共重合体（以下、「グラフト共重合体Ｂ２］ともいう。）；
から選択される１以上を含む。 (B) the olefin-based copolymer is
(B1) a copolymer containing an α-olefin monomer unit and an α,β-unsaturated carboxylic acid glycidyl ester monomer unit (hereinafter also referred to as "copolymer B1"); and (B2) a main chain containing a copolymer containing an α-olefin monomer unit and an α,β-unsaturated carboxylic acid alkyl ester monomer unit, and an α,β-unsaturated carboxylic acid alkyl ester monomer unit; A graft copolymer having a side chain containing a copolymer containing (hereinafter also referred to as "graft copolymer B2");
including one or more selected from
　共重合体Ｂ１及びグラフト共重合体Ｂ２から選択される１以上を含むことで、二色成形品の湿熱処理後の強度の低下を抑制できる。 By containing one or more selected from the copolymer B1 and the graft copolymer B2, it is possible to suppress the decrease in the strength of the two-color molded product after the wet heat treatment.
（共重合体Ｂ１）
　共重合体Ｂ１は、共重合成分としてα－オレフィン及びα，β－不飽和カルボン酸のグリシジルエステルを用いた共重合体であり、α－オレフィン単量体単位とα，β－不飽和カルボン酸のグリシジルエステル単量体単位とを含む。 (Copolymer B1)
Copolymer B1 is a copolymer using an α-olefin and a glycidyl ester of an α,β-unsaturated carboxylic acid as copolymerization components, and the α-olefin monomer unit and the α,β-unsaturated carboxylic acid and a glycidyl ester monomer unit of
　α－オレフィンとしては、特に限定されないが、炭素数が１～１０の直鎖状又は分岐状α－オレフィンが挙げられ、例えば、エチレン、プロピレン、１-ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン等が挙げられる。α－オレフィンは、上記から選択される１以上を用いることができる。中でも、エチレンを含むことが好ましい。 Examples of α-olefins include, but are not limited to, linear or branched α-olefins having 1 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1 -heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like. One or more α-olefins selected from the above can be used. Among them, it is preferable to contain ethylene.
　α－オレフィン単量体単位の含有量は、共重合体Ｂ１に対して５０～９８質量％であることが好ましく、６０～９６質量％であることがより好ましく、６５～９４質量％であることがさらに好ましい。 The content of α-olefin monomer units is preferably 50 to 98% by mass, more preferably 60 to 96% by mass, and 65 to 94% by mass relative to copolymer B1. is more preferred.
　α，β－不飽和酸のグリシジルエステルとしては、例えば、以下の一般式（Ｉ）：
Figure JPOXMLDOC01-appb-I000001
（但し、Ｒ１は、水素又は炭素数１以上１０以下のアルキル基を示す。）
に示される構造を有するものが挙げられる。 Glycidyl esters of α,β-unsaturated acids include, for example, the following general formula (I):
Figure JPOXMLDOC01-appb-I000001
(However, R 1 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.)
and those having the structure shown in
　上記一般式（Ｉ）で示される化合物としては、例えば、アクリル酸グリシジルエステル、メタクリル酸グリシジルエステル（ＧＭＡ）、エチルアクリル酸グリシジルエステル等が挙げられる。α，β－不飽和カルボン酸のグリシジルエステルは、１種単独で使用することも、２種以上を併用することもできる。中でも、メタクリル酸グリシジルエステルを含むことが好ましい。 Examples of the compound represented by the general formula (I) include glycidyl acrylate, glycidyl methacrylate (GMA), and glycidyl ethyl acrylate. Glycidyl esters of α,β-unsaturated carboxylic acids can be used singly or in combination of two or more. Among them, it is preferable to contain glycidyl methacrylate.
　共重合体Ｂ１が有するα，β－不飽和酸のグリシジルエステル単量体単位の含有量は、共重合体Ｂ１中に２～２０質量％であることが好ましく、２～１５質量％であることがより好ましく、３～１２質量％であることがさらに好ましい。
　樹脂組成物中のグリシジルエステル単量体単位の含有量の測定方法は、共重合体Ｂ１を０．２ｍｏＬ／Ｌ塩酸－ジオキサン溶液に溶解あるいは分散させてエチレングリコールモノメチルエーテルを添加した溶液に、滴定液として０．１Ｍ水酸化カリウム－エタノール溶液を用い、指示薬として０．１％クレゾールレッド－エタノール溶液を用いて測定し、算出することができる。 The content of the α,β-unsaturated acid glycidyl ester monomer unit in the copolymer B1 is preferably 2 to 20% by mass in the copolymer B1, and is 2 to 15% by mass. is more preferable, and 3 to 12% by mass is even more preferable.
The method for measuring the content of glycidyl ester monomer units in the resin composition is to dissolve or disperse the copolymer B1 in a 0.2 mol/L hydrochloric acid-dioxane solution and add ethylene glycol monomethyl ether to the solution. It can be measured and calculated using a 0.1 M potassium hydroxide-ethanol solution as a liquid and a 0.1% cresol red-ethanol solution as an indicator.
　共重合体Ｂ１は、さらに（メタ）アクリル酸エステル由来の構成単位を含有することができる。なお、以下、（メタ）アクリル酸エステルを（メタ）アクリレートともいう。例えば、（メタ）アクリル酸グリシジルエステルをグリシジル（メタ）アクリレートともいう。また、本明細書において、「（メタ）アクリル酸」は、アクリル酸とメタクリル酸との両方を意味し、「（メタ）アクリレート」は、アクリレートとメタクリレートとの両方を意味する。 The copolymer B1 can further contain structural units derived from (meth)acrylic acid esters. In addition, hereinafter, the (meth)acrylic acid ester is also referred to as (meth)acrylate. For example, glycidyl (meth)acrylate is also referred to as glycidyl (meth)acrylate. Moreover, in this specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid, and "(meth)acrylate" means both acrylate and methacrylate.
　（メタ）アクリル酸エステルとしては、特に限定されないが、例えば、アクリル酸エステル（例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸－ｎ－プロピル、アクリル酸イソプロピル、アクリル酸－ｎ－ブチル、アクリル酸－ｎ－ヘキシル、アクリル酸－ｎ－オクチル）、メタクリル酸エステル（例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸－ｎ－プロピル、メタクリル酸イソプロピル、メタクリル酸－ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸－ｎ－アミル、メタクリル酸－ｎ－オクチル）等が挙げられる。中でも、アクリル酸メチルが好ましい。（メタ）アクリル酸エステルは、１種単独で使用することもでき、２種以上を併用することもできる。
　（メタ）アクリル酸エステル単量体単位の含有量は、特に限定されないが、例えば、共重合体Ｂ１中０質量％以上３０質量％以下とすることができる。 The (meth)acrylic acid ester is not particularly limited, but examples thereof include acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic acid -n-hexyl, -n-octyl acrylate), methacrylates (e.g., methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid-n-amyl, methacrylate-n-octyl) and the like. Among them, methyl acrylate is preferred. The (meth)acrylic acid esters may be used singly or in combination of two or more.
The content of the (meth)acrylic acid ester monomer units is not particularly limited, but can be, for example, 0% by mass or more and 30% by mass or less in the copolymer B1.
　共重合体Ｂ１の具体例としては、例えば、エチレンを８０～９５質量％、メタクリル酸グリシジルエステルを５～２０質量％含む共重合体；エチレンを６０～８０質量％、メタクリル酸グリシジルエステルを１～８質量％、及びアクリル酸メチルを１５～３０質量％含む共重合体；等が挙げられる。 Specific examples of the copolymer B1 include, for example, a copolymer containing 80 to 95% by mass of ethylene and 5 to 20% by mass of glycidyl methacrylate; a copolymer containing 8% by mass and 15 to 30% by mass of methyl acrylate;
　共重合体Ｂ１は、従来公知の方法で共重合を行うことにより製造することができる。例えば、通常よく知られたラジカル重合反応により共重合を行うことによって、上記共重合体Ｂ１を得ることができる。共重合体Ｂ１の種類は、特に問われず、例えば、ランダム共重合体であっても、ブロック共重合体であってもよい。
　本実施形態で用いるオレフィン系共重合体は、本発明の効果を害さない範囲で、他の共重合成分由来の構成単位を含有することができる。 Copolymer B1 can be produced by copolymerization by a conventionally known method. For example, the above-mentioned copolymer B1 can be obtained by carrying out copolymerization by a generally well-known radical polymerization reaction. The type of copolymer B1 is not particularly limited, and may be, for example, a random copolymer or a block copolymer.
