WO2020022023A1

WO2020022023A1 - Polyarylene sulfide composition

Info

Publication number: WO2020022023A1
Application number: PCT/JP2019/026677
Authority: WO
Inventors: 尾崎想; 後藤博之; 山野直樹; 春成武
Original assignee: 東ソー株式会社
Priority date: 2018-07-25
Filing date: 2019-07-04
Publication date: 2020-01-30

Abstract

Provided is a polyarylene sulfide composition that is excellent in weld strength, heat cycle resistance, mold flowability and thin-wall flowability without deterioration in heat resistance, chemical resistance, dimensional stability, etc. The polyarylene sulfide composition comprises, per 100 parts by weight of a polyarylene sulfide (A) having a melt viscosity of 100-2000 poises when measured by a Koka flow tester provided with a die (diameter: 1 mm, length: 2 mm) at a measurement temperature of 315°C under a load of 10 kg, a modified ethylene copolymer resin (B) comprising (B1) or (B2) as follows and 15-100 parts by weight of a fibrous filler (C). (B1) 1-12 parts by weight of an ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer. (B2) 1-30 parts by weight of at least one modified ethylene-based copolymer selected from an ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer and a maleic anhydride graft modified ethylene-α-olefin copolymer and 0.1-3 parts by weight of isocyanurate, wherein the ratio of the isocyanurate/the modified ethylene-based copolymer(s) (parts by weight/parts by weight) falls within the range of 0.05-0.3.

Description

Polyarylene sulfide composition

The present invention provides a polyarylene sulfide composition having excellent weld strength, heat cycle resistance, molding fluidity, and thin-wall fluidity without impairing the inherent heat resistance, chemical resistance, and dimensional stability of polyarylene sulfide. More particularly, the present invention relates to a polyarylene sulfide composition particularly useful for electric parts such as electric / electronic parts, electric parts for automobiles, and water heater parts.

Polyarylene sulfide is a resin that exhibits excellent properties such as heat resistance, chemical resistance, mechanical properties, and dimensional stability. Utilizing these excellent properties, it is used for electrical and electronic equipment components, automotive equipment components, and OA equipment components. Widely used for etc. However, polyarylene sulfide has a drawback of being inferior in toughness (low-temperature impact resistance and heat cycle resistance), so that its use has been limited in some applications.

For an attempt to improve the toughness of polyarylene sulfide, for example, a resin composition comprising (a) polyarylene sulfide and (b) an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer (see, for example, Patent Document 1) ), (A) a composition obtained by melt-kneading polyphenylene sulfide and a non-block type polyfunctional isocyanate compound, and (b) an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer. Resin composition (for example, see Patent Document 2), (a) polyarylene sulfide, (b) an ethylene-α, β-unsaturated carboxylic acid alkyl ester-based copolymer, and (c) a specific type of alkoxy. A resin composition comprising a silane compound (for example, see Patent Document 3), (a) polyarylene sulfide, and (b) polyolefin. Emissions-based resin has been proposed, such as (c) a polymer containing an alkoxysilane group resin composition (for example, see Patent Document 4.).

方法 Also, a method of adding an active hydrogen group or a functional group-containing dihalogen aromatic compound when producing a polyarylene sulfide as a polyarylene sulfide has been proposed (see, for example, Patent Documents 5 and 6).

Furthermore, as a technique for improving the cold / heat resistance of polyarylene sulfide, blending a modified ethylene copolymer with polyarylene sulfide has been proposed. For example, a resin composition comprising polyarylene sulfide and an ethylene-based copolymer, a specific silane coupling agent (for example, see Patent Document 7), a resin composition comprising a specific polyarylene sulfide and a specific modified polyolefin (for example, Reference 8), etc. have been reported. Further, for example, a resin composition comprising polyphenylene sulfide, glass fiber, an olefin copolymer containing an epoxy group and an acid anhydride group, and a specific filler has been reported (for example, see Patent Document 9).

Although the purpose is different, a polyphenylene sulfide resin composition in which a polyamide resin and a specific ethylene copolymer are blended with a modified polyphenylene sulfide obtained by melt-kneading a non-blocking polyfunctional isocyanate with PPS (see, for example, Patent Document 10) .), A polyphenylene sulfide resin composition in which a modified polyphenylene sulfide obtained by melt-kneading polyphenylene sulfide with a non-block type polyfunctional isocyanate is mixed with an ethylene copolymer containing maleic anhydride (for example, see Patent Document 11). A polyphenylene sulfide resin composition in which a specific polyphenylene sulfide is mixed with a block-type polyfunctional isocyanate and a specific maleic anhydride-modified ethylene copolymer (for example, see Patent Documents 12 and 13) has been reported.

Japanese Patent Application Laid-Open No. 62-151460 Japanese Patent Application Laid-Open No. 02-255882 Japanese Patent Application Laid-Open No. 05-202245 Japanese Patent Application Laid-Open No. 04-164962 Japanese Patent Publication No. 05-052849 Japanese Patent No. 3582610 Japanese Patent Application Laid-Open No. 2008-144003 Japanese Patent Application Laid-Open No. 2007-106834 JP 2005-306926 A Japanese Patent No. 2704763 Japanese Patent No. 2789240 Japanese Patent No. 3968839 Japanese Patent No. 3968840

However, the resin compositions proposed in Patent Documents 1 to 4 have a problem that the toughness cannot be sufficiently satisfied.

Patent Documents 5 and 6 propose a method for producing polyarylene sulfide in which dichloroaniline is added. However, it is proposed to improve the adhesion to an epoxy resin, and the toughness of polyarylene sulfide is proposed. No mention is made of improvements.

Furthermore, the resin compositions proposed in Patent Documents 7 to 9 cannot be said to have sufficient cooling / heat resistance, which limits the use. Further, in the resin compositions proposed in Patent Documents 10 and 11, polyphenylene sulfide and polyfunctional isocyanate need to be melt-kneaded in advance, resulting in inferior productivity and no mention of cooling / heat resistance. It is. In addition, the resin compositions proposed in Patent Documents 12 and 13 are also inferior in mold contamination and have no mention of cold / heat resistance. That is, it has been difficult for all of these proposed resin compositions to simultaneously satisfy the cooling / heat resistance, mold contamination, and molding fluidity.

