WO2018056240A1 - Composition de résine de poly(sulfure d'arylène), article moulé et procédé de production - Google Patents

Composition de résine de poly(sulfure d'arylène), article moulé et procédé de production Download PDF

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Publication number
WO2018056240A1
WO2018056240A1 PCT/JP2017/033640 JP2017033640W WO2018056240A1 WO 2018056240 A1 WO2018056240 A1 WO 2018056240A1 JP 2017033640 W JP2017033640 W JP 2017033640W WO 2018056240 A1 WO2018056240 A1 WO 2018056240A1
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Prior art keywords
polyarylene sulfide
fatty acid
sulfide resin
resin composition
parts
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PCT/JP2017/033640
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English (en)
Japanese (ja)
Inventor
洋平 山口
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Dic株式会社
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Priority to JP2018541060A priority Critical patent/JP6753470B2/ja
Publication of WO2018056240A1 publication Critical patent/WO2018056240A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a polyarylene sulfide resin composition, a molded article, and a method for producing them.
  • PAS resin represented by polyphenylene sulfide (hereinafter also abbreviated as PPS) resin
  • PPS resin has excellent heat resistance and mechanical strength, chemical resistance, and molding processing. It is also excellent in performance and dimensional stability. Utilizing these characteristics, it is used as electrical / electronic equipment parts, automobile parts materials and the like.
  • epoxy resin adhesion Inadequate adhesion with a curable resin composition containing the following (hereinafter sometimes referred to as epoxy resin adhesion) has been a problem.
  • an oxidized polyethylene wax is added as a release agent to the polyarylene sulfide resin composition containing the polyarylene sulfide resin and the filler, and the epoxy resin adhesion of the molded product is increased.
  • a method for improving the balance between releasability and mechanical properties has also been proposed (see Patent Document 1).
  • the epoxy resin adhesion of the polyarylene sulfide resin molded product was low, and it was a level that was hardly practically sufficient.
  • the molded product has room for improvement in toughness, particularly bending elongation strength in the TD direction (perpendicular to the resin flow direction), and particularly when the molded product is to be thinned, There was a tendency for brittle fracture to occur. For this reason, improvement of the bending elongation strength especially in TD direction was also desired.
  • the problem to be solved by the present invention is to provide a polyarylene sulfide resin composition that is a molded article excellent in epoxy resin adhesion and a molded article excellent in epoxy resin adhesion obtained by molding it. It is another object of the present invention to provide a composite molded article obtained by bonding the molded article and a cured product of a curable resin composition containing an epoxy resin, and to provide a method for producing them.
  • the problem to be solved by the present invention is not only excellent in epoxy resin adhesion but also obtained by molding a polyarylene sulfide resin composition that is a molded product having excellent bending elongation strength in the TD direction.
  • a polyarylene sulfide resin composition that is a molded product having excellent bending elongation strength in the TD direction.
  • the present inventor blended polyarylene sulfide resin with one or more fatty acid metal salts selected from the group consisting of fatty acid esters and fatty acid alkali metal salts and fatty acid alkali metal earth salts.
  • one or more fatty acid metal salts selected from the group consisting of fatty acid esters and fatty acid alkali metal salts and fatty acid alkali metal earth salts.
  • the present invention comprises a polyarylene sulfide resin (A), a fatty acid ester (B), and one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts.
  • the fatty acid ester (B) is in the range of 0.01 to 5 parts by mass and the fatty acid metal salt (C) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is related with the polyarylene sulfide resin composition characterized by being a range.
  • the present invention relates to a molded article formed by molding the polyarylene sulfide resin composition.
  • the present invention relates to a composite molded product obtained by bonding a molded product obtained by molding the polyarylene sulfide resin composition and a cured product of a curable resin composition containing an epoxy resin.
  • the present invention also includes a polyarylene sulfide resin (A), a fatty acid ester (B), and one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts. It is related with the manufacturing method of the polyarylene sulfide resin composition characterized by melt-kneading as an essential component above the melting
  • a polyarylene sulfide resin composition that is a molded article excellent in epoxy resin adhesion, and a molded article excellent in epoxy resin adhesion obtained by molding the same are provided. And a cured product of a curable resin composition containing an epoxy resin can be provided, and a production method thereof can be provided.
