WO2019208377A1 - Composition de résine de poly(sulfure d'arylène), article moulé, article moulé composite et procédé de production associé - Google Patents

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

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WO2019208377A1
WO2019208377A1 PCT/JP2019/016595 JP2019016595W WO2019208377A1 WO 2019208377 A1 WO2019208377 A1 WO 2019208377A1 JP 2019016595 W JP2019016595 W JP 2019016595W WO 2019208377 A1 WO2019208377 A1 WO 2019208377A1
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epoxy
polyarylene sulfide
resin composition
parts
mass
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PCT/JP2019/016595
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English (en)
Japanese (ja)
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卓哉 西田
由希 出口
昌則 内潟
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Dic株式会社
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Priority to JP2020516280A priority Critical patent/JPWO2019208377A1/ja
Publication of WO2019208377A1 publication Critical patent/WO2019208377A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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 resin composition, a molded article, a composite molded article, and a method for producing them, including a polyarylene sulfide (hereinafter sometimes abbreviated as “PAS”) resin.
  • PAS polyarylene sulfide
  • PAS resins represented by polyphenylene sulfide (hereinafter sometimes abbreviated as “PPS”) resins are excellent in mechanical strength, heat resistance, chemical resistance, moldability, and dimensional stability. It is used as electrical / electronic equipment parts, automotive parts materials, etc.
  • these parts are bonded to a part material made of epoxy resin or the like as a secondary process.
  • PAS resins have relatively poor adhesion to other resins, especially adhesion to epoxy resins. Therefore, for example, when bonding PASs with epoxy adhesives, bonding PAS resins with other materials, or sealing electrical / electronic parts with epoxy resins, the adhesion between PAS resins and epoxy resins (hereinafter referred to as “bonding”) In some cases, the problem of “adhesiveness” is a problem.
  • PAS resin is inferior in toughness, it has a problem that it is brittle with respect to a thermal cycle by repeated low and high temperatures, or thermal shock, and inferior in thermal shock resistance. Further, when reinforced with a fibrous reinforcing material such as glass fiber, anisotropy occurs, and a phenomenon such as warping or twisting occurs in the molded product, and the dimensional stability is not sufficient.
  • a molded body made of a PAS resin composition obtained by blending PAS resin, bisphenol-type epoxy resin, novolac-type epoxy resin, glass fiber, and glass flake and melting and kneading has been proposed (patent).
  • Reference 2 The molded body was excellent in the thermal shock resistance even if it has an adhesiveness with an epoxy resin and a weld part, but there is still room for improvement in the thermal shock resistance, such as injection molding. There was still room for improvement in the thermal shock resistance in the direction perpendicular to the resin flow (TD direction) during melt molding.
  • the problem to be solved by the present invention is a polyarylene sulfide resin which is excellent in epoxy adhesiveness and has excellent thermal shock resistance, in particular, thermal shock resistance in the case of having a weld part, as well as excellent thermal shock resistance in the TD direction.
  • An epoxy resin (B) having an epoxy equivalent weight in the following range, an epoxy group-containing polyolefin (C), glass fiber (D1) and glass flake (D2), and the amount of epoxy groups in the composition It has been found that the above-mentioned problems can be solved by setting the amount in the range of 25 [ ⁇ mol] to 300 [ ⁇ mol] in 1 g of the composition, and the present invention has been completed.
  • the present invention provides a polyarylene sulfide resin composition
  • a polyarylene sulfide resin composition comprising a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1), and glass flakes (D2).
  • the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [ ⁇ mol] to 300 [ ⁇ mol]
  • the epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq. ] It relates to a polyarylene sulfide resin composition in the following range.
  • the present invention also relates to a molded article formed by melt molding the polyarylene sulfide resin composition.
  • the present invention also provides a polyarylene sulfide resin composition in which a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1), and glass flakes (D2) are melt-kneaded.
  • the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [ ⁇ mol] to 300 [ ⁇ mol]
  • the epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq.
  • the present invention relates to a method for producing a polyarylene sulfide resin composition in the following range.
  • this invention relates to the manufacturing method of the composite molded article which adhere
  • a molded article of a polyarylene sulfide resin composition having excellent epoxy adhesiveness and not only thermal shock resistance, particularly in the case of having a weld portion, but also excellent thermal shock resistance in the TD direction.
  • a polyarylene sulfide resin composition capable of providing the molded article, a composite molded article obtained by bonding the molded article and a cured product of a curable resin composition containing an epoxy resin, and a method for producing the same. be able to.
