Resin composition, molded article, composite, and use thereof

Abstract

Provided are: a resin composition which is capable of providing a molded article having excellent stress cracking resistance and which has excellent moldability; and a molded article obtained by molding the resin composition. Also provided are a composite having the molded body and a use thereof. The resin composition comprises a polyarylene sulfide resin A and a fluorine-containing elastomer B having a terminal functional group, the volume ratio of the polyarylene sulfide resin A to the fluorine-containing elastomer B is 99: 1-50: 50, the fluorine-containing elastomer B is dispersed in the polyarylene sulfide resin A, and the average dispersion particle size of the fluorine-containing elastomer B is less than 10 [mu] m.

Description

Technical Field

[0001] The present invention relates to a resin composition, a molded article, a composite, and uses thereof. Background Art

[0002] Polyarylene sulfide resins typified by polyphenylene sulfide resin are known as resins having excellent heat resistance, solvent resistance, electrical properties, dimensional stability, flame retardancy, etc. However, polyarylene sulfide resins lack toughness. Moreover, the tensile strength and impact resistance are poor. Therefore, improvement of polyarylene sulfide resins is being attempted. For example, Patent Document 1 proposes a resin composition in which a copolymer having a unit based on vinylidene fluoride and a unit based on chlorotrifluoroethylene is blended in a polyarylene sulfide resin to improve mechanical properties and the like. Prior Art Documents Patent Documents

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-517774 Summary of the Invention Technical Problem to be Solved by the Invention

[0004] However, the resin composition of Patent Document 1 has poor moldability during heat molding. Therefore, cracks are likely to occur on the molded article during heat molding. In addition, if the resin composition of Patent Document 1 is applied to, for example, forming a coating layer of an electric wire, even if a coating layer can be formed around the core wire, cracks are likely to occur on the coating layer when the electric wire is bent. Thus, the stress crack resistance is also insufficient.

[0005] The present invention provides a resin composition capable of obtaining a molded article having excellent stress crack resistance and excellent moldability, a molded article formed from the resin composition; and also provides a composite having the molded article and uses thereof. Means for Solving the Technical Problem

[0006] The present invention has the following aspects. [1] A resin composition comprising a polyarylene sulfide resin A and a fluorine-containing elastomer B having terminal functional groups, wherein the volume ratio of the polyarylene sulfide resin A to the fluorine-containing elastomer B is 99:1 to 50:50, the fluorine-containing elastomer B is dispersed in the polyarylene sulfide resin A, and the average dispersed particle diameter of the fluorine-containing elastomer B is less than 10 μm. [2] The resin composition according to [1], wherein the melt viscosity μ A of the polyarylene sulfide resin A and the melt viscosity μ B of the fluorine-containing elastomer B have a melt viscosity ratio of 0.3 or more. [3] The resin composition according to [1] or [2], wherein the terminal functional group is at least one selected from an iodine atom, an epoxy group, and an acid anhydride group. [4] The resin composition according to any one of [1] to [3], wherein the volume ratio of the polyarylene sulfide resin A to the fluorine-containing elastomer B is 95:5 to 50:50. [5] The resin composition according to any one of [1] to [4], wherein the melt viscosity μ of the resin composition is 300 to 420 Pa·s. [6] A molded article of the resin composition according to any one of [1] to [5]. [7] A composite body formed by compounding or laminating the molded article of [6] with other materials other than the molded article. [8] A wire or film having the molded article of [6] as an insulating member. Advantages of the Invention

[0007] According to the resin composition of the present invention, a molded article having excellent stress crack resistance can be obtained. Moreover, the resin composition of the present invention has excellent molding processability. The molded article of the present invention has excellent stress crack resistance. The composite body of the present invention has a molded article having excellent stress crack resistance. The wire or film of the present invention has an insulating member having excellent stress crack resistance. Detailed Embodiments

