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WO2018066637A1 - 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
WO2018066637A1
WO2018066637A1 PCT/JP2017/036242 JP2017036242W WO2018066637A1 WO 2018066637 A1 WO2018066637 A1 WO 2018066637A1 JP 2017036242 W JP2017036242 W JP 2017036242W WO 2018066637 A1 WO2018066637 A1 WO 2018066637A1
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WO
WIPO (PCT)
Prior art keywords
polyarylene sulfide
sulfide resin
resin composition
molded article
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/036242
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English (en)
Japanese (ja)
Inventor
卓哉 西田
耕太郎 森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2018543959A priority Critical patent/JP6701610B2/ja
Publication of WO2018066637A1 publication Critical patent/WO2018066637A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • 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.
  • these parts are bonded and bonded to a part material made of a curable resin such as an epoxy resin or a silicone resin or a metal as a secondary processing.
  • a curable resin such as an epoxy resin or a silicone resin or a metal
  • polyarylene sulfide resins have relatively poor adhesion to other resins, particularly adhesion to epoxy resins and silicone resins and bondability to metals. Therefore, for example, in the case of bonding between polyarylene sulfides using an epoxy adhesive or silicone resin, sealing of electrical / electronic parts using an epoxy resin or silicone resin, etc., curable properties including polyarylene sulfide resin and epoxy resin or silicone resin There has been a problem of poor adhesion with the resin composition or bondability between the polyarylene sulfide resin and other materials such as metal.
  • a polyarylene sulfide resin composition containing a polyarylene sulfide resin and a filler in order to improve a decrease in adhesiveness with a curable resin composition containing an epoxy resin (hereinafter sometimes referred to as epoxy resin adhesion), a polyarylene sulfide resin composition containing a polyarylene sulfide resin and a filler.
  • a method has also been proposed in which oxidized polyethylene wax is added as a release agent to improve the balance of epoxy resin adhesion, mold release and mechanical properties of the molded product (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.
  • silicone resin adhesiveness dimethylpolysiloxane, fatty acid ester, and silane cup are added to polyarylene sulfide resin.
  • silicone resin adhesiveness dimethylpolysiloxane, fatty acid ester, and silane cup are added to polyarylene sulfide resin.
  • the present inventors regardless of the type of material, in order to improve adhesiveness or bondability, a method using physical interaction, that is, the surface of the polyarylene sulfide resin molded product is irradiated with active energy rays. Then, although the method of increasing the contact area with the material to be bonded or joined by roughening the surface, the surface smoothness is maintained even when the active energy ray is irradiated to the surface of the polyarylene sulfide resin molded product. It was revealed that it was difficult to roughen the surface.
  • the problem to be solved by the present invention is a polyarylene sulfide resin composition capable of roughening the surface when the surface of the molded product is irradiated with active energy rays, a molded product thereof, and a production method thereof, , A method of irradiating an active energy ray to a molded product obtained by molding the polyarylene sulfide resin composition and surface roughening, and a molded product obtained by surface roughening contains an epoxy resin or a silicone resin.
  • An object of the present invention is to provide a polyarylene sulfide resin composite molded article in which other materials such as a curable resin composition and metal are bonded with good adhesion, and a method for producing the same.
  • the present inventor obtained active energy rays on the surface of a molded article comprising a polyarylene sulfide resin composition in which glass fibers, metal oxides and clay minerals are added to polyarylene sulfide resin. It has been found that the surface can be roughened by irradiation, and the present invention has been completed.
  • the present invention is a polyarylene sulfide resin composition
  • a polyarylene sulfide resin composition comprising (1) a polyarylene sulfide resin, a glass fiber, a metal oxide, and a clay mineral having a layered shape and cleavage.
  • the Mohs hardness of the metal oxide is smaller than the Mohs hardness of the glass fiber, and the difference is within a range of less than 1.5,
  • the metal oxide contains at least one selected from the group consisting of copper and chromium;
  • the polyarylene sulfide resin composition characterized by the above.