  • it is a metal block member used for the cold thermal shock resistance (heat cycle property) test of the TD direction of a molded article (without a weld part).
  • it is a molded article (without a weld part) used for the cold thermal shock resistance (heat cycle property) test of TD direction.
  • the polyarylene sulfide resin composition used in the present invention comprises a polyarylene sulfide resin (A), an epoxy resin (B), an epoxy group-containing polyolefin (C), glass fibers (D1), and glass flakes (D2).
  • a polyarylene sulfide resin composition comprising: With respect to 100 parts by mass of the polyarylene sulfide resin (A), the glass fiber ranges from 10 parts by mass to 350 parts by mass, the glass flake ranges from 1 part by mass to 250 parts by mass, In 1 g of the polyarylene sulfide resin composition, the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) is in the range of 25 [ ⁇ mol] to 300 [ ⁇ mol], The epoxy equivalent of the epoxy resin (B) is 100 [g / eq. ] 2400 [g / eq. It is characterized by being in the following range.
  • the polyarylene sulfide resin composition used in the present invention comprises 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 mol% to 3 mol% or less, particularly 0.01 mol% or more with respect to the total number of moles with other structural moieties. To 1 mol% or less.
  • 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 melt viscosity of the polyarylene sulfide resin used in the present invention is not particularly limited, but the melt viscosity (V6) measured at 300 ° C. is preferably in the range of 2 [Pa ⁇ s] to 1000 [Pa ⁇ s]. Furthermore, the range of 10 [Pa ⁇ s] to 500 [Pa ⁇ s] is more preferable because the balance between fluidity and mechanical strength is improved, and in particular, the range is 60 [Pa ⁇ s] to 200 [Pa ⁇ s]. s] The following range is particularly preferable. However, in the present invention, the melt viscosity (V6) is as follows.
  • the non-Newtonian index of the polyarylene sulfide resin (A) used in the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.90 or more and 2.00 or less.
  • the non-Newtonian index is preferably in the range of 0.90 to 1.50, more preferably in the range of 0.95 to 1.20. preferable.
  • 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 if necessary, added with a polyhalogenoaromatic compound and reacted, and the amount of water in the reaction system is 0.02 mol to 0.5 mol with respect to 1 mol of the organic polar solvent.
  • 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 the epoxy resin (B) as an essential component.
  • the epoxy resin used in the present invention is not particularly limited as long as the effects of the present invention are exhibited.
  • Examples thereof include bisphenol type epoxy resins, novolac type epoxy resins, and epoxy resins having a polyarylene ether structure ( ⁇ ).
  • bisphenol type epoxy resin is preferable because it has excellent adhesiveness and excellent thermal shock resistance, and particularly has excellent thermal shock resistance in the TD direction as well as thermal shock resistance when having a weld portion. Can be mentioned.
  • the thermal shock resistance As the epoxy equivalent of the epoxy resin used in the present invention, while reducing the gas generation amount at the time of melting, and excellent adhesion, not only the thermal shock resistance, particularly the thermal shock resistance when having a weld part, from the viewpoint of excellent thermal shock resistance in the TD direction, 2400 [g / eq. ], More preferably 2100 [g / eq. ], More preferably 1900 [g / eq. ] From the viewpoint of being in the following range and excellent in fluidity, it is preferably 100 [g / eq. ], More preferably 190 [g / eq. ], More preferably 210 [g / eq. ] The above range.
  • 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.
  • a bisphenol type epoxy resin while reducing the amount of gas generated at the time of melting, it has excellent adhesiveness, and also has a thermal shock property, particularly a thermal shock property in the case of having a weld portion, as well as a thermal shock in the TD direction. From the viewpoint of excellent properties, it is preferably 2400 [g / eq.
  • 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. When the epoxy resin is a novolak type epoxy resin, the gas generation amount at the time of melting is reduced, and the adhesiveness is excellent.
  • the TD direction From the viewpoint of excellent thermal shock resistance, it is preferably 300 [g / eq. ], More preferably 250 [g / eq. ] From the viewpoint of being in the following range and excellent in fluidity, it is preferably 100 [g / eq. ], More preferably 190 [g / eq. ] The above range.
  • epoxy resin (B) used in the present invention one or more of the above-mentioned various types can be used in combination.
  • the polyarylene sulfide resin composition of the present invention contains an epoxy group-containing polyolefin (C) as an essential component.
