JP2006063110A - Resin composition for molded products - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a molded article, containing mainly a thermoplastic resin improved with its mechanical properties. <P>SOLUTION: This resin composition is characterized by containing 100 pts. mass thermoplastic resin and 0.1-20 pts. mass epoxy resin expressed by formula (I) [wherein, (n) is 0.1 to 30 real number; R<SB>1</SB>, R<SB>2</SB>are each independently H, or a 1-5C substituted or non-substituted alkyl or alkoxy; R<SB>3</SB>, R<SB>4</SB>are each independently a 1-5C alkyl; (p), (q) are each independently an integer of 0-4; and X is H or a glycidyl group provided that ≥20% of the X is the glycidyl group]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition for molded articles, and more particularly, to a resin composition for molded articles that can be provided with a molded article that is made of a thermoplastic resin and a specific epoxy resin and has excellent physical properties.

  Thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, thermoplastic resins such as polycarbonate resin and polyamide resin, and styrene resins such as ABS resin can be molded by various processing methods. Used for.

  However, when these thermoplastic resins are used alone, the obtained physical properties such as mechanical properties and heat resistance are often unsatisfactory. For this reason, attempts have been made to improve physical properties by using a polymer alloy obtained by combining two or more kinds of resins, or by adding a reinforcing agent such as glass fiber.

  It is also known to add an ethylene copolymer having an epoxy group to improve the impact resistance of engineering plastics. For example, Patent Document 1 proposes adding a copolymer comprising an α-olefin, glycidyl methacrylate and vinyl acetate to a polyester resin, and Patent Document 2 proposes adding an α-olefin and glycidyl (meta) to a polycarbonate. It has been proposed to add copolymers with acrylates, but no satisfactory performance has yet been obtained.

  On the other hand, Patent Document 3 and Patent Document 4 propose an aqueous resin composition containing a bisphenol-type epoxy resin in which a part or all of secondary hydroxyl groups are glycidyl etherified. Is only described for use as a glass fiber sizing agent or paint.

  Japanese Patent Application No. 2003-400295 proposes a resin composition with improved adhesion, which is obtained by blending a specific epoxy resin with a polyphenylene sulfide resin.

JP-A-52-32045 JP 57-125253 A JP 2001-151857 A JP 2002-88229 A

  An object of the present invention is to provide a resin composition for molded articles, which is mainly composed of a thermoplastic resin and has improved mechanical properties.

  The present invention comprises 100 parts by mass of a thermoplastic resin excluding polyphenylene sulfide resin and 0.1 to 20 parts by mass of an epoxy resin represented by the following general formula (I). The object is achieved by providing a product.

（式中、ｎは０．１乃至３０の実数を表し、Ｒ₁ およびＲ₂ は、独立的に水素原子または置換もしくは非置換の炭素原子数１乃至５のアルキル基もしくはアルコキシ基であり、Ｒ₃ およびＲ₄ は、独立的に炭素原子数１乃至５のアルキル基であり、ｐおよびｑは、独立的に０または１〜４の整数を表し、Ｘは水素原子またはグリシジル基を表すが、Ｘの２０％以上はグリシジル基を表す。）

(In the formula, n represents a real number of 0.1 to 30, R ₁ and R ₂ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group or alkoxy group having 1 to 5 carbon atoms; ₃ and R ₄ are each independently an alkyl group having 1 to 5 carbon atoms, p and q independently represent 0 or an integer of 1 to 4, and X represents a hydrogen atom or a glycidyl group, 20% or more of X represents a glycidyl group.)

  Since the composition for molded products of the present invention is excellent in mechanical properties, adhesiveness, and colorability, it can be suitably used as various molded products.

  Hereinafter, the present invention will be described in more detail.

  First, the thermoplastic resin used in the present invention will be described. The thermoplastic resin is a thermoplastic resin excluding a polyphenylene sulfide resin. For example, a polyolefin resin, a vinyl chloride resin, a thermoplastic polyester resin, a styrene resin, a polycarbonate resin, a polyamide resin, a polyacetal resin, a polyphenylene ether resin. , Acrylic resin, fluorine resin, polyvinyl alcohol resin, polyallylsulfone resin, polysulfone resin, polyethersulfone resin, polyarylate resin, polyetherimide resin, polyphenylenesulfate resin, poly-p-oxybenzoate resin, polyetherether Examples thereof include ketone resins, polyaryl ketone resins, polyamideimide resins, and polyoxymethylene resins. Mixtures of these can also be used.