  • a polyarylene sulfide resin composition that is a molded product having not only excellent epoxy resin adhesion but also excellent bending elongation strength in the TD direction, and an epoxy resin obtained by molding the same.
  • the polyarylene sulfide resin composition of the present invention comprises at least one fatty acid metal salt selected from the group consisting of a polyarylene sulfide resin (A), a fatty acid ester (B), a fatty acid alkali metal salt and a fatty acid alkali metal earth salt.
  • Containing (C) as an essential component The fatty acid ester (B) is in the range of 0.01 to 5 parts by mass and the fatty acid metal salt (C) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is a range.
  • the polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin (A) as an essential component.
  • the polyarylene sulfide resin used in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded.
  • the polyarylene sulfide resin has the following general formula (1)
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). And, if necessary, the following general formula (2)
  • the trifunctional structural moiety represented by the formula (2) is preferably in the range of 0.001 to 3 mol%, particularly in the range of 0.01 to 1 mol%, based on the total number of moles with other structural moieties. It is preferable that
  • R 1 and R 2 in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin.
  • those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4) are exemplified.
  • the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para-position represented by the general formula (3). In terms of surface.
  • polyarylene sulfide resin is not limited to the structural portion represented by the general formulas (1) and (2), but the following structural formulas (5) to (8)
  • the structural site represented by the formula (1) and the structural site represented by the general formula (2) may be included at 30 mol% or less.
  • the structural site represented by the general formulas (5) to (8) is preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin.
  • the bonding mode thereof may be either a random copolymer or a block copolymer. Good.
  • the polyarylene sulfide resin may have a naphthyl sulfide bond or the like in its molecular structure, but is preferably 3 mol% or less with respect to the total number of moles with other structural sites, particularly 1 It is preferable that it is below mol%.
  • the physical properties of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.
  • the polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1000 [Pa ⁇ s], and has a good balance between fluidity and mechanical strength. Therefore, the range of 10 to 500 [Pa ⁇ s] is more preferable, and the range of 60 to 200 [Pa ⁇ s] is particularly preferable.
  • the non-Newtonian index of the polyarylene sulfide resin (A) used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00.
  • the non-Newtonian index is preferably in the range of 0.90 to 1.50, and more preferably in the range of 0.95 to 1.20.
  • Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance.
  • SR shear rate (second ⁇ 1 )
  • SS shear stress (dyne / cm 2 )
  • K represents a constant. The closer the N value is to 1, the closer the PPS is to a linear structure, and the higher the N value is, the more branched the structure is.
  • the method for producing the polyarylene sulfide resin (A) is not particularly limited.
  • Examples thereof include a method in which p-chlorothiophenol is self-condensed by adding other copolymerization components if necessary.
  • the method 2) is versatile and preferable.
  • an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization.
  • a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound in the organic polar solvent.
  • a sulfidizing agent are added to and reacted with a polyhalogenoaromatic compound as necessary, and the amount of water in the reaction system is in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent.
  • a method for producing a polyarylene sulfide resin by controlling see Japanese Patent Application Laid-Open No. 07-228699), and if necessary, a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent.
  • Polyhalogenoaromatic compound or other copolymerization component is added, and alkali metal hydrosulfide and organic acid alkali metal salt are added to sulfur source 1 While controlling the organic acid alkali metal salt in the range of 0.01 to 0.9 moles of water and the amount of water in the reaction system within the range of 0.02 moles or less per mole of the aprotic polar organic solvent, What is obtained by the method of making it react (refer pamphlet of WO2010 / 058713) is especially preferable.
  • dihalogenoaromatic compound examples include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and each of the above compounds Compounds having an alky
  • halogen atom contained in each compound is a chlorine atom or a bromine atom.
  • the post-treatment method of the reaction mixture containing the polyarylene sulfide resin obtained by the polymerization step is not particularly limited.
