JP4297772B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition, and more particularly, to a resin composition that can be provided with a molded product that is composed of a polyphenylene sulfide resin and a specific epoxy resin and has excellent physical properties and excellent adhesiveness.

Polyphenylene sulfide resin (PPS) is a resin excellent in heat resistance, chemical resistance, flame retardancy, and mechanical strength, and is therefore suitably used for various molded product applications.
Among molded products, for example, molded products used for automobile-related electrical components require secondary processing such as bonding to various materials such as metal, glass, and plastic materials, and sealing to molded containers. Very often.

  However, since polyphenylene sulfide resin has a defect that it is inferior in bonding property to various adhesives and adhesion to other materials, for example, a glass window material and a molded container made of polyphenylene sulfide resin are bonded with epoxy resin. When using molded products using polyphenylene sulfide resin in applications where secondary processing with various materials such as bonding with agents is used, sufficient adhesive strength cannot be obtained, bonding becomes difficult, etc. Cause problems.

  Moreover, it is known to mix | blend an epoxy resin with polyphenylene sulfide resin (for example, refer patent documents 1-5).

  Further, Patent Document 6 proposes to improve adhesion by combining a polyphenylene sulfide resin subjected to deionization treatment and an epoxy resin, and Patent Document 7 proposes an epoxy resin added to the polyphenylene sulfide resin. It has been proposed to improve the bondability to various adhesives and the adhesion to potting materials by adding epoxy resin cured products produced by the curing reaction between polyamines and specific amines such as polyamidoamine and polyethyleneimine. In addition, Patent Document 8 proposes blending a monoepoxy compound for the purpose of improving the adhesiveness of the polyphenylene sulfide resin.

  However, as proposed in Patent Documents 6 to 8, a resin composition capable of forming a molded product having satisfactory mechanical properties and adhesiveness only by blending an epoxy resin or a monoepoxy compound with a polyphenylene sulfide resin. I can't get it.

  On the other hand, Patent Documents 9 and 10 propose an aqueous resin composition containing a bisphenol-type epoxy resin in which a part or all of secondary hydroxyl groups are glycidyl etherified. Only the use of the composition as a glass fiber sizing agent or paint is described.

Japanese Patent Publication No.53-13391 JP 59-51944 A JP 59-51945 A JP-A-5-39370 Japanese Unexamined Patent Publication No. 63-286467 JP-A 64-69657 JP 7-11136 A JP-A-64-65171 JP 2001-151857 A JP 2002-88229 A

  An object of the present invention is to provide a resin composition mainly composed of polyphenylene sulfide resin and having improved mechanical properties and adhesiveness.

  The present invention provides a resin composition comprising 100 parts by mass of a polyphenylene sulfide resin and 0.1 to 40 parts by mass of an epoxy resin represented by the following general formula (I). The goal has been achieved.

  Since the resin composition of the present invention is excellent in mechanical properties and adhesiveness, it can be suitably used for molded products used in fields where excellent adhesive strength is required, particularly in automobile-related electrical components. It can be suitably used as an industrial material that is subjected to secondary processing such as bonding with other materials using an adhesive.

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

  Examples of the polyphenylene sulfide resin used in the present invention include polyphenylene sulfide resins having a repeating unit represented by the following [Chemical Formula 2]. In the present invention, among polyphenylene sulfide resins, those having a paraphenylene group of 70 to 100 mol%, particularly 80 to 100 mol% are preferably used.

  Further, in the polyphenylene sulfide resin, a part of the constituent components may be replaced with one or more selected from repeating units represented by the following [Chemical Formula 3].

  These polyphenylene sulfide resins can be produced by a conventional method, for example, a reaction between a halogen-substituted aromatic compound and an alkali sulfide, a condensation reaction in the presence of an alkali catalyst or a copper salt of a thiophenol, an aromatic compound, Can be synthesized by, for example, a condensation reaction in the presence of a Lewis acid catalyst with sulfur sulfide, and the production method can be arbitrarily selected according to the structure of the target polyphenylene sulfide resin.

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

  N represents 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, and the curability and physical properties of the coating film and molded product are reduced. A satisfactory resin composition cannot be obtained.

