WO2017069109A1 - Composition de résine de polysulfure d'arylène, produit moulé, et procédés de production de ladite composition et dudit produit - Google Patents

Composition de résine de polysulfure d'arylène, produit moulé, et procédés de production de ladite composition et dudit produit Download PDF

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Publication number
WO2017069109A1
WO2017069109A1 PCT/JP2016/080801 JP2016080801W WO2017069109A1 WO 2017069109 A1 WO2017069109 A1 WO 2017069109A1 JP 2016080801 W JP2016080801 W JP 2016080801W WO 2017069109 A1 WO2017069109 A1 WO 2017069109A1
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Prior art keywords
polyarylene sulfide
sulfide resin
resin
thioether
group
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PCT/JP2016/080801
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English (en)
Japanese (ja)
Inventor
早織 奈良
新也 宜保
井上　敏
高志 古沢
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Dic株式会社
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Priority to JP2017546546A priority Critical patent/JPWO2017069109A1/ja
Publication of WO2017069109A1 publication Critical patent/WO2017069109A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a polyarylene sulfide resin composition that can be molded under low temperature conditions and has excellent heat resistance.
  • Polyarylene sulfide resins are used in various applications such as electrical / electronic equipment parts and automobile parts, taking advantage of their excellent heat resistance and chemical resistance.
  • Various melt processing methods such as injection molding, extrusion molding, compression molding, blow molding and the like are used for molding thermoplastic resins such as polyarylene sulfide resins. It is widely used as a molding method suitable for mass production. In the injection molding method, the resin is heated to a temperature equal to or higher than the melting point to improve fluidity, and this is injected and filled into a mold heated to an appropriate temperature, cooled and solidified to obtain a molded product.
  • the appropriate mold temperature is relatively high, about 130 to 180 ° C, so the energy and time required to reheat the mold during the molding cycle greatly affect production efficiency. Therefore, it has been desired to develop a polyarylene sulfide resin that can be molded at a lower mold temperature.
  • the problem to be solved by the present invention is to provide a polyarylene sulfide resin composition that can be molded under a low temperature condition and also excellent in heat resistance, a molded product thereof, and a method for producing them.
  • the present inventors have found that in the arylene sulfide structure of the polyarylene sulfide resin, the bonding point of the arylene group is in the para position and the bonding point of the arylene group is in the para position.
  • the polyarylene sulfide resin composition obtained by melt-kneading two types of resin having both a site and a meta-position site is excellent in heat resistance while being moldable under low temperature conditions.
  • the headline and the present invention were completed.
  • the present invention is a polyarylene sulfide resin having an arylene thioether as a repeating unit, wherein the thioether and the arylene group have a para-bonding point (A), A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position. And a polyarylene sulfide resin composition comprising a resin (B).
  • the present invention is a polyarylene sulfide resin having an arylene thioether as a repeating unit, the resin (A) in which the bonding point of the thioether and the arylene group is para-position, A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position.
  • the present invention relates to a method for producing a polyarylene sulfide resin composition in which a resin (B) is melt-kneaded in a temperature range equal to or higher than the melting point of the resin (A).
  • the present invention relates to a molded article comprising the polyarylene sulfide resin composition.
  • the present invention provides a method for producing a molded article comprising a step of molding the polyarylene sulfide resin composition in a mold, wherein the mold temperature is in the range of 40 to 180 ° C. It relates to a manufacturing method.
  • the polyarylene sulfide resin composition of the present invention is a polyarylene sulfide resin having an arylene thioether as a repeating unit, the resin (A) in which the bonding point between the thioether and the arylene group is para-position, A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position.
  • Resin (B) is a polyarylene sulfide resin having an arylene thioether as a repeating unit, the resin (A) in which the bonding point between the thioether and the arylene group is para-position, A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thi
  • the polyarylene sulfide resin composition of the present invention has the following structural formula (X)
  • R 1 is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and k is an integer of 1 to 4.
  • the resin (A) is a polyarylene sulfide resin having an arylene thioether as a repeating unit, and the bonding point between the thioether and the arylene group is a para-position.
  • the arylene thioether may have a substituent, and in this case, the substituent may be substituted with 1 to 4 hydrogen atoms bonded to the carbon atom of the arylene group. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group.