  • the present invention also relates to (2) a polyarylene sulfide resin molded product obtained by molding the polyarylene sulfide resin composition described above.
  • the present invention also provides (3) polyarylene sulfide resin, glass fiber, metal oxide, and layered and cleaved clay mineral melt-kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide resin.
  • a method for producing a resin composition comprising: A range of 10 to 35 parts by weight of glass fiber and 1 to 30 parts by weight of metal oxide with respect to a total of 100 parts by weight of polyarylene sulfide resin, glass fiber, metal oxide and layered and cleaving clay mineral.
  • the Mohs hardness of the metal oxide is smaller than the Mohs hardness of the glass fiber, and the difference is within a range of less than 1.5,
  • the said metal oxide contains at least 1 sort (s) chosen from the group which consists of copper and chromium, It is related with the manufacturing method of the polyarylene sulfide resin composition characterized by the above-mentioned.
  • the present invention also relates to (4) a method for producing a polyarylene sulfide resin molded product, characterized by molding the polyarylene sulfide resin composition obtained by the production method described in (3) above.
  • the present invention also relates to (5) a surface roughening method for a polyarylene sulfide resin molded article, wherein the surface of the polyarylene sulfide resin molded article described in (2) is irradiated with active energy rays or ionizing radiation.
  • the surface of the polyarylene sulfide resin molded article described in (2) is irradiated with active energy rays or ionizing radiation, and the arithmetic average roughness (Ra) of the surface roughened surface is 2
  • the present invention relates to a method for producing a polyarylene sulfide resin molded article in the range of 8 to 5.0 ( ⁇ m).
  • the present invention also provides (7) the arithmetic average roughness of the surface roughened surface obtained by irradiating the surface of the polyarylene sulfide resin molded article according to (2) above with active energy ray irradiation or ionizing radiation irradiation.
  • a polyarylene sulfide resin molded article having (Ra) in the range of 2.8 to 5.0 ( ⁇ m) is contacted with a curable resin composition or a metal in a liquid state at least at the time of joining, and then the curing is performed.
  • the present invention relates to a method for producing a polyarylene sulfide resin composite molded article having a conductive resin composition or a metal in a solid state.
  • the present invention is (8) a polyarylene sulfide resin molded article in which the polyarylene sulfide resin molded article described in (2) above and a cured product or metal of a curable resin composition are joined,
  • the surface of the polyarylene sulfide resin molded article that comes into contact with the cured product or metal of the curable resin composition is in the range of arithmetic average roughness (Ra) 2.8 to 5.0 ( ⁇ m) of the surface roughened surface.
  • the present invention relates to a polyarylene sulfide resin composite molded product.
  • the polyarylene sulfide resin composition capable of roughening the surface, the molded product thereof, the production method thereof, A method of irradiating active energy rays to a molded product obtained by molding an arylene sulfide resin composition to roughen the surface, and a curable resin containing an epoxy resin or a silicone resin in the molded product obtained by roughening the surface It is possible to provide a polyarylene sulfide resin composite molded article in which other materials such as a composition and metal are bonded with good adhesiveness, and a method for producing the same.
  • the polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin 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 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 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 is not particularly limited.
  • 1) a dihalogenoaromatic compound in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogenoaromatic compound or other copolymerization component is added 2) A method of polymerizing a dihalogenoaromatic compound in a polar solvent in the presence of a sulfidizing agent, and adding a polyhalogenoaromatic compound or other copolymerization component if necessary, and 3) p-chloro.
  • Examples include a method in which ruthiophenol is self-condensed by adding other copolymerization components if necessary. Among these methods, 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 content of the polyarylene sulfide resin in the polyarylene sulfide resin composition of the present invention is 100 in total of the essential components of the polyarylene sulfide resin, the glass fiber, the metal oxide, and the layered and cleaved clay mineral. It is a range (remainder) excluding the total mass part of glass fiber, metal oxide, and layered and cleaved clay mineral with respect to the mass part, of which 15 to 88 parts by mass. Preferably, it is in the range of 45 to 70 parts by mass.
