WO2015098703A1 - Composition de résine de sulfure de polyarylène et produit moulé de cette dernière - Google Patents

Composition de résine de sulfure de polyarylène et produit moulé de cette dernière Download PDF

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WO2015098703A1
WO2015098703A1 PCT/JP2014/083586 JP2014083586W WO2015098703A1 WO 2015098703 A1 WO2015098703 A1 WO 2015098703A1 JP 2014083586 W JP2014083586 W JP 2014083586W WO 2015098703 A1 WO2015098703 A1 WO 2015098703A1
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polyarylene sulfide
resin composition
sulfide resin
group
resin
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PCT/JP2014/083586
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English (en)
Japanese (ja)
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昌則 内潟
昌志 國重
卓 島屋
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Dic株式会社
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Priority to JP2015554804A priority Critical patent/JP5935957B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

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  • the present invention includes a polyarylene sulfide resin (hereinafter sometimes abbreviated as PAS resin), and in particular, a polyarylene sulfide resin composition excellent in adhesiveness and fluidity with an epoxy resin and excellent in thermal shock resistance and It relates to the molded body.
  • PAS resin polyarylene sulfide resin
  • PAS resin is excellent in mechanical strength, heat resistance, chemical resistance, molding processability, and dimensional stability. Utilizing these characteristics, PAS resin is used as an electrical / electronic device part, an automobile part material, and the like.
  • PAS resins have relatively poor adhesion to other resins, especially adhesion to epoxy resins. Therefore, for example, when bonding PASs with epoxy adhesives, bonding PAS resins with other materials, or sealing electrical / electronic parts with epoxy resins, the adhesion between PAS resins and epoxy resins (hereinafter referred to as “bonding”) , Epoxy adhesion or simply adhesion) is a problem.
  • PAS resin compositions in which an epoxy resin is blended with a polyarylene sulfide resin, or a glass fiber with a polyarylene sulfide resin.
  • PAS resin compositions containing olefin polymers, epoxy resins, and glass flakes have been proposed (see Patent Documents 1 and 2).
  • this method uses a bisphenol A type epoxy resin as an epoxy resin, it has excellent epoxy adhesiveness and fluidity, but the thermal shock resistance is at a level that is hardly sufficient for practical use.
  • the problem to be solved by the present invention is to provide a PAS resin composition that can produce a molded article excellent in epoxy adhesion and thermal shock resistance and has excellent fluidity, and further molding the resin composition.
  • Another object of the present invention is to provide a PAS resin molded article excellent in epoxy adhesion and thermal shock resistance.
  • the present invention is a polyarylene sulfide resin composition containing a polyarylene sulfide resin (A) and a polyether polyol (B),
  • the polyether polyol has a branched structure in the molecule, and relates to a polyarylene sulfide resin composition.
  • the present invention relates to a molded article obtained by molding the polyarylene sulfide resin composition described above.
  • the present invention it is possible to produce a molded article excellent in epoxy adhesiveness and thermal shock resistance, and to provide a PAS resin composition excellent in fluidity. Further, epoxy adhesive formed by molding the resin composition and A PAS resin molded article having excellent thermal shock resistance can be provided.
  • FIG. 13 is a 13C-NMR chart of the polyether polyol (“HBP-100”) used in the examples.
  • the polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin (A) and a polyether polyol (B). Details will be described below.
  • 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.
  • the polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 5 to 1000 [Pa ⁇ s], and has a good balance between fluidity and mechanical strength. Therefore, the range of 5 to 100 [Pa ⁇ s] is more preferable, and the range of 5 to 50 [Pa ⁇ s] is particularly preferable.
  • V6 melt viscosity
  • 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 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 0.01-0.9 mol of an organic acid alkali metal salt with respect to the catalyst and a reaction while controlling the amount of water in the reaction system within a range of 0.02 mol with respect to 1 mol of the aprotic polar organic solvent (See the pamphlet of WO2010 / 058713).
  • dihalogenoaromatic compounds 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 group
  • the 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 polyether polyol (B) used in the present invention is a polyether polyol having a branched structure in the molecule.
  • the ratio of the polyether polyol (B) to the PAS resin (A) may be appropriately adjusted according to the purpose and use so as not to impair the effects of the present invention.