The olefinic copolymer used in the present embodiment can contain structural units derived from other copolymer components within a range that does not impair the effects of the present invention.
（グラフト共重合体Ｂ２）
　グラフト共重合体Ｂ２は、α－オレフィン単量体単位とα，β－不飽和カルボン酸アルキルエステル単量体単位とを含む共重合体を主鎖として含み、及び、α，β－不飽和カルボン酸アルキルエステル単量体単位の共重合体を側鎖として含むグラフト共重合体である。 (Graft copolymer B2)
Graft copolymer B2 contains as a main chain a copolymer containing α-olefin monomer units and α,β-unsaturated carboxylic acid alkyl ester monomer units, and α,β-unsaturated carboxylic acid It is a graft copolymer containing a copolymer of acid alkyl ester monomer units as a side chain.
　主鎖を構成する共重合体は、α－オレフィン単量体単位とα，β－不飽和カルボン酸アルキルエステル単量体単位とを含む共重合体であり、ランダム共重合体又はブロック共重合体であることが好ましく、その共重合体を不飽和カルボン酸及びその酸無水物及びそれらの誘導体からなる群より選択される１以上で変性したものであってもよい。 The copolymer constituting the main chain is a copolymer containing α-olefin monomer units and α,β-unsaturated carboxylic acid alkyl ester monomer units, and is a random copolymer or a block copolymer. and the copolymer may be modified with one or more selected from the group consisting of unsaturated carboxylic acids, acid anhydrides thereof, and derivatives thereof.
　α－オレフィンとしては、特に限定されないが、例えば、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン等が挙げられる。中でも、エチレンが好ましい。α－オレフィンは、上記から選択される１以上を用いることができる。 Examples of α-olefins include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1 - includes hexene and the like. Among them, ethylene is preferred. One or more α-olefins selected from the above can be used.
　α，β－不飽和カルボン酸アルキルエステルとしては、アクリル酸エステル（アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸イソプロピル、アクリル酸ｎ－ブチル、アクリル酸ｔ－ブチル、アクリル酸イソブチル、アクリル酸－ｎ－ヘキシル、アクリル酸－ｎ－アミル、アクリル酸－ｎ－オクチル、アクリル酸２エチルヘキシル、アクリル酸ヒドロキシエチル）、メタクリル酸エステル（メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸イソブチル、メタクリル酸－ｎ－ヘキシル、メタクリル酸－ｎ－アミル、メタクリル酸－ｎ－オクチル、メタクリル酸２エチルヘキシル、メタクリル酸ヒドロキシエチル）等を用いることができる。 Examples of α,β-unsaturated carboxylic acid alkyl esters include acrylic acid esters (methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, , n-hexyl acrylate, n-amyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate), methacrylate esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate , isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-amyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, hydroxy methacrylate ethyl) and the like can be used.
　変性剤として用いられる不飽和カルボン酸又はその酸無水物としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸、クロトン酸、メチルマレイン酸、メチルフマル酸、メサコン酸、シトラコン酸、グルタコン酸、マレイン酸モノメチル、マレイン酸モノエチル、フマル酸モノエチル、イタコン酸メチル、無水メチルマレイン酸、無水マレイン酸、無水メチルマレイン酸、無水シトラコン酸等が挙げられ、これらは１種単独で又は２種以上組み合わせて使用することができる。 Unsaturated carboxylic acids or acid anhydrides thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, and glutaconic acid. , monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methyl maleic anhydride, maleic anhydride, methyl maleic anhydride, citraconic anhydride, etc., which may be used alone or in combination of two or more. can be used
　主鎖を構成する共重合体の具体例としては、エチレンアクリル酸エチル共重合体（ＥＥＡ）、エチレンメタクリル酸メチル共重合体等のエチレンと（メタ）アクリル酸エステルとの共重合体等が挙げられる。
　なお、後述する比較例に示すように、主鎖を構成する共重合体そのものを（Ｂ）オレフィン系共重合体として使用した場合（側鎖を有しない場合）は、二色成形品の湿熱環境下での使用による強度の低下を抑制することができなかった。 Specific examples of the copolymer constituting the main chain include copolymers of ethylene and (meth)acrylic acid ester such as ethylene ethyl acrylate copolymer (EEA) and ethylene methyl methacrylate copolymer. be done.
In addition, as shown in the comparative example described later, when the copolymer itself constituting the main chain is used as the (B) olefin-based copolymer (when it does not have a side chain), the wet heat environment of the two-color molded product It was not possible to suppress the decrease in strength due to use under.
　主鎖を構成する共重合体の含有量は、共重合体Ｂ２中、５０～９０質量％であることが好ましく、６５～８０質量％であることがより好ましい。 The content of the copolymer constituting the main chain is preferably 50 to 90% by mass, more preferably 65 to 80% by mass, in the copolymer B2.
　主鎖を構成する共重合体の製造方法は、限定されず、従来公知の方法で共重合を行うことにより製造することができる。例えば、通常よく知られたラジカル重合反応により共重合を行うことによって、主鎖を構成する共重合体を得ることができる。 The method for producing the copolymer that constitutes the main chain is not limited, and it can be produced by carrying out copolymerization by a conventionally known method. For example, a copolymer that constitutes the main chain can be obtained by performing copolymerization by a generally well-known radical polymerization reaction.
　側鎖は、α，β－不飽和カルボン酸アルキルエステル単量体単位を含み、ランダム共重合体又はブロック共重合体であってもよい。 The side chain contains α,β-unsaturated carboxylic acid alkyl ester monomer units, and may be a random copolymer or a block copolymer.
　α，β－不飽和カルボン酸アルキルエステルとしては、アクリル酸エステル（アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸イソプロピル、アクリル酸ｎ－ブチル、アクリル酸ｔ－ブチル、アクリル酸イソブチル、アクリル酸－ｎ－ヘキシル、アクリル酸－ｎ－アミル、アクリル酸－ｎ－オクチル、アクリル酸２エチルヘキシル、アクリル酸ヒドロキシエチル）、メタクリル酸エステル（メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸イソブチル、メタクリル酸－ｎ－ヘキシル、メタクリル酸－ｎ－アミル、メタクリル酸－ｎ－オクチル、メタクリル酸２エチルヘキシル、メタクリル酸ヒドロキシエチル）等を用いることができる。 Examples of α,β-unsaturated carboxylic acid alkyl esters include acrylic acid esters (methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, , n-hexyl acrylate, n-amyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate), methacrylate esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate , isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-amyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, hydroxy methacrylate ethyl) and the like can be used.
　これらから選ばれる、組成が異なる２以上のα，β－不飽和カルボン酸アルキルエステル単量体単位を含むことが好ましい。中でも、アクリル酸エステルから選ばれる１以上と、メタクリル酸エステルから選ばれる１以上と、を用いることが好ましく、アクリル酸ブチルとメタクリル酸メチルとを用いることがより好ましい。 It preferably contains two or more α,β-unsaturated carboxylic acid alkyl ester monomer units with different compositions selected from these. Among them, one or more selected from acrylic acid esters and one or more selected from methacrylic acid esters are preferably used, and butyl acrylate and methyl methacrylate are more preferably used.
　側鎖の製造方法は、限定されず従来公知の方法で製造することができる。例えば、通常よく知られたラジカル重合反応により共重合を行うことによって、側鎖を構成する共重合体を得ることができる。 The method for producing the side chain is not limited and can be produced by a conventionally known method. For example, a copolymer that constitutes the side chain can be obtained by performing copolymerization by a generally well-known radical polymerization reaction.
　グラフト共重合体Ｂ２の具体例としては、例えば、エチレンエチルアクリレート共重合体を主鎖として含み、ブチルアクリレート－メチルメタクリレート共重合体を側鎖として含むグラフト共重合体等が挙げられる。 A specific example of the graft copolymer B2 is a graft copolymer containing an ethylene ethyl acrylate copolymer as a main chain and a butyl acrylate-methyl methacrylate copolymer as a side chain.