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 are methyl groups, and p and q are both 0, n is preferably a real number of 1 to 15.

  The epoxy resin represented by the general formula (I) used in the present invention is not limited by the production method. For example, a general-purpose bisphenol-based epoxy resin represented by the following chemical formula 2 and epichlorohydride It can be produced by polymerizing phosphorus.

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

  A polyfunctional epoxy resin represented by the general formula (I) is produced by reacting the bisphenol-based epoxy resin represented by the chemical formula 2 with the epichlorohydrin represented by the chemical formula 3. The reaction in this production method is specifically as shown in the following reaction formula [Chemical Formula 6].

As shown in the reaction formula, 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 the formula (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. Moreover, the reaction time of the said reaction is 2 to 30 hours.

  Examples of the catalyst used for the reaction include alkalis, Lewis acids, and interlayer transfer catalysts. Examples of the alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, and examples of the Lewis acid include boron trifluoride, tin chloride, zinc chloride and the like. 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-methyl-N -Ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodide and the like can be mentioned, and tetramethylammonium chloride is preferable.

  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 glycidylated hydroxyl group. Is used, 0.01 to 10% by mass, particularly 0.2 to 2% by mass, based on the total mass of the bisphenol-based epoxy resin represented by Chemical Formula 2 and the epichlorohydrin represented by Chemical Formula 3 % Is preferably used.

  Moreover, although the said reaction can also be performed in solvents, such as a hydrocarbon, ether, or a ketone, excess 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 above 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 the production method is applied to the production of the epoxy resin represented by the general formula (I). You can also. JP-A-1-168722 and JP-A-5-5020 propose a method for producing an epoxy resin using dimethyl sulfoxide, and the epoxy resin represented by the general formula (I) is proposed. Can also be produced by this method.

  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 the reaction conditions such as the type of catalyst and the amount of catalyst used, an epoxy resin having an arbitrary re-epoxidation rate can be produced.

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

  In addition, the bisphenol-based epoxy resin represented by Chemical Formula 2 used as a starting material in the reaction preferably has an epoxy equivalent of 400 to 2000, and more preferably 400 to 1000.

  The bisphenol-based epoxy resin represented by the chemical formula 2 is not particularly limited to the production method, and a commercially available product can be purchased and used, but the reaction formula shown in the following [Chemical Formula 7] It is also possible to manufacture according to

  As shown in the reaction formula of [Chemical Formula 7], by reacting the normal bisphenol-based epoxy resin represented by the chemical formula 4 with the epichlorohydrin represented by the chemical formula 3, the general formula A bisphenol-based epoxy resin represented by Formula 2 that can be used as a starting material for the epoxy resin represented by (I) can be produced.

  In the resin composition of the present invention, the amount of the epoxy resin represented by the general formula (I) is 0.1 to 40 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polyphenylene sulfide resin. It is. When the amount is less than 0.1 parts by mass, the adhesiveness cannot be sufficiently improved. When the amount exceeds 40 parts by mass, the inherent properties of the polyphenylene sulfide resin may be impaired.

  The resin composition 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, pyrocatechol, and fluoro Polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as loglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (ortho Cresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) Tan, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as novolak, bisphenol F novolac, terpene diphenol, etc .; polyglycidyl ether compounds of the above mononuclear polyhydric phenol compounds or ethylene oxide and / or propylene oxide adducts of polynuclear polyhydric phenol compounds A polyglycidyl ether compound of hydrogenated mononuclear polyhydric phenol compound; ethylene glycol, propylene glycol Polyol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycidyl ether of polyhydric alcohols such as 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 , Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as hexahydrophthalic acid and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylanily And epoxy compounds having a glycidylamino group such as bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3 Epoxy compounds of cyclic olefin compounds such as 1,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate An epoxidized conjugated diene polymer such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and a heterocyclic compound 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 polyphenylene sulfide resin. If the amount exceeds 20 parts by mass, the inherent properties of the polyphenylene sulfide resin may be impaired, which is not preferable.