  • the resin (A) has the structural moiety (x) represented by the structural formula (X) as a repeating unit, and the bonding point between the thioether and the arylene group in the structural moiety (x) is a parasite. It is rank. Specifically, it is a polyarylene sulfide resin having a structural site (p) represented by the following structural formula (X1) as a repeating unit.
  • R 1 is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and k is an integer of 1 to 4.
  • R 1 in the formula (X1) in the resin (A) is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group.
  • k is an integer of 2 or more
  • a plurality of R 1 present in the formula may be the same structural site, or may be different structural sites.
  • R 1 is preferably a hydrogen atom.
  • R 2 is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and r is an integer of 1 to 4.
  • the resin (A) When the resin (A) has the structural site (y) in addition to the structural site (p), it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. ) And the structural part (y), the proportion of the structural part (y) is preferably 30 mol% or less. Moreover, when the said resin (A) has the said structure site
  • the resin (A) includes, in addition to the structural sites (p) and (y), a branched structural site represented by the following structural formula (Z) and a naphthyl sulfide represented by the following structural formula (V). It may have a structural part.
  • the resin (A) When the resin (A) has these structural sites, it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength, so that the total of the structural site (p) and the structural site (y). However, it is preferably 3 mol% or less, particularly preferably 1 mol% or less.
  • R 3 and R 4 are each independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group; An integer of 6 and t is an integer of 1 to 3. ]
  • the melting point (Tm) of the resin (A) is preferably in the range of 270 to 300 ° C. because it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength.
  • the recrystallization temperature (Tc2) of the resin (A) is preferably in the range of 210 to 260 ° C. because it is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength.
  • the difference ⁇ T between the melting point (Tm) of the resin (A) and the recrystallization temperature (Tc2) is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength.
  • the range is preferable, and the range of 35 to 55 ° C. is more preferable.
  • the melt viscosity (V6) measured at 300 ° C. of the resin (A) is preferably in the range of 2 to 1000 [Pa ⁇ s] because the balance between fluidity and mechanical strength is good. A range of 500 [Pa ⁇ s] is more preferable, and a range of 2 to 200 [Pa ⁇ s] is particularly preferable.
  • the non-Newtonian index of the resin (A) is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.90 to 2.00, and is preferably in the range of 0.90 to 1.50. More preferably, the range is 0.95 to 1.20.
  • the shear stress (SS) were measured and calculated using the following formula. The closer the non-Newtonian index (N value) is to 1, the closer it is to a linear structure, and the higher the non-Newtonian index (N value), the more branched the structure is.
  • SR is the shear rate (second ⁇ 1 )
  • SS is the shear stress (dyne / cm 2 )
  • K is a constant.
  • the resin (A) can be produced by an ordinary method for producing a polyarylene sulfide resin, specifically, a dihalogenoaromatic compound, and if necessary, a polyhalogenoaromatic compound or other copolymer component.
  • a method of polymerizing in the presence of (Method 2), a method of self-condensing p-chlorothiophenol and other copolymerization components as necessary (Method 3), and the like is versatile and preferable.
  • an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added for the purpose of adjusting the degree of polymerization during the reaction.
  • hydrous sulfidation is performed on a mixture containing at least a heated organic polar solvent and an essential raw material dihalogenoaromatic compound as necessary, and a polyhalogenoaromatic compound as an optional raw material.
  • the agent is sequentially added and reacted at a rate at which water can be removed from the reaction mixture, and the amount of water in the reaction system is controlled to be in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent.
  • Examples of the dihalogenoaromatic compound and polyhalogenoaromatic compound used as a raw material for the resin (A) include p-dihalobenzene and 4,4′-dihalodiphenyl as essential raw materials for introducing the structural moiety (p) into the resin. From the group consisting of sulfide, 2,5-dihalotoluene, 2,5-dihaloanisole, 2,5-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,5-dihaloaniline, 2,5-dihalobiphenyl, etc.
  • One or more dihalogenoaromatic compounds selected may be mentioned, and optional raw materials used as necessary include p, p′-dihalodiphenyl ether, 4,4′-dihalobenzophenone, bis (4-halophenyl) methane, 4,4 '-Dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalobiphenyl, 1,4- Halonaphthalene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-
  • One or more polyhalogeno aromatic compounds selected from the group consisting of tetrahalobenzene, 1,4,6-trihalonaphthalene and the like can be mentioned. These may be used alone or in combination of two or more.