Thus, the present invention provides a polyarylene sulfide composition having excellent weld strength, heat cycle resistance, fluidity, and thin-wall fluidity without impairing the heat resistance, chemical resistance, and dimensional stability inherent to polyarylene sulfide. It is an object of the present invention to provide a polyarylene sulfide composition which is particularly useful for electric parts such as electric / electronic parts and automobile electric parts or water heater parts.

The present inventors have conducted intensive studies to solve the above problems, and as a result, at least a specific polyarylene sulfide, a specific modified ethylene copolymer resin, a polyarylene sulfide composition containing a fibrous filler, a weld They have found that a composition having excellent strength, heat cycle resistance, fluidity, and thin-wall fluidity can be obtained, and have completed the present invention.

That is, the present invention resides in the following [1] to [7].
[1] A polyarylene sulfide (A) having a melt viscosity of 100 to 2,000 poise measured at a temperature of 315 ° C. and a load of 10 kg using a Koka type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. A polyarylene sulfide, which comprises the following (B1) or (B2) as a modified ethylene copolymer resin (B) and 15 to 100 parts by weight of a fibrous filler (C) based on 100 parts by weight. Composition.

(B1) 1 to 12 parts by weight of an ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid butyl ester copolymer.

(B2) at least one modified ethylene copolymer selected from ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer and maleic anhydride graft-modified ethylene-α-olefin copolymer 1 to 30 parts by weight of the unified polymer and 0.1 to 3 parts by weight of the isocyanurate, and the ratio thereof is 0.05 to 0.3 parts by weight of the isocyanurate / the modified ethylene copolymer (parts by weight / part by weight). Within range.
[2] The polyarylene sulfide composition according to the above [1], wherein the polyarylene sulfide (A) is an amino group-modified polyarylene sulfide having a melt viscosity of 200 to 1000 poise.
[3] The polyarylene sulfide composition according to the above [1] or [2], wherein the polyarylene sulfide (A) is a high-pressure hot water-washed amino group-modified polyarylene sulfide.
[4] The polyarylene sulfide (A) according to any one of the above [1] to [3], wherein the polyarylene sulfide (A) is an amino group-modified polyarylene sulfide containing 0.05 to 5 mol% of amino groups. Polyarylene sulfide composition.
[5] The polyarylene sulfide composition according to any one of the above [1] to [4], wherein the isocyanurate is an aliphatic isocyanurate.
[6] The above-mentioned [1] to [5], further comprising a silane coupling agent comprising a trialkoxysilane coupling agent having a glycidoxy group and / or a trialkoxysilane coupling agent having an amino group. ] The polyarylene sulfide composition according to any one of [1] to [10].
[7] Any of the above-mentioned [1] to [6], further comprising at least one release agent selected from the group consisting of polyethylene wax, polypropylene wax and fatty acid amide-based wax. 3. The polyarylene sulfide composition according to item 1.

Hereinafter, the present invention will be described in detail.

The polyarylene sulfide (A) constituting the polyarylene sulfide composition of the present invention may be any one which belongs to a category generally called polyarylene sulfide. Examples of the polyarylene sulfide include p-phenylene sulfide unit , M-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, biphenylene sulfide unit, and a homopolymer or copolymer comprising the polyarylene sulfide. Specific examples of polyphenylene sulfide include poly (p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and polyphenylene sulfide ether. Among the particularly heat resistance, since the polyarylene sulfide composition having excellent strength properties, preferably a polyphenylene sulfide.

The polyarylene sulfide (A) has a melt viscosity of 100 to 2000 at a melt temperature of 315 ° C. and a load of 10 kg measured by a Koka type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. Poise's. Here, when it is less than 100 poise, the obtained composition has poor mechanical strength. On the other hand, when it exceeds 2,000 poise, the thin-wall fluidity is poor.

The polyarylene sulfide (A) can be produced by a method known as a method for producing a polyarylene sulfide. For example, an alkali metal sulfide or a polyhalogen aromatic compound can be produced in a polar solvent. It can be obtained by polymerization. Examples of the polar organic solvent at this time include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, dimethylacetamide, and the like. Anhydrous or hydrate of sodium, rubidium sulfide and lithium sulfide can be mentioned. Further, the alkali metal sulfide may be a product obtained by reacting an alkali metal hydrosulfide with an alkali metal hydroxide. Examples of the polyhalogen aromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4′-dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorodibiphenyl and the like can be mentioned.

Also, the polyarylene sulfide (A) may be a linear one or a one obtained by adding a small amount of a polyhalogen compound of trihalogen or more at the time of polymerization to introduce a slight crosslinked or branched structure. Even if a part and / or terminal of the molecular chain of the polyarylene sulfide is modified with a functional group such as a carboxyl group, a carboxy metal salt, an alkyl group, an alkoxy group, or a nitro group, it may be non-oxidizable such as nitrogen. May be subjected to heat treatment in an inert gas described above, or may be a mixture of these structures. The polyarylene sulfide (A) is subjected to a deionization treatment (acid washing or hot water washing, etc.) before or after heat curing, or a washing treatment with an organic solvent such as acetone or methyl alcohol to form ions, oligomers or the like. It may have reduced impurities. Furthermore, after the completion of the polymerization reaction, a heat treatment may be performed in an inert gas or an oxidizing gas to perform curing.

Further, as the polyarylene sulfide (A), it is possible to provide a polyarylene sulfide composition which is particularly excellent in cold heat resistance, mold contamination, molding fluidity, and weld strength. And more preferably an amino group-modified polyarylene sulfide containing 0.05 to 5 mol% of amino groups, and particularly preferably an amino group-modified polyarylene sulfide containing 0.1 to 3 mol% of amino groups. Is preferred. Examples of the amino group-modified polyarylene sulfide include the above-mentioned amino group-modified resins of polyarylene sulfide. Here, the amino group content is, for example, the absorption of amino group-modified polyarylene sulfide at 1900 cm ⁻¹ which is the CH out-of-plane bending vibration of the benzene ring in the infrared absorption spectrum and the NH stretching vibration of the amino group. The absorption at 3387 cm ^-1 is measured, and can be determined as the amino group content with respect to the phenyl group.

Examples of the method for producing the amino group-modified polyarylene sulfide include a method for copolymerizing an amino group-containing halogen aromatic compound in addition to the above-described method for producing the polyarylene sulfide. Is, for example, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 3,5-diaminochlorobenzene, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, -Amino-2-chlorotoluene, 3-chloro-m-phenylenediamine, 2,5-dibromoaniline, 2,6-dibromoaniline, 3,5-dibromoaniline, and mixtures thereof. 5-Dichloroaniline and 3,5-diaminochlorobenzene are preferred.