  • the range is preferably from 0.1 to 100 parts by mass, more preferably from 1 to 50 parts by mass based on 100 parts by mass of the resin (A). Since the polyether polyol (B) has a branched structure in the molecule and has a small radius of inertia, a resin composition having an extremely good fluidity even when blended with a PAS resin can be obtained by using within the above range. Furthermore, since flexibility can be imparted due to the branched structure, toughness and impact resistance can be imparted to the resin composition, and epoxy adhesiveness can be improved by the terminal hydroxyl group.
  • the polyether polyol used in the present invention is not particularly limited as long as it has a branched structure in the molecule, but preferably has a hydroxyl value in the range of 150 to 350 mgKOH / g, A range of 200 to 300 mg KOH / g is more preferable. Since the thing of the said range has many hydroxyl groups for molecular weight small, since the outstanding epoxy adhesiveness can be exhibited with a smaller addition amount, it is preferable.
  • the polyether polyol used in the present invention is not particularly limited as long as it has a branched structure in the molecule, but the number average molecular weight (Mn) is in the range of 1,000 to 4,000. It is preferable that the number average molecular weight (Mn) is in the range of 1,500 to 3,500. However, the number average molecular weight (Mn) is In the present invention, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC gel permeation chromatography
  • Measuring device HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation + TSK-GEL SuperHZM-M ⁇ 4 manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing; Multi-station GPC-8020 model II manufactured by Tosoh Corporation Measurement conditions; Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min standard; Calibration curve sample using monodisperse polystyrene; 0.2% by mass tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
  • the polyether polyol used in the present invention preferably has a primary hydrogen group (H1) and a secondary hydrogen group (H2) in the molecule.
  • the ratio between the primary hydrogen group (H1) and the secondary hydrogen group (H2) is not particularly limited, but is a total hydroxyl group obtained by adding the primary hydrogen group (H1) and the secondary hydrogen group (H2). It is preferable that the primary hydrogen group (H1) is 30 to 80% and the secondary hydrogen group (H2) is 70 to 20% with respect to the number.
  • the method for producing the polyether polyol that can be used in the present invention is not particularly limited.
  • the polyether polyol can be obtained by ring-opening reaction of hydroxyalkyloxetane (b1) and monofunctional epoxy compound (b2). it can.
  • the preferable manufacturing method of the polyether polyol used by this invention is explained in full detail.
  • hydroxyalkyl oxetane (b1) examples include those having a structure represented by the following formula (8).
  • R 3 in the formula (8) is a methylene group, an ethylene group or a propylene group
  • R 4 in the formula (8) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms
  • An alkoxyalkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms is represented.
  • Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a 2-ethylhexyl group.
  • alkoxyalkyl group having 1 to 5 carbon atoms Includes a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a propoxyethyl group.
  • hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
  • R 3 is a methylene group and R 4 is 1 to 1 carbon atoms from the viewpoint that the radius of inertia is smaller and effective in reducing the viscosity.
  • Compounds having 7 alkyl groups, especially 3-hydroxymethyl-3-ethyloxetane and 3-hydroxymethyl-3-methyloxetane are preferred.
  • examples of the monofunctional epoxy compound (b2) include olefin epoxide, alkyl glycidyl ether, alkyl glycidyl ester and the like.
  • olefin epoxide examples include propylene oxide, 1-butene oxide, 1-pentene oxide, 1-hexene oxide, 1,2-epoxyoctane, 1,2-epoxydodecane, cyclohexene oxide, and cyclooctene.
  • examples thereof include oxides, cyclododecene oxides, styrene oxides, and fluoroalkyl epoxides having 1 to 18 fluorine atoms.
  • alkyl glycidyl ether examples include methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, i-propyl glycidyl ether, n-butyl glycidyl ether, i-butyl glycidyl ether, and n-pentyl glycidyl ether.
  • alkyl glycidyl ester examples include glycidyl acetate, glycidyl propionate, glycidyl butyrate, glycidyl methacrylate, and glycidyl benzoate.
  • olefin epoxide is preferable because of good fluidity and low molecular weight, and propylene oxide, 1-butene oxide, 1-pentene oxide, or 1-hexene oxide is particularly preferable. .