  • the epoxy group-containing polyolefin further imparts a functional group, for example, by homopolymerization of ⁇ -olefin or copolymerization of different ⁇ -olefins
  • the ⁇ -olefin include those having 2 to 8 carbon atoms such as ethylene, propylene and butene-1.
  • an epoxy group (glycidyl group) is mentioned as a functional group.
  • the vinyl polymerizable compound having such a functional group 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.
  • 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.
  • the above-mentioned ethylene-propylene copolymer and ethylene-butene copolymer having an epoxy group are preferable from the viewpoint of improving mechanical strength, particularly toughness and impact resistance.
  • the epoxy group-containing polyolefin (C) used in the present invention one or more of the above-mentioned various types can be used in combination.
  • the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) in 1 g of the polyarylene sulfide resin composition described later is a predetermined amount.
  • the epoxy equivalent of the epoxy group-containing polyolefin (C) is preferably 5000 [g / eq. ], More preferably 4900 [g / eq. ], More preferably 4800 [g / eq. ] From the viewpoint of being in the following range and excellent in fluidity, preferably 1200 [g / eq. ], More preferably 1300 [g / eq. ], More preferably, 1400 [g / eq. ] The above range.
  • the present invention while reducing the amount of gas generated at the time of melting, it is excellent in adhesiveness, and further, not only thermal shock resistance, particularly in the case of having a weld part, but also in thermal shock resistance in the TD direction.
  • the total proportion of epoxy groups of the epoxy resin (B) and the epoxy group-containing polyolefin (C) in 1 g of the polyarylene sulfide resin composition is in the range of 25 [ ⁇ mol] or more, and adhesion and From the viewpoint of improving not only the thermal shock property, particularly the thermal shock property in the case of having a weld portion, but also the thermal shock property in the TD direction, a range of 30 [ ⁇ mol] or more is preferable, and a range of 35 [ ⁇ mol] or more is more preferable.
  • the range is 300 [ ⁇ mol] or less, and the range of 270 [ ⁇ mol] or less is preferred.
  • the range of 250 [ ⁇ mol] or less is
  • the ratio of the epoxy group of the epoxy resin (B) in 1 g of the polyarylene sulfide resin composition is in the range of 20 [ ⁇ mol] to 250 [ ⁇ mol]
  • the epoxy group-containing polyolefin (C) It is more preferable that the ratio of the epoxy group possessed by () is in the range of 5 [ ⁇ mol] to 50 [ ⁇ mol].
  • the blending ratios of the epoxy resin (B) and the epoxy group-containing polyolefin (C) in the polyarylene sulfide resin composition of the present invention are the same as the epoxy resin (B) and the epoxy group-containing polyolefin in 1 g of the polyarylene sulfide resin composition.
  • the epoxy resin (B) and the epoxy group-containing polyolefin (C) are blended at a blending ratio in which the total proportion of epoxy groups possessed by (C) is in the range of 25 [ ⁇ mol] to 300 [ ⁇ mol].
  • the epoxy resin (B) is in the range of 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin.
  • the epoxy group-containing polyolefin (C) is preferably in the range of 5 parts by mass or more and 30 parts by mass or less, and from the viewpoint of epoxy resin adhesion, thermal shock resistance, and impact resistance, it is 7 parts by mass or more. More preferred is a range, more preferred is a range of 9 parts by mass or more, and more preferred is a range of 28 parts by mass or less from the viewpoint of the amount of gas generated. preferable.
  • the epoxy resin (B) has an epoxy group amount from the viewpoint of excellent epoxy adhesiveness and thermal shock resistance, particularly not only the thermal shock resistance in the case of having a weld portion, but also excellent thermal shock resistance in the TD direction. Is preferably blended so as to be larger than the epoxy group amount of the epoxy group-containing polyolefin (C).
  • the polyarylene sulfide resin composition used in the present invention comprises glass fiber (D1) as an essential component.
  • the glass fiber chopped strands used for injection molding compounds are preferably used.
  • the fiber diameter and fiber length are not particularly limited as long as the effects of the present invention are not impaired, but the fiber diameter (diameter) is preferably in the range of 3 ⁇ m to 20 ⁇ m, more preferably in the range of 6 ⁇ m to 13 ⁇ m.
  • the length of the glass fiber is arbitrary, it is preferable to reduce the amount of deformation of the molded product due to the balance between the mechanical properties and deformation of the molded product, but the average fiber is preferred in terms of mechanical strength.