　グラフト共重合体Ｂ２の製造方法は、連鎖移動法、電離性放射線照射法等などの従来公知の方法で製造することができる。例えば、水中に懸濁させたエチレン及び極性単量体から形成されるオレフィン系重合体に、少なくともアクリル酸アルキルエステルを有するビニル系単量体を含むビニル系単量体、ラジカル重合性有機過酸化物の１種又は２種以上の混合物及びラジカル重合開始剤を含浸させ、ビニル系単量体とラジカル重合性有機過酸化物とをエチレン及び極性単量体から形成されるオレフィン系重合体中で共重合させて得たグラフト化前駆体を溶融混練することによりグラフト共重合体Ｂ２を得てもよい。 Graft copolymer B2 can be produced by conventionally known methods such as chain transfer method and ionizing radiation irradiation method. For example, an olefinic polymer formed from ethylene and a polar monomer suspended in water, a vinylic monomer containing at least a vinylic monomer having an acrylic acid alkyl ester, a radically polymerizable organic peroxide, and a radical polymerization initiator, and a vinyl monomer and a radically polymerizable organic peroxide in an olefin polymer formed from ethylene and a polar monomer. The graft copolymer B2 may be obtained by melt-kneading the grafted precursor obtained by copolymerization.
　（Ｂ）オレフィン系共重合体の含有量は、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対し２～３５質量部であり、好ましくは２．５～３３質量部であり、より好ましくは２．８～３３質量部であり、さらに好ましくは３～３２質量部である。
　（Ｂ）オレフィン系共重合体の含有量が、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して２質量部以上であることにより、二色成形品を湿熱環境下で使用した場合の強度低下を抑制する効果が十分に得られる。（Ｂ）オレフィン系共重合体の含有量が、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対し３５質量部以下であることにより、成形性が低下することを防ぐことができる。 The content of the olefin copolymer (B) is 2 to 35 parts by mass, preferably 2.5 to 33 parts by mass, more preferably 2.5 to 33 parts by mass, based on 100 parts by mass of the polybutylene terephthalate resin (A). It is 8 to 33 parts by mass, more preferably 3 to 32 parts by mass.
(B) The content of the olefin copolymer is 2 parts by mass or more with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, so that the strength of the two-color molded product decreases when used in a hot and humid environment. The effect of suppressing is sufficiently obtained. When the content of the (B) olefinic copolymer is 35 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, it is possible to prevent the moldability from deteriorating.
（（Ｃ）ポリカーボネート樹脂）
　樹脂組成物は、必要に応じて、（Ｃ）ポリカーボネート樹脂をさらに含んでいてもよい。（Ｃ）ポリカーボネート樹脂を含むことで、ポリカーボネート樹脂部材との初期密着性をより高めることができる。 ((C) polycarbonate resin)
The resin composition may further contain (C) a polycarbonate resin, if necessary. By including (C) a polycarbonate resin, the initial adhesion to the polycarbonate resin member can be further enhanced.
　（Ｃ）ポリカーボネート樹脂としては、ジヒドロキシ化合物と、ホスゲン又はジフェニルカーボネート等の炭酸エステルと、の反応により得られる重合体が挙げられる。 The (C) polycarbonate resin includes a polymer obtained by reacting a dihydroxy compound with a carbonate ester such as phosgene or diphenyl carbonate.
　ジヒドロキシ化合物としては、例えば、脂環族化合物（例えば、脂環式ジオール）及びビスフェノール化合物が挙げられるが、ビスフェノール化合物であることが好ましい。 Examples of dihydroxy compounds include alicyclic compounds (eg, alicyclic diols) and bisphenol compounds, but bisphenol compounds are preferred.
　ビスフェノール化合物としては、ビス（４－ヒドロキシフェニル）メタン、ビス（４－ヒドロキシ－３－メチルフェニル）メタン、１，１－ビス（４－ヒドロキシフェニル）エタン、１，１－ビス（４－ヒドロキシ－３－メチルフェニル）エタン、１，１－ビス（４－ヒドロキシフェニル）プロパン、２，２－ビス（４－ヒドロキシフェニル）プロパン（ビスフェノールＡ）、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３，５－ジメチルフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３－エチルフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３－ｔ－ブチルフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３－ブロモフェニル）プロパン、２，２－ビス（４－ヒドロキシフェニル）ブタン、２，２－ビス（４－ヒドロキシフェニル）－３－メチルブタン、２，２－ビス（４－ヒドロキシフェニル）ペンタン、２，２－ビス（４－ヒドロキシフェニル）ヘキサン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、２，２－ビス（４－ヒドロキシフェニル）オクタン、ビス（４－ヒドロキシフェニル）フェニルメタン、ビス（４－ヒドロキシフェニル）ジフェニルメタン、ビス（４－ヒドロキシフェニル）ジベンジルメタン、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルプロパン、２，２，２’，２’－テトラヒドロ３，３，３’，３’－テトラメチル－１，１’－スピロビ－［１Ｈ－インデン］－６，６’－ジオールなどのビス（ヒドロキシアリール）Ｃ１－１０アルカン、好ましくはビス（ヒドロキシアリール）Ｃ１－６アルカン；１，１－ビス（４－ヒドロキシフェニル）シクロペンタン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサンなどのビス（ヒドロキシアリール）Ｃ４－１０シクロアルカン；４，４’－ジヒドロキシジフェニルエーテル、４，４’－ジヒドロキシ－３，３’－ジメチルジフェニルエーテル等のジヒドロキシアリールエーテル；４，４’－ジヒドロキシジフェニルスルホン、４，４’－ジヒドロキシ－３，３’－ジメチルジフェニルスルホン等のジヒドロキシアリールスルホン；４，４’－ジヒドロキシジフェニルスルフィド、４，４’－ジヒドロキシ－３，３’－ジメチルジフェニルスルフィド等のジヒドロキシアリールスルフィド；４，４’－ジヒドロキシジフェニルスルフォキシド、４，４’－ジヒドロキシ－３，３’－ジメチルジフェニルスルフォキシド等のジヒドロキシアリールスルフォキシド；４，４’－ジヒドロキシジフェニルケトン、４，４’－ジヒドロキシ－３，３’－ジメチルジフェニルケトン等のジヒドロキシアリールケトンなどが挙げられる。 Bisphenol compounds include bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy- 3-methylphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methyl phenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-ethylphenyl)propane, 2,2-bis(4-hydroxy- 3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl) -3-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2, 2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)dibenzylmethane, 1,1-bis(4-hydroxy phenyl)-1-phenylpropane, 2,2,2′,2′-tetrahydro 3,3,3′,3′-tetramethyl-1,1′-spirobi-[1H-indene]-6,6′- bis(hydroxyaryl)C 1-10 alkanes, preferably bis(hydroxyaryl)C 1-6 alkanes, such as diols; 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxy bis(hydroxyaryl)C 4-10 cycloalkanes such as phenyl)cyclohexane; dihydroxyaryl ethers such as 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; 4,4′- Dihydroxyaryl sulfones such as dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide and the like dihydroxy aryl sulfide of; 4,4'-dihydroxy diph dihydroxyarylsulfoxide such as phenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;4,4'-dihydroxydiphenylketone,4,4'-dihydroxy-3,3' -Dihydroxyaryl ketones such as dimethyldiphenyl ketone.
　好ましい（Ｃ）ポリカーボネート樹脂としては、ビスフェノールＡ型ポリカーボネートが挙げられる。 A preferred (C) polycarbonate resin includes bisphenol A type polycarbonate.
　（Ｃ）ポリカーボネート樹脂は、ホモポリカーボネートであってもよいし、コポリカーボネートであってもよい。また、ポリカーボネート樹脂は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 (C) The polycarbonate resin may be a homopolycarbonate or a copolycarbonate. Moreover, polycarbonate resin may be used individually by 1 type, and may be used in combination of 2 or more type.
　（Ｃ）ポリカーボネート樹脂の溶融粘度は、ポリカーボネート樹脂部材との二色成形時の密着性をより高める観点から、ＩＳＯ１１４４３に準拠した、３００℃、１０００ｓｅｃ－１での溶融粘度として、０．４０ｋＰａ・ｓ以下であることが好ましく、０．３５ｋＰａ・ｓ以下であることがより好ましく、０．３０ｋＰａ・ｓ以下であることがさらに好ましい。
　なお、溶融粘度は、東洋精機製作所製キャピログラフを用い、キャピラリーとして１ｍｍφ×２０ｍｍＬ／フラットダイを使用し、バレル温度３００℃、せん断速度１０００ｓｅｃ－１で測定した値とする。 (C) The melt viscosity of the polycarbonate resin is 0.40 kPa s as the melt viscosity at 300 ° C. and 1000 sec -1 in accordance with ISO 11443 from the viewpoint of further improving the adhesion during two-color molding with the polycarbonate resin member. It is preferably 0.35 kPa·s or less, more preferably 0.30 kPa·s or less.