[0008] The definitions of the terms are as follows. The "volume" of the polyarylene sulfide resin A or the fluorine-containing elastomer B is a value calculated by dividing the mass (g) of the polyarylene sulfide resin A or the fluorine-containing elastomer B by its specific gravity (g / cm 3 ). The "specific gravity" of the polyarylene sulfide resin A or the fluorine-containing elastomer B is a value at 23°C measured by the water displacement (suspension) method. The "average dispersed particle diameter" of the fluorine-containing elastomer B is a value obtained by observing a molded article of the resin composition with a scanning electron microscope (SEM) and taking the arithmetic mean of the measured values of the maximum diameters of 100 randomly selected regions (dispersed particles). The "number average particle diameter" of the fluorine-containing elastomer B is the average of the maximum diameters of 100 particles randomly selected in an optical microscope observation. The "melt viscosity" is determined by the method described in the examples. The measurement conditions for the melt viscosity are temperature: 320°C, shear rate: 122 s -1 . "Melt flow rate" is the melt flow rate (MFR) specified in JIS K 7210-1:2014 (corresponding to the international standard ISO 1133-1:2011). The measurement conditions for the melt flow rate are temperature: 297 °C, load: 21 N. "Ends of polymer chains" refers to the concept that includes both the ends of the main chain and the ends of the side chains. "Main chain" refers to the main carbon chain of a chain compound, which is the backbone part with the largest number of carbon atoms. "Anhydride group" refers to the group represented by -C(=O)-O-C(=O)-. The "fluorine content" of fluorine-containing elastomer B represents the ratio of the mass of fluorine atoms to the total mass of all atoms constituting fluorine-containing elastomer B. The fluorine content is calculated based on the molar ratio of each unit in fluorine-containing elastomer B obtained by melt NMR measurement and total fluorine content measurement. "Storage elastic modulus G'" is the value measured under the conditions of 100 °C and 50 cpm according to ASTM D6204. "Mooney viscosity (ML 1+10 , 121 °C)" is the value measured at 121 °C according to JIS K6300-1:2000 (corresponding to the international standards ISO 289-1:2005, ISO 289-2:1994). "Tensile strength" and "tensile elongation" are determined by the methods described in the examples. "Flexural strength" and "flexural modulus" are determined by the methods described in the examples. "Izod impact strength" is determined by the methods described in the examples.

[0009] "Monomer" refers to a compound having a polymerizable carbon-carbon double bond. "Unit based on monomer" is the general term for the atomic group directly formed by the polymerization of 1 molecule of monomer and the atomic group obtained by partial chemical transformation of this atomic group. The unit based on monomer is abbreviated as "monomer unit". For example, the unit based on ethylene is denoted as "ethylene unit". The unit represented by formula a is denoted as "unit a". Units represented by other formulas are also recorded in the same way. The compound represented by formula 1 is denoted as "compound 1". Compounds represented by other formulas are also recorded in the same way. "~" indicating a numerical range means including the numerical values recorded before and after ~ as the lower limit value and the upper limit value. The numerical ranges disclosed in this specification can be combined arbitrarily with their lower limit values and upper limit values to form new numerical ranges.

[0010] <Resin composition> The resin composition of the present invention comprises a polyarylene sulfide resin A and a fluorine-containing elastomer B having terminal functional groups. The resin composition of the present invention may further comprise other components in addition to the polyarylene sulfide resin A and the fluorine-containing elastomer B as long as the effects of the invention are not impaired.

[0011] The volume ratio (A:B) of the polyarylene sulfide resin A to the fluorine-containing elastomer B is from 99:1 to 50:50, preferably from 95:5 to 50:50, more preferably from 90:10 to 50:50, still more preferably from 85:15 to 50:50, even more preferably from 80:20 to 50:50, particularly preferably from 75:25 to 55:45, and most preferably from 70:30 to 60:40. Since the volume proportion of the fluorine-containing elastomer B is above the lower limit value of the above volume ratio range, the resin composition has excellent moldability. Moreover, a molded article having excellent stress crack resistance can be obtained. In addition, the greater the volume proportion of the fluorine-containing elastomer B, the higher the impact resistance of the molded article. Since the volume proportion of the fluorine-containing elastomer B is below the upper limit value of the above volume ratio range, the characteristics of the polyarylene sulfide resin A such as heat resistance are easily exhibited.