  • the length is preferably at least 30 ⁇ m and longer, and is appropriately selected according to the required performance. Usually, the range of 50 ⁇ m to 2000 ⁇ m is preferable.
  • There is no restriction on the cross-sectional shape of the glass fiber and a round shape is usually used. A similar cross-sectional shape is preferable, and a flat cross-sectional shape is particularly preferable.
  • the glass fiber used in the present invention is preferably pretreated with a silane coupling agent or the like.
  • the blending ratio of the glass fibers is preferably in the range of 10 to 350 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin, and the viewpoint of improving heat resistance, mechanical strength, particularly thermal shock resistance. Is more preferably in the range of 20 parts by mass or more, more preferably in the range of 30 parts by mass or more, and from the viewpoint of improving dimensional stability and fluidity, it is in the range of 100 parts by mass or less. More preferably, the range is 80 parts by mass or less.
  • the polyarylene sulfide resin composition used in the present invention contains glass flakes (D2) as an essential component.
  • the glass flakes used in the present invention known glass flakes can be used as long as they are scale-like glass fillers.
  • the average particle diameter is in the range of 10 ⁇ m to 4000 ⁇ m and / or the average thickness is. What is a glass flake in the range of 0.1 ⁇ m or more to 20 ⁇ m or less is preferable, and the average particle diameter is in the range of 100 ⁇ m or more to 300 ⁇ m or less and / or the average thickness from the viewpoint of excellent moisture permeability and surface appearance. Is preferably in the range of 2 ⁇ m to 10 ⁇ m.
  • the average particle size is 100 ⁇ m or more and / or the average thickness is 2 ⁇ m or more, it suppresses the deterioration of the surface appearance that occurs because the glass flakes float with glass fibers on the surface of the molded product
  • an average particle size of 300 ⁇ m or less and / or an average thickness of 10 ⁇ m or less is used, part of the glass flakes is crushed during melt kneading, As a result of being easily formed, the phenomenon of floating on the surface of the molded article with glass fibers and impairing the surface appearance is preferable.
  • the average particle size and the average thickness mean a particle size of 50% cumulative degree obtained from a cumulative particle size distribution curve measured by a laser light diffraction method.
  • the glass flakes used in the present invention are preferably pretreated with a silane coupling agent or the like.
  • the linear expansion coefficient in the flow direction and the right-angle direction can be reduced, and the thermal shock resistance of repeating low and high temperatures can be improved.
  • the blending ratio of the glass flakes is not only the adhesiveness, heat resistance, mechanical strength, thermal shock resistance, particularly the thermal shock resistance in the case of having a weld part, but also cooling in the TD direction with respect to 100 parts by mass of the polyarylene sulfide resin. From the viewpoint of excellent impact properties and from the viewpoint of improving dimensional stability, it is preferably in the range of 1 part by mass or more, more preferably in the range of 20 parts by mass or more, and in the range of 30 parts by mass or more. More preferably. On the other hand, from the viewpoint of improving mechanical strength and moldability, a range of 250 parts by mass or less is preferable, a range of 100 parts by mass or less is more preferable, and a range of 80 parts by mass or less is more preferable.
  • the blending ratio of the glass fiber and the glass flake is not particularly limited as long as the effect of the present invention is achieved, but it is preferable that the blending ratio of the glass fiber is larger than the glass flake from the viewpoint of improving the mechanical strength, From the viewpoint of improving the dimensional stability, it is preferable that the blending ratio of the glass flake is larger than that of the glass fiber.
  • the polyarylene sulfide resin composition used in the present invention is a filler other than the glass fibers (D1) and the glass flakes (D2) as necessary, as long as the effects of the present invention are not impaired. (Referred to as “agent”) as an optional component.
  • agents known and conventional 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.
  • Examples of the filler are shapes.
  • fibrous fillers such as carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, wollastonite, and natural fibers can be used.
  • non-fibrous such as glass beads, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber, calcium sulfate Fillers can also be used.
  • other fillers are not essential components, and when added, the content is not particularly limited as long as the effects of the present invention are not impaired.
  • the content of the other filler is, for example, preferably 1 part by mass or more, more preferably 10 parts by mass or more, preferably 600 parts by mass, more preferably 100 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A).
  • the range is 200 parts by mass or less. In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.
  • the polyarylene sulfide resin composition used in the present invention can contain a silane coupling agent as an optional component, if necessary, within the range where the effects of the present invention are exhibited.
  • 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
  • alkoxysilane compounds are preferred because they can react with the polyarylene sulfide polymer via a functional group to give an apparent molecular weight.