  • the reaction mixture is left as it is, or an acid or a base is used.
  • the solvent is distilled off under reduced pressure or normal pressure, and then the solid after the solvent is distilled off is water, a reaction solvent (or an organic solvent having an equivalent solubility in a low molecular weight polymer), acetone, methyl ethyl ketone.
  • a solvent such as alcohols, and further neutralizing, washing with water, filtering and drying, or (3) after completion of the polymerization reaction, water,
  • a solvent such as acetone, methyl ethyl ketone, alcohol, etc.
  • water is added to the reaction mixture to wash with water. Filtration, if necessary, acid treatment at the time of washing with water, acid treatment and drying, (5) after completion of the polymerization reaction, the reaction mixture is filtered, and if necessary, once or twice or more with a reaction solvent Washing Further water washing, a method of filtering and drying, and the like.
  • the polyarylene sulfide resin may be dried in a vacuum or in an inert gas atmosphere such as air or nitrogen. May be.
  • the polyarylene sulfide resin composition of the present invention contains a fatty acid ester (B) as an essential component.
  • the fatty acid ester (B) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but an esterified product of a long-chain fatty acid having 12 or more carbon atoms and an alcohol is used. In particular, it is more preferable to use an esterified product of a long-chain fatty acid having 20 to 30 carbon atoms and an alcohol.
  • these fatty acids saturated fatty acids, unsaturated fatty acids, and derivatives thereof can be used, but it is particularly preferable to use saturated fatty acids.
  • Examples of the fatty acid contained in the fatty acid ester (B) used in the present invention include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicin It is preferable to use acid, adipic acid, sebacic acid, and derivatives thereof, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and derivatives thereof are more preferable, behenic acid, montanic acid and These derivatives are particularly preferred.
  • the alcohol examples include monohydric alcohols and polyhydric alcohols, among which polyhydric alcohols are preferred.
  • the monohydric alcohol is preferably an alcohol having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and examples thereof include methanol, ethanol, butanol, 2-ethylhexanol, stearyl alcohol and the like.
  • Examples of the polyhydric alcohol include polyhydric alcohols having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, or polymers thereof such as alkylene glycol (ethylene glycol, diethylene glycol, propylene glycol, etc.).
  • Diols Diols; triols such as glycerin, trimethylolpropane or derivatives thereof; tetraols such as pentaerythritol, sorbitan or derivatives thereof; and these polyhydric alcohols alone or as copolymers (for example, polyethylene glycol, And a polyoxyalkylene glycol such as polypropylene glycol or a copolymer, polyglycerin, etc.).
  • the average degree of polymerization of the polyoxyalkylene glycol is 2 or more (for example, in the range of 2 to 500), preferably in the range of 2 to 400, more preferably the average degree of polymerization of 16 or more, preferably in the range of 20 to 200. .
  • the fatty acid constituting the ester is a fatty acid having a carbon number of 12 or more, for example, saturated or unsaturated having a monovalent carbon number of 12 to 26 It is preferable to use fatty acids, saturated or unsaturated fatty acids having a divalent carbon number of 12 to 20, and the like.
  • fatty acid esters examples include ethylene glycol distearate, ethylene glycol dimontanate, glycerol monostearate, glycerol tripalmitate, polyglycerol tristearate, trimethylolpropane monopalmitate, Pentaerythritol monoundecylate, sorbitan monostearate, polyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.) monolaurate, monopalmitate, monostearate, dilaurate, dipalmitate, distearate, dibehenate, dimontanate, dioleate, Examples include dilinoleate.
  • fatty acid ester (B) examples include montanic acid ester wax (manufactured by Clariant Japan Co., Ltd. “Recolbe WE4” acid value 29 mg KOH / g, dropping point 81 ° C.), montanic acid ester wax (manufactured by Clariant Japan Co., Ltd.).
  • the acid value of the fatty acid ester (B) used in the present invention is not particularly limited as long as the effect of the present invention is exhibited.