The melt viscosity is a value measured using a capillograph manufactured by Toyo Seiki Seisakusho, using a capillary of 1 mmφ×20 mmL/flat die, a barrel temperature of 300° C., and a shear rate of 1000 sec −1 .
　（Ｃ）ポリカーボネート樹脂の含有量は、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して１～９０質量部であることが好ましく、１．５～９０質量部であることが好ましく、１．５～８８質量部であることがより好ましく、１．６～８７質量部であることが更に好ましい。（Ｃ）ポリカーボネート樹脂をポリブチレンテレフタレート樹脂１００質量部に対して１～９０質量部含有することで、ポリカーボネート樹脂部材との二色成形時の密着性をより向上することができるとともに、二色成形品の湿熱処理後の強度の低下をより抑制することができる。 The content of the polycarbonate resin (C) is preferably 1 to 90 parts by mass, preferably 1.5 to 90 parts by mass, preferably 1.5 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). It is more preferably from 1.6 to 87 parts by mass, more preferably from 1.6 to 87 parts by mass. (C) By containing 1 to 90 parts by mass of the polycarbonate resin with respect to 100 parts by mass of the polybutylene terephthalate resin, it is possible to further improve the adhesion with the polycarbonate resin member during two-color molding, and two-color molding It is possible to further suppress the decrease in the strength of the product after wet heat treatment.
（（Ｄ）無機充填剤）
　樹脂組成物は、必要に応じて、（Ｄ）無機充填剤をさらに含んでいてもよい。（Ｄ）無機充填剤をさらに含むことで、二色成形品における二色成形用樹脂組成物を含む部分の剛性をより向上させることができる。 ((D) inorganic filler)
The resin composition may further contain (D) an inorganic filler, if necessary. By further including (D) an inorganic filler, the rigidity of the portion containing the resin composition for two-color molding in the two-color molded article can be further improved.
　（Ｄ）無機充填剤としては、例えば、繊維状無機充填剤［例えば、ガラス繊維、アスベスト繊維、カーボン繊維、シリカ繊維、アルミナ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化珪素繊維、硼素繊維、チタン酸カリウム繊維、炭化珪素繊維、ウィスカー（炭化珪素、アルミナ、窒化珪素などのウィスカー）］、板状無機充填剤［例えば、タルク、マイカ、ガラスフレーク、グラファイトなど］、粉状無機充填剤［例えば、ガラスビーズ、ガラスパウダー、ミルドファイバー（ガラスなどのミルドファイバー）、ウォラストナイトなど］が挙げられる。これらの無機充填剤のうち、ガラス系無機充填剤（ガラス繊維、ガラスフレーク、ガラスビーズなど）、タルク、マイカ、ウォラストナイトなどが好ましく、中でもガラス繊維は、入手性や強度及び剛性の面から、好適に使用できる。また、板状や粉状の無機充填剤は、ポリブチレンテレフタレート樹脂組成物の成形収縮率や線膨張係数の異方性抑制の面から、好適に使用できる。これらの無機充填剤の使用に際しては、必要に応じ公知の表面処理剤を使用することができる。 (D) Inorganic fillers include, for example, fibrous inorganic fillers [e.g., glass fiber, asbestos fiber, carbon fiber, silica fiber, alumina fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, Boron fiber, potassium titanate fiber, silicon carbide fiber, whiskers (whiskers of silicon carbide, alumina, silicon nitride, etc.)], plate-like inorganic fillers [e.g., talc, mica, glass flakes, graphite, etc.], powdery inorganic fillers agents [eg, glass beads, glass powder, milled fiber (milled fiber such as glass), wollastonite, etc.]. Among these inorganic fillers, glass-based inorganic fillers (glass fibers, glass flakes, glass beads, etc.), talc, mica, wollastonite, etc. are preferable. , can be preferably used. Plate-like or powdery inorganic fillers can be preferably used from the viewpoint of suppressing the anisotropy of the molding shrinkage and linear expansion coefficient of the polybutylene terephthalate resin composition. When using these inorganic fillers, a known surface treatment agent can be used as necessary.
　（Ｄ）無機充填剤として繊維状無機充填剤を用いる場合、その形状は特に限定されないが、例えば平均長さは１００μｍ～５ｍｍ、より好ましくは２００μｍ～３ｍｍ程度とすることができ、平均繊維径は例えば１～５０μｍ、より好ましくは３～３０μｍ程度とすることができる。板状無機充填剤又は粉状無機充填剤を用いる場合、その平均粒子径も特に限定されないが、例えば０．１～１００μｍ、より好ましくは０．１～５０μｍ程度とすることができる。これらの（Ｄ）無機充填剤は、１種単独で又は２種以上組み合わせて使用できる。
　「平均長さ」、「平均繊維径」、及び「平均粒子径」は、樹脂組成物を６００℃で２時間加熱し灰化して灰化残渣を得、この灰化残渣をＣＣＤカメラ（例えば、株式会社セイシン企業製、動的画像解析法／粒子（状態）分析計ＰＩＴＡ－３）で撮影した画像を解析し、加重平均により算出することができる。 (D) When a fibrous inorganic filler is used as the inorganic filler, its shape is not particularly limited. For example, it can be about 1 to 50 μm, more preferably about 3 to 30 μm. When plate-like inorganic fillers or powdery inorganic fillers are used, the average particle size is not particularly limited, but can be, for example, about 0.1 to 100 μm, more preferably about 0.1 to 50 μm. These (D) inorganic fillers can be used individually by 1 type or in combination of 2 or more types.
"Average length", "average fiber diameter", and "average particle diameter" are obtained by heating the resin composition at 600 ° C. for 2 hours to obtain an ashing residue, and viewing this ashing residue with a CCD camera (for example, Seishin Enterprise Co., Ltd., dynamic image analysis method/particle (state) analyzer PITA-3) can be analyzed and calculated by weighted average.
　（Ｄ）無機充填剤の含有量は、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して、好ましくは０～８０質量部であり、より好ましくは０～７５質量部であり、さらに好ましくは０～７０質量部であり、よりさらに好ましくは１～６５質量部である。（Ｄ）無機充填剤を、（Ａ）ポリブチレンテレフタレート樹脂組成物１００質量部に対して８０質量部以下含有することで、二色成形品の湿熱処理後の強度低下の抑制効果を維持したまま二色成形品のポリブチレンテレフタレート樹脂を含む部分の機械的特性をより向上させることができる。
　一実施形態において、（Ｄ）無機充填剤の含有量は、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して３０～７５質量部とすることができ、３４．５～７２．５質量部とすることができる。 The content of the inorganic filler (D) is preferably 0 to 80 parts by mass, more preferably 0 to 75 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). 70 parts by mass, more preferably 1 to 65 parts by mass. (D) By containing 80 parts by mass or less of the inorganic filler with respect to 100 parts by mass of the polybutylene terephthalate resin composition (A), the effect of suppressing the decrease in strength after wet heat treatment of the two-color molded product is maintained. The mechanical properties of the portion containing the polybutylene terephthalate resin of the two-color molded product can be further improved.
In one embodiment, the content of the (D) inorganic filler can be 30 to 75 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, and 34.5 to 72.5 parts by mass. can do.
（その他の添加剤）
　樹脂組成物は、上記以外のその他の添加剤を含んでいてもよい。その他の添加剤としては、酸化防止剤、安定剤、分子量調整剤、紫外線吸収剤、帯電防止剤、着色剤、潤滑剤、離型剤、結晶化促進剤、結晶核剤、赤外線吸収剤、難燃剤、難燃助剤、耐加水分解性向上剤、流動性改良剤等が挙げられる。添加剤の含有量は、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して０．１～２０質量部とすることができる。 (Other additives)
The resin composition may contain other additives than those mentioned above. Other additives include antioxidants, stabilizers, molecular weight modifiers, ultraviolet absorbers, antistatic agents, colorants, lubricants, release agents, crystallization accelerators, crystal nucleating agents, infrared absorbers, flame retardants, Retardants, flame retardant auxiliaries, hydrolysis resistance improvers, fluidity improvers and the like can be mentioned. The content of the additive can be 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.
　樹脂組成物に（Ｃ）ポリカーボネート樹脂を添加する場合は、（Ａ）ポリブチレンテレフタレート樹脂と（Ｃ）ポリカーボネート樹脂との間のエステル交換を抑制するために、リン系の安定剤（第一リン酸カルシウム等のリン酸金属塩など）を添加することが好ましい。その他の添加剤の添加量は、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して、０．０１～２質量部とすることができる。 When (C) polycarbonate resin is added to the resin composition, in order to suppress transesterification between (A) polybutylene terephthalate resin and (C) polycarbonate resin, a phosphorus-based stabilizer (primary calcium phosphate, etc. (such as metal phosphate of ) is preferably added. The amount of the other additives added can be 0.01 to 2 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.