[0012] In the volume of the resin composition, the total volume of the polyarylene sulfide resin A and the fluorine-containing elastomer B is preferably 50 to 100% by volume, more preferably 60 to 99% by volume, and still more preferably 70 to 97% by volume. If the total volume of the polyarylene sulfide resin A and the fluorine-containing elastomer B is above the lower limit value within the above numerical range, moldability, stress crack resistance, and impact resistance are easily exhibited. If the total volume of the polyarylene sulfide resin A and the fluorine-containing elastomer B is 99% by volume or less, new characteristics brought about by other components are easily exhibited. In the volume of the resin composition, the total volume of other components is preferably 0 to 50% by volume, more preferably 1 to 40% by volume, and still more preferably 3 to 30% by volume.

[0013] In the resin composition of the present invention, the fluorine-containing elastomer B having terminal functional groups is dispersed in the polyarylene sulfide resin A in the form of fine particles. Therefore, the stress crack resistance of the molded article is improved. Moreover, the moldability of the resin composition is also enhanced.

[0014] The average dispersion particle size of the fluorine-containing elastomer B having terminal functional groups dispersed in the polyarylene sulfide resin A is less than 10 μm. Therefore, the stress crack resistance of the molded article is improved. Moreover, the moldability of the resin composition is also enhanced. The average dispersed particle diameter of the fluorine-containing elastomer B dispersed in the polyarylene sulfide resin A is preferably 0.1 to 9.5 μm, more preferably 0.5 to 8.0 μm, and still more preferably 0.7 to 6.0 μm. When the average dispersed particle diameter is above the lower limit value within the above numerical range, the impact resistance is more excellent. When the average dispersed particle diameter is below the upper limit value within the above numerical range, the moldability and stress crack resistance are more excellent.

[0015] (Polyarylene sulfide resin A) The polyarylene sulfide resin A (hereinafter sometimes referred to as "PAS resin") is a polymer containing the following unit a in a proportion of 70 mol% or more based on 100 mol% of all constituent units. [-Ar-S-] ··· Formula a

[0016] In Formula a, Ar is a divalent aromatic group. The divalent aromatic group contains one or more benzene rings. When the divalent aromatic group contains two or more benzene rings, the two or more benzene rings can form a condensed ring or can be bonded by a single bond or a linking group. Examples of the linking group include -O-, -S(=O)2-, -C(=O)-.

[0017] The divalent aromatic group may have a substituent. Examples of the substituent include an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxyl group, and a metal carboxylate (sodium salt, lithium salt, etc.). The carbon number of each of the alkyl group and the alkoxy group is, for example, 1 to 10.

[0018] Examples of unit a include the following unit a1 to unit a9. Unit a can be used alone or in combination of two or more.

[0019]

[0020] In Formula a4, R S is an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxyl group, or a metal carboxylate.

[0021] The PAS resin may also contain other units other than unit a. Examples of the other units other than unit a include polyfunctional units in which one or more -S- are further bonded to Ar of unit a. The polyfunctional unit has three or more bonds. When the PAS resin has a polyfunctional unit, the PAS resin has a branched structure or a crosslinked structure.

[0022] In the PAS resin, from the viewpoint of toughness, the proportion of unit a based on 100 mol% of all units is preferably 80 mol% or more, more preferably 85 mol% or more. The upper limit of the proportion of unit a is not particularly limited and can be 100 mol%.

[0023] As the PAS resin, from the viewpoint of heat resistance, polyphenylene sulfide resin (hereinafter also referred to as "PPS resin") is preferred. The PPS resin is a polymer containing unit a1 in a proportion of 70 mol% or more based on 100 mol% of all constituent units.

[0024] The PPS resin may also contain units a other than unit a1. As the units a other than unit a1, units a2 to a9 can be exemplified. The units a other than unit a1 can be used singly or in combination of two or more.

[0025] The PPS resin may also have other units other than units a. As the other units other than units a in the PPS resin, polyfunctional units in which one or more -S- are further bonded to the Ar of unit a can be exemplified, and units the same as other units in the PAS resin can be exemplified.

[0026] In the PPS resin, from the viewpoint of toughness, the proportion of unit a1 based on 100 mol% of all units is preferably 80 mol% or more, more preferably 85 mol% or more. The upper limit of the proportion of unit a1 is not particularly limited and can be 100 mol%.