  • the lower limit of the acid value of the fatty acid ester (B) is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, and particularly preferably 10 mgKOH / g or more.
  • the upper limit of the acid value of the fatty acid ester (B) is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and particularly preferably 50 mgKOH / g.
  • the adhesion between the molded product obtained by molding the polyarylene sulfide resin composition of the present invention and the epoxy resin is particularly improved, which is preferable.
  • the acid value can be measured by a method based on JISJK 0070. Specifically, it is measured as the number of milligrams of potassium hydroxide required to neutralize the free fatty acid contained in 1 g of wax.
  • the dropping point of the fatty acid ester (B) used in the present invention is preferably in the range of 50 ° C. or higher, more preferably in the range of 60 ° C. or higher, and most preferably in the range of 70 ° C. or higher.
  • the upper limit of the dropping point is preferably in the range of 100 ° C. or lower, more preferably in the range of 90 ° C. or lower, and most preferably in the range of 85 ° C. or lower.
  • the dropping point can be measured by a method based on ASTM D127. Specifically, using a metal nipple, it is measured as the temperature at which molten wax first drops from the metal nipple. In the following examples, it can be measured by the same method.
  • the fatty acid ester (B) not only improves the mold releasability of the molded product from the mold, but also suitably affects the continuous moldability. Furthermore, when it is within the above range, the fatty acid ester (B) tends to ooze out on the surface of the molded product. Further, when the polyarylene sulfide resin composition is melt-kneaded, the fatty acid ester (B) is sufficiently melted. Thereby, fatty acid ester (B) disperses
  • the content of the fatty acid ester (B) in the polyarylene sulfide resin composition is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is preferably in the range of -4.5 parts by mass, more preferably in the range of 0.1-4 parts by mass. When it is within the above range, it is excellent in epoxy resin adhesion while being excellent in mold releasability from the mold. In addition, it is possible to suppress deterioration of the mold and the appearance of the molded product during molding.
  • the polyarylene sulfide resin composition of the present invention contains one or more fatty acid metal salts (C) selected from the group consisting of fatty acid alkali metal salts and fatty acid alkali metal earth salts as essential components.
  • C fatty acid metal salts
  • the fatty acid metal salt (C) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but it is preferable to use a salt of a long chain fatty acid having a carbon number of 12 or more. In particular, it is more preferable to use a salt of a long-chain fatty acid having 20 to 30 carbon atoms.
  • these fatty acids saturated fatty acids, unsaturated fatty acids, and derivatives thereof can be used, but it is particularly preferable to use saturated fatty acids.
  • Fatty acids contained in the fatty acid metal salt (C) used in the present invention include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, Melicic acid, adipic acid, sebacic acid, and derivatives thereof are preferably used, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melissic acid, and derivatives thereof are more preferable, behenic acid, montanic acid And their derivatives are particularly preferred.
  • the salt contained in the fatty acid metal salt (C) used in the present invention is one or more fatty acid metal salts selected from alkali metal salts and / or fatty acid alkali metal earth salts, and exhibits the effects of the present invention. It is not particularly limited as long as it is one or more selected from the group consisting of alkali metals such as potassium, sodium and lithium, and alkaline earth metals such as calcium, magnesium and barium, and further potassium and sodium Particularly preferred are fatty acid metal salts containing one or more salts selected from calcium, lithium. When these fatty acid metal salts are used, the ring opening of the epoxy group in the curable resin composition containing the epoxy resin is promoted on the surface of the molded article formed by molding the polyarylene sulfide resin composition. preferable.
  • the content of one or more fatty acid metal salts (C) selected from the group consisting of alkali metal salts and fatty acid alkali metal earth salts in the polyarylene sulfide resin composition is 100 parts by mass of the polyarylene sulfide resin (A). Is preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.05 to 4.5 parts by mass, and most preferably in the range of 0.1 to 4 parts by mass.
  • the blending amount of the fatty acid metal salt (C) is within the above range, the adhesiveness with the epoxy resin can be improved, and the releasability from the mold at the time of molding can be improved.