Specific examples of the amino group-containing polyarylene sulfide include, for example, amino group-modified polyphenylene sulfide, amino group-modified polyphenylene sulfide sulfone, amino group-modified polyphenylene sulfide ketone, and amino group-modified polyphenylene sulfide ether. Amino group-modified poly (p-phenylene sulfide) is preferred because of its excellent heat resistance and strength properties.

As the amino group-modified polyarylene sulfide, a die having a diameter of 1 mm and a length of 2 mm was mounted because the polyarylene sulfide composition was excellent in weld strength, heat cycle resistance, melt fluidity, and thin moldability. The melt viscosity measured with a Koka type flow tester at a measurement temperature of 315 ° C. and a load of 10 kg is preferably from 200 to 1,000 poise, and particularly preferably from 300 to 800 poise.

The polyarylene sulfide (A), particularly the amino group-modified polyarylene sulfide, which constitutes the present invention, can efficiently remove impurities and the like and has excellent quality. It is preferable that the polyarylene sulfide is subjected to high-pressure hot water treatment and washed. As a condition of the high-pressure hot water treatment at that time, a method of washing with water having a temperature of 150 ° C. or more and 240 ° C. or less can be mentioned.

The modified ethylene copolymer resin (B) constituting the polyarylene sulfide composition of the present invention includes (B1) ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated butyl butyl ester copolymer. Or (B2) at least one modified ethylene selected from ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer and maleic anhydride graft-modified ethylene-α-olefin copolymer It is composed of a copolymer and isocyanurate.

Here, as the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid butyl ester copolymer as (B1), any one belonging to this category can be used. In particular, since the obtained polyarylene sulfide composition has excellent toughness, ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: α, β-unsaturated carboxylic acid butyl ester residue It is preferable that the ratio be in the range of base unit (weight ratio) = 60 to 93: 2 to 10: 5 to 30. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid butyl ester copolymer include, for example, (trade name) LOTADER @ AX8700 (manufactured by Arkema Corporation), Trade name) LOTADER @ AX8750 (manufactured by Arkema Co., Ltd.). As the polyarylene sulfide composition of the present invention, in particular, the amino group-modified polyarylene sulfide and the ethylene-α, β-unsaturated glycidyl-α-, β-unsaturated carboxylic acid butyl ester copolymer are combined. By combining them, a composition exhibiting superior weld strength and heat cycle resistance over the conventionally proposed polyarylene sulfide composition can be obtained.

At that time, the polyarylene sulfide composition was prepared by mixing ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated butyl ester copolymer 1 with respect to 100 parts by weight of polyarylene sulfide (A). Preferably, it contains up to 12 parts by weight.

Further, the modified ethylene copolymer constituting (B2) is an ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer and a maleic anhydride graft-modified ethylene-α-olefin copolymer And at least one modified ethylene copolymer selected from the group consisting of

As the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, any copolymer may be used as long as it belongs to this category. Among them, the obtained polyarylene sulfide composition has a low heat resistance. Ethylene residue unit: α, β-unsaturated carboxylic acid alkyl ester residue unit: maleic anhydride residue unit (weight ratio) = 50 to 98:40 to 1: 10-1. Preferably, there is. Specific examples of the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer include (trade name) Bondyne 5500 (manufactured by Arkema Corporation), (trade name) Bondine TX8030 (Arkema ( (Trade name) Bondyne AX8390 (manufactured by Arkema Co., Ltd.).

As the maleic anhydride graft-modified ethylene-α-olefin copolymer, any one may be used as long as it belongs to this category, and among them, the resulting polyarylene sulfide composition is excellent in cold resistance and the like. Ethylene residue unit: α-olefin residue unit: maleic anhydride residue unit (weight ratio) = 50-98: 45-1: 5-1-1. Maleic acid graft-modified linear low density polyethylene, maleic anhydride graft-modified ethylene-propylene rubber, and the like. The maleic anhydride graft-modified ethylene-α-olefin copolymer can be obtained by, for example, coexisting an ethylene-α-olefin copolymer, a peroxide, and maleic anhydride, and performing a grafting reaction. It is.

The amount of the modified ethylene copolymer is from 1 to 30 parts by weight based on 100 parts by weight of the polyarylene sulfide (A), since the resulting composition has excellent cold heat resistance and mold contamination. It is preferred that

The isocyanurate constituting the component (B2) may be any one called isocyanurate. Among them, aliphatic isocyanurate is a polyarylene sulfide composition having excellent cold / heat resistance. Is preferred. Examples of the aliphatic isocyanurate include 1,3,5-tris (6-isocyanatohex-1-yl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (6-isocyanatotetra-1-yl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris ( 6-isocyanatododec-1-yl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and the like. Particularly, the balance is excellent in cold heat resistance and low in mold contamination. An aliphatic isocyanurate having a molecular weight of 500 or more is preferred because a polyarylene sulfide composition having an excellent water resistance is obtained. The aliphatic isocyanurate may be a polymer such as a dimer or trimer, or an isocyanurate containing a polymer such as a dimer or trimer in an aliphatic isocyanurate monomer, and a polyarylene. It is an aliphatic isocyanurate containing at least 20% of isocyanate groups, since it is a polyarylene sulfide composition having excellent reactivity with sulfide and the modified ethylene copolymer constituting (B2), and excellent cooling and heat resistance. Is preferred.

The aliphatic isocyanurate may be one obtained by modifying a part of the aliphatic isocyanate with an alcohol such as 1,3-butanediol or 2,2,4-trimethyl-1,3-pentadiol. . Among these aliphatic isocyanurates, 1,3,5-tris (6-isocyanatohex-1-yl) -1,3,5-triazine-2, It is preferably 4,6 (1H, 3H, 5H) -trione. Specific examples of 1,3,5-tris (6-isocyanatohex-1-yl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione are (trade names) ) Coronate HXR (manufactured by Tosoh Corporation) and (trade name) Duranate TPA-100 (manufactured by Asahi Kasei Corporation).