  • a peroxide-free organic solvent such as diethyl ether, di-i-propyl ether, di-n-butyl ether, Di-i-butyl ether, di-t-butyl ether, t-amyl methyl ether, or dioxolane
  • the mass ratio of raw material component / organic solvent is 1/1 to 1/5, preferably 1 / 1.5-1 / 2. Dissolve at a rate of .5.
  • the obtained solution is cooled with stirring to ⁇ 10 to ⁇ 15 ° C., and then the polymerization initiator alone or in the solution state is 0.1 to 1 hour, preferably 0.3 to 0.5. Dripping over time.
  • the polymerization initiator can be used in a proportion of 0.01 to 1% by mass, preferably 0.75 to 0.3% by mass, based on the total mass of the raw material monomers.
  • the concentration of the polymerization initiator in the solution is preferably 1 to 90% by mass, particularly 25 to 50% by mass.
  • the polymerization solution is stirred until it reaches 25 ° C., then heated to a refluxing temperature, and the reaction is performed until all the raw material components are reacted over 0.5 to 3 hours.
  • the conversion rate of the raw material monomer can be controlled by confirming with GC, NMR, or IR spectrum.
  • the obtained polyether polyol is neutralized by stirring with an aqueous alkali hydroxide solution equivalent to the polymerization initiator, or by adding sodium alkoxide or potassium alkoxide equivalent to the polymerization initiator. After neutralization, the mixture is filtered and the target product is extracted with a solvent, and then the solvent is distilled off under reduced pressure to obtain the target polyether polyol.
  • examples of the hydrocarbon solvent include n-heptane, i-octane, and cyclohexane, and cyclohexane is particularly preferable from the viewpoint of solubility.
  • the ratio of the raw material monomer to the hydrocarbon solvent is preferably 1: 1 to 1:10, particularly 1: 2.5 to 1: 3.5, the former: the latter.
  • the temperature of the mixture is maintained at 0 to 25 ° C., preferably 5 to 15 ° C., particularly preferably 10 to 15 ° C., and then 0.01 to 1 mol% with respect to the total amount of raw material monomers under stirring, in particular 0.05 to 0.15 mol% of polymerization initiator is added at once.
  • the system becomes heterogeneous and the system temperature rises to 25-40 ° C.
  • the reaction mixture is heated to 40-70 ° C., preferably 50-60 ° C., and all the raw monomers are converted for 1-5 hours, preferably 2-3 hours. Perform the reaction until After completion of the reaction, the solution is neutralized and filtered in the same manner as in Method 1, and then the solvent is distilled off.
  • Method 3 In Method 3, first, a polymerization initiator in an amount of 0.01 to 1 mol%, particularly 0.05 to 0.15 mol%, is carbonized with a boiling point of 70 ° C. or higher with respect to the total amount of raw material monomers. It is dissolved in a hydrogen-based organic solvent and maintained at 0 to 25 ° C., preferably 5 to 15 ° C., particularly preferably 10 to 15 ° C.
  • examples of the hydrocarbon solvent include n-heptane, i-octane, and cyclohexane, and cyclohexane is particularly preferable from the viewpoint of solubility.
  • the concentration of the polymerization initiator in the hydrocarbon solvent is preferably 0.01 to 1% by mass, particularly 0.025 to 0.25% by mass.
  • the mixed mixture is continuously dropped at a ratio of 1/1 to 1/10, preferably 1/1 to 1/3, so that the temperature in the system becomes 20 to 35 ° C. Stirring is continued until the temperature in the system reaches 20 to 25 ° C. even after the dropping is completed.
  • the reaction mixture is heated to 40 to 70 ° C., preferably 50 to 60 ° C., and the reaction is performed for 1 to 5 hours, preferably 2 to 3 hours until all the raw material monomers are converted.
  • the conversion rate of the raw material monomer can be controlled by confirming with GC, NMR, or IR spectrum.
  • the solution is neutralized and filtered in the same manner as in Method 1, and then the solvent is distilled off.
  • Method 4 A polymerization initiator in an amount of 0.01 to 2 mol%, preferably 0.1 to 1.0 mol%, based on the total amount of hydroxyalkyloxetane (b1) and monofunctional epoxy compound (b2), Dilute with peroxide-free organic solvent.
  • the organic solvent is preferably an ether organic solvent such as methyl-t-butyl ether, methyl-cyclopentyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, di-i-propyl ether, di- -N-butyl ether, di-i-butyl ether, di-t-butyl ether, t-amyl methyl ether, or dioxolane. These solvents may be used singly or as a mixture.