  • the polyarylene sulfide resin composition of the present invention can contain a filler as an optional component, if necessary.
  • a filler known and commonly used materials can be used as long as they do not impair the effects of the present invention.
  • various fillers such as fibrous ones and non-fibrous ones such as granular or plate-like ones can be used.
  • a filler etc. are mentioned.
  • fiber fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, etc., natural fiber, etc.
  • Non-fibrous fillers such as calcium sulfate can also be used.
  • the filler is not an essential component, and when added, the content is not particularly limited as long as the effect of the present invention is not impaired.
  • the content of the filler is, for example, preferably in the range of 1 to 600 parts by mass, more preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). . In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.
  • the polyarylene sulfide resin composition of the present invention can contain a silane coupling agent as an optional component, if necessary.
  • the silane coupling agent is not particularly limited as long as the effects of the present invention are not impaired, but a silane coupling agent having a functional group that reacts with a carboxy group, for example, an epoxy group, an isocyanato group, an amino group, or a hydroxyl group is preferable. Can be mentioned.
  • silane coupling agents include epoxy groups such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • alkoxysilane compounds Containing alkoxysilane compounds, ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylethyldimethoxysilane , ⁇ -isocyanatopropylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as ⁇ -isocyanatopropyltrichlorosilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - ( -Aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and ⁇ -aminopropyltrime
  • the silane coupling agent is not an essential component, but when it is added, the amount added is not particularly limited as long as the effects of the present invention are not impaired, but the polyarylene sulfide resin (A) is 100 parts by mass. Is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass. Within such a range, the resin composition is preferable because it has good corona resistance and moldability, in particular, releasability, and the molded product exhibits excellent adhesiveness with the epoxy resin and further improves the mechanical strength.
  • the polyarylene sulfide resin composition of the present invention can contain a thermoplastic elastomer as an optional component, if necessary.
  • the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. Among these, polyolefin-based elastomers are preferable.
  • the content is not particularly limited as long as the effects of the present invention are not impaired, but in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A).
  • it is more preferably in the range of 0.1 to 5 parts by mass. Within such a range, the resulting polyarylene sulfide resin composition is preferred because the impact resistance is improved.
  • the polyolefin-based elastomer is obtained by, for example, homopolymerization of ⁇ -olefin or copolymerization of different ⁇ -olefins with a functionalized vinyl polymerizable compound in the case of further adding a functional group. It can be obtained by copolymerization.
  • the ⁇ -olefin include those having 2 to 8 carbon atoms such as ethylene, propylene and butene-1.
  • a carboxy group an acid anhydride group represented by the formula — (CO) O (CO) —, an ester thereof, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group Etc.
  • vinyl polymerizable compound having such a functional group examples include ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, and the like.
  • carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, and the like.
  • examples thereof include acids, itaconic acid and other ⁇ , ⁇ -unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters and acid anhydrides thereof), and glycidyl (meth) acrylate.
  • an ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the above-described epoxy group, carboxy group, and acid anhydride group are mechanically selected. It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.
  • the polyarylene sulfide resin composition of the present invention may further comprise a polyester resin, a polyamide resin, a polyimide resin, a polyetherimide resin, a polycarbonate resin, a polyphenylene ether resin, a polysulfone, depending on the intended use.
  • synthetic resins such as urethane resins and liquid crystal polymers can be contained as optional components.
  • the content of these resins varies depending on the purpose and cannot be specified in general, but in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). In order not to impair the effects of the present invention, it may be appropriately adjusted according to the purpose and application.
  • the polyarylene sulfide resin composition of the present invention includes other colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant aids, You may contain well-known and usual additives, such as a rust agent and a coupling agent, as an arbitrary component as needed. These additives are not essential components. For example, they are preferably in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A) so that the effects of the present invention are not impaired. It may be adjusted as appropriate according to the conditions.
  • the method for producing the polyarylene sulfide resin composition of the present invention comprises at least one selected from the group consisting of polyarylene sulfide resin (A), fatty acid ester (B), fatty acid alkali metal salt and fatty acid alkali metal earth salt.