The amount of the isocyanurate to be blended is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the polyarylene sulfide (A), since the resulting polyarylene sulfide composition is excellent in cold resistance and mold contamination. Parts by weight, and the compounding ratio of the isocyanurate and the modified ethylene-based polymer is in the range of 0.05 to 0.3 (the isocyanurate / modified ethylene-based polymer (parts by weight / part by weight)). It is preferred that

The α-olefin constituting the modified ethylene copolymer resin (B) refers to an α-olefin having 3 or more carbon atoms, such as propylene, butene-1, 4-methyl-pentene-1, hexene-1, Octene-1 and the like can be exemplified. Examples of the alkyl esters of α, β-unsaturated carboxylic acids include alkyl esters such as acrylic acid and methacrylic acid. Specific examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, and acrylic acid. Isopropyl, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate Butyl and the like. Examples of the α, β-unsaturated glycidyl carboxylate include glycidyl acrylate and glycidyl methacrylate.

Examples of the fibrous filler (C) constituting the polyarylene sulfide composition of the present invention include chopped strands having an average fiber diameter of 8 to 15 μm, particularly 6 to 14 μm, and flat glass having a fiber cross-sectional aspect ratio of 2 to 4. Glass fibers such as chopped strands, milled fibers, and rovings made of fibers; silane fibers; aluminosilicate glass fibers; hollow glass fibers; non-enameled glass fibers; carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers; Whiskers such as silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers, zinc oxide whiskers; metal fibers such as stainless steel fibers; rock wool, zirconia, alumina silica; Inorganic fibers such as barium titanate, silicon carbide, alumina, silica and blast furnace slag; organic fibers such as wholly aromatic polyamide fibers, phenolic resin fibers and wholly aromatic polyester fibers; mineral materials such as wollastenite and magnesium oxysulfate In particular, glass fibers having an average fiber diameter of 8 to 15 μm are polyarylene sulfide compositions having excellent weld strength and heat cycle resistance, and chopped strands having an average fiber diameter of 6 to 14 μm, Chopped strands made of flat glass fibers having an aspect ratio of 2 to 4 are preferable because they are polyarylene sulfide compositions excellent in cold heat resistance and molding fluidity. It is also possible to use a combination of two or more of these, and if necessary, a surface treatment with a functional compound such as an epoxy compound, an isocyanate compound, a silane compound or a titanate compound or a polymer may be used.

The polyarylene sulfide composition of the present invention contains 15 to 100 parts by weight of the fibrous filler (C) based on 100 parts by weight of the polyarylene sulfide (A). Is less than 15 parts by weight or more than 100 parts by weight, the obtained composition has poor heat cycle resistance.

The polyarylene sulfide composition of the present invention is particularly excellent in weld strength, heat cycle resistance, and molding fluidity, so that a trialkoxysilane coupling agent having a glycidyl group and / or a trialkoxysilane cup having an amino group can be obtained. It preferably contains a silane coupling agent composed of a ring agent. The silane capping agent at this time is not particularly limited as long as it is a trialkoxysilane coupling agent having a glycidyl group or an amino group, and as a specific example of those belonging to this category, 3-glycidoxy Propylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and the like. Can be The amount of the silane coupling agent is preferably 0.05 to 5% by weight.

ポリ The polyarylene sulfide composition of the present invention preferably contains a release agent in order to improve mold release properties and appearance when forming a molded article. As the release agent, for example, polyethylene wax, polypropylene wax, and fatty acid amide-based wax are preferably used. As the polyethylene wax and the polypropylene wax, general commercial products can be used. The fatty acid amide-based wax is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid and a diamine, and any one belonging to this category can be used, for example, stearic acid. (Trade name) LiteAmide WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), which is a polycondensate composed of sebacic acid and ethylenediamine. The compounding amount of the release agent is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.

The polyarylene sulfide composition of the present invention may contain a non-fibrous filler without departing from the purpose of the present invention. Examples of the non-fibrous filler include wollastonite, zeolite, and sericite. Silicates such as aluminum, kaolin, mica, pyrophyllite, talc, alumina silicate; oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide, iron oxide; calcium carbonate, magnesium carbonate, dolomite Carbonates such as calcium sulfate and barium sulfate; nitrides such as silicon nitride, boron nitride, and aluminum nitride; glass flakes, glass beads, and the like. Among them, mica, talc, calcium carbonate, and glass flakes can be exemplified. Glass beads are preferred. Further, the non-fibrous filler may be surface-treated with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, or the like.

Further, the polyarylene sulfide composition of the present invention may be any of various thermosetting resins and thermoplastic resins, for example, an epoxy resin, a cyanate ester resin, a phenol resin, a polyimide, a silicone resin, and a polyester, without departing from the purpose of the present invention. And at least one of polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, and the like.

In addition, the polyarylene sulfide composition of the present invention is a conventional heat stabilizer, an antioxidant, an ultraviolet absorber, a crystal nucleating agent, a foaming agent, a mold corrosion inhibitor, without departing from the purpose of the present invention. One or more additives such as a flame retardant, a flame retardant auxiliary, a coloring agent such as a dye and a pigment, and an antistatic agent may be used in combination.

加熱 As a method for producing the polyarylene sulfide composition of the present invention, a conventionally used heat-melt kneading method can be used. For example, a heat-melt kneading method using a single-screw or twin-screw extruder, a kneader, a mill, a Brabender or the like can be mentioned, and a melt-kneading method using a twin-screw extruder having excellent kneading ability is particularly preferable. In addition, the kneading temperature at this time is not particularly limited, and can be arbitrarily selected usually from 280 to 400 ° C. Further, the polyarylene sulfide composition of the present invention can be formed into an arbitrary shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, or the like.

The polyarylene sulfide composition of the present invention has excellent resistance to cold and heat, and has the properties of excellent mold contamination, molding fluidity, and thin-wall moldability required for molding. It is suitably used for electric and electronic parts, water heater parts, and automobile electric parts, for which it is desired to reduce the thickness of parts and use them as exterior parts due to needs.

The present invention provides a polyarylene sulfide composition having excellent weld strength, heat cycle resistance, molding fluidity, and thin-wall moldability without impairing the inherent heat resistance, chemical resistance, and dimensional stability of polyarylene sulfide. More particularly, the present invention relates to a polyarylene sulfide composition particularly useful for electric / electronic parts such as electric / electronic parts or automobile electric parts, and water heater parts.