（樹脂組成物）
　本実施形態に係る二色成形用樹脂組成物の溶融粘度は、ＩＳＯ１１４４３に準拠した、２６０℃、１０００ｓｅｃ－１での溶融粘度として、成形性の観点から、０．６ＫＰａ・ｓ以下であることが好ましく、０．５ＫＰａ・ｓ以下であることがより好ましい。
　なお、溶融粘度は、東洋精機製作所製キャピログラフを用い、キャピラリーとして１ｍｍφ×２０ｍｍＬ／フラットダイを使用し、バレル温度２６０℃、せん断速度１０００ｓｅｃ－１で測定した値とする。 (resin composition)
The melt viscosity of the resin composition for two-color molding according to the present embodiment is 0.6 KPa s or less from the viewpoint of moldability as a melt viscosity at 260 ° C. and 1000 sec -1 in accordance with ISO 11443. It is preferably 0.5 KPa·s or less, and more preferably 0.5 KPa·s or less.
The melt viscosity is a value measured using a capilograph manufactured by Toyo Seiki Seisakusho, using a capillary of 1 mmφ×20 mmL/flat die, a barrel temperature of 260° C., and a shear rate of 1000 sec −1 .
　樹脂組成物の製造方法は、特に限定されず、従来公知の方法で調製することができる。例えば、各成分を配合して、これらを１軸又は２軸押出機を用いて溶融混練処理することで、樹脂組成物の調製が行われる。 The method for producing the resin composition is not particularly limited, and it can be prepared by a conventionally known method. For example, the resin composition is prepared by blending each component and melt-kneading them using a single-screw or twin-screw extruder.
　本実施形態に係る二色成形用樹脂組成物は、ポリカーボネート樹脂部材との二色成形品の、湿熱環境下で使用された場合の強度低下を抑制することができる。
　一実施形態において、二色成形用樹脂組成物は、ポリカーボネート樹脂部材との二色成形品の、湿熱処理後の強度低下を抑制することができる。「湿熱処理」は、温度１２１℃、湿度１００％の環境下で２０３ｋＰａの水蒸気環境下で２４時間処理し、温度２３℃、湿度５０％の環境下で２４時間放置する処理を意味している。 The resin composition for two-color molding according to the present embodiment can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member when used in a moist and hot environment.
In one embodiment, the resin composition for two-color molding can suppress a decrease in strength of a two-color molded product with a polycarbonate resin member after wet heat treatment. “Wet heat treatment” means a process of treating for 24 hours in a steam environment of 203 kPa under an environment of 121° C. temperature and 100% humidity, and leaving it for 24 hours under an environment of 23° C. temperature and 50% humidity.
　二色成形用樹脂組成物は、自動車部品、電気・電子部品等の製造時に使用することができる。特に、二色成形用樹脂組成物は、湿熱環境下で使用された場合の強度低下を抑制することができるので、自動車部品の製造用として好ましく用いることができる。 The resin composition for two-color molding can be used when manufacturing automobile parts, electric/electronic parts, etc. In particular, since the resin composition for two-color molding can suppress the decrease in strength when used in a hot and humid environment, it can be preferably used for manufacturing automobile parts.
［成形品］
　本実施形態に係る成形品は、ポリカーボネート樹脂を含む部分と、上記した（二色成形用）樹脂組成物を含む部分とを有し、ポリカーボネート樹脂を含む部分と前記樹脂組成物を含む部分とは少なくとも一部で接して一体化されている。二色成形用樹脂組成物については、上記のとおりであるからここでは記載を省略する。 [Molding]
The molded article according to the present embodiment has a portion containing a polycarbonate resin and a portion containing the resin composition (for two-color molding), and the portion containing the polycarbonate resin and the portion containing the resin composition are At least a part of it touches and is integrated. Description of the resin composition for two-color molding is omitted here because it is as described above.
　「一体化されている」とは、ポリカーボネート樹脂を含む部分と前記樹脂組成物を含む部分とが、接着剤等を介さずに、少なくとも一部が直接接して一体的に形成されていることを意味している。 The term "integrated" means that the portion containing the polycarbonate resin and the portion containing the resin composition are integrally formed in direct contact at least partially without an adhesive or the like. means.
（ポリカーボネート樹脂を含む部分）
　ポリカーボネート樹脂を含む部分は、ポリカーボネート樹脂を射出成形して得ることができる。ポリカーボネート樹脂を含む部分は、二色成形に先立って成形される、ポリカーボネート樹脂の一次成形品であってよい。ポリカーボネート樹脂を含む部分は、インサート部材であってもよい。 (Parts containing polycarbonate resin)
The portion containing polycarbonate resin can be obtained by injection molding polycarbonate resin. The portion containing polycarbonate resin may be a primary molded article of polycarbonate resin that is molded prior to two-color molding. The portion containing the polycarbonate resin may be an insert member.
　ポリカーボネート樹脂を含む部分は、ポリカーボネート樹脂の含有量が７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましく、９５質量％であることがよりさらに好ましい。 The content of the polycarbonate resin in the portion containing the polycarbonate resin is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and 95% by mass. is even more preferable.
　ポリカーボネート樹脂としては、ジヒドロキシ化合物と、ホスゲン又はジフェニルカーボネート等の炭酸エステルと、の反応により得られる重合体が挙げられる。ジヒドロキシ化合物、並びに、ホスゲン又はジフェニルカーボネート等の炭酸エステルとしては、特に限定されず、例えば、上記した二色成形用樹脂組成物に加えることができる（Ｃ）ポリカーボネート樹脂で説明したものから選択して用いることができる。 Polycarbonate resins include polymers obtained by reacting dihydroxy compounds with phosgene or carbonic acid esters such as diphenyl carbonate. The dihydroxy compound and the carbonate ester such as phosgene or diphenyl carbonate are not particularly limited, and can be added to the two-color molding resin composition described above. can be used.
　ポリカーボネート樹脂は、二色成形用樹脂組成物に加えることができる（Ｃ）ポリカーボネート樹脂と同じ組成のものを使用することができ、異なる組成のものを使用することもできる。
　ポリカーボネート樹脂の粘度平均分子量、及び溶融粘度（ＩＳＯ１１４４３に準拠した、３００℃、１０００ｓｅｃ－１での溶融粘度）は、特に限定されず、例えば上記した樹脂組成物に加えることができる（Ｃ）ポリカーボネート樹脂で説明したものと同様にすることができる。 The polycarbonate resin may have the same composition as (C) the polycarbonate resin that can be added to the resin composition for two-color molding, or may have a different composition.
The viscosity-average molecular weight and melt viscosity of the polycarbonate resin (melt viscosity at 300° C. and 1000 sec −1 in accordance with ISO 11443) are not particularly limited, and for example, (C) polycarbonate resin can be added to the resin composition described above. can be similar to that described in
　ポリカーボネート樹脂には、必要に応じて、無機充填剤、エラストマーを含有してもよく、さらに酸化防止剤、安定剤、分子量調整剤、紫外線吸収剤、帯電防止剤、着色剤、潤滑剤、離型剤、結晶化促進剤、結晶核剤、赤外線吸収剤、難燃剤、難燃助剤、耐加水分解性向上剤、流動性改良剤等の添加剤を含有してもよい。添加剤の添加量は、ポリカーボネート樹脂１００質量部に対して０．１～２０質量部とすることができる。 If necessary, the polycarbonate resin may contain inorganic fillers and elastomers, and may further contain antioxidants, stabilizers, molecular weight modifiers, ultraviolet absorbers, antistatic agents, colorants, lubricants, and release agents. Additives such as a crystallization accelerator, a crystal nucleating agent, an infrared absorber, a flame retardant, a flame retardant auxiliary, a hydrolysis resistance improver, and a fluidity improver may be contained. The amount of the additive added can be 0.1 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin.
　ポリカーボネート樹脂を含む部分は、二色成形用樹脂組成物との二色成形時の密着性をより高めるために、表面の少なくとも一部にアンカー構造を有していることが好ましい。
　アンカー構造は、ポリカーボネート樹脂成形品表面の突起、孔、くぼみなどのアンダーカットにより形成することができる。 The portion containing the polycarbonate resin preferably has an anchor structure on at least a part of the surface in order to further enhance the adhesion to the resin composition for two-color molding during two-color molding.