  • the polyarylene sulfide resin composition of the present invention contains glass fiber as an essential component.
  • the glass fiber used in the present invention preferably has an average diameter of 20 ⁇ m or less, and more preferably 1 to 15 ⁇ m further increases the balance of physical properties (strength, rigidity, heat-resistant rigidity, impact strength), and further increases the molding warpage. This is preferable in terms of further reduction.
  • glass fibers having a circular cross-sectional shape are generally used in many cases. However, in the present invention, there is no particular limitation.
  • the length of the glass fiber is not specified and can be selected from a long fiber type (roving) or a short fiber type (chopped strand). In this case, the number of focusing is preferably about 100 to 5000. Further, if the average length of the glass fiber in the thermoplastic resin composition after kneading the thermoplastic resin composition is 0.1 mm or more, so-called milled fiber, a pulverized product of strands called glass powder may be used, Alternatively, a continuous single fiber sliver may be used.
  • the composition of the raw material glass is preferably non-alkali, and examples thereof include E glass, C glass, and S glass. In the present invention, E glass is preferably used.
  • the glass fiber is preferably surface-treated with a silane coupling agent such as ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, etc.
  • the adhesion amount is usually from 0.01 to 1% by mass of the glass fiber mass.
  • a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin or a urethane resin, a resin having a film forming ability and a heat. What was surface-treated with a mixture of a stabilizer, a flame retardant, etc. can also be used.
  • the content of the glass fiber in the polyarylene sulfide resin composition of the present invention is 100 parts by mass in total of the essential components of the polyarylene sulfide resin, the glass fiber, the metal oxide, and the layered and cleaved clay mineral.
  • the range is 10 to 35 parts by mass, preferably 12 to 30 parts by mass.
  • the polyarylene sulfide resin composition of the present invention it is usually preferable that the polyarylene sulfide resin and the glass fiber occupy 60% by mass or more of all components.
  • the polyarylene sulfide resin composition of the present invention contains a metal oxide as an essential component.
  • the metal atom preferably includes at least one selected from the group consisting of copper and chromium, and more preferably includes copper and chromium.
  • Specific examples of metal oxides that can be used in the present invention include CuFe 0.5 B 0.5 O 2.5 , CuAl 0.5 B 0.5 O 2.5 , CuGa 0.5 B 0. .5 O 2.5, CuB 2 O 4 , CuB 0.7 O 2, CuMo 0.7 O 3, CuMo 0.5 O 2.5, CuMoO 4, CuWO 4, CuSeO 4, CuCr 2 O 4 include It is done.
  • the number average particle size of the metal oxide is not particularly limited as long as the effects of the present invention are not impaired, but since the surface of the molded article is roughened, it is preferable that the particle size of the metal oxide is larger. It is preferably from ⁇ 50 ⁇ m, more preferably from 0.05 to 30 ⁇ m. If it is too soft, it will be destroyed by contact with the glass fiber during melt-kneading and the above particle diameter cannot be maintained, so it is preferable to have a smaller Mohs hardness within a range of less than 1.5 relative to the Mohs hardness of the glass fiber. .
  • the glass fiber preferably has a Mohs hardness in the range of 5.5 or more, more preferably in the range of 5.5 to 8, and further preferably in the range of 5.5 to 7.5. And a metal oxide having a Mohs hardness of preferably in the range of 4.0 to 6.5, more preferably in the range of 4.0 to 6.0. On the other hand, it is preferable to use a combination of metal oxides having a smaller Mohs hardness within a range of less than 1.5.
  • the content of the metal oxide is a total of 100 essential components of the polyarylene sulfide resin, the glass fiber, the metal oxide, and the layered and cleaved clay mineral. It is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 2 to 25 parts by mass, and still more preferably in the range of 3 to 18 parts by mass with respect to parts by mass. Further, it is preferable to combine with a clay mineral described later, since surface roughening proceeds even with a small content.
  • the polyarylene sulfide resin composition of the present invention contains a clay mineral having a layered shape and a cleavage property as an essential component.