  • the solvent is used at a ratio of 1 / 0.25 to 1/5, preferably 1 / 0.5 to 1/3.
  • the solution diluted with an appropriately selected organic solvent is kept at ⁇ 15 to 60 ° C., preferably 0 to 45 ° C., particularly preferably 10 to 30 ° C.
  • the mixture in a ratio of 2 to 1/3, preferably 1 / 0.5 to 1 / 1.5, has a temperature in the system of ⁇ 15 to 60 ° C., preferably 0 to 45 ° C., particularly preferably Is continuously added dropwise at 10 to 30 ° C. Further, 0.2 to 5 times, preferably 0.5 to 1.5 times, monofunctional epoxy compound (b2) on a molar basis with respect to the above hydroxyalkyloxetane (a1) is added to the temperature in the above system.
  • the temperature in the system is maintained at 10 to 50 ° C., preferably 20 to 35 ° C., and the reaction is carried out until all of the hydroxyalkyloxetane (b1) and the monofunctional epoxy compound (b2) are converted.
  • the conversion of the hydroxyalkyl oxetane (b1) and the monofunctional epoxy compound (b2) can be controlled by confirming with GC, NMR, or IR spectrum.
  • the pressure of the above reaction can be performed not only at normal pressure but also in a pressure-resistant vessel under pressurized conditions.
  • the reaction under pressure is effective.
  • the temperature in the system during addition of the raw material can be 0 to 60 ° C., preferably 10 to 45 ° C.
  • the obtained polyether polyol is added with hydrotalcite 0.3 to 20 times, preferably 0.4 to 15 times the polymerization initiator, to adsorb the polymerization initiator, and this is filtered off. Thereafter, the solvent is distilled off under reduced pressure to obtain the desired polyether polyol.
  • the treatment of the polymerization initiator is neutralized by stirring with an aqueous alkali hydroxide solution equivalent to the polymerization initiator or by adding sodium alkoxide or potassium alkoxide equivalent to the polymerization initiator, and the target product is extracted with a solvent. Processing is also possible. Further, when BF 3 is used as a polymerization initiator, neutralization with sodium fluoride followed by adsorption removal of the neutralized salt with zeolite.
  • Method 4 is that the reaction conversion rate of hydroxyalkyl oxetane (b1) and monofunctional epoxy compound (b2) in the ring-opening reaction reaches 98% or more.
  • the polyether polyol obtained by removing the polymerization initiator and the solvent can suppress the residual amount of hydroxyalkyl oxetane (b1) to 1% or less.
  • the monofunctional epoxy compound (b2) includes a compound having a low boiling point and a compound having mutagenicity, but these can be reacted almost completely, and the risk due to release into the environment is extremely low. It is a manufacturing method.
  • the conversion rate of the reaction is high, polyether polyol can be obtained almost quantitatively, so that the production method has a high yield.
  • the polymerization initiator that can be used for the production of the polyether polyol of the present invention, for example, H 2 SO 4 , HCl, HBF 4 , HPF 6 , HSbF 6 , HAsF 6 , p-toluenesulfonic acid, tri-toluenesulfonic acid, Bronsted acids such as fluoromethanesulfonic acid, Lewis acids such as BF 3 , AlCl 3 , TiCl 4 , SnCl 4 , triarylsulfonium-hexafluorophosphate, triarylsulfonium-antimonate, diaryliodonium-hexafluoro Onium salt compounds such as phosphate, diaryliodonium-antimonate, N-benzylpyridinium-hexafluorophosphate, N-benzylpyridinium-antimonate, triphenylcarbonium-tetrafluoroborate, trif Tripheny
  • BF 3 is a Bronsted acid as a Lewis acid.
  • HPF 6 it is preferable.
  • polyether polyol (B) includes various structures obtained by ring-opening reaction of hydroxyalkyl oxetane (b1) and monofunctional epoxy compound (b2).
  • b1 hydroxyalkyl oxetane
  • b2 monofunctional epoxy compound
  • R 5 represents a structure other than the epoxy group of the monofunctional epoxy compound (b2)) and the monofunctional epoxy compound (b2) represented by the ring opening.
  • the polyether polyol is composed of a repeating unit represented by the following structure and a structural unit appropriately selected from terminal structural units.