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

詳細 Details of the polyarylene sulfide, modified ethylene copolymer resin, fibrous filler, isocyanurate, silane coupling agent, and release agent used in Examples and Comparative Examples are shown below.

<Polyarylene sulfide (A)>
Amino group-containing poly (p-phenylene sulfide) (A1-2) (hereinafter simply referred to as PPS (A1-2)): Melt viscosity of 430 poise.
Amino group-containing poly (p-phenylene sulfide) (A2-2) (hereinafter simply referred to as PPS (A2-2)): a melt viscosity of 800 poise.
Amino group-containing poly (p-phenylene sulfide) (A3-2) (hereinafter simply referred to as PPS (A3-2)): a melt viscosity of 300 poise.
Poly (p-phenylene sulfide) (A'4-2) (hereinafter simply referred to as PPS (A'4-2)): Melt viscosity 500 poise.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-5)): Melt viscosity: 800 poise.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-6)): Melt viscosity: 430 poise.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-7)): Melt viscosity of 3000 poise.
Amino group-substituted poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-8)): Amino group content 0.1 mol%, melt viscosity 1200 poise.
Amino group-substituted poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-9)): 0.6 mol% of amino group, melt viscosity 500 poise.
Amino group-substituted poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-10)): amino group content 0.6 mol%, melt viscosity 3000 poise.

<Modified ethylene copolymer resin (B)>
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid butyl ester copolymer (B1-1) (hereinafter simply referred to as modified ethylene copolymer (B1-1)): LOTADER AX8700 (trade name) manufactured by Arkema Co., Ltd., ethylene residue unit: glycidyl methacrylate ester residue unit: butyl acrylate ester residue unit (weight ratio) = 67: 8: 25
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid butyl ester copolymer (B1-2) (hereinafter simply referred to as modified ethylene copolymer (B1-2)): LOTADER AX8750 (trade name) manufactured by Arkema Co., Ltd., ethylene residue unit: methacrylic acid glycidyl ester residue unit: acrylate butyl ester residue unit (weight ratio) = 70: 5: 25
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid vinyl ester copolymer (B′-3) (hereinafter, simply referred to as polyethylene copolymer (B′-3)). ): Manufactured by Sumitomo Chemical Co., Ltd., (trade name) Bond First 2B, ethylene residue unit: glycidyl methacrylate ester residue unit: vinyl acetate ester residue unit (weight ratio) = 83: 12: 5
Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B2-4) (hereinafter, referred to as modified ethylene copolymer (B2-4)): manufactured by Arkema Co., Ltd. (Product name) Bondyne AX8390.
Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B2-5) (hereinafter referred to as modified ethylene copolymer (B2-5)): manufactured by Arkema Co., Ltd. (Product name) Bondine TX8030.

<Fibrous filler (C)>
Glass fiber (C-1); manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91; fiber diameter 9 μm, fiber length 3 mm.
Glass fiber (C-2); chopped strand (trade name) T-760H manufactured by NEC Corporation.
Glass fiber (C-3); Chopped strand (trade name) CSG-3PA 830 manufactured by Nitto Boseki Co., Ltd.

<Isocyanurate (D)>
Isocyanurate (D-1); Coronate HXR (trade name) manufactured by Tosoh Corporation (isocyanate content 21.8%, molecular weight 504).
Isocyanurate (D-2); manufactured by Asahi Kasei Corporation, (trade name) Duranate TPA-100 (isocyanate content 23.2%, molecular weight 504).
Aromatic polyfunctional isocyanate (D-3); Polymeric MDI, manufactured by Tosoh Corporation, trade name: Millionate MR-100 (isocyanate content 31.0%, average molecular weight 450).
Aliphatic isocyanate (D-4); hexamethylene diisocyanate, manufactured by Tosoh Corporation (isocyanate content: 50.0%, molecular weight: 168).

<Silane coupling agent (E)>
Trialkoxysilane coupling agent having a glycidyl group (E-1); KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd .; 3-glycidoxypropyltrimethoxysilane.

<Release agent (F)>
Release agent (F-1); Kyoeisha Chemical Co., Ltd., (trade name) Light Amide WH-255.
Carnauba wax (F-2); manufactured by Nikko Rika Co., Ltd., (trade name) purified carnauba powder No. 1.

Synthesis Example 1
In a 50-liter autoclave equipped with a stirrer, 6214 g of Na ₂ S.2.9H ₂ O and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream to obtain 1355 g. Of water was distilled off. After cooling the system to 140 ° C., 7116 g of p-dichlorobenzene, 79 g of 3,5-dichloroaniline (about 1 mol% based on the total amount of p-dichlorobenzene and 3,5-dichloroaniline), N-methyl- 5000 g of 2-pyrrolidone was added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and a solid content was isolated by a centrifuge. The solid content was washed with hot water at 200 ° C. and dried at 100 ° C. for 24 hours to obtain amino group-containing poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A1-1)).

(4) This PPS (A1-1) was cured at 200 ° C. for 4 hours in a nitrogen atmosphere to obtain amino group-containing poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A1-2)). The melt viscosity of PPS (A1-2) was 430 poise.

Synthesis Example 2
In a 50-liter autoclave equipped with a stirrer, 6214 g of Na ₂ S.2.9H ₂ O and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream to obtain 1355 g. Of water was distilled off. After cooling the system to 140 ° C., 7174 g of p-dichlorobenzene, 16 g of 3,5-dichloroaniline (about 1 mol% based on the total amount of p-dichlorobenzene and 3,5-dichloroaniline), N-methyl- 5000 g of 2-pyrrolidone was added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and a solid content was isolated by a centrifuge. The solid was washed with hot water at 220 ° C. and dried at 100 ° C. for 24 hours to obtain amino group-containing poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A2-1)).

(4) This PPS (A2-1) was cured at 250 ° C. for 4 hours in a nitrogen atmosphere to obtain amino group-containing poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A2-2)). The melt viscosity of PPS (A2-2) was 800 poise.

Synthesis Example 3
In a 50-liter autoclave equipped with a stirrer, 6214 g of Na ₂ S.2.9H ₂ O and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream to obtain 1355 g. Of water was distilled off. After cooling the system to 140 ° C., 7045 g of p-dichlorobenzene, 158 g of 3,5-dichloroaniline (about 2 mol% based on the total amount of p-dichlorobenzene and 3,5-dichloroaniline), N-methyl- 5000 g of 2-pyrrolidone was added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and a solid content was isolated by a centrifuge. The solid was washed with hot water at 170 ° C. and dried at 100 ° C. for 24 hours to obtain amino group-containing poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A3-1)).