  Examples of the polyolefin resin include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, ethylene / vinyl acetate copolymer, polymethylpentene, polybutene-1, poly-3-methylbutene, and poly- Α-olefin homopolymers or copolymers such as 3-methylpentene, ethylene / propylene blocks or random copolymers, polyunsaturated compounds such as these α-olefins and conjugated or nonconjugated dienes, acrylic acid, Examples thereof include copolymers with methacrylic acid and vinyl acetate.

  The vinyl chloride resin is not particularly limited to polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. For example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinyl chloride, chlorination Polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer Polymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile solution, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene Copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester Copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers and other vinyl chloride resins, and their blends or other chlorines. Synthetic resins not containing, for example, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blends with polyester, block Examples thereof include a copolymer and a graft copolymer.

Examples of the thermoplastic polyester resin include one or a mixture of two or more dicarboxylic acid components such as terephthalic acid and naphthalenedicarboxylic acid, and mainly ethylene glycol, propylene glycol, butylene glycol, 1,4-hexanedimethanol, and the like. Examples thereof include those obtained from one or a mixture of two or more glycol components.
Examples of copolymer components other than the above include isophthalic acid, phthalic acid, tetrabromophthalic acid, tetrabromoterephthalic acid, methyl isophthalic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, phenylene diacetic acid, Dicarboxylic acids such as oxalic acid, succinic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, dodecadioic acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; diethylene glycol, polyethylene glycol , Polypropylene glycol, neopentyl glycol, xylylene glycol and the like; hydroquinone, resorcin, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) Bisphenols such as phenyl) sulfone; ethylene oxide / propylene oxide adducts of bisphenols; oxycarboxylic acids such as oxybenzoic acid, oxyethoxybenzoic acid, oxynaphthoic acid, and glycolic acid.
Further, as the branching component, for example, tricarballylic acid, trimesic acid, trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, pentalit and the like may be copolymerized in a small amount.

  Examples of the styrenic resin include polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile butadiene styrene (ABS) resin, chlorinated polyethylene acrylonitrile styrene (ACS) resin, styrene acrylonitrile (SAN) resin, and acrylonitrile butyl acrylate styrene (AAS). Examples thereof include styrene polymer compounds such as resins, butadiene styrene resins, styrene maleic resins, styrene maleimide resins, ethylene propylene acrylonitrile styrene (AES) resins, and butadiene methyl styrene (MBS) resins.

  The polyamide resin is not particularly limited in its production method and structure, and is a polymer obtained by a conventional method from dicarboxylic acid, diamine and carboxylic acid amine, and lactams such as ε-caprolactam and ω-laurolactam. , 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, carboxylic acid amines such as p-aminobenzoic acid, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodeca Diamines such as methylenediamine, m-xylylenediamine, p-xylylenediamine, o-phenylenediamine, p-phenylenediamine, bis (aminopropyl) piperazine, adipic acid, peric acid, azelaic acid, sebacic acid, dodecane Examples of the monomer include dicarboxylic acids such as diacid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Examples of polyamides produced by combining these monomers include nylon 6, nylon 12, nylon 46, nylon 66, and the like.

  The polycarbonate resin is preferably a polymer carbonate of bisphenols. Examples of the bisphenol used here include bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) 2,2-bis (4-hydroxy-). 3-methylphenyl) propane, 4,4-bis (hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2bis (4-hydroxy-3,5-dibromo Alkane bisphenols such as phenyl) propane; divalent phenol ethers such as bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether; p, p′-dihydroxybiphenyl 3,3′-dichloro-4,4′-dihydroxybiphenyl, etc. Dihydroxybiphenyls such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, etc .; 1,4-dihydroxy-2,5-dichlorobenzene, 1, Dihydroxybenzenes such as 4-dihydroxy-3-methylbenzene; resorcinol, hydroquinone, halo and alkyl substituted dihydroxybenzenes, and bis (4-hydroxyphenyl) sulfoxide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide Dihydroxyphenyl sulfoxide such as Various bisphenols and trisphenols other than those described above are also used to obtain the polycarbonate resin. Furthermore, in order to prepare the said polycarbonate resin, the mixture of the material illustrated above can also be used.

