WO2016093309A1 - ポリアリーレンスルフィド樹脂組成物、成形品、複合成形品および複合成形品の製造方法 - Google Patents
ポリアリーレンスルフィド樹脂組成物、成形品、複合成形品および複合成形品の製造方法 Download PDFInfo
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- WO2016093309A1 WO2016093309A1 PCT/JP2015/084645 JP2015084645W WO2016093309A1 WO 2016093309 A1 WO2016093309 A1 WO 2016093309A1 JP 2015084645 W JP2015084645 W JP 2015084645W WO 2016093309 A1 WO2016093309 A1 WO 2016093309A1
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- polyarylene sulfide
- molded article
- sulfide resin
- resin composition
- resin
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- VOVJEXLDAMDFBR-UHFFFAOYSA-N Cc(cc1)ccc1-c(cc1)ccc1NC Chemical compound Cc(cc1)ccc1-c(cc1)ccc1NC VOVJEXLDAMDFBR-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N Cc(cc1)ccc1N Chemical compound Cc(cc1)ccc1N RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N Cc(cc1)ccc1OC Chemical compound Cc(cc1)ccc1OC CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on 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; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Definitions
- the present invention includes a polyarylene sulfide resin, and in particular, is excellent in various properties of the polyarylene sulfide resin such as rigidity, heat resistance, dimensional stability, chemical resistance, and cold / heat resistance, and excellent in mold releasability. Furthermore, the present invention relates to a polyarylene sulfide resin molded article excellent in mechanical strength of a cured product and adhesiveness to a silicone resin, and a polyarylene sulfide resin composition for providing the molded article.
- PAS resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin
- PPS resin has excellent mechanical strength, heat resistance, chemical resistance, moldability, and dimensional stability. Using these characteristics, they are used as electrical / electronic equipment parts, automobile parts materials, and the like.
- the polyarylene sulfide resin has insufficient adhesion to the silicone resin compared to other resin engineering plastics.
- studies have been made on mixing or alloying with a different resin.
- Patent Document 1 discloses a polyarylene sulfide resin composition in which PTFE and a reinforcing material are blended with a polyarylene sulfide resin. It is described that the polyarylene sulfide resin composition and the molded product thereof are excellent in mechanical properties, electrical insulation and fluidity, and further excellent in adhesiveness with an epoxy resin.
- a polyarylene sulfide resin composition containing a small amount of PTFE and a reinforcing material and a molded product thereof are also known (Patent Document 2).
- Patent Document 2 a polyarylene sulfide resin composition containing a small amount of PTFE and a reinforcing material and a molded product thereof.
- the polyarylene sulfide resin composition and the molded product thereof can improve the silicone adhesion, the releasability at the time of molding is insufficient, for example, when the mold is opened after injection molding, The frequency with which the molded product sticks to the mold (fixed side) is high, causing the Z-shaped portion formed in the molded product to be damaged by the sprue lock pin (Z pin).
- JP 2009-30030 A JP-A-10-237301
- the problem to be solved by the present invention is to form a polyarylene sulfide resin that maintains the mechanical properties and the like inherent in the polyarylene sulfide resin molded product, and is excellent in silicone resin adhesion and releasability.
- a polyarylene sulfide resin composition for providing the molded product, a molded product formed by molding the polyarylene sulfide resin composition, and sealing or joining the molded product with a silicone resin It is providing the manufacturing method of the composite molded article which has the process of hardening a silicone resin.
- the present inventors formulated polyarylene sulfide resin (A), dimethylpolysiloxane (B), fatty acid ester (C) and silane coupling agent (D) as essential components. It has been found that the above-mentioned problems can be solved by the polyarylene sulfide resin thus formed, and the present invention has been completed.
- the present invention relates to a polyarylene sulfide resin composition
- a polyarylene sulfide resin composition comprising polyarylene sulfide resin (A), dimethylpolysiloxane (B), fatty acid ester (C) and silane coupling agent (D) as essential components.
- the present invention relates to a molded product formed by molding the polyarylene sulfide resin composition.
- the present invention also relates to a composite molded product obtained by bonding the molded product and a cured product made of a silicone resin.
- the present invention relates to a method for producing a composite molded article having a step of curing or curing the silicone resin after sealing or bonding the molded article with a silicone resin.
- a polyarylene sulfide resin molded article and a molded article thereof having excellent properties such as mechanical properties inherent to the polyarylene sulfide resin composition molded article and excellent in silicone resin adhesion and releasability
- a polyarylene sulfide resin composition can be provided, and a composite molded product obtained by bonding the molded product and a silicone resin can be provided.
- the polyarylene sulfide resin composition of the present invention comprises a polyarylene sulfide resin (A), a dimethylpolysiloxane (B), a fatty acid ester (C), and a silane coupling agent (D) as essential components. Details will be described below.
- the polyarylene sulfide resin composition of 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 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). It is a resin having a structural site as a repeating unit.
- R 1 and R 2 in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin.
- a compound bonded at the para position represented by the following formula (2) is preferable.
- 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 structural formula (2). In terms of surface.