  The resin composition of the present invention can be used in combination with an epoxy resin curing agent usually used for epoxy resins. 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. In addition, these polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acid are used in a conventional manner. Polyepoxy addition-modified products produced by reacting them with these; amidation-modified products produced by reacting these polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid; The conventional polyamines are reacted with 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. Mannich-modified products and the like that is produced by. 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 polyphenylene sulfide resin. If the amount exceeds 20 parts by mass, the inherent properties of the polyphenylene sulfide resin may be impaired, which is not preferable.

  A fibrous or granular reinforcing agent can be used in the resin composition 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, This, glass beads, glass balloons, quartz, quartz glass, silicon nitride, silicon carbide, inorganic fillers such as Saroyan, organic reinforcing fillers such as aramid fibers.

  The amount of these fibrous or granular reinforcing agents used is based on a total of 100 parts by mass of the polyphenylene sulfide resin, the epoxy resin represented by the general formula (I), and other epoxy resins described above that are optionally used. , Preferably, an arbitrary amount can be selected from the range of 400 parts by mass or less depending on the application.

  A phosphorus-based, phenol-based or sulfur-based antioxidant can be added to the 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'-methylene bis (4,6-di-tert-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'-isopropylidenediphenol polyphosphite, bis (Octylphenyl) bis [ , 4'-n-butylidenebis (2-tert-butyl-5-methylphenol)], 1,6-hexanediol diphosphite, tetratridecyl, 4,4'-butylidenebis (2-tert-butyl-5-methyl) Phenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10- Examples thereof include phosphaphenanthrene-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-bi (4-Hydroxy-3-tertiarybutylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (4,6-ditertiarybutylphenol), 2,2′-ethylidenebis (4,6-ditertiary) Tributylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3- Tert-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 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 pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include β-alkyl mercaptopropionic esters of polyols.

  Moreover, a ultraviolet absorber and a hindered amine light stabilizer can be used for the resin composition of this 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 -Methacryloyloxyethoxyethoxy) benzophenone, 2-hydroxybenzophenones such as 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-tertiary) 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) 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of benzotriazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-tria 2- (2-hydroxyphenyl) -1, such as 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 ′ Substituted oxanilides such as dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p Cyanoacrylates such as 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-N (1,2,2,6,6-pentamethyl-4-piperidyl) amino -s- triazin-6-ylamino) undecane.

  In the resin composition of the present invention, as an additive, in addition to the above-mentioned phosphorus-based, phenol-based or sulfur-based antioxidant, ultraviolet absorber and hindered amine-based light stabilizer, it is used for polyphenylene sulfide resin as necessary. Additives such as fillers, colorants, cross-linking agents, antistatic agents, anti-plateout agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifogging agents, antifoggants, antifungal agents, bactericides Agents, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents, and the like can also be blended. Although the usage-amount of these additives can be suitably determined according to the use etc. of the resin composition of this invention, Preferably it shall be 100 mass parts or less in total with respect to 100 mass parts of polyphenylene sulfide resin.

  The resin composition of the present invention can be used for molded products that are bonded to various materials such as metal, glass, plastic and the like by an adhesive and used in fields where excellent adhesive strength is required. The resin composition of the present invention is particularly suitable for molded containers that are used after being subjected to secondary processing such as bonding with an adhesive in automobile-related electrical components. Examples of the automobile-related electrical component include an inter-vehicle distance sensor.

  Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples. However, 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 polyfunctional epoxy resin EP-1 In a flask equipped with a reflux device, a stirring device, a decompression device and a dropping device, a 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 were charged. 9.5 parts by mass of sodium hydroxide was added as a 48% by mass aqueous solution in the dropping device, and this aqueous sodium hydroxide solution was added dropwise at 50 to 60 ° C. under reflux over 2 hours at 80 torr. Removed by boiling 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%).

[Production Example 2] Production of multifunctional epoxy resin EP-2 In a flask equipped with a reflux device, a stirring device, a decompression device and a dropping device, a bisphenol A epoxy resin 2 (epoxy equivalent 650, n = 3.4) 65 parts 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, and the reaction product containing the by-product salt and dimethyl sulfoxide is dissolved in 150 parts by mass of methyl isobutyl ketone, and further 30% by mass sodium hydroxide. 2 parts by mass of the aqueous solution was 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%).