  • the halogen atom contained in each compound is preferably a chlorine atom or a bromine atom.
  • the post-treatment method of the reaction mixture containing the resin (A) obtained by each of the production methods is not particularly limited.
  • an acid or a base may be added to the reaction mixture after completion of the polymerization reaction as necessary.
  • the solid after distilling off the solvent is one or more with water, the solvent used during the polymerization reaction, other organic solvents such as acetone, methyl ethyl ketone, alcohol compounds, etc.
  • a method of washing twice, further neutralizing, washing with water, filtering and drying (Method 1), and the reaction mixture after completion of the polymerization reaction is added to water, acetone, methyl ethyl ketone, alcohol compound, ether compound, halogenated hydrocarbon, aromatic hydrocarbon , Precipitating solvents such as aliphatic hydrocarbons (solvents that are soluble in the solvent used during the polymerization reaction and that are poor solvents for at least polyarylene sulfide)
  • a method for precipitating solid products such as polyarylene sulfide and inorganic salts, filtering them, washing and drying (Method 2), and for the reaction mixture after completion of the polymerization reaction, was used during the polymerization reaction After adding a solvent (or an organic solvent having an equivalent solubility with respect to a low molecular weight polymer), stirring and filtering to remove the low molecular weight polymer, once with a solvent such as water, acetone, methyl ethyl
  • a method of washing several times, further neutralizing, washing with water, filtering and drying (Method 3), a method of adding water and, if necessary, an acid to the reaction mixture after completion of the polymerization reaction, and filtering and washing the washed product (Method 4)
  • a method of filtering the reaction mixture, washing with a reaction solvent one or more times as necessary, further washing with water, filtering and drying (Method 5) and the like can be mentioned.
  • the polyarylene sulfide resin may be dried in a vacuum, or in an inert gas atmosphere such as air or nitrogen. .
  • the resin (A) thus obtained has a molecular end that is a carboxyl group or an alkali metal carboxylate.
  • the resin (B) is a polyarylene sulfide resin having an arylene thioether as a repeating unit, and a structural site (p) in which the bonding point of the thioether and the arylene group is bonded at the para position, and a structural site ( m).
  • the arylene thioether may have a substituent, and in this case, the substituent may be substituted with 1 to 4 hydrogen atoms bonded to the carbon atom of the arylene group. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group.
  • the resin (B) has the structural site (x) represented by the structural formula (X) as a repeating unit, and the bonding point between the thioether and the arylene group in the structural site (x) is a parasite. It has both a structural site (p) that is a position and a structural site (m) that is a meta position.
  • a polyarylene sulfide resin having as a repeating unit both a structural moiety (p) represented by the following structural formula (X1) and a structural moiety (m) represented by the following structural formula (X2). is there.
  • R 1 is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and k is an integer of 1 to 4.
  • the molar ratio [(p) / (m)] of the structural part (p) and the structural part (m) of the resin (B) can be molded under low temperature conditions, but also has good heat resistance.
  • it is preferably in the range of 99/1 to 60/40, more preferably in the range of 95/5 to 75/25.
  • R 1 in the formulas (X1) and (X2) in the resin (B) is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group. It is.
  • k is an integer of 2 or more
  • a plurality of R 1 present in the formula may be the same structural site, or may be different structural sites.
  • R 1 is preferably a hydrogen atom.
  • the resin (B) has a structural site (y) represented by any of the following structural formulas (Y1) to (Y6) in addition to the structural site (p) and the structural formula (m). Also good.
  • R 2 is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and r is an integer of 1 to 4.
  • the structural part (p) When the resin (B) has the structural part (y), since it becomes a polyarylene sulfide resin composition having excellent heat resistance while being moldable under low temperature conditions, the structural part (p), It is preferable that the ratio of the structural site (y) to the total of (m) and (y) is 30 mol% or less. Moreover, when the said resin (B) has the said structure site
  • the resin (B) is represented by the structural site (p), (m), (y), a branched structural site represented by the following structural formula (Z), or the following structural formula (V). It may have a naphthyl sulfide structure site.
  • the structural sites (p), (m ) And (y), preferably 3 mol% or less, particularly preferably 1 mol% or less.
  • R 3 and R 4 are each independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group; An integer of 6 and t is an integer of 1 to 3. ]
  • the melting point (Tm) of the resin (B) is preferably 200 ° C. or higher because it becomes a polyarylene sulfide resin composition that can be molded under low temperature conditions and is also excellent in heat resistance. A range of 280 ° C. is more preferable.