  • the fatty acid metal salt (C) as an essential component is melt-kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide resin (A).
  • the preferable manufacturing method of the polyarylene sulfide resin composition of the present invention is such that each of the essential components of the polyarylene sulfide resin (A), the fatty acid ester (B), and the fatty acid metal salt (C) is used so as to have the above-described content.
  • optional components such as fillers are put in various forms such as powder, pellets, strips, ribbon blender, Henschel mixer, V blender, etc., dry blended, then Banbury mixer, mixing roll,
  • a temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin preferably a temperature range in which the melting point is + 10 ° C. or higher, more preferably Temperature range of melting point + 10 ° C.
  • melting point + 100 ° C. more preferably temperature of melting point +20 to melting point + 50 ° C. It can be manufactured through a step of melt-kneading in a range. Addition and mixing of each component to the melt kneader may be performed simultaneously or may be performed separately.
  • the melt kneader is preferably a biaxial kneader / extruder from the viewpoint of dispersibility and productivity.
  • the resin component discharge rate is in the range of 5 to 500 (kg / hr)
  • the screw rotational speed is 50 to 500 (rpm). It is preferable to melt-knead while appropriately adjusting the range of the above, and melt-knead under conditions where the ratio (discharge amount / screw rotation number) is in the range of 0.02 to 5 (kg / hr / rpm) Is more preferable.
  • the position of the side feeder is preferably such that the ratio of the distance from the extruder resin charging part to the side feeder with respect to the total screw length of the twin-screw kneading extruder is in the range of 0.1 to 0.9. In particular, the range of 0.3 to 0.7 is particularly preferable.
  • the polyarylene sulfide resin composition of the present invention obtained by melt-kneading comprises the polyarylene sulfide resin (A), the fatty acid ester (B), the fatty acid alkali metal salt and the fatty acid alkali metal earth, which are essential components. It is a molten mixture containing one or more fatty acid metal salts (C) selected from the group consisting of salts, optional components added as necessary, and components derived therefrom, and after the melt-kneading, pellets, chips, After being processed into a form such as a granule or powder, it is preferably subjected to preliminary drying at a temperature of 100 to 150 ° C., if necessary, and used for various moldings.
  • C fatty acid metal salts
  • the polyarylene sulfide resin composition of the present invention produced by the above production method uses a polyarylene sulfide resin as a matrix, and the fatty acid ester (B) and the aliphatic metal salt (C) as essential components in the matrix. And a morphology having a structure in which components derived therefrom and optional components added as necessary are dispersed. As a result, not only the epoxy resin adhesion of the molded product and the MD direction but also the mechanical strength in the TD direction, in particular, the bending elongation strength in the TD direction, becomes favorable, which is preferable.
  • the reason why the polyarylene sulfide resin molded article of the present invention exhibits excellent adhesion to a curable resin composition containing an epoxy resin is not limited to a specific mechanism of action, but the following may be considered. sell. That is, on the surface of the molded article of the present invention, a carboxylate anion (—COO ⁇ ) derived from a functional group present in the fatty acid ester (B) and the aliphatic metal salt (C) serves as a basic catalyst (nucleophile).
  • the reactivity of the epoxy group is improved, and the aliphatic metal salt (C ) Is an alkali metal atom or an alkali metal earth atom, for example, ionization energy is small even when compared with other metal atoms of the periodic table such as zinc atom (Zn), and tends to dissociate. Therefore, as a result of generating more carboxylate anions and promoting the ring opening of the epoxy group as described above, the reactivity of the epoxy group can be further improved, Epoxy resin adhesive is considered to have improved.
  • the polyarylene sulfide resin composition of the present invention can be subjected to various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. It is suitable for injection molding because of its excellent properties.
  • various molding conditions are not particularly limited, and can be usually molded by a general method.
  • the resin temperature is in the temperature range above the melting point of the polyarylene sulfide resin, preferably in the temperature range above the melting point + 10 ° C., more preferably in the temperature range from the melting point + 10 ° C. to the melting point + 100 ° C., more preferably the melting point.