  • blending the clay mineral is preferable because appropriate surface roughening is possible even if the content of the metal oxide is reduced.
  • Examples of the clay mineral include talc, hydrotalcite, smectite, mica, dicite, nacrete, halloyite, antigolite, monoclinic chrysotile stone, orthorhombic chrysotile stone, parachrysolite stone, lizard stone, and ames.
  • Examples thereof include kaolinite such as stone, kelly stone, bercherin, greener stone and nupore stone, among which talc, hydrotalcite and smectite are preferable, and talc and hydrotalcite are more preferable.
  • the content of the clay mineral is a total of 100 masses of the essential components of the polyarylene sulfide resin, the glass fiber, the metal oxide, and the layered and cleaved clay mineral.
  • the amount is preferably in the range of 1 to 20 parts by weight, more preferably in the range of 2 to 15 parts by weight, and still more preferably in the range of 2 to 10 parts by weight.
  • the clay mineral used in the present invention preferably has a Mohs hardness smaller than that of the metal oxide, specifically, a range of 2.5 or less is preferable, and a range of 2 or less is more preferable.
  • Use of a clay mineral having a Mohs hardness in this range is preferable from the viewpoint of suppressing the destruction of the metal oxide during melt kneading. Although it is not a fixed theory, we believe that the effect is due to the role of cushioning material.
  • the polyarylene sulfide resin composition of the present invention can contain a filler other than the essential components (hereinafter simply referred to as 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.
  • 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 fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite and calcium sulfate are also used. it can.
  • 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 filler content is, for example, preferably in the range of 0.01 to 10% by mass and more preferably in the range of 0.1 to 5% by mass in the polyarylene sulfide resin composition. In such a range, it is preferable because good mechanical strength and moldability can be imparted to the resin composition.
  • 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, its content is not particularly limited as long as the effects of the present invention are not impaired, but the polyarylene sulfide resin composition contains 0%.
  • the range is preferably from 0.01 to 10% by mass, and more preferably from 0.1 to 5% 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 polyarylene sulfide resin composition preferably has a range of 0.01 to 10% by mass, More preferably, it is in the range of 0.1 to 5% 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 defined generally.
  • the effect of the present invention is within the range of 0.01 to 20% by mass in the polyarylene sulfide resin composition. May be appropriately adjusted and used according to the purpose and application so as not to impair.
  • 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.
  • additives such as a rust agent and a coupling agent, as an arbitrary component as needed.
  • these additives are not essential components.
  • the polyarylene sulfide resin composition preferably in the range of 0.01 to 20% by mass, appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention. Can be used.
  • the method for producing the polyarylene sulfide resin composition according to the present invention includes a polyarylene sulfide resin, the glass fiber, the metal oxide, each essential component of the clay mineral, and an optional filler such as a filler. Using the component as an essential component, it is melt-kneaded at a melting point or higher of the polyarylene sulfide resin.
  • a preferred method for producing the polyarylene sulfide resin composition of the present invention is such that the polyarylene sulfide resin, the essential components of the glass fiber, the metal oxide, and the clay mineral, and, if necessary, the above-described content are obtained. Then, optional components such as fillers are put into ribbon blenders, Henschel mixers, V blenders, etc.
  • melt kneader such as a shaft extruder and kneader, and 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 a melting point + 10 ° C to Temperature range where the melting point is + 100 ° C., more preferably a temperature where the melting point is +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 is an optional component added as necessary, polyarylene sulfide resin, glass fiber, metal oxide and clay mineral as essential components And a melt mixture containing components derived from them, and after the melt-kneading, they are processed into a form such as pellets, chips, granules, and powders by a known method and then pre-dried at a temperature of 100 to 150 ° C. as necessary. It is preferable to apply to various moldings.
  • 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 glass fiber, the metal oxide, and the clay mineral, which are essential components, are derived from the matrix. A dispersed morphology is formed by the components and optional components added as necessary. As a result, the surface roughening of the polyarylene sulfide resin molded article by active energy ray irradiation proceeds, which is preferable.