  • 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 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. 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 used in the present invention can contain a thermoplastic elastomer other than the epoxy group-containing polyolefin (C) as an optional component, as necessary, within the range where the effects of the present invention are exhibited.
  • 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 with respect to 100 parts by mass of the polyarylene sulfide resin (A), preferably 0.01 parts by mass or more.
  • the range is preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. 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.
  • the functional group is not particularly limited as long as it is a functional group other than an epoxy group, and examples thereof include carboxy groups, acid anhydride groups represented by the formula — (CO) O (CO) —, those Ester, amino group, hydroxyl group, mercapto group, isocyanate group, or oxazoline group.
  • 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 used in the present invention can contain a resin other than the epoxy resin (B) and the epoxy group-containing polyolefin (C) as an optional component within a range not impairing the effects of the present invention.
  • resins include polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, polyether ketone resins, polyarylenes.
  • polyethylene resin excluding epoxy group-containing polyolefin (C)
  • polypropylene resin excluding epoxy group-containing polyolefin (C)
  • polytetrafluoroethylene resin polydifluoroethylene resin
  • polystyrene resin ABS resin
  • Synthetic resins such as urethane resins and liquid crystal polymers
  • the content of these resins varies depending on the purpose and cannot be specified unconditionally, but from 0.01 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). In the following range, it may be appropriately adjusted according to the purpose and use so as not to impair the effects of the present invention.
  • the polyarylene sulfide resin composition used in the present invention is a colorant, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, foaming, as long as the effects of the present invention are not impaired.
  • You may contain well-known and usual additives, such as an agent, a flame retardant, a flame retardant adjuvant, a rust preventive agent, and a mold release agent, as an arbitrary component as needed. These additives are not essential components.
  • the effect of the present invention is not impaired, preferably in the range of 0.01 parts by mass to 1000 parts by mass. It may be used by appropriately adjusting according to the purpose and application.
  • mold release agents examples include natural waxes such as carnauba wax, metal salts of higher fatty acids such as zinc stearate, and polyolefin waxes such as oxidized or non-oxidized polyethylene wax.
  • the epoxy resin or epoxy group-containing polyolefin used in the present invention is melt kneaded in the presence of a component acting as a so-called curing agent (hereinafter referred to as a curing agent acting component) such as a phenol resin, an amine (active hydrogen compound), or a carboxylic acid anhydride.
  • a curing agent acting component such as a phenol resin, an amine (active hydrogen compound), or a carboxylic acid anhydride.
  • the epoxy group disappears due to curing reaction (addition reaction with active hydrogen compound, copolycondensation reaction with acid anhydride), so the proportion of curing agent active component in polyarylene sulfide resin composition is in the epoxy resin component
  • the active group in the curing agent working component is 0.1 equivalent or less, more preferably 0.01 equivalent or less, and most preferably 0 equivalent, that is, absent (less than the detection limit amount) with respect to 1 epoxy group in total. It is.
  • the polyarylene sulfide resin composition used in the present invention comprises polyarylene sulfide resin (A), epoxy resin (B), epoxy group-containing polyolefin (C), glass fiber (D1), and glass flake (D2) as essential components.
  • the polyarylene sulfide resin (A) is obtained by a production method including a step of melt-kneading at a melting point or higher.
  • a preferred method for producing the polyarylene sulfide resin composition used in the present invention is that the polyarylene sulfide resin (A), the epoxy resin (B), the epoxy group-containing polyolefin (C) and the glass flakes (
  • Each component of D2) and optional components such as other fillers and additives as described above can be used in various forms such as powders, pellets, strips, etc. for ribbon blenders, Henschel mixers, V blenders, etc.
  • a known melt kneader such as a Banbury mixer, a mixing roll, a single or twin screw extruder and a kneader, and the glass fiber (D1) is extruded from the side feeder of the melt extruder.
  • the resin temperature in the extruder is not less than the melting point of the polyarylene sulfide resin, preferably not less than the melting point + 10 ° C., more preferably not less than the melting point + 10 ° C., more preferably not less than the melting point + 20 ° C., preferably not more than the melting point + 100 ° C., more preferably It can be manufactured through a step of melt kneading in a temperature range of melting point + 50 ° C. or less. 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 viewpoints of dispersibility and productivity.