  These thermoplastic aromatic polycarbonate resins are prepared, for example, by reacting a dihydric phenol and a carbonate precursor. As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used. Examples of the carbonyl halide include carbonyl bromide, carbonyl chloride, and mixtures thereof. Examples of the carbonate ester include diphenyl carbonate, di (chlorophenyl) carbonate, ditolyl carbonate, dinaphthyl carbonate, and mixtures thereof. Examples of the haloformate include divalent phenol haloformates such as hydroquinone bischloroformate and glycol haloformates such as ethylene glycol haloformate. Of these, carbonyl chloride, known as phosgene, is particularly preferred.

  The thermoplastic aromatic polycarbonate resin is prepared using a molecular weight modifier and an acid acceptor. Examples of the molecular weight modifier include phenol, cyclohexanol, methanol, p-tert-butylphenol, p-bromophenol, and preferably p-tert-butylphenol is used. Examples of the acid acceptor include an organic or inorganic acid acceptor. Examples of the organic acid acceptor include pyridine, triethylamine, and dimethylaniline. Examples of the inorganic acid acceptor include alkali or alkaline earth metal. Any one of hydroxides, carbonates, bicarbonates or phosphates is used.

  Among the thermoplastic resins described above, aromatic polyester resins, polycarbonate resins, styrene resins, and polyamide resins are preferred as the thermoplastic resin used in the present invention.

Next, the epoxy resin represented by the general formula (I) used in the present invention will be described. In the general formula (I), examples of the alkyl group having 1 to 5 carbon atoms represented by R _{1 to} R ₄ include groups such as methyl, ethyl, propyl, and butyl. R ₁ and R ₂ Examples of the alkoxy group having 1 to 5 carbon atoms represented by: methoxy, ethoxy, propoxy, butoxy and the like.

  N is a real number of 0.1 to 30, preferably 1 to 15. X represents a hydrogen atom or a glycidyl group, and 20 to 100% of X must be a glycidyl group, and particularly preferably 25 to 100% is a glycidyl group. Here, the real number represented by n and the ratio of the glycidyl group in X (hereinafter referred to as re-epoxidation rate) both represent average values. When n is less than 0.1 or less than 20% of X is a glycidyl group, the content of the trifunctional or higher polyfunctional epoxy compound is reduced, so that the curability and coating film properties can be satisfied. I can't get it.

In the general formula (I), the epoxy resin represented by the general formula (I) is such that R ₁ and R ₂ are both hydrogen atoms or both methyl groups, p and q are both 0, n Is a real number from 1 to 15.

  The epoxy resin represented by the general formula (I) used in the present invention is not limited by its production method. For example, a general-purpose bisphenol-based epoxy resin represented by the following chemical formula 2 and epichlorohydrin Can be produced by polymerization.

（式中、ｎ、Ｒ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、ｐおよびｑは、前記一般式（Ｉ）中のｎ、Ｒ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、ｐおよびｑと同じである。）

_{(Wherein, n, R 1, R 2} , R 3, R 4, p and q are, n in the general formula (I), the same as _{R 1, R 2, R 3} , R 4, p and q .)

  Epichlorohydrin used for producing the epoxy resin represented by the general formula (I) is also called 1,2-epoxy-3-chloropropane, and is a colorless and transparent liquid having a structure represented by the following chemical formula 3. The dl-form and the l-form are known, and usually refer to the dl-form, and any of them may be used for producing the epoxy resin.

  A polyfunctional epoxy resin represented by the general formula (I) can be produced by reacting the bisphenol-based epoxy resin represented by the chemical formula 2 with the epichlorohydrin represented by the chemical formula 3. The production method is specifically as shown in the following reaction formula (1).