- polyarylene sulfide resin is not limited to the structural part represented by the formula (1), but the following structural formulas (3) to (6)
- the structural site represented by the formula (1) may be included at 30 mol% or less of the total with the structural site represented by the formula (1).
- the structural portion represented by the above formulas (3) to (6) 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. .
- polyarylene sulfide resin has the following formula (7) in its molecular structure.
- 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.
- melt viscosity The polyarylene sulfide resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but the melt viscosity (V6) measured at 300 ° C. is preferably in the range of 2 to 1000 [Pa ⁇ s], Furthermore, the range of 2 to 500 [Pa ⁇ s] is more preferable, and the range of 2 to 200 [Pa ⁇ s] is particularly preferable because the balance between fluidity and mechanical strength is good.
- the non-Newtonian index of the polyarylene sulfide resin used in the present invention is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably in the range of 0.90 to 2.00.
- the non-Newtonian index is preferably in the range of 0.90 to 1.50, and more preferably in the range of 0.95 to 1.20.
- Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance.
- SR shear rate (second ⁇ 1 )
- SS shear stress (dyne / cm 2 )
- K represents a constant. The closer the N value is to 1, the closer the PPS is to a linear structure, and the higher the N value is, the more branched the structure is.
- the method for producing the polyarylene sulfide resin (A) is not particularly limited.
- Examples thereof include a method in which p-chlorothiophenol is self-condensed by adding other copolymerization components if necessary.
- the method 2) is versatile and preferable.
- an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization.
- a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound in the organic polar solvent.
- a sulfidizing agent are added to and reacted with a polyhalogenoaromatic compound as necessary, and the amount of water in the reaction system is in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent.
- a method for producing a polyarylene sulfide resin by controlling see Japanese Patent Application Laid-Open No. 07-228699), and a dihalogenoaromatic compound and if necessary 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
- the organic acid alkali metal salt in an amount of 0.01 to 0.9 mol with respect to the catalyst and the amount of water in the reaction system are controlled within a range of 0.02 mol or less with respect to 1 mol of the aprotic polar organic solvent. Those obtained by the method (see pamphlet of WO2010 / 058713) are particularly preferred.
- 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 And compounds having an alkyl
- 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 comprises dimethylpolysiloxane (B) as an essential component.
- the dimethylpolysiloxane used in the present invention is a polymer having a dimethylsiloxane bond (—Si (CH 3 ) 2 —O—) in the main chain, and the Si atom has an organic group other than a methyl group. May be. Examples of such an organic group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group, allyl group, 1-butenyl group, and 1-hexenyl group, preferably vinyl group and allyl group. And particularly preferably a vinyl group.
- Such an alkenyl group may be bonded to the Si atom at the end of the molecular chain, or may be bonded to the Si atom in the middle of the molecular chain. Further, a polymer obtained by increasing the molecular weight of the dimethylpolysiloxane by addition polymerization of the alkenyl group may be used. From the viewpoint of the curing reaction rate, an alkenyl group-containing polyorganosiloxane in which an alkenyl group is bonded only to the silicon atom at the end of the molecular chain is preferable.
- the dimethylpolysiloxane is preferably a linear dimethylpolysiloxane.
- the dimethylpolysiloxane (B) is preferably a silicone rubber having thermoplasticity and in the form of a solid rubber or a solid powder at room temperature (15 ° C. to 35 ° C.). Addition of the component (B) is advantageous in that the releasability of the molded product is remarkably improved, and as a result, high surface smoothness and excellent silicone resin adhesiveness can be provided.
- the dimethylpolysiloxane may be silicone rubber particles, in which case the average particle size is not particularly limited and may be appropriately selected depending on the intended purpose, but the volume average particle size is 0.01 ⁇ m. Is preferably 30 ⁇ m, more preferably 0.1 ⁇ m to 15 ⁇ m. When the volume average particle size is 0.01 ⁇ m or more, dispersibility of the polyarylene sulfide resin (A), the fatty acid ester (C), and the silane coupling agent (D) is improved, and surface smoothness is improved. When it is 30 ⁇ m or less, impact resistance tends to be improved, and when it is 15 ⁇ m or less, it is more preferable.
- the volume average particle diameter can be measured by, for example, a laser diffraction method.
- the true specific gravity of the dimethylpolysiloxane (B) component is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.90 to 1.5, more preferably 0.95 to 1.4. preferable.
- the number of siloxane bonds in the dimethylpolysiloxane (B) component is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 to 15,000, and more preferably in the range of 500 to 12,000. More preferably, the range of 2,000 to 10,000 is particularly preferable, and the range of 4,000 to 8,000 is most preferable.
- the dimethylpolysiloxane used in the present invention either a linear dimethylpolysiloxane or a dimethylpolysiloxane having a structure obtained by crosslinking a linear dimethylpolysiloxane can be preferably used.
- dimethylpolysiloxane when the number of siloxane bonds is 20 or more, it tends to be difficult to bleed out from the surface of the molded product, and when it is 2000 or more, it bleeds out from the surface of the molded product. It is more preferable because it is difficult and the tensile strength in the TD direction such as TD bending strength and TD bending elongation tends to be improved.