  • the polyarylene sulfide resin composition of the present invention is a molded article by melt molding by various molding methods such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. Can be manufactured, but is particularly suitable for injection molding because of its excellent releasability.
  • Various molding conditions in the melt molding are not particularly limited, and the molding can be usually performed by a general method.
  • the melt molding is performed, for example, in a molding machine in a temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably in the temperature range of the melting point + 10 ° C., more preferably in the temperature range of the melting point + 10 ° C.
  • the resin is discharged from the resin discharge port and injected into a mold or the like, for example.
  • the mold temperature may also be set to a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 120 to 180 ° C.
  • the molded product obtained by molding the polyarylene sulfide resin composition of the present invention obtained as described above is treated with active energy rays, and the surface thereof has, for example, an arithmetic average roughness (Ra) of 2.8. It can be roughened to a range of ⁇ 5.0 ( ⁇ m), more preferably to a range of 3.0 to 4.0 ( ⁇ m).
  • the surface of the molded article can be roughened using a known method as long as the surface of the polyarylene sulfide resin molded article can be roughened in a non-contact manner by physical action such as atoms, electrons, and active energy rays.
  • the treatment include irradiation with active energy rays such as ultraviolet rays, infrared to far infrared rays, laser beams, microwaves, corona discharge, arc discharge, and plasma treatment.
  • the irradiation output of the active energy ray is not particularly limited as long as the effect of the present invention is not impaired, and may be adjusted by a preliminary experiment or the like appropriately performed. For example, it is preferably in the range of 1 to 20 W, and more preferably 5 to 12 W.
  • the area to be surface roughened of the polyarylene sulfide resin molded article is not particularly limited as long as the effects of the present invention are not impaired, but the polyarylene sulfide resin molded article and other materials other than that in the finally obtained composite molded article
  • the area ratio is preferably 1% or more, more preferably 10% or more, and even more preferably 50% or more, because more excellent adhesive strength can be imparted. % Is particularly preferable, and 100% is most preferable.
  • the molded product formed by molding the polyarylene sulfide resin composition of the present invention is preferably roughened by a non-contact surface roughening treatment (etching treatment) by irradiation with active energy rays. Can do.
  • etching treatment non-contact surface roughening treatment
  • any material can be used as long as it is a material in which at least the contact surface is in a liquid state at the time of joining and then becomes a solid state. Even if it is any thing, the outstanding adhesiveness can be exhibited.
  • examples of such a material include, but are not limited to, a curable resin composition containing an epoxy resin and a silicone resin, and other materials such as metals.
  • the polyarylene sulfide resin composite molded article of the present invention is a molded article obtained by molding the polyarylene sulfide resin composition of the present invention. It can be manufactured by curing or solidifying a material whose contact surface with the surface of the molded product is in a liquid state, for example, a curable resin composition containing an epoxy resin or a silicone resin, or another material such as a metal. it can.
  • the curable resin composition containing an epoxy resin, a silicone resin, or the like referred to here preferably contains a curing agent or a curing catalyst.
  • the epoxy resin is not particularly limited as long as it is a polymer compound having two or more epoxy groups in the molecule.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type Bisphenol type epoxy resin represented by epoxy resin or tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin represented by biphenyl type epoxy resin or tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolac epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, brominated pheno Novolak type epoxy resins represented by novolak type epoxy resins.
  • epoxy resins are used as a curable resin composition containing a curing agent, and are preferably used by being subjected to a curing reaction by applying heat energy, light energy, or the like.
  • 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 it is excellent in curability and heat resistance and resistance of the cured product. Since a cured product having excellent chemical properties can be obtained, the amount is preferably such that the active groups in the curing agent are 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups in the epoxy resin component.
  • the curing agent is not particularly limited as long as it is generally used as a curing agent for epoxy resins.
  • amine-type curing agents phenol resin-type curing agents, acid anhydride-type curing agents, and latent properties. Examples thereof include a curing agent.