As shown in the reaction formula (1), by reacting the bisphenol-based epoxy resin represented by the chemical formula 2 with an excess amount of epichlorohydrin represented by the chemical formula 3 in the presence of a catalyst, the general formula A polyfunctional epoxy resin represented by (I) can be obtained.
The reaction is performed at a reaction temperature in the range of 50 to 80 ° C. under a reduced pressure of 30 to 250 Torr. The reaction time of the reaction is 2 to 30 hours.

  Examples of the catalyst used in the reaction include alkalis, Lewis acids, and interlayer transfer catalysts. Here, examples of the alkali include sodium hydroxide, potassium hydroxide, and calcium hydroxide, and examples of the Lewis acid include boron trifluoride, tin chloride, and zinc chloride. For example, tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N -Butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl -N-methylmorpholinium iodide N-allyl-N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N- Examples thereof include methyl-N-ethylpiperidinium acetate and N-methyl-N-ethylpiperidinium iodide, and tetramethylammonium chloride is preferred.

In the reaction, the amount of epichlorohydrin represented by the chemical formula 3 is used in the range of 1 equivalent or more, particularly 2 to 10 equivalents relative to 1 equivalent of the hydroxyl group of the bisphenol-based epoxy resin represented by the chemical formula 2. Is preferred. In addition, when the alkali is used, the catalyst is preferably used in an amount of 0.1 to 2.0 mol, particularly 0.3 to 1.5 mol, based on 1 equivalent of the hydroxyl group to be glycidylated, When using a transfer catalyst, it is preferable to use 0.01-10 mass% with respect to the total mass of a reaction agent, especially 0.2-2 mass%.
The reaction can be carried out in a solvent such as hydrocarbon, ether or ketone, but an excessive amount of epichlorohydrin can also be used as a solvent.

  After the reaction is completed, unreacted epichlorohydrin is filtered and removed, and a desalting and washing process can be performed using a solvent such as ketones and purified water.

  The method for producing the epoxy resin represented by the general formula (I) is described in, for example, H. BATZER AND SA ZAHIR, JOURNAL OF APPLIED POLYMER SCIENCE, VOL 19, PP.609-617 (1975). Yes. JP-A-5-239181 proposes a method for producing a glycidyl ether of a secondary alcohol, and this method can also be applied. JP-A-1-168722 and JP-A-5-5020 propose a method for producing an epoxy resin using dimethyl sulfoxide, and this method can also be used.

  In the epoxy resin represented by the general formula (I), 20 to 100% of X in the general formula (I) is a glycidyl group, but the excess amount of the epichlorohydrin, reaction temperature, reaction pressure, reaction time. By adjusting reaction conditions such as the type and amount of catalyst used, an epoxy resin having an arbitrary re-epoxidation rate can be produced.

  The multifunctional epoxy resin represented by the general formula (I) obtained by the reaction has an epoxy equivalent of 200 to 600, and n has a value of 0.1 to 30. .

  The bisphenol-based epoxy resin represented by the chemical formula 2 used as a starting material in the reaction is preferably one having an epoxy equivalent of 400 to 2000, and preferably 400 to 1000. Is more preferable.

  The bisphenol-based epoxy resin represented by the chemical formula 2 is not particularly limited by the production method, and a commercially available product can be purchased and used, but is produced according to the following reaction formula (2). It is also possible.

  As shown in the reaction formula (2), the normal bisphenol-based epoxy resin represented by the chemical formula 4 is reacted with the epichlorohydrin represented by the chemical formula 3 to be used as a starting material. The bisphenol-type epoxy resin represented by Chemical Formula 2 can be produced.

  In the resin composition for molded products of the present invention, the amount of the epoxy resin represented by the general formula (I) is 0.1 to 20 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 10 parts by mass. If the amount is less than 0.1 parts by mass, the adhesiveness cannot be sufficiently improved. If the amount exceeds 20 parts by mass, the inherent properties of the thermoplastic resin may be impaired.