  • the resin discharge port may be injected into the mold and molded.
  • the mold temperature may be set to a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 120 to 180 ° C.
  • the molded product formed by molding the polyarylene sulfide resin composition of the present invention not only has excellent adhesion to an epoxy resin, but also improves the bending elongation of the resin, particularly in the TD direction, and moldability during injection molding. Can do.
  • the composition of the present invention is excellent in adhesiveness with a curable resin composition containing an epoxy resin.
  • the curable resin composition containing an epoxy resin is preferably a composition obtained by mixing an epoxy resin and a curing agent.
  • the epoxy resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include bisphenol-type epoxy resins and novolac-type epoxy resins. Among these, bisphenol-type resins are excellent in adhesion. An epoxy resin is mentioned as a preferable thing.
  • Examples of the epoxy resin of the bisphenol type epoxy resin include glycidyl ethers of bisphenols, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, Examples thereof include bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and tetrabromobisphenol A type epoxy resin.
  • novolac type epoxy resin examples include novolac type epoxy resins obtained by reacting novolac type phenol resins obtained by condensation reaction of phenols and aldehydes with epihalohydrin. Specific examples include phenol novolacs. Type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, and brominated phenol novolak type epoxy resin. *
  • epoxy resins are preferably used after being cured with a curing agent.
  • the curing agent for curing the epoxy resin is not particularly limited as long as it is generally used as a curing agent for the epoxy resin.
  • a curing agent for the epoxy resin for example, an amine type curing agent, a phenol resin type curing agent, An acid anhydride type hardening
  • amine type curing agent known ones can be used, and aliphatic polyamines, aromatic polyamines, heterocyclic polyamines, their epoxy adducts, Mannich modified products, and polyamide modified products can be used. Specifically, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis ( 4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di- Examples thereof include p-aminobenzoate. Of these
  • phenol resin type curing agent known ones can be used, for example, bisphenols such as bisphenol A, bisphenol F, and biphenol, tri (hydroxyphenyl) methane, 1,1,1-tri (hydroxyphenyl) ethane. And trifunctional phenolic compounds such as phenol novolac, cresol novolac and the like.
  • acid anhydride type curing agent known ones can be used.
  • methyl nadic acid hexahydrophthalic anhydride
  • hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.
  • latent curing agents examples include dicyandiamide, imidazole, BF3-amine complex, and guanidine derivatives.
  • curing agents can be used alone or in combination of two or more.
  • a curing accelerator can be used in appropriate combination as long as the effects of the present invention are not impaired.
  • Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
  • the curable resin composition containing an epoxy resin used in the present invention may be allowed to undergo a curing reaction in the absence of a solvent, but benzene, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, methyl acetate, acetonitrile Curing reaction in a solvent such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachloroethylene, N-methylpyrrolidone, isopropyl alcohol, isobutanol, and t-butyl alcohol May be.
  • a solvent such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachloroethylene, N-methylpyr
  • the use ratio of the epoxy resin and the curing agent is not particularly limited as long as it is a known ratio within a range not impairing the effect of the present invention, but is excellent in curability. Since a cured product having excellent heat resistance and chemical resistance of the cured product can be obtained, 0.7 to 1.5 equivalents of active groups in the curing agent with respect to a total of 1 equivalent of epoxy groups in the epoxy resin component The amount to be is preferred.
  • the molded product formed by molding the polyarylene sulfide resin composition of the present invention is excellent in adhesiveness to the epoxy resin, the polyarylene sulfide resin and the cured product of the curable resin composition containing the epoxy resin are bonded. It can be suitably used as a composite molded article.
  • the production method may be a known method as long as the effects of the present invention are not impaired, but a molded product formed by molding a polyarylene sulfide resin composition and a curable resin composition containing an epoxy resin are brought into contact with each other. And a method of curing the curable resin composition.