  • a polyorganosiloxane having a three-dimensional network structure including a trifunctional siloxane unit, a tetrafunctional siloxane unit, etc. is used in combination with a polyorganosiloxane having a linear structure as necessary. It may be.
  • the polyorganosiloxane usually refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the following general formula (10) and a mixture thereof.
  • R 1 to R 6 are independently selected from an organic functional group, a hydroxyl group, and a hydrogen atom.
  • the main unit constituting the polyorganosiloxane is monofunctional [R 1 R 2 R 3 SiO 1/2 ] (triorganosylhemioxane), bifunctional [R 4 R 5 SiO 2/2 ] (diorganosiloxane), trifunctional [R 6 SiO 3/2 ] (organosilsesquioxane), tetrafunctional [SiO 4/2 ] (silicate), and these 4 types Since the difference in the properties of the polyorganosiloxane appears by changing the composition ratio of the units, it may be appropriately selected so as to obtain desired characteristics.
  • the silicone resin can be cured by applying heat energy, light energy, or the like in the presence of a known curing catalyst.
  • examples of the metal material include copper, nickel, gold, silver, palladium, and aluminum, and one or two or more of them may be mixed. Among these, copper is more preferable.
  • these metal materials are in a solid state in the production process, the surface is kept in a molten state by the treatment by the active energy ray irradiation, and the surface is joined to the surface roughened surface of the polyarylene sulfide resin molded product. After that, there are a method of cooling and solidifying and adhering, and a method of applying to the surface of the polyarylene sulfide resin molded article whose surface is roughened when it is melted and in a liquid state.
  • Examples of main applications of the complex are protection / support members for box-shaped electrical / electronic component integrated modules, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, Capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, electronic circuit, LSI, IC, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, terminal block , Semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts and other electrical and electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, Acoustic parts, audio ⁇ Audio / video equipment parts such as laser discs, compact discs, DVD discs, Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, water heaters, hot water in baths, temperature sensors, etc.
  • Machine-related parts Optical instruments such as microscopes, binoculars, cameras, watches, etc., precision machine-related parts: alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, relay blocks, inhibitor switches, exhaust gas valves, etc.
  • Each Valves various fuel / exhaust / intake pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear Sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, warm air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, Distributor, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor -Core, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing It can also be applied to automobile / vehicle-related parts such as brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and other various uses.
  • TEM-35B twin-screw extruder
  • the obtained pellets were supplied to an injection molding machine (SG75-HIPRO ⁇ MIII) manufactured by Sumitomo-Nestal Co., Ltd., which was set to a cylinder temperature of 320 ° C., and the mold for ASTM No. 1 dumbbell piece molding was adjusted to a mold temperature of 130 ° C. The mold was used for injection molding to obtain ASTM No. 1 dumbbell pieces.
  • an injection molding machine SG75-HIPRO ⁇ MIII
  • the obtained ASTM No. 1 dumbbell piece was subjected to surface roughening of 10 mm long ⁇ 5 m wide by irradiation with active energy rays (spot diameter 70 ⁇ m, moving speed 4 m / s, output 7 W). The following various evaluation tests were performed using this test piece. The results of the test and evaluation are shown in Tables 1 to 4.
  • Arithmetic average roughness Ra was measured according to JIS B 0601: 2013. That is, the surface roughened surface of the ASTM No. 1 dumbbell piece was measured using a surface roughness measuring device (manufactured by Mitutoyo Corporation, contour shape measuring device Surf Test SV-3000CNC).
  • Comparative Example 2 did not contain a metal oxide and had insufficient absorption of active energy rays, so that a sufficient surface roughening (etching) effect could not be obtained.
  • Comparative Example 3 since the glass fiber is small, the surface unevenness is small and the surface smoothness is good. On the other hand, in Comparative Example 4, there were many glass fibers, and active energy rays were reflected, so that a sufficient surface roughening (etching) effect was not obtained.
  • Comparative Examples 5 and 6 have insufficient absorption of active energy rays, and a sufficient surface roughening (etching) effect was not obtained.