  • a resin component discharge rate ranging from 5 (kg / hr) to 500 (kg / hr) or less
  • a screw It is preferable to melt-knead while adjusting the rotation speed from 50 (rpm) to 500 (rpm) as appropriate, and the ratio (discharge amount / screw rotation speed) is 0.02 (kg / hr / rpm).
  • the position of the side feeder is 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 biaxial kneading extruder is preferably 0.1 or more, more preferably 0.3 or more. Therefore, the range is preferably 0.9 or less, more preferably 0.7 or less.
  • the polyarylene sulfide resin composition used in the present invention obtained by melt-kneading is composed of the essential components polyarylene sulfide resin (A), epoxy resin (B), epoxy group-containing polyolefin (C) and glass fiber ( D1), glass flakes (D2), and a molten mixture containing optional components to be added as necessary and components derived from them, and after the melt-kneading, they are processed into pellets, chips, granules, powders and the like by known methods Then, it is preferable to perform preliminary drying at a temperature of 100 ° C. or higher and 150 ° C. or lower as necessary to provide various types of molding.
  • the polyarylene sulfide resin composition used in the present invention produced by the above production method has a polyarylene sulfide resin as a matrix, and the epoxy resin (B) and the epoxy group-containing polyolefin (C) as essential components in the matrix.
  • a glass fiber (D1), glass flake (D2), a component derived therefrom, and a morphology in which an optional component added as necessary is dispersed are formed.
  • the polyarylene sulfide resin molded article can have excellent epoxy resin adhesion, heat resistance, mechanical strength, thermal shock resistance, and dimensional stability.
  • the molded article of the present invention can be obtained by melt-molding the polyarylene sulfide resin composition.
  • a melt molding a general method may be used, which can be used for various moldings such as injection molding, insert molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, In particular, it is excellent in releasability, so it is suitable for injection molding applications.
  • various molding conditions are not particularly limited, and can be usually molded by a general method.
  • the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably the melting point + 10 ° C.
  • 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.) or higher, preferably 120 ° C. or higher, preferably 300 ° C. or lower, more preferably 180 ° C. or lower.
  • the polyarylene sulfide resin molded product used in the present invention is excellent in adhesiveness, that is, 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, novolac type epoxy resins, and epoxy resins having a polyarylene ether structure ( ⁇ ). Of these, bisphenol-type epoxy resins are preferred because of their excellent adhesiveness.
  • 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.
  • the curing agent is not particularly limited as long as it is generally used as a curing agent for epoxy resins.
  • an amine type curing agent, a phenol resin type curing agent, an acid anhydride type curing agent, and a latent property examples thereof include a curing agent.
  • 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 is obtained, the active group in the curing agent is from 0.7 equivalent to 1. An amount in the range of 5 equivalents or less is preferred.
  • the molded product formed by molding the polyarylene sulfide resin composition used in the present invention is excellent in epoxy resin adhesion, it is a composite molded product formed by bonding with a cured product of a curable resin composition containing an epoxy resin. It can be used suitably.
  • the composite molded article of the present invention can be produced by a method including a step of adhering a molded article formed by melt molding a polyarylene sulfide resin composition and a cured product of a curable resin composition containing an epoxy resin. .
  • the adhesive between the molded product and the cured product may be a known method as long as the effects of the present invention are not impaired.
  • the molded product is brought into contact with a curable resin composition containing an epoxy resin, and the curable resin is contacted.
  • a method including a step of curing the composition may be mentioned.
  • at least a part of the surface to be bonded to the curable resin composition at the time of bonding preferably 50% or more, more preferably the entire surface is heated and melted, and then a curable resin containing an epoxy resin.
  • the method of making a composition contact and hardening this curable resin composition is also mentioned.
  • the curable resin composition is cured by bringing the curable resin composition in an uncured state into contact with the molded article and then completely curing the curable resin composition, After being in a cured state (so-called B-stage state), it can be completely cured by contacting with the molded product.
  • the composite molded product of the present invention can be used for various applications.
  • main applications include housings for electronic devices such as various home appliances, mobile phones, and PCs (Personal Computers), protection / support members for box-type electrical / electronic component integrated modules, multiple individual semiconductors or modules, 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, microphone, 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, irons , Hair dryer, rice cooker parts , Microwave oven parts, audio 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, water heater and bath
  • application area 12.9 mm ⁇ 12.9 mm.
  • the other side was bonded to the coated surface, fixed using a clip, and heated and cured / adhered in a hot air dryer set at 135 ° C. for 3 hours. After cooling at 23 ° C. for 1 day, the spacer was removed, and the obtained test piece was obtained.