  • Examples of the main applications of the composite molded body include housings for electronic devices such as various home appliances, mobile phones, and PCs (Personal Computers), protective / support members for box-shaped electrical / electronic component integrated modules, a plurality of Individual semiconductor or module, sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker , Microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts and other electrical and electronic parts; VTR parts , TV parts, iron, hair dryer Ears, rice cooker parts, microwave oven parts, acoustic parts, audio / video equipment parts such as audio / laser disc / compact disc / DVD disc / Blu-ray disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, Or home appliances such
  • the obtained pellets were supplied to a Sumitomo-Nestal injection molding machine (SG75-HIPRO ⁇ MIII) set at a cylinder temperature of 320 ° C., using an ISO D2 plate molding die adjusted to a mold temperature of 130 ° C. Injection molding was performed and the specimen was cut into an ISO D2 plate. The obtained test piece was measured for TD bending strength and TD bending elongation by a measuring method based on ISO178.
  • the blending ratio of the blended resins and materials represents parts by mass, and the followings were used.
  • A1 Polyphenylene sulfide (“LR-2G” manufactured by DIC Corporation, melt viscosity (V6) 80 [Pa ⁇ s])
  • A2 Polyphenylene sulfide (“T-2G” manufactured by DIC Corporation, melt viscosity (V6) 55 [Pa ⁇ s])
  • B1 Montanic acid ester wax (Clariant Japan Co., Ltd. “Ricolb WE4” acid value 29 mg KOH / g, dropping point 81 ° C.)
  • B2 Montanic acid ester wax (Clariant Japan Co., Ltd.

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

Abstract

L'invention porte sur une composition de résine de poly(sulfure d'arylène) qui produit des articles moulés ayant une solidité et une adhésivité exceptionnelles par rapport aux résines époxy, et sur des articles moulés constitués de la composition de résine de poly(sulfure d'arylène). L'invention concerne également des articles moulés composites obtenus en liant ces articles moulés et un produit durci de résine époxy. Plus spécifiquement, l'invention concerne : une composition de résine de poly(sulfure d'arylène) contenant en tant que composants essentiels une résine de poly(sulfure d'arylène) (A), un ester d'acide gras (B) qui est situé dans la plage de 0,01 à 5 parties en masse pour 100 parties en masse de la résine de poly(sulfure d'arylène) (A), et un ou plusieurs sels métalliques d'acide gras (C) choisis dans le groupe constitué par les sels de métaux alcalins d'acides gras et les sels de métaux alcalino-terreux d'acides gras, les sels métalliques d'acides gras (C) étant situés dans une plage de 0,01 à 5 parties en masse pour 100 parties en masse de la résine de poly(sulfure d'arylène) (A) ; des articles moulés ; des articles moulés composites avec un produit durci de résine époxy ; et des procédés de production de ceux-ci.
PCT/JP2017/033640 2016-09-21 2017-09-19 Composition de résine de poly(sulfure d'arylène), article moulé et procédé de production WO2018056240A1 (fr)

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JPH0578575A (ja) * 1991-09-19 1993-03-30 Asahi Chem Ind Co Ltd ポリアリーレンスルフイド樹脂の組成物
JP2001354855A (ja) * 2000-06-12 2001-12-25 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィド樹脂組成物及びその成形体
JP2003301108A (ja) * 2002-04-11 2003-10-21 Toray Ind Inc ポリアリーレンサルファイド樹脂組成物
WO2004111131A1 (fr) * 2003-05-26 2004-12-23 Polyplastics Co., Ltd. Composition de resine retardatrice de flamme
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KR20200130384A (ko) * 2018-04-25 2020-11-18 디아이씨 가부시끼가이샤 폴리아릴렌설피드 수지 조성물, 성형품, 복합 성형품 및 그들의 제조 방법
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KR102488363B1 (ko) 2018-04-25 2023-01-17 디아이씨 가부시끼가이샤 폴리아릴렌설피드 수지 조성물, 성형품, 복합 성형품 및 그들의 제조 방법
US12054591B2 (en) 2018-04-25 2024-08-06 Dic Corporation Poly(arylene sulfide) resin composition, molded article, composite molded article, and methods respectively for producing said products

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