  • Tables 1 to 4 represent parts by mass, and the materials are as follows.
  • PPS A-1) “MA-520” manufactured by Linear PPS DIC Corporation (peak molecular weight 35000, melt viscosity (V6) 160 Pa ⁇ s)
  • GF B-1) glass fiber “T-717H” manufactured by Nippon Electric Glass Co., Ltd.
  • HF5000PJ (aspect ratio ⁇ 20, D 50/20 ( ⁇ m), Mohs hardness 1.0) Clay mineral (D-2) Hydrotalcite “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd. (aspect ratio 2.6, D 50 /0.4 ( ⁇ m), Mohs hardness 1.0)
  • Additive (E-1) Amino group-containing alkoxysilane additive (E-2) Epoxy group-containing alkoxysilane additive (e-3) Carbon black (Denka Black Granules manufactured by Denki Kagaku Kogyo Co., Ltd.) average particle size 35 nm )
  • Mohs hardness a 10-step Mohs hardness that is generally used as an index of the hardness of minerals was used.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un article moulé en résine de poly(sulfure d'arylène) qui peut être soumis à une rugosification de surface lorsqu'il est irradié par des rayons d'énergie active, une composition de résine qui fournit l'article moulé en résine de poly(sulfure d'arylène), et des procédés de production dudit article moulé en résine de poly(sulfure d'arylène) et de ladite composition de résine. L'invention concerne également un procédé de rugosification de surface par irradiation de l'article moulé en résine de poly(sulfure d'arylène) avec des rayons d'énergie active, un article moulé composite en résine de poly(sulfure d'arylène) dans lequel un autre matériau tel qu'une composition de résine durcissable ou un métal est lié avec une adhésivité suffisante à un article moulé obtenu par rugosification de surface, et un procédé de production dudit article moulé composite en résine de poly (sulfure d'arylène). Plus spécifiquement, l'invention concerne : une composition de résine de poly(sulfure d'arylène) comprenant des fibres de verre, un oxyde métallique, et un minéral argileux stratifié et clivable, l'oxyde métallique ayant une faible dureté Mohs de moins de 1,5 fois celle des fibres de verre et l'oxyde métallique comprenant du cuivre et/ou du chrome ; un article moulé ; un article moulé composite ; et des procédés de production de la composition de résine de poly(sulfure d'arylène), de l'article moulé et de l'article moulé composite.
PCT/JP2017/036242 2016-10-07 2017-10-05 Composition de résine de poly(sulfure d'arylène), article moulé, et procédé de production Ceased WO2018066637A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019045578A (ja) * 2017-08-30 2019-03-22 キヤノン株式会社 トナー
WO2020246459A1 (fr) * 2019-06-04 2020-12-10 Dic株式会社 Composition de résine de sulfure de polyarylène, article moulé obtenu par moulage de celle-ci, stratifié et son procédé de production
WO2022044482A1 (fr) * 2020-08-25 2022-03-03 Dic株式会社 Composition de résine de sulfure de polyarylène, article moulé, et procédés de fabrication associés