  • the recrystallization temperature (Tc2) of the resin (B) is 200 ° C. or lower because it becomes a polyarylene sulfide resin composition having excellent heat resistance while being moldable under low temperature conditions. The temperature is preferably in the range of 130 to 160 ° C.
  • the difference ⁇ T between the melting point (Tm) of the resin (B) and the recrystallization temperature (Tc2) is 20 ° C. or higher because it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength.
  • the temperature is preferably in the range of 50 to 100 ° C.
  • the melt viscosity (V6) measured at 300 ° C. of the resin (B) is preferably in the range of 2 to 1000 [Pa ⁇ s] because the balance between fluidity and mechanical strength is good.
  • a range of 500 [Pa ⁇ s] is more preferable, and a range of 2 to 200 [Pa ⁇ s] is particularly preferable.
  • the non-Newtonian index of the resin (B) is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.90 to 2.00, and is preferably in the range of 0.90 to 1.50. More preferably, the range is 0.95 to 1.20.
  • the resin (B) can be produced by the same method as the resin (A) described above.
  • Examples of the dihalogenoaromatic compound and polyhalogenoaromatic compound used as the raw material for the resin (B) include p-dihalobenzene and 4,4′-dihalodiphenyl as essential raw materials for introducing the structural moiety (p) into the resin. From the group consisting of sulfide, 2,5-dihalotoluene, 2,5-dihaloanisole, 2,5-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,5-dihaloaniline, 2,5-dihalobiphenyl, etc.
  • Poriharogeno aromatic least one compound which can be cited. These may be used alone or in combination of two or more.
  • the halogen atom contained in each compound is preferably a chlorine atom or a bromine atom.
  • the mass ratio of the component for introducing the structural site (p) and the component for introducing the structural site (m) is the same as that of the resin (B) described above. According to the molar ratio [(p) / (m)] between the structural site (p) and the structural site (m).
  • the resin (B) thus obtained has a molecular end that is a carboxyl group or an alkali metal carboxylate.
  • the polyarylene sulfide resin composition of the present invention is a melt-kneaded product obtained by melt-kneading the resin (A) and the resin (B).
  • the blending mass ratio [(A) / (B)] of the resin (A) and the resin (B) at this time is a polyarylene sulfide resin that can be molded under low temperature conditions and has excellent heat resistance.
  • the range is preferably from 95/5 to 40/60, more preferably from 90/10 to 70/30, because it is a composition.
  • the melting point (Tm) is 270 ° C. or more and the recrystallization temperature (Tc 2) is 210 ° C. or less. preferable. Further, it is particularly preferable that the melting point (Tm) is in the range of 270 ° C. to 290 ° C. and the recrystallization temperature (Tc 2) is in the range of 180 to 210 ° C. Further, the difference ⁇ T between the melting point (Tm) and the recrystallization temperature (Tc2) is preferably 70 ° C. or more, particularly preferably in the range of 70 to 90 ° C.
  • the melt viscosity (V6) measured at 300 ° C. of the polyarylene sulfide resin composition of the present invention is in the range of 2 to 1000 [Pa ⁇ s] because the balance between fluidity and mechanical strength is good.
  • the range is preferably 2 to 500 [Pa ⁇ s], more preferably 2 to 200 [Pa ⁇ s].
  • the non-Newtonian index of 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 is preferably in the range of 0.90 to 2.00, preferably 0.90 to 1.50. Is more preferable, and a range of 0.95 to 1.20 is particularly preferable.
  • the polyarylene sulfide resin composition of the present invention includes a filler, a silane coupling agent, other resins, a colorant, a heat stabilizer, an ultraviolet stabilizer, and a foaming agent.
  • a rust inhibitor, a flame retardant, and a lubricant may be contained.
  • the filler may be in any shape such as fibrous, granular, plate-like, specifically, glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, Fibrous fillers such as fibers such as calcium sulfate and calcium silicate, natural fibers such as wollastonite, glass beads, glass flakes, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica And non-fibrous fillers such as mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads. These may be used alone or in combination of two or more.
  • silane coupling agent examples include epoxy group-containing alkoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the other resins include polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, polyether ketone resins, poly Arylene resin, polyolefin resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenol resin, urethane resin, liquid crystal polymer, silicone resin, or other synthetic resin, or fluorine rubber And other elastomers.