[0027] The polymerization method of the PAS resin is not particularly limited. Examples include a method of reacting sodium sulfide with at least p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfone solvent such as sulfolane. At this time, in order to adjust the degree of polymerization, alkali metal carboxylates such as sodium acetate and lithium acetate can be added. After the polymerization is completed, the obtained resin can be washed. After washing, it can be further treated with an aqueous solution containing an acid such as hydrochloric acid or acetic acid, a water-organic solvent mixture, or a salt solution such as ammonium chloride.

[0028] Depending on the manufacturing method, the PAS resin has a linear PAS resin and a crosslinked PAS resin in terms of molecular structure. The linear PAS resin is linear and does not have a branched structure or a crosslinked structure. The crosslinked PAS resin has a branched structure or a crosslinked structure. The PAS resin obtained by any manufacturing method can be used, but from the viewpoint of improving the toughness of the resin composition, a linear PAS resin is preferred.

[0029] (Fluorine-containing elastomer B) The fluorine-containing elastomer B is a fluorine-containing elastic copolymer having a storage elastic modulus G' of 80 or more at 100 °C and 50 cpm and not having a melting point, which is different from a fluororesin. The fluorine-containing elastomer B has terminal functional groups. Therefore, the moldability of the resin composition is improved. As the terminal functional groups, from the viewpoint of moldability, at least one selected from an iodine atom, an epoxy group, and an acid anhydride group is preferred, and an iodine atom is more preferred.

[0030] The terminal functional groups possessed by the fluorine-containing elastomer B can be bonded to the ends of the polymer chains of the fluorine-containing elastomer B, can also be bonded to the side groups, or can be bonded to both the ends and the side groups of the polymer chains. From the perspective of molding processability, the terminal functional groups are preferably bonded to at least the ends of the polymer chains of the fluorine-containing elastomer B.

[0031] The content of the terminal functional groups possessed by the fluorine-containing elastomer B is not particularly limited. When the fluorine-containing elastomer B has, for example, iodine atoms as the terminal functional groups, the content of the iodine atoms as the terminal functional groups is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.05 to 1.0% by mass relative to the total mass of the fluorine-containing elastomer B. When the content of the iodine atoms is above the lower limit value within the above numerical range, the molding processability of the resin composition is more excellent. When the content of the iodine atoms is below the upper limit value within the above numerical range, it is easy to obtain the fluorine-containing elastomer B.

[0032] As the fluorine-containing elastomer B having terminal functional groups, a fluorine-containing elastomeric copolymer containing one or more units based on the following monomer m1 is preferred. Monomer m1 is at least one monomer selected from tetrafluoroethylene (hereinafter also referred to as "TFE"), hexafluoropropylene (hereinafter also referred to as "HFP"), vinylidene fluoride (hereinafter also referred to as "VdF"), and chlorotrifluoroethylene (hereinafter also referred to as "CTFE"). Monomer m1 can be used alone or in combination of two or more.

[0033] The fluorine-containing elastomer B having terminal functional groups can be a fluorine-containing elastomeric copolymer having two or more monomer m1 units, or can be a fluorine-containing elastomeric copolymer having one or more monomer m1 units and one or more units based on the following monomer m2 that can copolymerize with monomer m1. Monomer m2 is at least one monomer selected from ethylene (hereinafter also referred to as "E"), propylene (hereinafter also referred to as "P"), perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE"), vinyl fluoride (hereinafter also referred to as "VF"), 1,2-difluoroethylene (hereinafter also referred to as "DiFE"), 1,1,2-trifluoroethylene (hereinafter also referred to as "TrFE"), 3,3,3-trifluoro-1-propene (hereinafter also referred to as "TFP3"), 1,3,3,3-tetrafluoropropene, and 2,3,3,3-tetrafluoropropene. Monomer m2 can be used alone or in combination of two or more.

[0034] PAVE is the following compound 1. CF2=CF(OR F )···Formula 1 In Formula 1, R Fis a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms.

[0035] As the PAVE, perfluoro(methyl vinyl ether) (hereinafter also referred to as "PMVE"), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether) (hereinafter also referred to as "PPVE"), and perfluoro(butyl vinyl ether) can be mentioned. Among them, as the PAVE, PMVE and PPVE are preferred, and PMVE is more preferred. The PAVE can be used alone or in combination of two or more.