  The resin composition for molded products of the present invention can be used in combination with other epoxy resins other than the epoxy resin represented by the general formula (I). Examples of the epoxy resin include hydroquinone, resorcin, pyro Polyglycidyl ether compounds of mononuclear polyphenol compounds such as catechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene Bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxy Phenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as bisphenol A novolac, bisphenol F novolac, terpene diphenol; polyglycidyl of the above mononuclear polyhydric phenol compound or polynuclear polyhydric phenol compound with ethylene oxide and / or propylene oxide adduct Ether compound; polyglycidyl ether compound of hydrogenated mononuclear polyphenol compound; ethylene glycol Polyglycidyl ethers of polyhydric alcohols such as propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, Itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid , Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as hexahydrophthalic acid, endomethylenetetrahydrophthalic acid and glycidyl methacrylate; Epoxy compounds having a glycidylamino group such as N, N-diglycidylaniline and bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, etc. Examples include epoxidized products of cyclic olefin compounds; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be internally crosslinked by a prepolymer of a terminal isocyanate.

  When these other epoxy resins are used, the amount used is preferably 20 parts by mass or less, more preferably 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When it exceeds 20 mass parts, there exists a possibility of inhibiting the characteristic which the said thermoplastic resin has originally.

  The resin composition for molded articles of the present invention can be used in combination with a commonly used epoxy resin curing agent. Examples of the epoxy resin curing agent include polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, and the like. And aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Also, these polyamines and various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid are used in a conventional manner A polyepoxy addition-modified product produced by reacting with the above; an amidation-modified product produced by reacting these organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid; These polyamines and aldehydes such as formaldehyde and phenols having at least one aldehyde-reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, and resorcin Such as Mannich-modified product is prepared by reacting in a conventional manner and the like. Furthermore, latent curing agents such as dicyandiamide, acid anhydrides, and imidazoles can also be used.

  The amount of these epoxy resin curing agents used is preferably 20 parts by mass or less, particularly 10 parts by mass or less, with respect to 100 parts by mass of the thermoplastic resin. When it exceeds 20 mass parts, there exists a possibility of inhibiting the characteristic which the said thermoplastic resin has originally.

A fibrous or granular reinforcing agent can be used for the resin composition for molded articles of the present invention.
Examples of the fibrous reinforcing agent include glass fiber, shirasu glass fiber, alumina fiber, carbon fiber, silicon carbide fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, gypsum fiber, metal fiber, silicon nitride and the like. Examples of the particulate reinforcing agent include, for example, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, nephenline cinnite, talc, talpulgite, wollastonite, PMF (processed mineral fiber), ferrite, silicon chloride, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, zirconium oxide, iron oxide, calcium sulfate, barium sulfate, disulfide Molybdenum, graphite Gypsum, glass beads, glass balloons, quartz, quartz glass, silicon nitride, silicon carbide, inorganic fillers such as Saroyan, such as organic reinforcing fillers such as aramid fibers.

  The amount of these fibrous or granular reinforcing agents used is preferably 400 parts by mass or less, depending on the application, with respect to a total of 100 parts by mass of the thermoplastic resin and epoxy resin.

  A phosphorus-based, phenol-based or sulfur-based antioxidant can be added to the molded resin composition of the present invention.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, G Lauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4-isopropylidenediphenol pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4- Isopropylidene diphenyl phosphite, bis [2,2′-methylenebis (4,6-diamilphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4-isopropylidene diphenol polyphosphite, bis (octylphenyl) ) ·Screw [ 4,4-n-butylidenebis (2-tert-butyl-5-methylphenol)], 1,6-hexanediol diphosphite, tetratridecyl, 4,4-butylidenebis (2-tert-butyl-5-methylphenol) ) Diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10-phos Examples include phaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl- 4-hydroxyphenoxy) -s-triazine, 2,2-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4-butylidenebis (4,6-ditert-butylphenol), 2,2-ethylidenebis (4,6-ditert-butylphenol) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tertiary) Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5 -Ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbe Zen, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4- Hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3- Tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane], triethylene glycol bis [β -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic acid esters.