- the number of siloxane bonds in the dimethylpolysiloxane (B) component is obtained, for example, by determining the molecular weight (Mw) of dimethylpolysiloxane by the following GPC measurement, and this is determined as the dimethylsiloxane bond unit (—Si (CH 3 ) 2 —O— It can also be determined by dividing by the molecular weight (74).
- GPC measurement and measurement device “HLC-8320 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL G1000HXL” + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (differential refraction diameter)
- Data processing “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation Column temperature: 40 ° C
- Developing solvent Tetrahydrofuran flow rate: 1.0 ml / min Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
- Monodisperse polystyrene “A-500” manufactured by Tosoh Corporation “A-2500” manufactured by Tosoh Corporation “F-1” manufactured by Tosoh Corporation “F-4” manufactured by Tosoh Corporation “F-20” manufactured by Tosoh Corporation “F-128” manufactured by Tosoh Corporation “F-380” manufactured by Tosoh Corporation Measurement sample: 1 mg of resin (solvent-soluble component) was dissolved in 1 ml of tetrahydrofuran and then filtered through a microfilter (pore size 0.45 ⁇ m) (50 ⁇ l).
- the dimethylpolysiloxane (B) component may be impregnated in silica (hereinafter sometimes referred to as “silica impregnation (B)”), and the periphery of the dimethylpolysiloxane (B) is three-dimensional. It may be one coated with a silicone resin powder having a crosslinked structure (hereinafter sometimes referred to as “silicone composite particles”).
- silica hereinafter sometimes referred to as “silica impregnation (B)”
- silicone resin powder having a crosslinked structure hereinafter sometimes referred to as “silicone composite particles”.
- the content of the silicone rubber particle (B) component is 65% by mass or more and 75% by mass or less, impact resistance is improved and smoothness tends to be improved, which is preferable.
- the coverage of the coating component (silicone resin powder having a three-dimensional crosslinked structure) with respect to the dimethylpolysiloxane (B) component is 50% or less. It is preferable. It is preferable that the coverage is 50% or less because impact resistance is improved and smoothness tends to be improved.
- a commercial item may be used for the said dimethylpolysiloxane (B) component, and what was synthesize
- Specific examples of commercial products of the dimethylpolysiloxane (B) component include trade names such as KMP-597, KMP-598, KMP-594, X-52-875 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Silicone rubber particles; silicone composite particles such as KMP-605 and X-52-7030 (manufactured by Shin-Etsu Chemical Co., Ltd.); silica impregnation (B ) Component.
- the content of dimethylpolysiloxane (B) in the polyarylene sulfide resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but preferably with respect to 100 parts by mass of the polyarylene sulfide resin (A).
- the range of 0.01 to 20.0 parts by mass is preferable, and the range of 0.05 to 10.0 parts by mass is more preferable. If it is 0.01 mass part or more, it will be excellent in a mold release property, and if it is 20.0 mass parts or less, it is preferable because it tends to be excellent in mechanical properties, heat resistance, and silicone resin adhesion.
- the polyarylene sulfide resin composition of the present invention comprises a fatty acid ester (C) as an essential component.
- fatty acid ester used in the present invention include esters of aliphatic alcohols and aliphatic carboxylic acids.
- Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol.
- the number of carbon atoms of the alcohol is preferably 3 to 32, more preferably 5 to 30.
- mystyryl alcohol, stearyl alcohol, oleyl alcohol, and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol as trihydric or higher alcohols.
- dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol as trihydric or higher alcohols.
- examples of glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, and sorbitol are not limited thereto.
- the aliphatic carboxylic acid may be a saturated fatty acid and / or an unsaturated fatty acid, and is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred.
- the fatty acid ester of the present invention is preferable in that all esters (full esters) are excellent in thermal stability at high temperatures.
- Saturated fatty acids include butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, Saturated fatty acids include succinic acid, lindelic acid, tuzuic acid, succinic acid, myristooleic acid, zomarinic acid, petroceric acid, oleic acid, vaccenic acid, gadoleic acid, whale oil acid, erucic acid, shark oil acid, linoleic acid , Hiragoic acid, eleostearic acid, bunicic acid, tricosanoic acid, linolenic acid, moloctic acid, parinaric acid, arachidonic acid, sardine acid, hiragasic acid, and nisic acid.
- the content of the fatty acid ester (C) in the polyarylene sulfide resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is 0.1% relative to 100 parts by mass of the polyarylene sulfide resin (A). It is preferably in the range of 005 to 5.0 parts by mass, more preferably in the range of 0.01 to 1.0 parts by mass, and further in the range of 0.05 to 0.5 parts by mass. preferable. In such a range, the polyarylene sulfide resin composition is preferable because the molded article exhibits excellent adhesiveness with the silicone resin while having good release properties.
- the polyarylene sulfide resin composition of the present invention comprises a silane coupling agent (D) as an essential component.
- the silane coupling agent (D) used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but a silane 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.