  • the formulas (10) to (14) are structural units derived from the hydroxyalkyloxetane (b1), the formulas (10) to (12) represent repeating units, and the formulas (13) and (13) Formula (14) represents a terminal structural unit.
  • Formula (15) to Formula (17) are structural units derived from the monofunctional epoxy compound (b2), and Formula (15) represents a repeating unit.
  • Formula (16) and Formula (17) Represents a terminal structural unit.
  • a branched structure is formed by repeating units selected from the above formulas (10) to (12) and (15), and the above formulas (13), (14), and It has a terminal structural unit selected from (16) and formula (17). These repeating units and terminal structural units may be present at random, or the above formulas (10) to (12) constitute the central part of the molecular structure and have the terminal structural units at the ends. It may be.
  • the quaternary carbon atom in the polyether polyol used in the present invention can be confirmed by, for example, C-NMR.
  • the polyarylene sulfide resin composition of the present invention may contain a thermoplastic elastomer (C) in order to impart excellent impact resistance, particularly cold thermal shock resistance.
  • the thermoplastic elastomer (C) is preferably an elastomer having a melting point of 300 ° C. or lower and having rubber elasticity at room temperature because of excellent dispersibility when melt-kneaded with the polyarylene sulfide resin (A). .
  • a polyolefin elastomer or a nitrile elastomer is preferable from the viewpoints of excellent heat resistance, easy mixing, and remarkable effect of improving impact resistance.
  • thermoplastic elastomer (C) is a functional group that is reactive with the polyarylene sulfide resin (A) and the polyether polyol (B) from the viewpoint of imparting further excellent impact resistance, particularly cold thermal shock resistance.
  • a hydroxyl group, a carboxy group, a mercapto group, an epoxy group, an amino group, an isocyanato group, a vinyl group a structure represented by the following structural formula (1) and a structural formula ( 2) Structure represented
  • R represents an alkyl group having 1 to 8 carbon atoms
  • having at least one functional group selected from the group consisting of It may be referred to as “polyolefin having a functional group”.
  • the polyolefin having the functional group can be obtained, for example, by copolymerization of an ⁇ -olefin and a monomer such as a vinyl polymerizable compound having the functional group.
  • a monomer such as a vinyl polymerizable compound having the functional group.
  • the ⁇ -olefin include ⁇ -olefins having 2 to 8 carbon atoms such as ethylene, propylene, and butene-1.
  • the vinyl polymerizable compound having a functional group include ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid, and the like.
  • ⁇ - ⁇ -unsaturated dicarboxylic acids and derivatives thereof such as unsaturated dicarboxylic acids having 4 to 10 carbon atoms, mono- and diesters thereof, acid anhydrides thereof, etc., ⁇ such as glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate , ⁇ -unsaturated acid glycidyl ester and the like.
  • a polyolefin having an amino group or an isocyanate group can be obtained, for example, by reacting a polyolefin modified with the above carboxylic acid with a polyvalent amine such as alkylene diamine or alkylene diisocyanate or a polyvalent isocyanate.
  • alkylene diamines examples include ethylene diamine, pentamethylene diamine, hexamethylene diamine, ethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and the like.
  • the polyolefin having a hydroxyl group at the molecular end is obtained by polymerizing a conjugated diene monomer by a known method such as anionic polymerization and hydrolyzing the resulting polymer as described in, for example, WO11 / 158906. Obtained by hydrogenation above.
  • the polyolefin having a vinyl group can be obtained by thermally decomposing a high molecular weight polyolefin, particularly polypropylene, as described in, for example, JP-A No.
  • a polyolefin having a mercapto group can be subjected to a conversion reaction from a terminal vinylidene group to an SH group with respect to the polyolefin having the vinyl group, and a reaction particularly preferable in the present invention is described in, for example, JP-A-2004-107508.
  • thioacetic acid can be converted into a mercapto group by using thioacetic acid ester together with a radical initiator, followed by hydrolysis under alkaline conditions.
  • thermoplastic elastomer that can be used in the present invention is represented by a carboxy group, an epoxy group, an amino group, an isocyanato group, a structure represented by the following structural formula (1), and a structural formula (2). Structure
  • a polyolefin having at least one functional group selected from the group consisting of An ethylene-propylene copolymer or an ethylene-butene copolymer having a functional group is preferred for improving toughness and impact resistance.