(4) This PPS (A3-1) was cured at 170 ° C. for 4 hours in a nitrogen atmosphere to obtain amino group-containing poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A3-2)). The melt viscosity of PPS (A3-2) was 300 poise.

Synthesis Example 4
In a 50-liter autoclave equipped with a stirrer, 6214 g of Na ₂ S.2.9H ₂ O and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream to obtain 1355 g. Of water was distilled off. After cooling the system to 140 ° C., 7188 g of p-dichlorobenzene and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and a solid content was isolated by a centrifuge. The solid was washed with hot water at 200 ° C. and dried at 100 ° C. for 24 hours to obtain poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A′4-1)).

(4) This PPS (A'4-1) was cured at 200 ° C. for 4 hours in a nitrogen atmosphere to obtain poly (p-phenylene sulfide) (hereinafter, referred to as PPS (A'4-2)). The melt viscosity of PPS (A'4-2) was 500 poise.

Synthesis Example 5 (Synthesis of PPS (A-5))
In a 50-liter autoclave equipped with a stirrer, 6214 g of sodium sulfide 2.9 hydrate and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream to remove 1355 g of water. Distilled off. After cooling the system to 140 ° C., 7115 g of p-dichlorobenzene and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the solid content was isolated by a centrifuge. The solid was repeatedly washed with warm water and dried at 100 ° C. for 24 hours to obtain poly (p-phenylene sulfide) having a melt viscosity of 400 poise. Next, the dried poly (p-phenylene sulfide) is charged into a batch type rotary kiln-type baking apparatus, and cured at 250 ° C. for 3 hours in a nitrogen atmosphere to obtain PPS (A-5) having a melt viscosity of 800 poise. Obtained.

Synthesis Example 6 (Synthesis of PPS (A-6))
In a 50-liter autoclave equipped with a stirrer, 5607 g of a 47% aqueous sodium hydrogen sulfide solution, 3807 g of a 48% aqueous sodium hydroxide solution, and 10773 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 200 ° C. while stirring under a nitrogen stream. 4533 g of water was distilled off. After the system was cooled to 170 ° C., 7060 g of p-dichlorobenzene and 5943 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C., polymerization was performed at 225 ° C. for 1 hour, and further, the temperature was raised to 250 ° C., and polymerization was performed at 250 ° C. for 2 hours. Further, 1503 g of water was injected at 250 ° C., the temperature was raised again to 255 ° C., and polymerization was performed at 255 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and a solid content was isolated by a centrifuge. The solid content was washed with N-methyl-2-pyrrolidone at 130 ° C., then twice with acetone successively, and further dried under a nitrogen stream with 0.2% hydrochloric acid and warm water, and then dried at 100 ° C. overnight. As a result, a linear poly (p-phenylene sulfide) having a melt viscosity of 430 poise (hereinafter referred to as PPS (A-6)) was obtained.

Synthesis Example 7 (Synthesis of PPS (A-7))
In a 50-liter autoclave equipped with a stirrer, 6214 g of sodium sulfide 2.9 hydrate and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream to remove 1355 g of water. Distilled off. After cooling the system to 140 ° C., 7115 g of p-dichlorobenzene and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the solid content was isolated by a centrifuge. The solid was repeatedly washed with warm water and dried at 100 ° C. for 24 hours to obtain poly (p-phenylene sulfide) having a melt viscosity of 400 poise. Next, the dried poly (p-phenylene sulfide) is charged into a batch-type rotary kiln-type baking apparatus, and cured at 250 ° C. for 3 hours in an oxygen atmosphere to obtain PPS (A-7) having a melt viscosity of 3000 poise. Obtained.

Synthesis Example 8 (Synthesis of PPS (A-8))
In a 50-liter autoclave equipped with a stirrer, 6214 g of flaky sodium sulfide (Na ₂ S.2.9H ₂ O) and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream. Then, 1355 g of water was distilled off. After the system was cooled to 140 ° C., 7278 g of p-dichlorobenzene, 11.7 g of 3,5-dichloroaniline and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymer was isolated by a centrifuge. The solid was repeatedly washed with warm water and dried at 100 ° C. for 24 hours to obtain an amino-substituted poly (p-phenylene sulfide) having a melt viscosity of 400 poise. Next, the dried amino group-substituted poly (p-phenylene sulfide) is charged into a batch-type rotary kiln-type baking apparatus, and cured at 240 ° C. for 2 hours in an air atmosphere to obtain a melt viscosity of 1200 poise and an amino acid based on phenyl group. PPS (A-8) having a group content of 0.1 mol% was obtained.

Synthesis Example 9 (Synthesis of PPS (A-9))
In a 50-liter autoclave equipped with a stirrer, 6214 g of flaky sodium sulfide (Na ₂ S.2.9H ₂ O) and 17000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. while stirring under a nitrogen stream. Then, 1355 g of water was distilled off. After the system was cooled to 140 ° C., 7150 g of p-dichlorobenzene, 47 g of 3,5-dichloroaniline and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The temperature of this system was raised to 225 ° C. over 2 hours, and polymerized at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes, and polymerization was further performed at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymer was isolated by a centrifuge. The polymer was washed repeatedly with warm water and dried at 100 ° C. for 24 hours to obtain amino-substituted poly (p-phenylene sulfide) having a melt viscosity of 250 poise. Next, the dried amino group-substituted poly (p-phenylene sulfide) is charged into a batch-type rotary kiln-type baking apparatus, and cured at 250 ° C. for 5 hours in a nitrogen atmosphere to obtain a melt viscosity of 500 poise and an amino group to phenyl group. PPS (A-9) having a content of 0.6 mol% was obtained.

Synthesis Example 10 (Synthesis of PPS (A-10))
PPS (A-9) having an amino group content of 0.6 mol% obtained in Synthesis Example 9 was further charged into a batch-type rotary kiln-type baking apparatus, and cured at 250 ° C. for 2 hours in an air atmosphere. PPS (A-10) having a melt viscosity of 3,000 poise and an amino group content of 0.6 mol% based on the phenyl group was obtained.

評価 Evaluation and measurement methods for the obtained polyarylene sulfide and polyarylene sulfide composition are shown below.