  Moreover, a ultraviolet absorber and a hindered amine light stabilizer can be used for the resin composition for molded articles of the present invention.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4- (2- 2-hydroxybenzophenones such as methacryloyloxyethoxyethoxy) benzophenone and 5,5-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2 -Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl- 5-methylphenyl) -5-chlorobenzotriazole, 2- 2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7-9mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3) 5-dicumylphenyl) benzotriazole, 2,2-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzo 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol esters of triazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- ( 2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-tri 2- (2-hydroxyphenyl) -1, such as gin, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3, Benzoates such as 5-ditert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2-ethoxyoxanilide, 2-ethoxy-4-dodecyl Substituted oxanilides such as oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3 And cyanoacrylates such as-(p-methoxyphenyl) acrylate.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butyl Tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6 -Tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6- Tetramethi -4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [ 2,4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetra Azadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane 1,6,11-tris [2,4-bis (N-butyl Such as N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino -s- triazin-6-ylamino) undecane and the like.

  In addition, the resin composition for molded products of the present invention may contain additives used for thermoplastic resins, for example, fillers, colorants, cross-linking agents, antistatic agents, plate-out preventing agents, surfaces, if necessary. Treatment agent, lubricant, flame retardant, fluorescent agent, antifogging agent, antifoggant, antifungal agent, bactericidal agent, metal deactivator, mold release agent, pigment, processing aid, antioxidant, light stabilizer, A foaming agent etc. can be mix | blended.

  The resin composition for molded products of the present invention can be suitably used for various molded products such as vehicle applications, electrical appliances, office equipment, communication equipment, building materials, sundries, filaments, and processed yarns.

  Hereinafter, the present invention will be described in detail with reference to production examples, examples and comparative examples. However, the scope of the present invention is not limited to the following examples. In addition, the following manufacture example shows the manufacture example of the epoxy resin represented by the said general formula (I), and G represents a re-epoxidation rate in the following manufacture example.

Production Example 1 Production of Multifunctional Epoxy Resin EP-1 In a flask equipped with a reflux device, a stirring device, a decompression device, and a dropping device, bisphenol A-based epoxy resin 1 (epoxy equivalent 475, n = 2.1) 47 .5 parts by mass, epichlorohydrin 95 parts by mass and tetramethylammonium chloride 0.2 parts by mass are charged, and 9.5 parts by mass of sodium hydroxide is placed in the dropping apparatus as a 48% by mass aqueous solution. This aqueous sodium hydroxide solution was added dropwise at 80 torr at an internal temperature of 50 to 60 ° C. over 2 hours under reflux, and at the same time, water was removed by azeotropic distillation. Thereafter, the mixture was further reacted for 2 hours, cooled and filtered, and the solvent was removed by evaporation with an evaporator to obtain the desired multifunctional epoxy resin EP-1 (epoxy equivalent 275, G = 87%, softening point 40 ° C.).

Production Example 2: Production of polyfunctional epoxy resin EP-2 In a flask equipped with a reflux device, a stirring device, a decompression device, and a dropping device, bisphenol A-based epoxy resin 2 (epoxy equivalent 650, n = 3.4) 65 Part by mass, 130 parts by mass of epichlorohydrin and 81.0 parts by mass of dimethyl sulfoxide were charged. 15 parts by mass of sodium hydroxide was gradually added with stirring at 70 ° C., and the mixture was further reacted for 3 hours. Next, most of the unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reactive product containing the by-product salt and dimethyl sulfoxide is dissolved in 150 parts by mass of methyl isobutyl ketone, and a 30% by mass aqueous sodium hydroxide solution is further added. 2 parts by mass were added and reacted at 70 ° C. for 2 hours. After washing with water and oil-water separation, the solvent was removed by evaporation with an evaporator to obtain the desired multifunctional epoxy resin EP-2 (epoxy equivalent 295, G = 90%, softening point 75 ° C.).

Production Example 3: Production of polyfunctional epoxy resin EP-3 In a flask equipped with a reflux apparatus, a stirring apparatus, a decompression apparatus, and a dropping apparatus, bisphenol A-based epoxy resin 3 (epoxy equivalent 900, n = 5.1) 90 Part by mass, 180 parts by mass of epichlorohydrin and 0.2 parts by mass of tetramethylammonium chloride are charged, and 20 parts by mass of sodium hydroxide is put in the dropping apparatus as a 48% by mass aqueous solution. This aqueous sodium hydroxide solution was added dropwise at 80 torr at an internal temperature of 50 to 60 ° C. over 2 hours under reflux, and at the same time, water was removed by azeotropic distillation. Thereafter, the mixture was further reacted for 2 hours, cooled and filtered, and the solvent was removed by evaporation with an evaporator to obtain the desired polyfunctional epoxy resin EP-3 (epoxy equivalent 340, G = 75%, softening point 95 ° C.).