  • the modification ratio of each monomer component with respect to the ⁇ -olefin is not particularly limited, but the modification site in the copolymer is converted to the mass of each monomer, and the ratio is 0 as the ratio with respect to 100 mass of the copolymer.
  • the range of 1 to 15 parts by mass, particularly 0.5 to 10 parts by mass is preferable.
  • thermoplastic elastomer that can be used in the present invention is preferably meltable and mixed and dispersible at the temperature at which the polyarylene sulfide resin is kneaded. From this point, an elastomer having a melting point of 300 ° C. or lower and rubber elasticity at room temperature is more preferable.
  • the thermoplastic elastomer that can be used in the present invention is one that has a glass transition point of ⁇ 40 ° C. or lower, especially in consideration of heat resistance, ease of mixing, and freezing resistance. Since it has rubber elasticity, it is preferable.
  • the glass transition point is preferably as low as possible in terms of improving freezing resistance, but usually it is preferably in the range of ⁇ 180 to ⁇ 40 ° C., particularly preferably in the range of ⁇ 150 to ⁇ 40 ° C.
  • the amount used can be adjusted while adjusting in the range of 0.1 to 99.9% by mass of the whole elastomer.
  • the polyolefin (C1) may be copolymerized with other olefinic monomers such as acrylonitrile, styrene, vinyl acetate and vinyl ether in addition to the various monomer components described above within a range not impairing the effects of the present invention. .
  • the melt viscosity of the thermoplastic elastomer that can be used in the present invention is not particularly limited, but it is in the range of 1 to 20 (g / 10 min) as measured by melt flow rate (temperature 190 ° C., load 2.16 kg). Are preferred.
  • the ratio of the thermoplastic elastomer (C) to the PAS resin (A) may be appropriately adjusted according to the purpose and use so as not to impair the effects of the present invention.
  • 0.5 to 20 masses of the thermoplastic elastomer (C) with respect to 100 mass parts of the polyarylene sulfide resin (A). Is preferably in the range of 1 part by weight, and more preferably in the range of 1 to 10 parts by weight.
  • the resin composition of the present invention may further contain an epoxy resin (D) from the viewpoint of further improving the adhesion with other resins such as an epoxy resin.
  • the epoxy resin (D) is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include bisphenol type epoxy resins and novolac type epoxy resins.
  • Examples of the epoxy resin of the bisphenol type epoxy resin include glycidyl ethers of bisphenols, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, bisphenol. S-type epoxy resin, bisphenol AD-type epoxy resin, tetrabromobisphenol A-type epoxy resin, dihydroxynaphthalene-type epoxy resin, etc. are mentioned, and among these, bisphenol A-type epoxy resin is preferable.
  • the novolac type epoxy resin includes novolac type epoxy resins obtained by reacting novolac type phenol resins obtained by condensation reaction of phenols and aldehydes with epihalohydrin. Specific examples include phenol novolac type epoxy resins.
  • cresol novolac type epoxy resin cresol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, brominated phenol novolac type epoxy resin, among which phenol novolac Type epoxy resin and cresol novolac epoxy resin are preferable.
  • the ratio of the epoxy resin (D) to the polyarylene sulfide resin (A) may be appropriately adjusted according to the purpose and use so as not to impair the effects of the present invention.
  • it is in the range of 0.5 to 20 parts by mass of the epoxy resin (D) with respect to 100 parts by mass of the polyarylene sulfide resin (A). Is more preferable, and the range of 1 to 10 parts by mass is more preferable.
  • the resin composition of the present invention preferably further contains a filler (E) in order to further improve performance such as mechanical strength, in particular, thermal shock strength, heat resistance, and dimensional stability.
  • a filler (E) in order to further improve performance such as mechanical strength, in particular, thermal shock strength, heat resistance, and dimensional stability.
  • the filler used in the present invention is not an essential component, but when used, 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 filler (E) it is more preferable to use glass fiber and at least one selected from the group consisting of glass beads, glass flakes, and calcium carbonate.
  • the blending ratio is in the range of 10 to 200 parts by mass in total of at least one selected from the group consisting of glass fibers, glass beads, glass flakes, and calcium carbonate with respect to 100 parts by mass of the polyarylene sulfide resin. It is preferable. Furthermore, among them, the blending ratio of the glass fiber and at least one selected from the group consisting of glass beads, glass flakes, and calcium carbonate is preferably 20:80 to 80:20 on a mass basis.