～ Melt viscosity measurement ～
Measurement of melt viscosity at a measuring temperature of 315 ° C. and a load of 10 kg with a Koka type flow tester (CFT-500, manufactured by Shimadzu Corporation) equipped with a die having a diameter of 1 mm and a length of 2 mm. Was done.

～ Measurement of weld strength ～
A test piece was prepared by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S), and a tensile tester (Shimazu Seisakusho, (trade name) Autograph AG-5000B) was used. The measurement was performed according to ASTM D638.

～ Heat cycle resistance ～
Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S), insert molding of a rectangular parallelepiped steel (carbon steel) measuring 30 mm x 20 mm x 10 mm was performed at a cylinder temperature of 310 ° C and a mold temperature. The test was performed at 135 ° C. to prepare a heat cycle-resistant test piece coated with a polyarylene sulfide composition having a thickness of 1 mm. After holding the obtained test piece at 150 ° C. for 30 minutes, it is subjected to a cooling and heating cycle in which holding at −40 ° C. for 30 minutes is one cycle, and the cycle is continued until cracks are visually observed. The number of cold cycle treatments in which generation was observed was evaluated as heat cycle resistance. It was judged that the samples having the number of heat treatment cycles of 250 or more were excellent in heat cycle resistance.

~ Evaluation of molding fluidity 1 ~
The obtained polyarylene sulfide composition was adjusted to a cylinder temperature of 310 ° C. and a mold temperature of 135 ° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE-75S), and the thickness was 1 mm. Molding fluidity was determined from the flow length when injection molding was performed at 100 MPa in a spiral flow mold. Those having a flow length of 150 mm or more were determined to have excellent molding fluidity.

-Measurement of amino group content in polyarylene sulfide-
From the infrared absorption spectrum, the absorption at 1900 cm ^-1 which is the CH out-of-plane bending vibration of the benzene ring and the absorption at 3387 cm ^-1 which is the NH stretching vibration of the amino group were measured. The amino group content was determined as the content with respect to.

~ Measuring molding fluidity 2 ~
An injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SE75S (trade name) SE75S) was fitted with a mold having a groove with a depth of 1 mm and a width of 10 mm formed in a spiral shape. The polyarylene sulfide composition was charged into a hopper of the injection molding machine set at an injection pressure of 190 MPa, an injection speed of maximum, an injection time of 1.5 seconds, and a mold temperature of 135 ° C., and was injected. Then, a length of the spiral groove in the mold melt-flowed was measured as a molding fluidity. Molding fluidity exceeding 200 mm was judged to exhibit practically sufficient fluidity.

~ Measuring mold contamination ~
The mold surface after using the obtained polyarylene sulfide composition as a test piece was visually observed. The evaluation criteria are shown below.
：: No deposit is observed on the mold surface.
×: A slight amount of deposit is observed on the mold surface or molding is impossible.

Example 1
A twin screw extruder (manufactured by Toshiba Machine Co., Ltd.) heated at a cylinder temperature of 310 ° C. was blended at a ratio of 97.1% by weight of PPS (A1-2) and 2.9% by weight of a modified ethylene copolymer (B1-1). (Trade name) TEM-35-102B). On the other hand, the glass fiber (C-1) is put into a hopper of a side feeder of the twin-screw extruder, melt-kneaded at a screw rotation speed of 200 rpm, and a molten composition flowing out of a die is cooled and cut, and then pelletized. A polyarylene sulfide composition was prepared. At that time, the composition ratio of the polyarylene sulfide composition was 68% by weight of PPS (A1-2), 2% by weight of modified ethylene copolymer (B1-1), and 30% by weight of glass fiber (C-1). .

The polyarylene sulfide composition was charged into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SE75) heated to a cylinder temperature of 310 ° C., and a test piece for measuring weld strength, heat cycle resistance A test piece for measuring the fluidity and a test piece for measuring the fluidity were each formed and evaluated. Table 1 shows the results.

ポリ The obtained polyarylene sulfide composition was excellent in evaluation of weld strength, heat cycle resistance, and molding fluidity 1.

Examples 2 to 7
Except that the polyarylene sulfide (A), the modified ethylene copolymer resin (B), the fibrous filler (C), the silane coupling agent (E), and the release agent (F) were used in the proportions shown in Table 1, A polyarylene sulfide composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

全て All the obtained polyarylene sulfide compositions were excellent in evaluation of weld strength, heat cycle resistance, and molding fluidity 1.

Comparative Examples 1 to 6
Except that the polyarylene sulfide (A), the modified ethylene copolymer resin (B), the fibrous filler (C), the silane coupling agent (E), and the release agent (F) were used in the proportions shown in Table 2, A polyarylene sulfide composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.

組成 The compositions obtained from Comparative Examples 1 to 6 were inferior in heat cycle resistance. The compositions obtained from Comparative Examples 3, 4, and 5 were inferior in weld strength. The composition obtained from Comparative Example 5 had poor molding fluidity 1 evaluation.

Example 8
Based on 100 parts by weight of the PPS (A-5) obtained in Synthesis Example 5, 14 parts by weight of the modified ethylene copolymer (B2-4), 2.4 parts by weight of isocyanurate (D-1), and mold release 0.2 part by weight of the agent (F-1) was uniformly mixed in advance and charged into a hopper of a twin-screw extruder (trade name: TEM-35-102B, manufactured by Toshiba Machine Co.) heated to a cylinder temperature of 300 ° C. On the other hand, the glass fiber (C-2) was charged from a hopper of a side feeder of the twin-screw extruder so as to be 50 parts by weight with respect to 100 parts by weight of PPS (A-5), and was melt-kneaded and pelletized. A poly (p-phenylene sulfide) composition (hereinafter sometimes referred to as a PPS composition) was produced. The resulting PPS composition was evaluated for cold heat resistance, fluidity 2, and mold contamination. Table 3 shows the evaluation results.

(4) The obtained PPS composition had little mold contamination and had practically sufficient cold heat resistance. The evaluation of molding fluidity 2 also showed a practically sufficient value.

Examples 9 to 15
The polyarylene sulfide (A), the modified ethylene copolymer resin (B), the isocyanurate (D) and the release agent (F) were blended in the composition ratios shown in Table 3, and charged into a hopper of a twin-screw extruder. The fibrous filler (C) was charged into the hopper of the side feeder of the twin-screw extruder so that the composition ratio shown in Table 3 was obtained, and a PPS composition was prepared in the same manner as in Example 8, and Example 8 was prepared. The evaluation was performed in the same manner as described above. Table 3 shows the evaluation results.