- a coupling agent is preferable.
- 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 content of the silane coupling agent (D) in the polyarylene sulfide resin composition of the present invention 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),
- the range is preferably from 0.01 to 2.0 parts by mass, and more preferably from 0.1 to 1.0 part by mass. In such a range, the polyarylene sulfide resin composition is preferable because the molded article exhibits excellent adhesiveness with the silicone resin while having good release properties.
- the polyarylene sulfide resin composition of the present invention preferably further contains a filler in addition to the above components in order to further improve performance such as mechanical strength, particularly thermal shock strength, heat resistance, and dimensional stability.
- the filler used in the present invention is not an essential component, but when added, it is more than 0 parts by weight, usually 1 part by weight or more, more preferably 10 parts by weight or more, relative to 100 parts by weight of the polyarylene sulfide resin.
- various performances can be improved according to the purpose of the filler to be added, such as strength, rigidity, heat resistance, heat dissipation and dimensional stability.
- fibers such as glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and natural fibers such as wollastonite.
- Non-fibrous fillers such as magnesium and glass beads can also be used.
- 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 resin such as urethane resin and liquid crystal polymer, or elastomer such as fluorine rubber is blended as an optional component.
- these resins are not essential components, but when added, the amount used varies depending on the purpose and cannot be specified in general, but with respect to 100 parts by mass of the polyarylene sulfide resin (A). In the range of 0.01 to 1000 parts by mass, it may be appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention.
- the polyarylene sulfide resin composition of the present invention is within a range not impairing the effects of the present invention, as additives during molding processing, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive agent Various additives such as additives, flame retardants and lubricants are blended as optional components as required.
- the amount of these additives used varies depending on the purpose and cannot be generally defined, but in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A), What is necessary is just to adjust suitably according to the objective and the use so that the effect of this invention may not be impaired.
- the method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited, and the polyarylene sulfide resin (A), dimethylpolysiloxane (B), fatty acid ester (C) and silane coupling agent (D) are essential components. Melt-knead at a melting point or higher of the polyarylene sulfide resin (A). More specifically, the essential components of polyarylene sulfide resin (A), dimethylpolysiloxane (B), fatty acid ester (C) and silane coupling agent (D) as raw materials and, if necessary, fillers, etc. The other optional ingredients in the powder, pellets, strips, etc.
- melt kneader such as a kneader and a neater
- 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 equal to or higher than 10 ° C.
- 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, more preferably melt-kneaded under the condition that the ratio (discharge amount / screw rotation number) is 0.02 to 5 (kg / hr / rpm). .
- the position of the side feeder is preferably such that the ratio of the distance from the extruder resin charging portion to the side feeder with respect to the total screw length of the biaxial kneading extruder is 0.1 to 0.9. Of these, 0.3 to 0.7 is particularly preferable.
- the polyarylene sulfide resin composition of the present invention obtained by melt-kneading in this way is an essential component of polyarylene sulfide resin (A), dimethylpolysiloxane (B), fatty acid ester (C), silane coupling agent ( D), a melt-kneaded product containing optional components to be added as necessary and components derived therefrom, and after the melt-kneading, it is processed into a form of pellets, chips, granules, powders, etc. by a known method, and then necessary Accordingly, it is preferable to perform preliminary drying at a temperature of 100 to 150 ° C. and to provide various types of molding.
- the polyarylene sulfide resin composition of the present invention can be subjected to various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. It is suitable for injection molding because of its excellent properties.
- various molding conditions are not particularly limited, and can be usually molded by a general method.
- the resin temperature is in the temperature range above the melting point of the polyarylene sulfide resin, preferably in the temperature range above the melting point + 10 ° C., more preferably in the temperature range from the melting point + 10 ° C. to the melting point + 100 ° C., more preferably the melting point.
- the resin discharge port may be injected into the mold and molded.
- the mold temperature may be set to a known temperature range, for example, a room temperature (23 ° C.) to 300 ° C., preferably 120 to 180 ° C.
- the molded product of the polyarylene sulfide resin composition thus obtained is excellent in adhesiveness with the silicone resin. For this reason, it is suitably used for bonding silicone resins.
- silicone resins For example, by sealing or bonding a plate-like or box-shaped molded product made of a polyarylene sulfide resin composition with a silicone resin, the silicone resin is cured.
- a composite molded product obtained by bonding a molded product formed by molding the polyarylene sulfide resin composition and a cured product formed of a silicone resin is obtained.
- Main examples of applications of composite molded products 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, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, terminal block, semiconductor, liquid crystal, FDD carriage , FDD chassis, motor brush holder, parabolic antenna, electric / electronic parts represented by computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs ⁇ Con For audio / video equipment parts such as Kutto Disc / DVD Disc / Blu-ray Disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, water heaters, hot water in baths, temperature sensor, etc.
- audio / video equipment parts such as Ku
- Representative home, office electrical product parts office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs, motor parts, writers, typewriters, etc.
- 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 valves, etc.