  • chopped strands used for injection molding compounds can be preferably used, and in particular, The diameter is in the range of 3 to 20 ⁇ m, preferably in the range of 6 to 13 ⁇ m, and the strand length is preferably in the range of 3 to 6 mm.
  • glass flakes known ones can be used as long as the effects of the present invention are not impaired.
  • glass flakes having an average particle diameter in the range of 10 to 4000 ⁇ m can be preferably used.
  • What is a glass flake having a thickness in the range of 0.1 to 20 ⁇ m can be preferably used.
  • glass beads known ones can be used as long as the effects of the present invention are not impaired.
  • those having an average particle diameter in the range of 1 to 100 ⁇ m can be preferably used.
  • Specific examples include soda lime glass beads, low alkali glass beads, potash glass beads, and quartz glass beads.
  • calcium carbonate known ones can be used as long as the effects of the present invention are not impaired.
  • those having an average particle diameter in the range of 0.1 to 300 ⁇ m can be preferably used.
  • Specific examples include precipitated calcium carbonate, heavy calcium carbonate, and calcium carbonate whisker.
  • the average particle diameter and the average thickness mean a particle size of 50% cumulative degree obtained from a cumulative particle size distribution curve measured by a laser light diffraction method.
  • the 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.
  • polyether sulfone resin polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, silicone resin
  • polyarylene sulfide resin composition containing a synthetic resin such as a phenol resin, a urethane resin, or a liquid crystal polymer, or an elastomer such as fluorine rubber or silicone rubber.
  • the amount of these resins used varies depending on the purpose and cannot be generally defined, but is in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). In order not to impair the effects of the present invention, it may be appropriately adjusted according to the purpose and application.
  • a coupling agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent are used as additives during molding.
  • Various additives such as an agent, a rust inhibitor, a flame retardant, and a lubricant can be contained.
  • 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 of using these additives also differs depending on the purpose and cannot be specified in general.
  • the coupling agent (F) is used after pre-processing in a filler. However, it is preferable to use it alone as an additive.
  • a coupling agent such as silane or titanium is used as such a coupling agent (F).
  • a silane coupling agent is preferable, and 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.
  • examples of such 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 production method of the PAS resin composition of the present invention is not particularly limited.
  • D) and other additives such as filler (E) and coupling agent (F) are charged into ribbon, Henschel mixer, V-blender, etc. in various forms such as powder, beret, and strip Examples thereof include a method of melt-kneading using a Banbury mixer mixing roll, a single-screw or twin-screw extruder, a knee, and the like after dry blending. Among them, a typical method is melt-kneading using a single-screw or twin-screw extruder having a sufficient kneading force.
  • the PAS resin composition of the present invention can be used for various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. Because it is excellent, it is suitable for injection molding.
  • the molded article of the obtained polyarylene sulfide resin composition is excellent in epoxy adhesiveness. For this reason, for example, after sealing or joining a curable resin such as an epoxy resin or a silicone resin to a molded product formed into various shapes such as a plate shape or a box shape made of a polyarylene sulfide resin composition, By curing the curable resin, it is possible to obtain a composite molded product obtained by bonding a molded body formed by molding the polyarylene sulfide resin composition and a cured product made of the curable resin.
  • a curable resin such as an epoxy resin or a silicone resin
  • the PAS resin composition of the present invention has various performances such as mechanical strength, heat resistance, and dimensional stability inherent to the PAS resin. For this reason, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers, microphones , Headphones, small motors, magnetic head bases, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts, VTR parts, TV parts, irons, hair dryers Home appliances such as rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc.
  • valve alternator terminal Water-related parts, valve alternator terminal, alternator connector, IC regulator, light meter potentiometer base, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel Pump, engine cooling water joy , Carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioning thermostat base, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse Connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp It is widely useful as a material for various applications such as housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, HEV condenser cases, vehicle
  • [Peak molecular weight of PAS resin] The conditions for measuring the peak molecular weight of the PPS resin are as follows: apparatus: SSC-7000 (manufactured by Senshu Kagaku), column: UT-805L (manufactured by Showa Denko), solvent: 1-chloronaphthalene, column temperature: 210 ° C., detector: UV Using a detector (360 nm), the molecular weight distribution was measured using six types of monodisperse polystyrene for calibration, the vertical axis was d (weight) / dLog (molecular weight), and the horizontal axis was differential weight molecular weight distribution with Log (molecular weight). The peak molecular weight was read from the horizontal axis.