ＰＰ The obtained PPS composition had low mold contamination and had practically sufficient cold heat resistance. The evaluation of molding fluidity 2 also showed a practically sufficient value.

Comparative Examples 7 to 13
The polyarylene sulfide (A), the modified ethylene copolymer resin (B), the isocyanurate (D) and the release agent (F) were blended in the composition ratio shown in Table 4, and charged into a hopper of a twin-screw extruder. The fibrous filler (C) was charged into the hopper of the side feeder of the twin-screw extruder so that the composition ratio shown in Table 4 was obtained, and a composition was prepared in the same manner as in Example 8; The evaluation was performed in the same manner as described above. Table 4 shows the evaluation results.

組成 The compositions obtained in Comparative Examples 7, 8, 9, and 11 were inferior in cold / heat resistance. The compositions obtained in Comparative Examples 9, 10 and 11 were inferior in mold contamination. The compositions obtained in Comparative Examples 12 and 13 were inferior in the evaluation of molding fluidity 2.

Example 16
13 parts by weight of the modified ethylene copolymer (B2-4), 1.9 parts by weight of isocyanurate (D-1), and release from 100 parts by weight of the PPS (A-8) obtained in Synthesis Example 8 0.2 part by weight of the agent (F-2) was uniformly mixed in advance and charged into a hopper of a twin-screw extruder (trade name: TEM-35-102B, manufactured by Toshiba Machine Co., Ltd.) heated to a cylinder temperature of 300 ° C. On the other hand, the glass fiber (C-2) was charged from a hopper of a side feeder of the twin-screw extruder so as to be 50 parts by weight with respect to 100 parts by weight of PPS (A-8), and was melt-kneaded and pelletized. A PPS composition was prepared. The resulting PPS composition was evaluated for cold heat resistance, fluidity, mold contamination, and weld strength. Table 5 shows the evaluation results.

The obtained PPS composition had low mold contamination, and had practically sufficient cold heat resistance and weld strength. The evaluation of molding fluidity 2 also showed a practically sufficient value.

Examples 17 to 24
PPS (A), modified ethylene copolymer resin (B), isocyanurate (D) and mold release agent (F) were blended in the composition ratio shown in Table 5, and charged into a hopper of a twin-screw extruder to obtain a fibrous material. Filler (C) was charged into the hopper of the side feeder of the twin-screw extruder so that the composition ratio shown in Table 5 was obtained, and a PPS composition was prepared in the same manner as in Example 16; Was evaluated by the following method. Table 5 shows the evaluation results.

ＰＰ The obtained PPS composition had low mold contamination and had practically sufficient cold heat resistance. Further, the molding fluidity also showed a practically sufficient value. Further, the weld strength was excellent.

Comparative Examples 14 to 20
The PPS (A), the modified ethylene copolymer resin (B), the isocyanurate (D), and the release agent (F) were blended in the composition ratios shown in Table 6, and the mixture was charged into a hopper of a twin-screw extruder to obtain a fiber. The filler (C) was charged into a hopper of a side feeder of a twin-screw extruder so as to have a composition ratio shown in Table 6, and a composition was prepared in the same manner as in Example 16; Evaluation was performed in the same manner. Table 6 shows the evaluation results.

組成 The compositions obtained in Comparative Examples 14, 15, 16, and 18 were inferior in heat resistance. Further, the compositions obtained in Comparative Examples 16, 17 and 18 were inferior in mold contamination, and in Comparative Example 17, no test piece was prepared. The compositions obtained in Comparative Examples 19 and 20 were inferior in the evaluation of molding fluidity 2.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

It should be noted that Japanese Patent Application No. 2018-139331 filed on July 25, 2018, Japanese Patent Application No. 2018-155235 filed on August 22, 2018, and Japanese Patent Application No. 2018-155235 filed on February 6, 2019. The entire contents of the specification, claims, drawings and abstract of application 2019-19461 are hereby incorporated by reference as the disclosure of the specification of the present invention.

The polyarylene sulfide composition of the present invention does not impair heat resistance, chemical resistance, dimensional stability, etc., and has high weld strength, heat cycle resistance, molding fluidity, and thin-wall fluidity. It is particularly useful for electric / electronic parts such as electronic parts or automobile electric parts, and for water heater parts.

Claims

100 parts by weight of a polyarylene sulfide (A) having a melt viscosity of 100 to 2,000 poise measured at a temperature of 315 ° C. and a load of 10 kg with a Koka type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. On the other hand, a polyarylene sulfide composition comprising the following (B1) or (B2) as a modified ethylene copolymer resin (B) and 15 to 100 parts by weight of a fibrous filler (C).
(B1) 1 to 12 parts by weight of an ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid butyl ester copolymer.
(B2) at least one modified ethylene copolymer selected from ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer and maleic anhydride graft-modified ethylene-α-olefin copolymer 1 to 30 parts by weight of the unified polymer and 0.1 to 3 parts by weight of the isocyanurate, and the ratio thereof is 0.05 to 0.3 parts by weight of the isocyanurate / the modified ethylene copolymer (parts by weight / part by weight). Within range.
The polyarylene sulfide composition according to claim 1, wherein the polyarylene sulfide (A) is an amino group-modified polyarylene sulfide having a melt viscosity of 200 to 1000 poise.
The polyarylene sulfide composition according to claim 1 or 2, wherein the polyarylene sulfide (A) is an amino group-modified polyarylene sulfide washed with high-pressure hot water.
The polyarylene sulfide composition according to any one of claims 1 to 3, wherein the polyarylene sulfide (A) is an amino group-modified polyarylene sulfide containing 0.05 to 5 mol% of amino groups. .
5. The polyarylene sulfide composition according to claim 1, wherein the isocyanurate is an aliphatic isocyanurate.
The method according to any one of claims 1 to 5, further comprising a silane coupling agent comprising a trialkoxysilane coupling agent having a glycidoxy group and / or a trialkoxysilane coupling agent having an amino group. The polyarylene sulfide composition according to the above.
The polyarylene according to any one of claims 1 to 6, further comprising at least one release agent selected from the group consisting of polyethylene wax, polypropylene wax, and fatty acid amide wax. Sulfide composition.