Production Example 4: Production of polyfunctional epoxy resin EP-4 In a flask equipped with a reflux apparatus, a stirring apparatus, a decompression apparatus, and a dropping apparatus, a bisphenol F-based epoxy resin (epoxy equivalent: 500, n = 2.7) 50 Part by mass, 100 parts by mass of epichlorohydrin, and 0.4 parts by mass of tetramethylammonium chloride are charged, and 12 parts by mass of sodium hydroxide is placed in the dropping apparatus as a 48% by mass aqueous solution. This aqueous sodium hydroxide solution was added dropwise at 80 torr at an internal temperature of 50 to 60 ° C. over 2 hours under reflux, and at the same time, water was removed by azeotropic distillation. Thereafter, the mixture was further reacted for 2 hours, cooled and filtered, and the solvent was removed by evaporation with an evaporator to obtain the desired polyfunctional epoxy resin EP-4 (epoxy equivalent 270, G = 84%, softening point 50 ° C.).

Example 1 and Comparative Example 1
Polyethylene terephthalate (PET) having an intrinsic viscosity [η] of 0.72, chipped strand glass fibers having a fiber length of 3 mm, and the polyfunctional epoxy resins obtained by the above production examples are shown in Table 1 below (units for blending amounts). : Parts by mass), uniformly mixed for 5 minutes in a V-type blender, extruded at a cylinder temperature of 270 ° C. to produce pellets, and then the pellets were molded at a cylinder temperature of 280 ° C. and a mold temperature of 140 ° C. A test piece was prepared by injection molding under the condition of a cycle of 60 seconds.
About this test piece, according to JIS K 7110, it put into the original (before heating) and 160 degreeC oven, and measured the Izod impact strength (N) with a 1/4 notch after 500 hours progress (after heating).
In addition, as an adhesion test, two 3 mm-thick test pieces were prepared by using an epoxy two-component adhesive (main agent: Adeka Resin EPU-11 [Asahi Denka Kogyo Co., Ltd. urethane modified epoxy resin, epoxy equivalent = 225], curing agent. Bonding with a bonding area of 12.5 mm × 25 mm at room temperature using Grandmide 656 [Asahi Denka Kogyo Co., Ltd. polyamide polyamine, amine value 450], main agent / curing agent (mass ratio) = 100/50); After leaving to cure for 7 days, the tensile shear adhesive strength (MPa) was measured according to JIS K 6850.
The results are shown in Table 1.

Example 2
Polycarbonate resin powder (PC) and the polyfunctional epoxy resin obtained by the above production example were blended in the proportions shown in Table 2 below (unit of blending amount: parts by mass), dried at 100 ° C. for 16 hours, and then at 280 ° C. Extrusion was performed to produce pellets. Using this pellet, injection processing was performed at 300 ° C. to prepare a predetermined test piece, and the Izod impact strength (N) with 1/4 notch was measured according to JIS K 7110 (before heating). Moreover, it tested similarly about what heated the test piece for 168 hours (after a heating).
The same adhesion test as in Example 1 was performed. Further, the colorability of the test piece was visually evaluated (evaluation criteria: ：: no coloring, ◯: almost no coloring, Δ: slightly coloring, × large coloring).
The results are shown in Table 2.

Example 3
Polycarbonate resin (PC), α-methylstyrene-modified ABS resin (α-methylstyrene content 37.5% by mass) and the polyfunctional epoxy resins obtained by the above production examples are shown in the following Table 3 in proportions (of the blending amount). (Unit: part by mass), and after dry blending, pelletized with an extruder. This was injection molded at 280 ° C. using an injection molding machine to prepare a test piece, and the Izod impact strength (N) with 1/4 notch was measured according to JIS K 7110.
The results are shown in Table 3.