  • the strain rate was 5 mm / min
  • the distance between the fulcrums was 60 mm
  • the value divided by the adhesion area was defined as the epoxy adhesive strength (MPa).
  • a steel insert block member having a length of 25 mm, a width of 40 mm, and a thickness of 10 mm connects the midpoints of the sides in the vertical direction of the member, and has a thickness of 3.55 mm on a straight line parallel to the side in the horizontal direction of the member.
  • the insert block member is held inside the injection mold by using the two through holes and two steel cylindrical pins installed in the injection mold.
  • the entire outer periphery of the insert block member is coated with a polyphenylene sulfide resin composition having a thickness of 1 mm, and we Using an injection molding die which is designed to part d is formed to obtain the polyphenylene sulfide resin composition pellets were injection-molded moldings.
  • the temperature is maintained at ⁇ 40 ° C./1 hour to 140 ° C./1 hour. The thermal shock test which makes a cycle was implemented, and the number of cycles until a crack generate
  • the insert block member (M) is installed so as to be held inside the injection molding die and melted.
  • the polyphenylene sulfide resin composition flows from the side F 1 side to the F 2 side, and a gate portion and a liquid escape portion are formed so that a weld portion is not formed.
  • pellets of the polyphenylene sulfide resin composition are injection molded to obtain a molded product (P).
  • a thermal shock test was conducted in a gas-phase type thermal shock tester with a temperature cycle of ⁇ 40 ° C./1 hour to 170 ° C./1 hour held as one cycle of the thermal cycle. It was measured.
  • Polyphenylene sulfide resin (A-1) The one produced by the following (Production Example 1) was used.
  • the amount of SMAB in the autoclave was 0.147 mol per mol of sulfur atoms present in the autoclave.
  • the theoretical dehydration amount is 27.921 g, so 609 g (33.8 mol) of the remaining water amount in the autoclave is 878 g (48.8 mol).
  • the amount of water in the autoclave was 0.065 mol per mol of sulfur atoms present in the autoclave.
  • Step 2 After the dehydration step, the internal temperature was cooled to 160 ° C., NMP46.343 kg (467.5 mol) was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per 1 mol of NMP charged in step 2.
  • the gauge pressure reached 0.00 MPa
  • the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower.
  • the distilled vapor of p-DCB and water was condensed by a condenser and separated by a decanter, and p-DCB was returned to the autoclave.
  • the amount of distilled water was 228 g (12.7 mol).
  • Step 3 The water content in the autoclave at the start of Step 3 was 41 g (2.3 mol), 0.005 mol per mol of NMP charged in Step 2, and 0.010 mol per mol of sulfur atoms present in the autoclave. .
  • the amount of SMAB in the autoclave was 0.147 mol per mol of sulfur atoms present in the autoclave, as in Step 1.
  • the temperature was raised from an internal temperature of 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 1 hour, then heated to 250 ° C. and stirred for 1 hour.
  • the gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.40 MPa.
  • the temperature was raised by pressurizing to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. After maintaining at a liquid temperature of 240 ° C. for 2 hours, the reaction was allowed to proceed with stirring at a liquid temperature of 260 ° C. for 3 hours, and the upper part of the autoclave was sprinkled to cool. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. The maximum pressure during the reaction was 0.85 MPa.
  • Epoxy resin (b-1) Bisphenol A type epoxy resin “Epiclon 7050” manufactured by DIC Corporation (epoxy equivalent 1900 [g / eq.])
  • the epoxy equivalent of the epoxy resin conforms to JIS K7236 (2001). This is the value measured.
  • B-2 Cresol novolac-type epoxy resin “Epiclon N-695P” (epoxy equivalent 210 [g / eq.]) Manufactured by DIC Corporation
  • B-3 Bisphenol A type epoxy resin “Epiclon HM-101” manufactured by DIC Corporation (epoxy equivalent 3900 [g / eq.])
  • B-4 Bisphenol A type epoxy resin “Epicoat 1009” manufactured by Japan Epoxy Resin Co., Ltd. (epoxy equivalent 2900 [g / eq.])
  • Polyolefin resin (c-1) ethylene / methyl acrylate / glycidyl methacrylate (67/27/6 mass%) copolymer “Bond First 7M” (epoxy equivalent 2369 [g / eq.]) Manufactured by Sumitomo Chemical Co., Ltd.
  • the epoxy equivalent of the polyolefin resin is a calculated value based on each component in the raw material and its ratio. In addition, each component in the raw material and its ratio can be confirmed from delivery specifications, catalogs, etc.