JP2022065423A (ja) * 2020-10-15 2022-04-27 日鉄ケミカル＆マテリアル株式会社 積層体の製造方法および処理方法、当該製造方法および処理方法で用いる感光性樹脂組成物
CN114901458A (zh) * 2019-12-27 2022-08-12 Dic株式会社 复合结构体及其制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013144767A (ja) * 2011-03-18 2013-07-25 Mitsubishi Engineering Plastics Corp 熱可塑性樹脂組成物、樹脂成形品、及びメッキ層付樹脂成形品の製造方法
JP2013144768A (ja) * 2011-12-14 2013-07-25 Mitsubishi Engineering Plastics Corp 熱可塑性樹脂組成物、樹脂成形品、及びメッキ層付樹脂成形品の製造方法
JP2015120908A (ja) * 2013-12-20 2015-07-02 エーエムエス−パテント アクチェンゲゼルシャフト プラスチック成形材料及びその使用
JP2015218323A (ja) * 2014-05-21 2015-12-07 三菱エンジニアリングプラスチックス株式会社 ペレット、ペレットの製造方法、樹脂成形品、および、メッキ層付樹脂成形品の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013144767A (ja) * 2011-03-18 2013-07-25 Mitsubishi Engineering Plastics Corp 熱可塑性樹脂組成物、樹脂成形品、及びメッキ層付樹脂成形品の製造方法
JP2013144768A (ja) * 2011-12-14 2013-07-25 Mitsubishi Engineering Plastics Corp 熱可塑性樹脂組成物、樹脂成形品、及びメッキ層付樹脂成形品の製造方法
JP2015120908A (ja) * 2013-12-20 2015-07-02 エーエムエス−パテント アクチェンゲゼルシャフト プラスチック成形材料及びその使用
JP2015218323A (ja) * 2014-05-21 2015-12-07 三菱エンジニアリングプラスチックス株式会社 ペレット、ペレットの製造方法、樹脂成形品、および、メッキ層付樹脂成形品の製造方法

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019045578A (ja) * 2017-08-30 2019-03-22 キヤノン株式会社 トナー
WO2020246459A1 (fr) * 2019-06-04 2020-12-10 Dic株式会社 Composition de résine de sulfure de polyarylène, article moulé obtenu par moulage de celle-ci, stratifié et son procédé de production
JPWO2020246459A1 (ja) * 2019-06-04 2021-12-09 Dic株式会社 ポリアリーレンスルフィド樹脂組成物、これを成形してなる成形品、積層体、およびそれらの製造方法
CN113906105A (zh) * 2019-06-04 2022-01-07 Dic株式会社 聚芳硫醚树脂组合物、将其成型而成的成型品、层叠体和它们的制造方法
JP7028368B2 (ja) 2019-06-04 2022-03-02 Dic株式会社 ポリアリーレンスルフィド樹脂組成物、これを成形してなる成形品、積層体、およびそれらの製造方法
US12344744B2 (en) 2019-06-04 2025-07-01 Dic Corporation Polyarylene sulfide resin composition, molded article obtained by molding same, laminate, and production method thereof
TWI838534B (zh) * 2019-06-04 2024-04-11 日商Ｄｉｃ股份有限公司 聚伸芳硫醚樹脂組成物、將其成形而成的成形品、積層體、及彼等之製造方法
EP3981825A4 (fr) * 2019-06-04 2023-01-11 DIC Corporation Composition de résine de sulfure de polyarylène, article moulé obtenu par moulage de celle-ci, stratifié et son procédé de production
CN114901458A (zh) * 2019-12-27 2022-08-12 Dic株式会社 复合结构体及其制造方法
JP7070811B1 (ja) * 2020-08-25 2022-05-18 Dic株式会社 ポリアリーレンスルフィド樹脂組成物、成形品およびそれらの製造方法
CN115989201A (zh) * 2020-08-25 2023-04-18 Dic株式会社 聚芳硫醚树脂组合物、成型品及它们的制造方法
WO2022044482A1 (fr) * 2020-08-25 2022-03-03 Dic株式会社 Composition de résine de sulfure de polyarylène, article moulé, et procédés de fabrication associés
CN115989201B (zh) * 2020-08-25 2025-07-22 Dic株式会社 聚芳硫醚树脂组合物、成型品及它们的制造方法
KR102864480B1 (ko) 2020-08-25 2025-09-25 디아이씨 가부시끼가이샤 폴리아릴렌설파이드 수지 조성물, 성형품 및 그들의 제조 방법
JP2022065423A (ja) * 2020-10-15 2022-04-27 日鉄ケミカル＆マテリアル株式会社 積層体の製造方法および処理方法、当該製造方法および処理方法で用いる感光性樹脂組成物
JP7517942B2 (ja) 2020-10-15 2024-07-17 日鉄ケミカル＆マテリアル株式会社 積層体の製造方法および処理方法、当該製造方法および処理方法で用いる感光性樹脂組成物

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