[0036] The fluorine-containing elastomer B having a terminal functional group may further have one or more units based on a monomer m3 copolymerizable with the monomer m1. The monomer m3 is a monomer copolymerizable with the monomer m1 and is a monomer other than the monomers m1 and m2 that will form an elastic copolymer with the copolymer of the monomer m1. The monomer m3 can be used alone or in combination of two or more. The proportion of the monomer m3 unit is preferably 20 mol% or less, more preferably 5 mol% or less, and particularly preferably 0 mol% based on all the units constituting the fluorine-containing elastomer B.

[0037] As the monomer m3, a monomer having a terminal functional group can be used. In the case of synthesizing the fluorine-containing elastomer B having an iodine atom as a terminal functional group, an iodine atom can be introduced into the side chain of the fluorine-containing elastomer B by using a monomer having an iodine atom. Examples of the monomer having an iodine atom include: vinyl iodide, 4-iodo-3,3,4,4-tetrafluoro-1-butene, 2-iodo-1,1,2,2-tetrafluoro-1-ethoxyethylene, 2-iodo-ethyl vinyl ether, allyl iodide, 1,1,2,3,3,3-hexafluoro-2-iodo-1-(perfluoroethoxy)propane, 3,3,4,5,5,5-hexafluoro-4-iodoheptane, trifluoroiodoethane, 2-iodopentafluoro(ethyl vinyl ether). The monomer having an iodine atom can be used alone or in combination of two or more.

[0038] In the case of synthesizing the fluorine-containing elastomer B having an epoxy group as a terminal functional group, an epoxy group can be introduced into the side chain of the fluorine-containing elastomer B by using a monomer having an epoxy group. Examples of the monomer having an epoxy group include: glycidyl (meth)acrylate, glycidyl β-methyl (meth)acrylate and other glycidyl esters of (meth)acrylic acid; allyl glycidyl ether, allyl methyl glycidyl ether and other allyl glycidyl ethers; 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate and other vinyl-based monomers containing an alicyclic epoxy group. The monomer having an epoxy group can be used alone or in combination of two or more.

[0039] In the case of synthesizing a fluorine-containing elastomer B having an acid anhydride group as a terminal functional group, an acid anhydride group can be introduced into the side group of the fluorine-containing elastomer B by using a monomer having an acid anhydride group. Examples of the monomer having an acid anhydride group include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and maleic anhydride. The monomer having an acid anhydride group can be used alone or in combination of two or more.

[0040] The fluorine-containing elastomer B having a terminal functional group preferably has all units constituting the fluorine-containing elastomer B composed of two or three monomer m1 units, or composed of one or more monomer m1 units and one or more monomer m2 units. However, as long as it is within the range not affecting the properties of the resin composition, the fluorine-containing elastomer B may also contain units other than these as impurities and the like.

[0041] Examples of the fluorine-containing elastomer B having a terminal functional group include the following three copolymers. · A copolymer containing TFE units and P units, · A copolymer containing HFP units and VdF units (excluding copolymers containing P units), · A copolymer containing TFE units and PAVE units (excluding copolymers containing P units or VdF units), The total proportion of the respective units specifically shown in these three copolymers is preferably 50 mol% or more relative to all units constituting the copolymer.

[0042] Examples of the copolymer containing TFE units and P units include the following copolymers. Hereinafter, each of the exemplified copolymers has a terminal functional group. A copolymer composed of TFE units and P units, A copolymer composed of TFE units, P units, and VF units, A copolymer composed of TFE units, P units, and VdF units, A copolymer composed of TFE units, P units, and E units, A copolymer composed of TFE units, P units, and TFP units, A copolymer composed of TFE units, P units, and PAVE units, A copolymer composed of TFE units, P units, and 1,3,3,3-tetrafluoropropene units, A copolymer composed of TFE units, P units, and 2,3,3,3-tetrafluoropropene units, A copolymer composed of TFE units, P units, and TrFE units, A copolymer composed of TFE units, P units, and DiFE units, A copolymer composed of TFE units, P units, VdF units, and TFP units, A copolymer composed of TFE units, P units, VdF units, and PAVE units. Among them, as the copolymer containing TFE units and P units, a copolymer composed of TFE units and P units is preferred.