  • C-5 Ethylene / maleic anhydride / ethyl acrylate copolymer “Bondaine AX8390” manufactured by Sumitomo Chemical Co., Ltd.
  • C-6 Polyester elastomer “Perprene P150B” manufactured by Toyobo Co., Ltd. (a copolymer comprising an aromatic polyester and an aliphatic polyether)
  • Inorganic filler (d-1): Glass fiber (glass fiber chopped strand having a fiber diameter of 10 ⁇ m and a length of 3 mm)
  • D-2 Glass flakes (“REFG-301” manufactured by Nippon Sheet Glass Co., Ltd., average thickness 5 ⁇ m, average particle size 160 [ ⁇ m])
  • (e-1) Calcium montanate (“CaV-102” manufactured by Clariant Japan Co., Ltd.)
  • E-2 Ethylenediamine / stearic acid / sebacic acid polycondensate “Right Amide WH-255” manufactured by Kyoeisha Chemical Co., Ltd.

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Abstract

L'invention concerne : un article moulé d'une composition de résine de poly(sulfure d'arylène) (PAS) présentant une excellente adhésivité époxy et une excellente résistance aux chocs thermiques, en particulier non seulement la résistance aux chocs thermiques traitée lorsqu'une partie soudée est incluse mais également la résistance aux chocs thermiques dans la direction transversale (TD) ; une composition de résine PAS qui permet de fournir ledit article moulé ; et un article moulé composite fabriqué par liaison dudit article moulé et d'un produit durci d'une composition de résine durcissable comprenant une résine époxyde ; et un procédé de production associé. Plus précisément, l'invention concerne : une composition de résine PAS résultant du mélange d'une résine PAS, d'une résine époxyde, d'une polyoléfine contenant un groupe époxy, de fibres de verre et de flocons de verre, par rapport à 100 parties en masse de la résine PAS, la teneur en fibres de verre étant de 10 à 350 parties en masse et la teneur en flocons de verre étant de 1 à 250 parties en masse, la teneur totale en groupes époxy inclus dans la résine époxyde et la polyoléfine contenant une résine époxyde étant de 25 à 300 µmoles pour 1 g de composition de résine PAS, et l'équivalent époxy de la résine époxyde étant de 100 à 2 400 g/éq. ; un article moulé de ladite composition de résine PAS ; un article moulé composite de ce dernier ; et un procédé de production associé.
PCT/JP2019/016595 2018-04-25 2019-04-18 Composition de résine de poly(sulfure d'arylène), article moulé, article moulé composite et procédé de production associé WO2019208377A1 (fr)

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WO2021193079A1 (fr) * 2020-03-27 2021-09-30 Dic株式会社 Composition de résine pour moulage, et article moulé
JPWO2022190723A1 (fr) * 2021-03-09 2022-09-15
JP7424181B2 (ja) 2020-04-20 2024-01-30 東レ株式会社 ポリフェニレンスルフィド樹脂組成物および成形体
JP7484509B2 (ja) 2020-07-09 2024-05-16 東レ株式会社 ポリフェニレンサルファイド樹脂組成物からなる成形品の接合方法、および接合部を含む成形品の製造方法

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JP2009030030A (ja) * 2007-06-27 2009-02-12 Toray Ind Inc ポリフェニレンスルフィド樹脂組成物およびそれからなる成形品
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JP2015066735A (ja) * 2013-09-27 2015-04-13 東レ株式会社 ポリフェニレンスルフィド樹脂組成物からなる成形品と金属箔を接合した複合成形品および複合成形品の製造方法

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JP7004119B1 (ja) * 2020-03-27 2022-01-21 Dic株式会社 成形用樹脂組成物及び成形体
JP7424181B2 (ja) 2020-04-20 2024-01-30 東レ株式会社 ポリフェニレンスルフィド樹脂組成物および成形体
JP7484509B2 (ja) 2020-07-09 2024-05-16 東レ株式会社 ポリフェニレンサルファイド樹脂組成物からなる成形品の接合方法、および接合部を含む成形品の製造方法
JPWO2022190723A1 (fr) * 2021-03-09 2022-09-15
WO2022190723A1 (fr) * 2021-03-09 2022-09-15 Dic株式会社 Composition de résine de sulfure de polyarylène, article moulé, et procédés de production de ladite composition de résine de sulfure de polyarylène et dudit article moulé
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