The anchor structure can be formed by undercuts such as protrusions, holes, and depressions on the surface of the polycarbonate resin molded product.
　ポリカーボネート樹脂を含む部分、二色成形用樹脂組成物を含む部分、及び二色成形品全体の大きさ及び形状は、限定されず、用途に応じた大きさ及び形状とすることができる。
　ポリカーボネート樹脂を含む部分と前記樹脂組成物を含む部分とが板状である場合、ポリカーボネート樹脂を含む部分の一辺と樹脂組成物を含む部分の一辺とが接していてもよい。樹脂組成物を含む部分がポリカーボネートを含む部分の周囲の少なくとも一部（又は全体）を取り囲んでいてもよい。 The size and shape of the portion containing the polycarbonate resin, the portion containing the resin composition for two-color molding, and the entire two-color molded article are not limited, and can be set according to the application.
When the portion containing the polycarbonate resin and the portion containing the resin composition are plate-shaped, one side of the portion containing the polycarbonate resin may be in contact with one side of the portion containing the resin composition. The portion containing the resin composition may surround at least a portion (or the entirety) of the portion containing the polycarbonate.
　一実施形態において、成形品は、二色成形品である。「二色成形品」は、ここでは、ポリカーボネート樹脂と上記した二色成形用樹脂組成物とが二色成形法により射出成形された成形品のことを意味している。二色成形品であることは、二色成形品における樹脂組成物を含む部分とポリカーボネート樹脂を含む部分とが、接着層やねじ等を介さずに、少なくとも一部が接するように一体的に成形されていることで区別することができる。また、二色成形品は、接合面に超音波溶着や振動溶着などによる摺動跡や摩耗粉又はバリがないことや、レーザー溶着などによる溶融プール跡などがないことにより区別することができる。 In one embodiment, the molded article is a two-color molded article. The term "two-color molded article" as used herein means a molded article obtained by injection-molding a polycarbonate resin and the above-described resin composition for two-color molding by a two-color molding method. Being a two-color molded product means that the part containing the resin composition and the part containing the polycarbonate resin in the two-color molded product are integrally molded so that at least a part is in contact without an adhesive layer, screws, etc. It can be distinguished by being A two-color molded product can be distinguished by having no traces of sliding, wear powder, or burrs due to ultrasonic welding, vibration welding, or the like on the joint surface, or traces of molten pools due to laser welding, or the like.
　成形品の製法は、二色成形であることが好ましく、例えば、予めポリカーボネート樹脂を射出成形して得た一次成形品（ポリカーボネート樹脂成形品）を金型キャビティ内に配置した状態で、当該ポリカーボネート樹脂成形品の少なくとも一部に接するように二色成形用樹脂組成物を射出成形して成形品を得ることができる。 The molded product is preferably manufactured by two-color molding. For example, a primary molded product (polycarbonate resin molded product) obtained by injection molding polycarbonate resin in advance is placed in a mold cavity, and the polycarbonate resin is molded. A molded article can be obtained by injection-molding the resin composition for two-color molding so as to be in contact with at least a part of the molded article.
　一実施形態において、成形品は、さらに金属（合金）及び／又は無機固体からなるインサート部材とともに射出成形して得られるインサート成形品とすることもできる。金属（合金）及び／又は無機固体の材質は限定されない。
　インサート成形品の製法は特に限定されない。例えば、予めポリカーボネート樹脂を射出成形して得た一次成形品（ポリカーボネート樹脂部材）を、金属及び／又は無機固体からなるインサート部材とともに金型キャビティ内に配置した状態で、当該ポリカーボネート樹脂成形品及びインサート部材上にポリブチレンテレフタレート樹脂組成物を射出成形して二色成形品を得ることができる。
　また、ポリカーボネート樹脂成形品を射出成形する際に金型キャビティ内に金属及び／又は無機固体からなるインサート部材を配置してインサート部材上にポリカーボネート樹脂を射出成形することにより、インサート部材を有するポリカーボネート樹脂成形品を得た後、当該インサート部材を有するポリカーボネート樹脂成形品を金型キャビティ内に配置した状態で、ポリブチレンテレフタレート樹脂組成物を射出成形することにより二色成形品を得ることもできる。 In one embodiment, the molded product can also be an insert molded product obtained by injection molding together with an insert member made of a metal (alloy) and/or an inorganic solid. The material of the metal (alloy) and/or inorganic solid is not limited.
The manufacturing method of the insert-molded product is not particularly limited. For example, a primary molded product (polycarbonate resin member) obtained by injection molding a polycarbonate resin in advance is placed in a mold cavity together with an insert member made of a metal and / or an inorganic solid, and the polycarbonate resin molded product and the insert are placed in the mold cavity. A two-color molded article can be obtained by injection-molding the polybutylene terephthalate resin composition onto the member.
Further, when a polycarbonate resin molded product is injection molded, an insert member made of a metal and/or an inorganic solid is placed in the mold cavity and the polycarbonate resin is injection molded on the insert member to obtain a polycarbonate resin having an insert member. After obtaining the molded article, a two-color molded article can be obtained by injection molding a polybutylene terephthalate resin composition in a state in which the polycarbonate resin molded article having the insert member is placed in the mold cavity.
　一実施形態において、二色成形品の接合強度（初期強度）が、２０ＭＰａを超えていることが好ましく、２０．６ＭＰａ以上であることがより好ましい。初期強度が２０ＭＰａを超えていると、接合強度に優れた二色成形品とすることができる。 In one embodiment, the joint strength (initial strength) of the two-color molded product preferably exceeds 20 MPa, more preferably 20.6 MPa or more. When the initial strength exceeds 20 MPa, a two-color molded article having excellent bonding strength can be obtained.
　一実施形態において、二色成形品の、温度１２１℃、湿度１００％、２０３ｋＰａの水蒸気環境下で２４時間処理し、温度２３℃、湿度５０％で２４時間放置する湿熱処理後の接合強度が、前記湿熱処理前の接合強度に対して、２０％を超えることが好ましく、４０％以上であることがより好ましく、５０％以上であることがさらに好ましく、７０％以上であることがよりさらに好ましい。成形品は、湿熱処理前の引張強さに対する湿熱処理後の引張強さの割合（引張強さの保持率）が２０％を超えるので、湿熱環境で使用された場合の強度の低下を抑制することができる。 In one embodiment, the two-color molded product is treated for 24 hours in a water vapor environment at a temperature of 121 ° C., a humidity of 100%, and 203 kPa, and the bonding strength after the wet heat treatment is left for 24 hours at a temperature of 23 ° C. and a humidity of 50%. It is preferably more than 20%, more preferably 40% or more, even more preferably 50% or more, and even more preferably 70% or more of the bonding strength before the wet heat treatment. The molded product has a ratio of tensile strength after wet heat treatment to tensile strength before wet heat treatment (tensile strength retention rate) exceeds 20%, so it suppresses a decrease in strength when used in a hot and humid environment. be able to.
　本実施形態に係る成形品は、自動車部品、電気・電子部品等の種々の用途において使用することができる。特に、この二色成形品は、湿熱環境下で使用されても強度が低下することを抑制することができるので、自動車部品として好ましく用いることができる。 The molded product according to this embodiment can be used in various applications such as automobile parts, electric/electronic parts, and the like. In particular, this two-color molded article can be preferably used as an automobile part because it can suppress a decrease in strength even when used in a hot and humid environment.
　以下に実施例を示して本発明を更に具体的に説明するが、これらの実施例により本発明の解釈が限定されるものではない。 Although the present invention will be described more specifically by showing examples below, the interpretation of the present invention is not limited by these examples.
［使用原料］
　実施例及び比較例で使用した原料を以下に示す。
　Ａ：ポリブチレンテレフタレート樹脂（ポリプラスチックス株式会社製、固有粘度（ＩＶ）：０．８８ｄＬ／ｇ）
　Ｂ－ｉ：住友化学株式会社製「ボンドファースト（登録商標）７Ｌ」、共重合成分として、エチレンを７０質量％、メタクリル酸グリシジルエステルを３質量％、及びアクリル酸メチルを２７質量％含む。
　Ｂ－ｉｉ：住友化学株式会社製「ボンドファースト（登録商標）２Ｃ」、共重合成分として、エチレンを９４質量％、メタクリル酸グリシジルエステルを６質量％含む。
　Ｂ－ｉｉｉ：住友化学株式会社製「ボンドファースト（登録商標）Ｅ」、共重合成分として、エチレンを８８質量％、メタクリル酸グリシジルエステルを１２質量％含む。
　Ｂ－ｉｖ：日油株式会社製、エチレンエチルアクリレート（主鎖）とブチルアクリレート－メチルメタクリレート（側鎖）のグラフト共重合体
　Ｂ－ｖ：ＥＮＥＯＳ　ＮＵＣ社製、エチレンエチルアクリレート共重合体、「ＮＵＣ（登録商標）－６５７０」
　Ｃ：ポリカーボネート樹脂（帝人株式会社製、溶融粘度：０．２７ｋＰａ・ｓ）
　Ｄ：ガラス繊維（日本電気硝子株式会社製、ＥＣＳ０３Ｔ－１２７）
　Ｅ：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル社製　１００４Ｋ） [raw materials used]
Raw materials used in Examples and Comparative Examples are shown below.