- Fuel and exhaust ⁇ Various intake system 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, crank Shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot 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, Wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid It can also be applied to automobile / vehicle-related parts such as bobbins, engine oil filters, ignition device cases, and other various uses.
- the obtained pellets are supplied to an injection molding machine (SG75-HIPRO ⁇ MIII) manufactured by Sumitomo-Nestal with the cylinder temperature set at 320 ° C., and the mold for ISO Type-A dumbbell piece molding is adjusted to a mold temperature of 130 ° C. Was subjected to injection molding to obtain ISO Type-A dumbbell pieces.
- the obtained dumbbell pieces were measured for tensile strength and tensile elongation by a measuring method based on ISO 527-1 and 2.
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Abstract
Description
本発明のポリアリーレンスルフィド樹脂組成物はポリアリーレンスルフィド樹脂(A)を必須成分として配合してなる。本発明に使用するポリアリーレンスルフィド樹脂は、芳香族環と硫黄原子とが結合した構造を繰り返し単位とする樹脂構造を有するものであり、具体的には、下記式(1)
本発明に用いるポリアリーレンスルフィド樹脂は、本発明の効果を損ねない限り特に限定されないが、300℃で測定した溶融粘度(V6)が2~1000〔Pa・s〕の範囲であることが好ましく、さらに流動性および機械的強度のバランスが良好となることから2~500〔Pa・s〕の範囲がより好ましく、特に2~200〔Pa・s〕の範囲であることが特に好ましい。但し、本発明において、溶融粘度(V6)は、ポリアリーレンスルフィド樹脂を高化式フローテスター(島津製作所製「CFT-500C」)を用い、300℃、荷重:1.96×106Pa、L/D=10mm/1mmにて、6分間保持した後に溶融粘度を測定した値とする。
本発明に用いるポリアリーレンスルフィド樹脂の非ニュートン指数は、本発明の効果を損ねない限り特に限定されないが、0.90~2.00の範囲であることが好ましい。リニア型ポリアリーレンスルフィド樹脂を用いる場合には、非ニュートン指数が0.90~1.50の範囲であることが好ましく、さらに0.95~1.20の範囲であることがより好ましい。このようなポリアリーレンスルフィド樹脂は機械的物性、流動性、耐磨耗性に優れる。ただし、非ニュートン指数(N値)は、キャピログラフを用いて300℃、オリフィス長(L)とオリフィス径(D)の比、L/D=40の条件下で、剪断速度及び剪断応力を測定し、下記式を用いて算出した値である。
前記ポリアリーレンスルフィド樹脂(A)の製造方法としては、特に限定されないが、例えば1)硫黄と炭酸ソーダの存在下でジハロゲノ芳香族化合物を、必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加えて、重合させる方法、2)極性溶媒中でスルフィド化剤等の存在下にジハロゲノ芳香族化合物を、必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加えて、重合させる方法、3)p-クロルチオフェノールを、必要ならばその他の共重合成分を加えて、自己縮合させる方法、等が挙げられる。これらの方法のなかでも、2)の方法が汎用的であり好ましい。反応の際に、重合度を調節するためにカルボン酸やスルホン酸のアルカリ金属塩を添加したり、水酸化アルカリを添加しても良い。上記2)方法のなかでも、加熱した有機極性溶媒とジハロゲノ芳香族化合物とを含む混合物に含水スルフィド化剤を水が反応混合物から除去され得る速度で導入し、有機極性溶媒中でジハロゲノ芳香族化合物とスルフィド化剤とを、必要に応じてポリハロゲノ芳香族化合物と加え、反応させること、及び反応系内の水分量を該有機極性溶媒1モルに対して0.02~0.5モルの範囲にコントロールすることによりポリアリーレンスルフィド樹脂を製造する方法(特開平07-228699号公報参照。)や、固形のアルカリ金属硫化物及び非プロトン性極性有機溶媒の存在下でジハロゲノ芳香族化合物と必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加え、アルカリ金属水硫化物及び有機酸アルカリ金属塩を、硫黄源1モルに対して0.01~0.9モルの有機酸アルカリ金属塩および反応系内の水分量を非プロトン性極性有機溶媒1モルに対して0.02モル以下の範囲にコントロールしながら反応させる方法(WO2010/058713号パンフレット参照。)で得られるものが特に好ましい。ジハロゲノ芳香族化合物の具体的な例としては、p-ジハロベンゼン、m-ジハロベンゼン、o-ジハロベンゼン、2,5-ジハロトルエン、1,4-ジハロナフタレン、1-メトキシ-2,5-ジハロベンゼン、4,4’-ジハロビフェニル、3,5-ジハロ安息香酸、2,4-ジハロ安息香酸、2,5-ジハロニトロベンゼン、2,4-ジハロニトロベンゼン、2,4-ジハロアニソール、p,p’-ジハロジフェニルエーテル、4,4’-ジハロベンゾフェノン、4,4’-ジハロジフェニルスルホン、4,4’-ジハロジフェニルスルホキシド、4,4’-ジハロジフェニルスルフィド、及び、上記各化合物の芳香環に炭素原子数1~18のアルキル基を有する化合物が挙げられ、ポリハロゲノ芳香族化合物としては1,2,3-トリハロベンゼン、1,2,4-トリハロベンゼン、1,3,5-トリハロベンゼン、1,2,3,5-テトラハロベンゼン、1,2,4,5-テトラハロベンゼン、1,4,6-トリハロナフタレンなどが挙げられる。また、上記各化合物中に含まれるハロゲン原子は、塩素原子、臭素原子であることが望ましい。