  • the method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited.
  • the resin (A), the resin (B) as a raw material, and the other components described above as necessary are mixed with powder, beret, fine powder.
  • a known melt kneader such as a Banbury mixer mixing roll, a single or twin screw extruder, and a knee.
  • a temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin composition preferably The temperature range of melting point + 10 ° C. or more, more preferably the temperature range of melting point + 10 ° C. to melting point + 100 ° C., more preferably And a method of melt-kneading at a temperature range of a point + 20 ⁇ mp + 50 ° C..
  • a typical method is melt-kneading using a single-screw or twin-screw extruder having a sufficient kneading force.
  • the polyarylene sulfide 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, and transfer molding. Especially, it can use suitably for an injection molding application taking advantage of the effect of this invention which can be fabricated under low temperature conditions.
  • the various conditions for molding the polyarylene sulfide resin composition of the present invention by injection molding are not particularly limited, and can be usually molded by a general method. Prior to molding, the appearance and mechanical properties of the molded product are improved by preliminary drying at a temperature of 100 to 150 ° C.
  • the cylinder temperature may be a temperature equal to or higher than the melting point of the polyarylene sulfide resin composition, but is preferably 300 ° C. or higher in order to obtain sufficient fluidity.
  • the mold temperature is usually set in the range of 130 to 180 ° C. However, since the polyarylene sulfide resin composition of the present invention has excellent low-temperature moldability, even under relatively low temperature conditions of 130 ° C. or less.
  • the mold temperature is more preferably 120 ° C. or less, and preferably in the range of 40 to 120 ° C. Therefore, the polyarylene sulfide resin composition of the present invention can be molded by molding in a mold having a mold temperature in the range of 40 to 180 ° C, more preferably in the range of 40 to 120 ° C.
  • the molded product obtained by using the polyarylene sulfide resin composition of the present invention can be used for various applications by taking advantage of its excellent heat resistance, for example, a protective / support member for a box-shaped electrical / electronic component integrated module, Multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, electronics Representative of circuit, LSI, IC, 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, computer related parts, etc.
  • Electricity / electricity Parts VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / video equipment parts such as audio / laser discs / compact discs / DVD discs / Blu-ray discs, lighting parts, refrigerator parts , Air conditioner parts, typewriter parts, word processor parts, home appliances such as water heaters, bath water volume, water sensor parts such as temperature sensors, office computer parts, office computer parts, telephone equipment parts, facsimile Machine-related parts represented by related parts, copier-related parts, cleaning jigs, motor parts, writers, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternators Terminal, alternator connector, IC regulator , Potentiometer base for light diamond, relay block, inhibitor switch, various valves such as exhaust gas valve, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint,
  • melt viscosity (V6) at 300 ° C. of the polyarylene sulfide resin and the polyarylene sulfide resin composition was 300 ° C. under a load of 1.96 ⁇ using a flow tester “CFT-500D” manufactured by Shimadzu Corporation. It measured after hold
  • maintaining for 6 minutes on the conditions of 10 ⁇ 6 > Pa, L / D 10 (mm) / 1 (mm).
  • the melting point (Tm) or (Tm2), recrystallization temperature (Tc2), glass transition temperature (Tg), and melt crystallization temperature (Tmc) of the polyarylene sulfide resin and the polyarylene sulfide resin composition are resin or resin.
  • the composition was melted at 350 ° C. and then rapidly cooled to prepare an amorphous film. Approximately 4 mg was weighed from this film and measured using a differential scanning calorimeter (“DSC8500” manufactured by Perkin Elmer).
  • Production Example 1 Production of polyarylene sulfide resin (A-1) In a 150 liter autoclave equipped with a pressure gauge, a thermometer, a condenser blade connected to a condenser, and a bottom valve, a 14.148 kg of a 47.55 mass% sodium hydrogen sulfide aqueous solution, 9.541 kg of 48.8 mass% sodium hydroxide aqueous solution and 38.0 kg of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 12.150 kg of water (the amount of water remaining was 1.13 moles per mole of sodium hydrogen sulfide).
  • the autoclave was sealed and cooled to 180 ° C., and 17.464 kg of paradichlorobenzene and 16.0 kg of N-methyl-2-pyrrolidone were charged.