A: Polybutylene terephthalate resin (manufactured by Polyplastics Co., Ltd., intrinsic viscosity (IV): 0.88 dL / g)
Bi: "Bond First (registered trademark) 7L" manufactured by Sumitomo Chemical Co., Ltd., containing 70% by mass of ethylene, 3% by mass of glycidyl methacrylate, and 27% by mass of methyl acrylate as copolymer components.
B-ii: “Bond First (registered trademark) 2C” manufactured by Sumitomo Chemical Co., Ltd., containing 94% by mass of ethylene and 6% by mass of glycidyl methacrylate as copolymer components.
B-iii: “Bond First (registered trademark) E” manufactured by Sumitomo Chemical Co., Ltd., containing 88% by mass of ethylene and 12% by mass of glycidyl methacrylate as copolymer components.
B-iv: NOF Corporation, ethylene ethyl acrylate (main chain) and butyl acrylate-methyl methacrylate (side chain) graft copolymer B-v: ENEOS NUC Co., ethylene ethyl acrylate copolymer, "NUC (Registered Trademark)-6570”
C: Polycarbonate resin (manufactured by Teijin Limited, melt viscosity: 0.27 kPa s)
D: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-127)
E: Bisphenol A type epoxy resin (1004K manufactured by Mitsubishi Chemical Corporation)
［実施例１～１１、比較例１～５］
（二色成形用樹脂組成物の作製）
　表１、２に示す割合で原料を混合し、二軸押出機（日本製鋼所製ＴＥＸ３０）を用いて、シリンダー温度２６０℃、スクリュ回転１３０ｒｐｍで溶融混練して押出し、実施例１～１１、比較例１～５の樹脂組成物（二色成形用樹脂組成物）を作製した。 [Examples 1 to 11, Comparative Examples 1 to 5]
(Preparation of resin composition for two-color molding)
The raw materials were mixed at the ratios shown in Tables 1 and 2, and melt-kneaded and extruded using a twin-screw extruder (TEX30, manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 260 ° C. and a screw rotation of 130 rpm. Resin compositions of Examples 1 to 5 (resin compositions for two-color molding) were prepared.
（ポリカーボネート樹脂部材の作製）
　ポリカーボネート樹脂を１２０℃で５時間乾燥させた後、シリンダー温度２８５℃、金型温度９０℃の条件で短冊状試験片（５０ｍｍ×１０ｍｍ×厚さ２ｍｍ）を作製し、その後２３℃、５０％ＲＨで２４時間放置した。 (Production of polycarbonate resin member)
After drying the polycarbonate resin at 120 ° C. for 5 hours, a strip-shaped test piece (50 mm × 10 mm × thickness 2 mm) was prepared under the conditions of a cylinder temperature of 285 ° C. and a mold temperature of 90 ° C., then 23 ° C., 50% RH. and left for 24 hours.
（二色成形品の試験片の作製）
　上記で得られたポリカーボネート樹脂の短冊状試験片（ポリカーボネート樹脂部材）をインサート部材として金型内に配し、上記で得られた二色成形用樹脂組成物を用いてシリンダー温度２８５℃、金型温度９０℃にてインサート成形し、図１に示す形状を有する二色成形品の試験片を作製した。
　図１に示すように、試験片１０は、ポリカーボネート樹脂を含む部分１の大きさが５０ｍｍ×１０ｍｍ×厚さ２ｍｍであり、二色成形用樹脂組成物を含む部分２の大きさが５０ｍｍ×１０ｍｍ×厚さ２ｍｍであり、ポリカーボネート樹脂を含む部分と二色成形用樹脂組成物を含む部分とが一つの接合面で接して一体的に形成されている。試験片１０の全体の大きさは、１００ｍｍ×１０ｍｍ×厚さ２ｍｍである。 (Preparation of test piece of two-color molded product)
The strip-shaped test piece (polycarbonate resin member) of the polycarbonate resin obtained above was placed in the mold as an insert member, and the resin composition for two-color molding obtained above was used at a cylinder temperature of 285 ° C. and the mold Insert molding was performed at a temperature of 90° C. to prepare a test piece of a two-color molded product having the shape shown in FIG. 1 .
As shown in FIG. 1, the test piece 10 has a portion 1 containing polycarbonate resin with a size of 50 mm × 10 mm × thickness 2 mm, and a portion 2 containing the resin composition for two-color molding with a size of 50 mm × 10 mm. × 2 mm in thickness, and the portion containing the polycarbonate resin and the portion containing the resin composition for two-color molding are integrally formed in contact with each other at one joint surface. The overall size of the test piece 10 is 100 mm x 10 mm x 2 mm thick.
［評価］
　上記で得られた二色成形用樹脂組成物、及び二色成形品について、以下の評価を行った。結果を表１，２に示す。 [evaluation]
The resin composition for two-color molding and the two-color molding obtained above were evaluated as follows. Tables 1 and 2 show the results.
（樹脂組成物の溶融粘度）
　二色成形用樹脂組成物を、東洋精機製キャピログラフを用い、φ１ｍｍ×２０ｍｍのフラットダイのキャピラリーを用いて、バレル温度２６０℃、滞留時間９分にて、せん断速度１０００ｓｅｃ－１での溶融粘度を測定した。 (Melt viscosity of resin composition)
A resin composition for two-color molding is used with a Toyo Seiki Capilograph, using a flat die capillary of φ 1 mm × 20 mm, at a barrel temperature of 260 ° C., a residence time of 9 minutes, and a shear rate of 1000 sec -1 . It was measured.
（二色成形品の初期強度）
　上記で得られた二色成形品の試験片を、万能試験機を用いて、つかみ具間距離５０ｍｍ、速度５ｍｍ／ｍｉｎで引張試験を行い、破断時の最大応力を接合強度として測定し初期強度とした。 (Initial strength of two-color molded product)
A test piece of the two-color molded product obtained above is subjected to a tensile test using a universal testing machine at a distance between grips of 50 mm and a speed of 5 mm / min. and
（二色成形品の湿熱処理後の強度）
　上記試験片を、滅菌機を用いて１２１℃、１００％ＲＨ、２０３ｋＰａの水蒸気環境で２４時間湿熱処理し、温度２３℃、湿度５０％で２４時間放置した（湿熱処理）。その後、万能試験機を用いて、つかみ具間距離５０ｍｍ、速度５ｍｍ／ｍｉｎで引張試験を行い、破断時の最大応力を接合強度として測定した。初期強度に対する前記接合強度の割合を算出し、湿熱処理後の強度保持率（％）とした。 (Strength after wet heat treatment of two-color molded product)
Using a sterilizer, the test piece was subjected to wet heat treatment in a steam environment of 121° C., 100% RH, and 203 kPa for 24 hours, and left at a temperature of 23° C. and a humidity of 50% for 24 hours (wet heat treatment). Thereafter, using a universal testing machine, a tensile test was performed at a gripper distance of 50 mm and a speed of 5 mm/min, and the maximum stress at breakage was measured as the bonding strength. The ratio of the bonding strength to the initial strength was calculated and used as the strength retention rate (%) after wet heat treatment.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１に示すように、（Ｂ）オレフィン系共重合体としての組成を満たす共重合体Ｂ－ｉ～Ｂ－ｉｖを、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対し２～３５質量部含む実施例１～１１の樹脂組成物は、ポリカーボネート樹脂部材との二色成形品とした場合に、初期強度に対する湿熱処理後の強度の保持率が２０％を超えており、湿熱処理後の強度の低下を抑制することができる。また、この二色成形品は、初期強度が２０ＭＰａを超えており高い接合強度を実現できている。 As shown in Table 1, 2 to 35 parts by mass of (B) copolymers Bi to B-iv satisfying the composition as an olefinic copolymer is contained with respect to 100 parts by mass of (A) polybutylene terephthalate resin. When the resin compositions of Examples 1 to 11 were formed into a two-color molded product with a polycarbonate resin member, the retention rate of the strength after the wet heat treatment with respect to the initial strength exceeded 20%, and the strength after the wet heat treatment. Decrease can be suppressed. In addition, this two-color molded article has an initial strength of over 20 MPa, and a high bonding strength can be achieved.