[0043] As the copolymer containing HFP units and VdF units, the following copolymers can be cited. A copolymer composed of HFP units and VdF units, A copolymer composed of TFE units, VdF units, and HFP units, A copolymer composed of TFE units, VdF units, HFP units, and TFP units, A copolymer composed of TFE units, VdF units, HFP units, and PAVE units, A copolymer composed of VdF units, HFP units, and TFP units, A copolymer composed of VdF units, HFP units, and PAVE units. Among them, as the copolymer containing HFP units and VdF units, a copolymer composed of HFP units and VdF units is preferred.

[0044] As the copolymer containing TFE units and PAVE units, a copolymer composed of TFE units and PAVE units can be cited. Among them, a copolymer composed of TFE units and PMVE units and a copolymer composed of TFE units, PMVE units, and PPVE units are preferred, and a copolymer composed of TFE units and PMVE units is more preferred.

[0045] As other examples of the fluorine-containing elastomer B having terminal functional groups, the following examples can be cited. A copolymer composed of TFE units, VdF units, and 2,3,3,3-tetrafluoropropene units, A copolymer composed of VdF units and PAVE units, A copolymer composed of VdF units and 2,3,3,3-tetrafluoropropene units, A copolymer composed of E units and HFP units.

[0046] As the fluorine-containing elastomer B having terminal functional groups, a copolymer containing TFE units and P units, a copolymer containing HFP units and VdF units, and a copolymer containing TFE units and PAVE units are preferred, a copolymer containing TFE units and P units is more preferred, and a copolymer composed of TFE units and P units is particularly preferred. The copolymer composed of TFE units and P units has good thermal stability during melt compounding. Therefore, the transportability during melt compounding is stable.

[0047] From the viewpoint of the impact resistance of the molded body, the proportion of each unit constituting the fluorine-containing elastomer B having terminal functional groups is preferably in the following range. In the copolymer composed of TFE units and P units, the molar ratio of each unit (hereinafter referred to as "TFE:P", and other molar ratios are also recorded in the same manner) is preferably 30 to 80:70 to 20, more preferably 40 to 70:60 to 30, and still more preferably 50 to 60:50 to 40. In the copolymer composed of TFE units, P units and VF units, TFE:P:VF is preferably 30 to 60:60 to 20:0.05 to 40. In the copolymer composed of TFE units, P units and VdF units, TFE:P:VdF is preferably 30 to 60:60 to 20:0.05 to 40. In the copolymer composed of TFE units, P units and E units, TFE:P:E is preferably 20 to 60:70 to 30:0.05 to 40. In the copolymer composed of TFE units, P units and TFP units, TFE:P:TFP is preferably 30 to 60:60 to 30:0.05 to 20. In the copolymer composed of TFE units, P units and PAVE units, TFE:P:PAVE is preferably 40 to 70:60 to 29.95:0.05 to 20. In the copolymer composed of TFE units, P units and 1,3,3,3-tetrafluoropropene units, TFE:P:1,3,3,3-tetrafluoropropene is preferably 30 to 60:60 to 20:0.05 to 40. In the copolymer composed of TFE units, P units and 2,3,3,3-tetrafluoropropene units, TFE:P:2,3,3,3-tetrafluoropropene is preferably 30 to 60:60 to 20:0.05 to 40. In the copolymer composed of TFE units, P units and TrFE units, TFE:P:TrFE is preferably 30 to 60:60 to 20:0.05 to 40. In the copolymer composed of TFE units, P units and DiFE units, TFE:P:DiFE is preferably 30 to 60:60 to 20:0.05 to 40. In the copolymer composed of TFE units, P units, VdF units and TFP units, TFE:P:VdF:TFP is preferably 30 to 60:60 to 20:0.05 to 40:0.05 to 20. In the copolymer composed of TFE unit, P unit, VdF unit and PAVE unit, the ratio of TFE:P:VdF:PAVE is preferably 30-70:60-20:0.05-40:0.05-20.