  • the liquid temperature was set to 150 ° C., and nitrogen gas was used to increase the gauge pressure to 0.1 MPa, and the temperature increase was started.
  • the temperature reached 260 ° C.
  • watering was started on the top of the autoclave, and the reaction was carried out at 260 ° C. for 2 hours while adjusting the liquid temperature so as not to decrease.
  • the maximum pressure during the reaction was 0.87 MPa.
  • the temperature was lowered and sprinkling cooling at the top of the autoclave was stopped.
  • the polyarylene sulfide resin (A-1) was obtained by drying at 120 ° C. for 15 hours using a hot air circulating dryer.
  • the resulting polyarylene sulfide resin (A-1) has a melting point (Tm) of 280 ° C., a recrystallization temperature (Tc2) of 231 ° C., a difference ⁇ T between them of 49 ° C. and a melt viscosity (V6) at 300 ° C. It was 52 Pa ⁇ s.
  • Production Example 2 Production of polyarylene sulfide resin (A-2) In a 150 liter autoclave equipped with a pressure gauge, a thermometer, a condenser blade connected to a condenser, and a bottom valve, a 14.148 kg of a 47.55 mass% sodium hydrogen sulfide aqueous solution, 9.474 kg of 48.7 mass% sodium hydroxide aqueous solution and 38.0 kg of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 12.150 kg of water (the amount of water remaining was 1.13 moles per mole of sodium hydrogen sulfide).
  • the autoclave was sealed and cooled to 180 ° C., and 17.129 kg of paradichlorobenzene and 16.0 kg of N-methyl-2-pyrrolidone were charged.
  • the liquid temperature was set to 150 ° C., and nitrogen gas was used to increase the gauge pressure to 0.1 MPa, and the temperature increase was started.
  • the maximum pressure during the reaction was 0.86 MPa.
  • the temperature was lowered and sprinkling cooling at the top of the autoclave was stopped.
  • the bottom valve was opened, and the reaction slurry was transferred to a 150 liter flat filter and filtered under pressure at 120 ° C.
  • the mixture was stirred at 150 ° C. under reduced pressure for 2 hours to distill off N-methyl-2-pyrrolidone.
  • the obtained cake was washed and filtered with 50 kg of warm water at 70 ° C., and further washed and filtered with 25 kg of warm water 7 times.
  • the resulting polyphenylene sulfide resin (A-2) has a melting point (Tm) of 279 ° C., a recrystallization temperature (Tc 2) of 238 ° C., a difference ⁇ T between them of 41 ° C. and a melt viscosity (V6) at 300 ° C. of 612 Pa. ⁇ It was s.
  • the amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave.
  • the theoretical dehydration amount is 27.921 g. Therefore, of the remaining water amount of 621 g in the autoclave, 401 g is N-methyl-2-pyrrolidone and water. It was consumed in the hydrolysis reaction with sodium oxide and was not present in the autoclave as water, and the remaining 220 g remained in the autoclave in the form of water or crystal water.
  • the amount of water in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.
  • the internal temperature was cooled to 160 ° C., a mixed solution of 25.0 g of 1,3,5-trichlorobenzene and 47.492 kg of N-methyl-2-pyrrolidone was charged, and the temperature was raised to 185 ° C.
  • the amount of water in the autoclave was 0.025 mol per mol of N-methyl-2-pyrrolidone charged in Step 2.
  • the gauge pressure reached 0.00 MPa
  • the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower.
  • the distilled vapor of paradichlorobenzene and water was condensed by a condenser and separated by a decanter, and paradichlorobenzene was returned to the autoclave.
  • the amount of distilled water was 179 g
  • the water content in the autoclave was 41 g
  • 0.005 mol per mol of N-methyl-2-pyrrolidone charged after dehydration and 0.010 mol per mol of sulfur atoms present in the autoclave. there were.
  • the amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave, as in dehydration.
  • the temperature was raised from an internal temperature of 200 ° C. to 230 ° C.
  • the resulting polyarylene sulfide resin (A-3) has a melting point (Tm) of 284 ° C., a recrystallization temperature (Tc2) of 245 ° C., a difference ⁇ T between them of 39 ° C., and a melt viscosity (V6) at 300 ° C. 505 Pa ⁇ s.