　表２に示すように、オレフィン系共重合体を含まない比較例１の樹脂組成物は、二色成形品の初期強度は２０ＭＰａを超えているものの、初期強度に対する湿熱処理後の強度の保持率が０％（湿熱処理後の二色成形品が既に剥離している、もしくは引張試験においてチャッキング時に剥離、または接合強度が０ＭＰaのことをいう）であり、湿熱処理後の強度の低下を抑制することができない。
　オレフィン系共重合体としてエチレンエチルアクリレート共重合体を使用した比較例２，４では、二色成形品の初期強度が２０ＭＰａ未満であるとともに、初期強度に対する湿熱処理後の強度の保持率が０％であり湿熱処理後の強度の低下を抑制することができない。ポリエステル樹脂の加水分解抑制に効果のあるエポキシ樹脂Ｅを添加してもその傾向を改善することができなかった（比較例４）。
　（Ｂ）オレフィン系共重合体に替えてエポキシ樹脂を用いた比較例３の樹脂組成物は、初期強度は２０ＭＰａを超えているものの、初期強度に対する湿熱処理後の強度の保持率が０％であり、湿熱処理後の強度の低下を抑制することができない。
　（Ｂ）オレフィン系共重合体としての組成を満たす共重合体Ｂ－ｉｉｉを用いた場合でも、その含有量が（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対し２質量部未満であると、初期強度は２０ＭＰａを超えているものの、初期強度に対する湿熱処理後の強度の保持率が０％であり、湿熱処理後の強度の低下を抑制することができない。 As shown in Table 2, the resin composition of Comparative Example 1, which does not contain an olefin copolymer, has an initial strength of two-color molded article exceeding 20 MPa, but the retention rate of strength after wet heat treatment relative to the initial strength. is 0% (meaning that the two-color molded product after wet heat treatment has already peeled, or peeled during chucking in a tensile test, or the bonding strength is 0 MPa), suppressing the decrease in strength after wet heat treatment. Can not do it.
In Comparative Examples 2 and 4, in which an ethylene ethyl acrylate copolymer was used as the olefin-based copolymer, the initial strength of the two-color molded article was less than 20 MPa, and the retention of strength after wet heat treatment relative to the initial strength was 0%. Therefore, the decrease in strength after wet heat treatment cannot be suppressed. Even if epoxy resin E, which is effective in suppressing hydrolysis of polyester resin, was added, this tendency could not be improved (Comparative Example 4).
(B) The resin composition of Comparative Example 3, in which an epoxy resin was used instead of the olefin-based copolymer, had an initial strength of more than 20 MPa, but the retention of strength after wet heat treatment relative to the initial strength was 0%. Therefore, the decrease in strength after wet heat treatment cannot be suppressed.
(B) Even when the copolymer B-iii that satisfies the composition as the olefinic copolymer is used, if the content is less than 2 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, the initial Although the strength exceeds 20 MPa, the retention rate of the strength after the wet heat treatment relative to the initial strength is 0%, and the decrease in the strength after the wet heat treatment cannot be suppressed.
　本実施形態に係る二色成形用樹脂組成物は、ポリカーボネート樹脂部材との二色成形品の強度低下を抑制することができるため、自動車部品、電気・電子部品等の種々の用途に利用することができ、産業上の利用可能性を有している。 Since the resin composition for two-color molding according to the present embodiment can suppress a decrease in the strength of a two-color molded product with a polycarbonate resin member, it can be used for various applications such as automobile parts, electric and electronic parts. and has industrial applicability.
１０　試験片
１　　ポリカーボネート樹脂を含む部分
２　　二色成形用樹脂組成物を含む部分 10 Test piece 1 Portion containing polycarbonate resin 2 Portion containing resin composition for two-color molding

Claims (8)

  1. 　ポリカーボネート樹脂部材との二色成形用樹脂組成物であり、
    　樹脂組成物が、
    　（Ａ）ポリブチレンテレフタレート樹脂と、（Ｂ）オレフィン系共重合体と、を含み、
    　（Ｂ）オレフィン系共重合体が、
    　（Ｂ１）α－オレフィン単量体単位とα，β－不飽和カルボン酸グリシジルエステル単量体単位とを含む共重合体；及び
    　（Ｂ２）α－オレフィン単量体単位とα，β－不飽和カルボン酸アルキルエステル単量体単位とを含む共重合体を主鎖として含み、及び、α，β－不飽和カルボン酸アルキルエステル単量体単位を含む重合体を側鎖として含むグラフト共重合体；
    から選択される１以上を含み、
    　（Ｂ）オレフィン系共重合体の含有量が、（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対し２～３５質量部である、ポリカーボネート樹脂部材との二色成形用樹脂組成物。     A resin composition for two-color molding with a polycarbonate resin member,
    The resin composition
    (A) a polybutylene terephthalate resin and (B) an olefin-based copolymer,
    (B) the olefin-based copolymer is
    (B1) a copolymer containing an α-olefin monomer unit and an α,β-unsaturated carboxylic acid glycidyl ester monomer unit; and (B2) an α-olefin monomer unit and α,β-unsaturation a graft copolymer containing as a main chain a copolymer containing a carboxylic acid alkyl ester monomer unit, and a polymer containing an α,β-unsaturated carboxylic acid alkyl ester monomer unit as a side chain;
    including one or more selected from
    (B) A resin composition for two-color molding with a polycarbonate resin member, wherein the content of the olefin copolymer is 2 to 35 parts by mass based on 100 parts by mass of the (A) polybutylene terephthalate resin.
  2. 　（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して１～９０質量部の（Ｃ）ポリカーボネート樹脂をさらに含む、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, further comprising 1 to 90 parts by mass of (C) a polycarbonate resin per 100 parts by mass of (A) polybutylene terephthalate resin.
  3. 　（Ｂ１）α－オレフィン単量体単位とα，β－不飽和カルボン酸のグリシジルエステル単量体単位とを含む共重合体中のグリシジルエステル単量体単位の含有量が、２～１５質量％である、請求項１又は２に記載の樹脂組成物。 (B1) The content of glycidyl ester monomer units in the copolymer containing α-olefin monomer units and α,β-unsaturated carboxylic acid glycidyl ester monomer units is 2 to 15% by mass. The resin composition according to claim 1 or 2, which is
  4. 　（Ａ）ポリブチレンテレフタレート樹脂の、ｏ－クロロフェノール中、温度３５℃で測定した固有粘度が０．６５～１．１５ｄＬ／ｇである、請求項１から３のいずれか一項に記載の樹脂組成物。 The resin according to any one of claims 1 to 3, wherein (A) the polybutylene terephthalate resin has an intrinsic viscosity of 0.65 to 1.15 dL/g measured in o-chlorophenol at a temperature of 35°C. Composition.
  5. 　（Ａ）ポリブチレンテレフタレート樹脂１００質量部に対して０～８０質量部の（Ｄ）無機充填剤をさらに含む、請求項１から４のいずれか一項に記載の樹脂組成物。 (A) The resin composition according to any one of claims 1 to 4, further comprising 0 to 80 parts by mass of (D) an inorganic filler with respect to 100 parts by mass of polybutylene terephthalate resin.
  6. 　溶融粘度が０．６ＫＰａ・ｓ以下である、請求項１から５のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, which has a melt viscosity of 0.6 KPa·s or less.
  7. 　ポリカーボネート樹脂を含む部分と、請求項１から６のいずれか一項に記載の樹脂組成物を含む部分とを有し、ポリカーボネート樹脂を含む部分と前記樹脂組成物を含む部分とが少なくとも一部で接して一体化されている、成形品。 A part containing a polycarbonate resin and a part containing the resin composition according to any one of claims 1 to 6, wherein at least a part of the part containing the polycarbonate resin and the part containing the resin composition A molded product that is in contact and integrated.
  8. 　自動車部品である、請求項７に記載の成形品。 The molded article according to claim 7, which is an automobile part.
PCT/JP2022/030924 2021-08-16 2022-08-16 Resin composition for double molding and molded article of same WO2023022139A1 (en)

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