本発明のポリアリーレンスルフィド樹脂組成物はジメチルポリシロキサン(B)を必須成分として配合してなる。本発明で用いるジメチルポリシロキサンは、ジメチルシロキサン結合(-Si(CH3)2-O-)を主鎖中に有する重合体であり、前記Si原子は、メチル基以外の有機基を有していてもよい。このような、有機基としては、ビニル基、アリル基、1-ブテニル基、1-ヘキセニル基などの炭素原子数2~8のアルケニル基を例示することができ、好ましくはビニル基、アリル基であり、特に好ましくはビニル基である。かかるアルケニル基は、分子鎖の末端のSi原子に結合していてもよいし、分子鎖の途中のSi原子に結合していてもよい。さらに該アルケニル基の付加重合により、前記ジメチルポリシロキサンが高分子量化されたものを用いてもよい。
硬化反応速度の面からは、アルケニル基が分子鎖末端のケイ素原子のみに結合したアルケニル基含有ポリオルガノシロキサンであることが好ましい。前記ジメチルポリシロキサンは、直鎖状のジメチルポリシロキサンであることが好ましい。
また、前記ジメチルポリシロキサン(B)は、熱可塑性を有し、常温(15℃~35℃)で固形ゴム状あるいは固形粉末状であるシリコーンゴムであることが好ましい。
前記(B)成分を配合すると、成形品の離形性が著しく向上し、その結果、高い表面平滑性、優れたシリコーン樹脂接着性を兼ね備えることができる点で有利である。
測定装置 :東ソー株式会社製「HLC-8320 GPC」
カラム :東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G1000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器 :RI(示差屈折径)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.10」
カラム温度:40℃
展開溶媒 :テトラヒドロフラン
流速 :1.0ml/分
標準試料 :前記「GPC-8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
単分散ポリスチレン:
東ソー株式会社製「A-500」
東ソー株式会社製「A-2500」
東ソー株式会社製「F-1」
東ソー株式会社製「F-4」
東ソー株式会社製「F-20」
東ソー株式会社製「F-128」
東ソー株式会社製「F-380」
測定試料 :樹脂1mg(溶剤可溶分)をテトラヒドロフラン1mlに溶解させた後、マイクロフィルター(ポアサイズ0.45μm)でろ過したもの(50μl)。
ただし、前記ジメチルポリシロキサン(B)成分が前記シリカ含浸(B)成分である場合、該シリカ含浸(B)成分中のジメチルポリシロキサン(B)成分の含有量は、本発明の効果を損ねなければ特に限定されるものではないが、50%質量以上95質量%以下であることが好ましく、さらに65%質量以上75質量%以下であることがより好ましい。前記シリコーンゴム粒子(B)成分の含有量が65質量%以上75質量%以下であると、耐衝撃性が向上することや、平滑性が良くなる傾向となり好ましい。
また、前記ジメチルポリシロキサン(B)が前記シリコーン複合粒子である場合、該ジメチルポリシロキサン(B)成分に対する該被覆成分(3次元架橋構造を有するシリコーン樹脂粉末)の被覆率が50%以下であることが好ましい。前記被覆率が50%以下であると、耐衝撃性が向上することや、平滑性が良くなる傾向にあり好ましい。
前記ジメチルポリシロキサン(B)成分の市販品の具体例としては、商品名で、KMP-597、KMP-598、KMP-594、X-52-875(以上、信越化学工業株式会社製)等のシリコーンゴム粒子;KMP-605、X-52-7030(以上、信越化学工業株式会社製)等のシリコーン複合粒子;GENIOPLAST(登録商標) Pellet S(旭化成ワッカーシリコーン株式会社製)等のシリカ含浸(B)成分などが挙げられる。
本発明のポリアリーレンスルフィド樹脂組成物は脂肪酸エステル(C)を必須成分として配合してなる。本発明で用いる脂肪酸エステルとしては、脂肪族アルコールと脂肪族カルボン酸とのエステルが挙げられる。
かかる脂肪族アルコールは1価アルコールであっても2価以上の多価アルコールであってもよい。また該アルコールの炭素原子数は、好ましくは3~32、より好ましくは5~30である。具体例としてはミスチリルアルコール、ステアリルアルコール、オレイルアルコール、2価アルコールとしては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ネオペンチルグリコール、1,6-ヘキサンジオールが、3価以上のアルコールとしては、グリセリン、ジグリセリン、トリグリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリトリトール、ジペンタエリトリトール、マンニトール、ソルビトールが例示されるが、これらに限定されるものではない。