  • the temperature was increased by pressurizing to 1 kg / cm 2 G using nitrogen gas at a liquid temperature of 150 ° C. While stirring at a liquid temperature of 220 ° C. for 3 hours, an 80 ° C. refrigerant was passed through a coil wound around the outside of the upper part of the autoclave to cool it. Thereafter, the temperature was raised, and the mixture was stirred at a liquid temperature of 260 ° C. for 3 hours. Then, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. The maximum pressure during the reaction was 8.91 kg / cm 2 G.
  • the obtained slurry was washed twice with warm water and filtered to obtain a filter cake containing about 50% by mass of water.
  • 60 kg of water and 100 g of acetic acid were added to the filter cake to re-slurry, stirred at 50 ° C. for 30 minutes, and then filtered again.
  • the pH of the slurry was 4.6.
  • the operation of adding 60 kg of water to the obtained filter cake and stirring for 30 minutes and then filtering again was repeated 5 times.
  • the obtained filter cake was dried in a hot air circulating dryer at 120 ° C. for 4.5 hours to obtain a white powdered polyarylene sulfide resin (B-1).
  • the resulting polyarylene sulfide resin (B-1) has a melting point (Tm) of 230 ° C., a recrystallization temperature (Tc 2) of 155 ° C., a difference ⁇ T between them of 75 ° C., and a melt viscosity (V6) at 300 ° C. It was 45 Pa ⁇ s.
  • the resulting polyarylene sulfide resin (B-2) has a melting point (Tm) of 249 ° C., a recrystallization temperature (Tc2) of 160 ° C., a difference ⁇ T between them of 89 ° C., and a melt viscosity (V6) at 300 ° C. 22 Pa ⁇ s.
  • a polyarylene sulfide resin (B-4) was obtained in the same manner as in Production Example 4.
  • the resulting polyarylene sulfide resin (B-4) has a melting point (Tm) of 212 ° C., a recrystallization temperature (Tc2) of 147 ° C., a difference ⁇ T between them of 65 ° C., and a melt viscosity (V6) at 300 ° C. It was 21 Pa ⁇ s.
  • a polyarylene sulfide resin (B-5) was obtained in the same manner as in Production Example 4.
  • the resulting polyarylene sulfide resin (B-5) had a melt viscosity (V6) at 300 ° C. of 31 Pa ⁇ s.
  • Example 1 After mixing 60 parts by mass of polyarylene sulfide resin (A-1) and 40 parts by mass of polyarylene sulfide resin (B-1) in a powder state, a small twin-screw extruder (“Compounder 15” manufactured by DSM Explorer) Kneading is performed at a kneading temperature of 320 ° C., a rotation speed of 250 rpm, and a residence time of 1 minute, and the melt is extruded in a strand form from a head attached to the small twin-screw extruder and cut into a length of 2 mm. The pellet of the polyarylene sulfide resin composition (1) was obtained.
  • a small twin-screw extruder (“Compounder 15” manufactured by DSM Explorer) Kneading is performed at a kneading temperature of 320 ° C., a rotation speed of 250 rpm, and a residence time of 1 minute, and the melt is extruded in a
  • the melting point (Tm) and recrystallization temperature (Tc2) of the polyarylene sulfide resin composition (1) were measured, and the difference ⁇ T between them was calculated.
  • the results are shown in Table 1. The higher the melting point (Tm), the lower the recrystallization temperature (Tc2), and the larger the ⁇ T, the better the low-temperature moldability and the better the heat resistance.
  • Burr generation test The pellet obtained above was melted at 320 ° C. with an injection molding machine (“SE75DU” manufactured by Sumitomo Heavy Industries, Ltd.), and a mold for molding Type-A dumbbell specimen (surface roughness of the mold surface).
  • SE75DU injection molding machine
  • Type-A dumbbell specimen surface roughness of the mold surface.
  • the burr length ( ⁇ m) was measured and evaluated. The results are shown in Table 2.
  • the average value of the total score of five people was calculated and evaluated according to the following criteria. The results are shown in Table 2.
  • the average value of total points is 0 points. Average value of total points is more than 0 to less than 1 point ... “ ⁇ ” Average value of total points is more than 1 to 2 points ... “ ⁇ ” The average value of the total points is more than 2 points.
  • the pellet obtained above was melted at 320 ° C. with an injection molding machine (“SE75DU” manufactured by Sumitomo Heavy Industries, Ltd.), and a mold for molding a Type-A dumbbell specimen (surface of the mold surface)
  • SE75DU injection molding machine
  • a Type-A dumbbell test piece was molded at a cylinder temperature of 320 ° C. and a mold temperature of 60 ° C. using a roughness Rz value of 30 ⁇ m.