  • a steel insert block member having a length of 25 mm, a width of 40 mm, and a thickness of 10 mm connects the midpoints of the sides in the vertical direction of the member, and has a thickness of 3.55 mm on a straight line parallel to the side in the horizontal direction of the member.
  • the insert block member is held inside the injection mold by using the two through holes and the two steel cylindrical pins installed in the injection mold.
  • the entire outer periphery of the insert block member is designed to be coated with the polyphenylene sulfide resin composition having a thickness of 1 mm.
  • the polyphenylene sulfide resin composition pellets were injection-molded moldings.
  • the temperature is maintained at ⁇ 40 ° C./1 hour to 140 ° C./1 hour. The thermal shock test which makes a cycle was implemented, and the number of cycles until a crack generate
  • the blended resins and materials in Tables 1 to 10 are as follows.
  • PPS A1 “MA-520” manufactured by linear PPS DIC Corporation peak molecular weight 45000, melt viscosity (V6) 200 Pa ⁇ s)
  • A2 “MA-501” made by linear PPS DIC Corporation peak molecular weight 28000, melt viscosity (V6) 15 Pa ⁇ s)
  • Polyol resin B1 Branched polyether polyol resin “HBP-100” manufactured by DIC Corporation (Hydroxyl value 260 mgKOH / g, number average molecular weight 2600)
  • Thermoplastic Elastomer C1 Ethylene-Glycidyl Methacrylate-Methyl Acrylate Copolymer “Bond First 7L” manufactured by Tomo Chemical Industry Co., Ltd.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne : une composition de résine de sulfure de polyarylène comprenant une résine de sulfure de polyarylène et un polyol de polyéther, ladite composition de résine étant caractérisée en ce que le polyol de polyéther présente une structure ramifiée dans sa molécule ; et un article moulé produit par moulage de la composition de résine. L'invention concerne plus précisément : une composition de résine de sulfure de polyarylène permettant la production d'un article moulé ayant une excellente adhésivité époxy et d'excellentes propriétés de résistance aux chocs à des températures froides et chaudes et qui présente une excellente fluidité ; et un article moulé de résine de sulfure de polyarylène qui est produit par moulage de la composition de résine et présente une excellente adhésivité époxy et d'excellentes propriétés de résistance aux chocs à des températures froides et chaudes.
PCT/JP2014/083586 2013-12-25 2014-12-18 Composition de résine de sulfure de polyarylène et produit moulé de cette dernière WO2015098703A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018161768A (ja) * 2017-03-24 2018-10-18 Dic株式会社 複合成形品及びその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6469657A (en) * 1987-09-08 1989-03-15 Toray Industries Polyphenylene sulfide resin composition
JPH08311201A (ja) * 1995-05-16 1996-11-26 Tonen Chem Corp 接着性に優れたポリアリーレンスルフィド
JP2006282698A (ja) * 2005-03-31 2006-10-19 Dainippon Ink & Chem Inc 多分岐ポリエーテルポリオール及びウレタン系樹脂組成物
JP2008111105A (ja) * 2006-10-06 2008-05-15 Dainippon Ink & Chem Inc プラスチック基材用カチオン重合性接着剤、それを用いた積層体及び偏光板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6469657A (en) * 1987-09-08 1989-03-15 Toray Industries Polyphenylene sulfide resin composition
JPH08311201A (ja) * 1995-05-16 1996-11-26 Tonen Chem Corp 接着性に優れたポリアリーレンスルフィド
JP2006282698A (ja) * 2005-03-31 2006-10-19 Dainippon Ink & Chem Inc 多分岐ポリエーテルポリオール及びウレタン系樹脂組成物
JP2008111105A (ja) * 2006-10-06 2008-05-15 Dainippon Ink & Chem Inc プラスチック基材用カチオン重合性接着剤、それを用いた積層体及び偏光板

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018161768A (ja) * 2017-03-24 2018-10-18 Dic株式会社 複合成形品及びその製造方法

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