Example 4
Unstabilized HI-PS resin, ethylenebis (stearylamide) (EBSA), 4,4′-butylidenebis (6-tert-butyl-m-cresol) (AO) and polyfunctional epoxy obtained by the above preparation example The resin was blended at the ratio shown in Table 4 below (unit of blending amount: parts by mass) and dry blended, and then dried at 80 ° C. for 6 hours. Next, pellets were prepared using a twin screw extruder (L / D = 30, vent-up 40 mmHg) with a cylinder temperature of 220 ° C. and a rotation speed of 200 rpm, and then the pellets were dried at 80 ° C. for 6 hours. Using this pellet, an injection molding machine (1 ounce, cylinder temperature 180 ° C. and 190 ° C., nozzle temperature 200 ° C., mold 60 × 36 × 2 mm, mold temperature 60 ° C., injection 15 seconds, cooling 30 seconds cycle) A test piece was prepared.
About this test piece, according to JIS K 7110, it put into the original (before heating) and 110 degreeC oven, and measured the Izod impact strength (N) with a 1/4 notch after 1 week and 2 weeks progress.
The results are shown in Table 4.

Example 5
Nylon 6 and the polyfunctional epoxy resin obtained by the above production example are blended in the proportions shown in the following Table 5 (unit of blending amount: parts by mass) and dry blended, 3.5 ounce, in-line screw type injection molding machine (Cylinder temperatures: 220 ° C., 240 ° C., 240 ° C., 235 ° C.) were used to prepare test pieces.
About this test piece, tensile yield strength (MPa) and elongation (%) were measured according to JIS K 7161, bending strength (MPa) was measured according to JIS K 7171, and 1/4 notch was further measured according to JIS K 7110. The attached Izod impact strength (N) was measured.
The results are shown in Table 5.

Example 6
Polybutylene terephthalate resin (PBT), α-methylstyrene-modified ABS resin (α-methylstyrene content 37.5% by mass) and the ratios shown in Table 6 below for the polyfunctional epoxy resins obtained by the above production examples (compounding) (Unit of amount: part by mass), dry blended, and then pelletized with an extruder. This was injection molded at 280 ° C. using an injection molding machine to prepare a test piece.
About this test piece, Izod impact strength (N) with 1/4 notch was measured according to JIS K 7110.
The results are shown in Table 6.

Example 7
Nylon 6, α-methylstyrene-modified ABS resin (α-methylstyrene content 37.5% by mass) and the ratio of polyfunctional epoxy resins obtained by the above production examples shown in Table 7 below (unit of blending amount: mass) Part), dry blended, and pelletized with an extruder. This was injection molded at 280 ° C. using an injection molding machine to prepare a test piece.
About this test piece, Izod impact strength (N) with 1/4 notch was measured according to JIS K 7110.
The results are shown in Table 7.

The following is clear from the above examples and comparative examples.
When the thermoplastic resin is used alone, the mechanical properties are inferior, and even if a general-purpose bisphenol A type epoxy resin is combined with this, the effect of improving the mechanical properties is not sufficient. In addition, when a novolac type epoxy resin is combined, although the mechanical properties are improved, the colorability is remarkably lowered.

On the other hand, in the case of the present invention in which a thermoplastic resin and a specific epoxy resin are used in combination, a product having excellent mechanical properties and excellent colorability and adhesiveness can be obtained.

Claims (3)

A resin composition for molded articles, comprising 100 parts by mass of a thermoplastic resin excluding a polyphenylene sulfide resin and 0.1 to 20 parts by mass of an epoxy resin represented by the following general formula (I).

(In the formula, n represents a real number of 0.1 to 30, R ₁ and R ₂ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group or alkoxy group having 1 to 5 carbon atoms; ₃ and R ₄ are each independently an alkyl group having 1 to 5 carbon atoms, p and q independently represent 0 or an integer of 1 to 4, and X represents a hydrogen atom or a glycidyl group, 20% or more of X represents a glycidyl group.) In the epoxy resin represented by the general formula (I), in the general formula (I), R ₁ and R ₂ are both hydrogen atoms or both methyl groups, p and q are both 0, n The resin composition for molded articles according to claim 1, wherein is a real number of 1 to 15. The resin composition for molded articles according to claim 1 or 2, wherein the thermoplastic resin is at least one selected from an aromatic polyester resin, a polycarbonate resin, a styrene resin, and a polyamide resin.