  • the surface roughness (Rz value) of the obtained test piece was measured using a scanning probe microscope (“SPM-9600” manufactured by Keyence Corporation).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne : une composition de résine de polysulfure d'arylène pouvant être moulée à basse température et présentant une excellente résistance à la chaleur ; un produit moulé à partir de cette dernière ; et des procédés de production de la composition et du produit. Plus spécifiquement, l'invention concerne : une composition de résine de polysulfure d'arylène caractérisée en ce qu'elle contient une résine (A) qui est une résine de polysulfure d'arylène ayant un thioéther d'arylène en tant que motif de répétition, et dans laquelle le point de liaison entre le thioéther et le groupe arylène est en position para, et une résine (B) qui est une résine de polysulfure d'arylène ayant un thioéther d'arylène en tant que motif de répétition, et qui a un site de structure (p) et un site de structure (m) où le point de liaison entre le thioéther et le groupe arylène se lie respectivement en position para et en position méta ; un produit moulé à partir de cette dernière ; et des procédés de production de la composition et du produit.
PCT/JP2016/080801 2015-10-20 2016-10-18 Composition de résine de polysulfure d'arylène, produit moulé, et procédés de production de ladite composition et dudit produit WO2017069109A1 (fr)

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JP2018100364A (ja) * 2016-12-21 2018-06-28 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
JP2020063339A (ja) * 2018-10-16 2020-04-23 Dic株式会社 樹脂組成物およびその成形体
WO2020116434A1 (fr) * 2018-12-06 2020-06-11 Dic株式会社 Composition de résine et corps moulé de cette dernière
WO2022030212A1 (fr) * 2020-08-06 2022-02-10 株式会社クレハ Composition de résine de sulfure de polyphénylène, et matériau d'amortissement contenant celle-ci

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JPS63265618A (ja) * 1987-04-24 1988-11-02 Kureha Chem Ind Co Ltd 熱成形ポリアリ−レンスルフイド容器及びその製造法
JP2004059708A (ja) * 2002-07-26 2004-02-26 Toray Ind Inc ポリアリーレンサルファイド共重合体
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018100364A (ja) * 2016-12-21 2018-06-28 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
JP2020063339A (ja) * 2018-10-16 2020-04-23 Dic株式会社 樹脂組成物およびその成形体
WO2020080289A1 (fr) * 2018-10-16 2020-04-23 Dic株式会社 Composition de résine et article moulé de celle-ci
CN113166491A (zh) * 2018-12-06 2021-07-23 Dic株式会社 树脂组合物及其成形体
JPWO2020116434A1 (ja) * 2018-12-06 2021-02-15 Dic株式会社 樹脂組成物およびその成形体
KR20210064337A (ko) * 2018-12-06 2021-06-02 디아이씨 가부시끼가이샤 수지 조성물 및 그 성형체
WO2020116434A1 (fr) * 2018-12-06 2020-06-11 Dic株式会社 Composition de résine et corps moulé de cette dernière
EP3892677A4 (fr) * 2018-12-06 2022-08-24 DIC Corporation Composition de résine et corps moulé de cette dernière
KR102499526B1 (ko) * 2018-12-06 2023-02-14 디아이씨 가부시끼가이샤 수지 조성물 및 그 성형체
CN113166491B (zh) * 2018-12-06 2023-03-24 Dic株式会社 树脂组合物及其成形体
WO2022030212A1 (fr) * 2020-08-06 2022-02-10 株式会社クレハ Composition de résine de sulfure de polyphénylène, et matériau d'amortissement contenant celle-ci
JPWO2022030212A1 (fr) * 2020-08-06 2022-02-10
CN115768835A (zh) * 2020-08-06 2023-03-07 株式会社吴羽 聚苯硫醚树脂组合物和包含该聚苯硫醚树脂组合物的减振材料
JP7373668B2 (ja) 2020-08-06 2023-11-02 株式会社クレハ ポリフェニレンスルフィド樹脂組成物およびこれを含む制振材
CN115768835B (zh) * 2020-08-06 2024-07-02 株式会社吴羽 聚苯硫醚树脂组合物和包含该聚苯硫醚树脂组合物的减振材料

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