[Production Example 3] Production of polyfunctional epoxy resin EP-3 In a flask equipped with a reflux device, a stirring device, a decompression device and a dropping device, a bisphenol A epoxy resin 3 (epoxy equivalent 900, n = 5.1) 90 parts by mass, 180 parts by mass of epichlorohydrin and 0.2 parts by mass of tetramethylammonium chloride were charged. 20 parts by mass of sodium hydroxide is added as a 48% by mass aqueous solution in the dropping apparatus, and this aqueous sodium hydroxide solution is added dropwise at 50 to 60 ° C. under reflux over 2 hours at 80 torr, and at the same time water is azeotropically distilled. Removed. 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%).

[Production Example 4] Production of polyfunctional epoxy resin EP-4 A bisphenol F-based epoxy resin (epoxy equivalent: 500, n = 2.7) was placed in a flask equipped with a reflux device, a stirring device, a decompression device, and a dropping device. 50 parts by mass, 100 parts by mass of epichlorohydrin and 0.4 parts by mass of tetramethylammonium chloride were charged. 12 parts by weight of sodium hydroxide is added as a 48% by weight aqueous solution in the dropping apparatus, and this aqueous sodium hydroxide solution is added dropwise at 50 to 60 ° C. under reflux over 2 hours at 80 torr. At the same time, the water is azeotropically distilled. Removed. 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-4 (epoxy equivalent 270, G = 84%).

[Examples 1-4 and Comparative Examples 1-2]
Polyphenylene sulfide resin (manufactured by Polyplastics Co., Ltd .; W214A), glass fiber (manufactured by Asahi Fiber Glass Co., Ltd .; 256S) and the polyfunctional epoxy resin obtained by the above production example were used and listed in Table 1 below. By blending, pellets were prepared at 300 ° C. and 150 rpm using a twin screw extruder. Using this pellet, a predetermined test piece was prepared at a resin temperature of 330 ° C. and a mold temperature of 120 ° C. by an injection molding machine, and the following tests were performed. The test results are shown in Table 1 below.

(Adhesive strength)
A test piece having a thickness of 3 mm and a steel plate (G-3141) were bonded to an epoxy two-component adhesive (main agent; Adeka Resin EPU-78-20S: manufactured by Asahi Denka Kogyo Co., Ltd., curing agent; Adeka Hardener EH-205S: Asahi Adhesion area of 12.5 mm × 25 mm using Denka Kogyo Co., Ltd., cured at room temperature for 30 minutes, cured at 80 ° C. for 1 hour, and in accordance with JIS K 6850, tensile shear adhesion (MPa) Was measured.

(IZOD)
According to JIS K 7110, Izod impact strength (kgfcm / cm) with 1/4 notch was measured.

(HDT)
The deflection temperature under load (° C.) was measured according to JIS K 7207.

(Bending test)
The bending strength (MPa) and bending elastic modulus (MPa) were measured in accordance with JIS K 7171.

(Tensile test)
Tensile strength (MPa) and tensile elongation (%) were measured according to JIS K7113.

(hardness)
Rockwell hardness (HRR) was measured according to JIS K 7202-2.

  As is apparent from Table 1, when the polyphenylene sulfide resin is used alone, the bonding property with the adhesive is inferior (Comparative Example 1), and even if this is combined with a general-purpose bisphenol A type epoxy resin, the adhesiveness is not good. The improvement effect is not sufficient (Comparative Example 2).

  On the other hand, when the polyphenylene sulfide resin and the epoxy resin represented by the general formula (I) are used in combination, a molded product having excellent mechanical properties and excellent adhesion can be obtained (Examples). 1-4).

Claims (3)

A resin composition comprising 100 parts by mass of a polyphenylene sulfide resin and 0.1 to 40 parts by mass of an epoxy resin represented by the following 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, and n is a real number of 1 to 15. The resin composition according to claim 1.   The resin composition according to claim 1 or 2, which is used for automobile-related electrical component applications.