本発明のポリアリーレンスルフィド樹脂組成物はシランカップリング剤(D)を必須成分として配合してなる。本発明で用いるシランカップリング剤(D)としては、本発明の効果を損ねなければ特に限定されないが、カルボキシ基と反応する官能基、例えば、エポキシ基、イソシアナト基、アミノ基または水酸基を有するシランカップリング剤が好ましいものとして挙げられる。このようなシランカップリング剤としては、例えば、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有アルコキシシラン化合物、γ-イソシアナトプロピルトリメトキシシラン、γ-イソシアナトプロピルトリエトキシシラン、γ-イソシアナトプロピルメチルジメトキシシラン、γ-イソシアナトプロピルメチルジエトキシシラン、γ-イソシアナトプロピルエチルジメトキシシラン、γ-イソシアナトプロピルエチルジエトキシシラン、γ-イソシアナトプロピルトリクロロシラン等のイソシアナト基含有アルコキシシラン化合物、γ-(2-アミノエチル)アミノプロピルメチルジメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン等のアミノ基含有アルコキシシラン化合物、γ-ヒドロキシプロピルトリメトキシシラン、γ-ヒドロキシプロピルトリエトキシシラン等の水酸基含有アルコキシシラン化合物が挙げられる。
表1~2に記載する組成成分および配合量にしたがい、各材料をタンブラーで均一に混合した。その後、東芝機械株式会社製ベント付き2軸押出機「TEM-35B」に前記配合材料を投入し、樹脂成分吐出量25kg/hr、スクリュー回転数250rpm、樹脂成分の吐出量(kg/hr)とスクリュー回転数(rpm)との比率(吐出量/スクリュー回転数)=0.1(kg/hr・rpm)、設定樹脂温度330℃で溶融混練してポリアリーレンスルフィド樹脂組成物のペレットを得た。
このペレットを用いて以下の各種評価試験を行った。試験及び評価の結果は、表1~2に示した。
得られたペレットをシリンダー温度320℃に設定した住友-ネスタール社製射出成形機(SG75-HIPRO・MIII)に供給し、金型温度130℃に温調したISO Type-Aダンベル片成形用金型を用いて射出成形を行い、ISO Type-Aダンベル片を得た。得られたダンベル片をISO 527-1および2に準拠した測定方法で引張強度、引張伸びを測定した。
得られたペレットをシリンダー温度320℃に設定した住友-ネスタール社製射出成形機(SG75-HIPRO・MIII)に供給し、金型温度130℃に温調したISO D2プレート成形用金型を用いて射出成形を行い、ISO D2プレートに切削して試験片を作成した。得られた試験片をISO 178に準拠した測定方法でTD曲げ強度、TD曲げ伸びを測定した。
得られたペレットをシリンダー温度320℃に設定した住友-ネスタール社製射出成形機(SG75-HIPRO・MIII)に供給し、金型温度130℃に温調したASTM1号ダンベル片成形用金型を用いて射出成形を行い、ASTM1号ダンベル片を得た。得られたASTM1号ダンベル片を中央から2等分し、後述するシリコーン樹脂との接触面積が50mm2となるように作成したスペーサー(厚さ:1.8~2.2mm、開口部:5mm×10mm)を2等分したASTM1号ダンベル片2枚の間に挟み、クリップを用い固定した後開口部にシリコーン樹脂(ダウ・コーニング株式会社製「SE-1714」)を注入し、135℃に設定した熱風乾燥機中で3時間加熱し硬化・接着させた。23℃下で1日冷却後スペーサーを外し、得られた試験片を用いて歪み速度1mm/min、支点間距離80mm、23℃下でインストロン社製引張試験機を用い引張破断強さを測定し、接着面積で除した値を接着強度とした。
ISO Type-Aダンベルを成形時、100ショット中、金型に成形品が取られた個数(すなわち、射出成形後、金型を開いた際に、成形品が金型に張り付いた個数、つまりスプルーロックピン(Zピン)により成形品に賦形されたZ形状部が破損した個数)をカウントした。
PPS
A1 DIC株式会社製ポリアリーレンスルフィド樹脂「DIC.PPS(V6溶融粘度20Pa・s、非NT指数1.1)」
A2 DIC株式会社製ポリアリーレンスルフィド樹脂「DIC.PPS(V6溶融粘度700Pa・s、非NT指数1.7)」
B1 ジメチルポリシロキサン(球状シリコーンゴムパウダー(直鎖状のジメチルポリシロキサンを架橋した構造を持つシリコーンゴムの微粉末)、平均粒径13μm、粒径分布2~30μm)信越化学工業株式会社製「KMP-598」
B2 ジメチルポリシロキサン(ジメチルポリシロキサン(分子量Mw=530,000、シロキサン結合数(分子量Mw/74)=7,162)をヒュームドシリカに含浸。ジメチルポリシロキサン/ヒュームドシリカ=65/35(質量比))旭化成ワッカーシリコーン株式会社製「GENIOPLAST PELLET S」
C2 ポリエチレンワックス BASF株式会社製「Luwax AH6」
D1 3-アミノプロピルトリエトキシシラン
D2 γ-グリシドキシプロピルトリメトキシシラン
E1 ガラス繊維チョップドストランド(Eガラス、繊維直径10μm、繊維長3mm、エポキシ系収束剤)
F1 PTFE ダイキン工業株式会社製「モールディングパウダーM-112」
Claims (7)
- ポリアリーレンスルフィド樹脂(A)、ジメチルポリシロキサン(B)、脂肪酸エステル(C)およびシランカップリング剤(D)を必須成分として配合してなるポリアリーレンスルフィド樹脂組成物。
- 前記脂肪酸エステル(C)が、炭素原子数3~32の脂肪族アルコールと、炭素原子数3~32の脂肪族カルボン酸とのエステルである請求項1記載のポリアリーレンスルフィド樹脂組成物。
- 溶融混練物である請求項1又は2記載のポリアリーレンスルフィド樹脂組成物。
- シリコーン樹脂接着用である請求項1~3のいずれか一項記載のポリアリーレンスルフィド樹脂組成物。
- 請求項1~4のいずれか一項記載のポリアリーレンスルフィド樹脂組成物を成形してなる成形品。
- 請求項5記載の成形品と、シリコーン樹脂からなる硬化物とが接着してなる複合成形品。
- 請求項5記載の成形品をシリコーン樹脂で封止または接合した後、当該シリコーン樹脂を硬化する工程を有する複合成形品の製造方法。
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KR1020177013172A KR102341089B1 (ko) | 2014-12-12 | 2015-12-10 | 폴리아릴렌설피드 수지 조성물, 성형품, 복합 성형품 및 복합 성형품의 제조 방법 |
EP15867286.5A EP3231844B1 (en) | 2014-12-12 | 2015-12-10 | Polyarylene sulfide resin composition, molded article, composite molded article, and method for producing composite molded article |
JP2016563733A JP6646877B2 (ja) | 2014-12-12 | 2015-12-10 | ポリアリーレンスルフィド樹脂組成物、成形品、複合成形品および複合成形品の製造方法 |
CN201580067794.6A CN107109060B (zh) | 2014-12-12 | 2015-12-10 | 聚芳硫醚树脂组合物、成形品、复合成形品及复合成形品的制造方法 |
US15/531,834 US20170313880A1 (en) | 2014-12-12 | 2015-12-10 | Polyarylene sulfide resin composition, molded article, composite molded article, and method for producing composite molded article |
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US (1) | US20170313880A1 (ja) |
EP (1) | EP3231844B1 (ja) |
JP (2) | JP6646877B2 (ja) |
KR (1) | KR102341089B1 (ja) |
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Cited By (3)
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WO2017057558A1 (ja) * | 2015-10-02 | 2017-04-06 | Dic株式会社 | ポリアリーレンスルフィド樹脂組成物、成形品及び製造方法 |
JP2018053003A (ja) * | 2016-09-26 | 2018-04-05 | Dic株式会社 | ポリアリーレンスルフィド樹脂組成物、成形品及び製造方法 |
WO2022080129A1 (ja) * | 2020-10-16 | 2022-04-21 | ポリプラスチックス株式会社 | 水を含む流体と接触し得る車両用冷却系部品 |
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WO2019208374A1 (ja) * | 2018-04-25 | 2019-10-31 | 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、複合成形品及びそれらの製造方法 |
JP6876261B2 (ja) * | 2018-12-06 | 2021-05-26 | Dic株式会社 | 樹脂組成物およびその成形体 |
JPWO2021100758A1 (ja) * | 2019-11-19 | 2021-05-27 | ||
CN114729188A (zh) * | 2019-11-19 | 2022-07-08 | 东丽株式会社 | 汽车冷却部件用聚苯硫醚树脂组合物及汽车冷却部件 |
US20230040667A1 (en) * | 2019-12-27 | 2023-02-09 | Dic Corporation | Composite structure and manufacturing method thereof |
WO2023150058A2 (en) * | 2022-02-01 | 2023-08-10 | Ticona Llc | Polymer compositions for an electric vehicle |
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- 2015-12-10 US US15/531,834 patent/US20170313880A1/en not_active Abandoned
- 2015-12-10 KR KR1020177013172A patent/KR102341089B1/ko active IP Right Grant
- 2015-12-10 EP EP15867286.5A patent/EP3231844B1/en active Active
- 2015-12-10 CN CN201580067794.6A patent/CN107109060B/zh active Active
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JP6939871B2 (ja) | 2021-09-22 |
JP2020037708A (ja) | 2020-03-12 |
JP6646877B2 (ja) | 2020-02-14 |
EP3231844B1 (en) | 2019-11-27 |
CN107109060A (zh) | 2017-08-29 |
EP3231844A4 (en) | 2018-07-25 |
KR20170095193A (ko) | 2017-08-22 |
US20170313880A1 (en) | 2017-11-02 |
EP3231844A1 (en) | 2017-10-18 |
CN107109060B (zh) | 2021-06-18 |
KR102341089B1 (ko) | 2021-12-20 |
JPWO2016093309A1 (ja) | 2017-10-12 |
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