[0048] In the copolymer composed of HFP unit and VdF unit, the ratio of HFF:VdF is preferably 99-5:1-95. In the copolymer composed of TFE unit, VdF unit and HFP unit, the ratio of TFE:VdF:HFP is preferably 20-60:1-40:20-60. In the copolymer composed of TFE unit, VdF unit, HFP unit and TFP unit, the ratio of TFE:VdF:HFP:TFP is preferably 30-60:0.05-40:60-20:0.05-20. In the copolymer composed of TFE unit, VdF unit, HFP unit and PAVE unit, the ratio of TFE:VdF:HFP:PAVE is preferably 30-70:60-20:0.05-40:0.05-20. In the copolymer composed of VdF unit, HFP unit and TFP unit, the ratio of VdF:HFF:TFP is preferably 1-90:95-5:0.05-20. In the copolymer composed of VdF unit, HFP unit and PAVE unit, the ratio of VdF:HFF:PAVE is preferably 20-90:9.95-70:0.05-20.

[0049] In the copolymer composed of TFE unit and PAVE unit, the ratio of TFE:PAVE is preferably 40-70:60-30. In the case of the copolymer composed of TFE unit and PMVE unit, the ratio of TFE:PMVE is preferably 40-70:60-30. In the copolymer composed of TFE unit, PMVE unit and PPVE unit, the ratio of TFE:PMVE:PPVE is preferably 40-70:3-57:3-57.

[0050] In the copolymer composed of TFE unit, VdF unit and 2,3,3,3-tetrafluoropropene unit, the ratio of TFE:VdF:2,3,3,3-tetrafluoropropene is preferably 1-30:30-90:5-60. In the copolymer composed of VdF unit and PAVE unit, the ratio of VdF:PAVE is preferably 3-95:97-5. In the copolymer composed of VdF unit and 2,3,3,3-tetrafluoropropene unit, the ratio of VdF:2,3,3,3-tetrafluoropropene is preferably 30-95:70-5. In the copolymer composed of E unit and HFP unit, the ratio of E:HFP is preferably 40 to 60:60 to 40.

[0051] The fluorine content of the fluorine-containing elastomer B is preferably 50 to 74% by mass, more preferably 55 to 70% by mass. The fluorine content is preferably 57 to 60% by mass in the copolymer composed of TFE unit and P unit, 66 to 71% by mass in the copolymer composed of HFP unit and VdF unit, and 66 to 70% by mass in the copolymer composed of TFE unit and PMVE unit. When the fluorine content is above the lower limit value within the above numerical range, the heat resistance and chemical resistance are improved. When the fluorine content is below the upper limit value within the above numerical range, the impact resistance is improved.

[0052] The storage elastic modulus G' of the fluorine-containing elastomer B is preferably 80 to 800, more preferably 100 to 800, and further preferably 120 to 600. The larger the storage elastic modulus G', the larger the molecular weight of the fluorine-containing elastomer B and the higher the entanglement density of the molecular chains. When the storage elastic modulus G' of the fluorine-containing elastomer B is within the above numerical range, the mechanical properties such as tensile strength are improved.

[0053] The number-average molecular weight of the fluorine-containing elastomer B is preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000,000, further preferably 20,000 to 800,000, and particularly preferably 50,000 to 600,000. When the number-average molecular weight of the fluorine-containing elastomer B is above the lower limit value within the above numerical range, the impact resistance and mechanical properties are improved. When the number-average molecular weight of the fluorine-containing elastomer B is below the upper limit value within the above numerical range, the fluidity and dispersibility are improved. As a result, the flexibility is improved.

[0054] The Mooney viscosity (ML 1+10 , 121 °C) of the fluorine-containing elastomer B is preferably 10 to 300, more preferably 20 to 280, and further preferably 30 to 250. The Mooney viscosity is a measure of the molecular weight. The larger the Mooney viscosity value, the larger the molecular weight. In addition, the smaller the Mooney viscosity value, the smaller the molecular weight. The Mooney viscosity (ML 1+10 , 121 °C) of the fluorine-containing elastomer B is above the lower limit value within the above numerical range, then the impact resistance and mechanical properties are improved. The Mooney viscosity (ML 1+10 , 121 °C) of the fluorine-containing elastomer B is below the upper limit value within the above numerical range, then the fluidity and dispersibility are improved. As a result, the molding processability of the resin composition is more excellent.

[0055] The fluorine-containing elastomer B can be used alone as one kind, or two or more kinds can be used in combination, but it is preferably used alone as one kind. The fluorine-containing elastomer B can be commercially available or can be synthesized from various raw materials by various methods. The fluorine-containing elastomer B can be synthesized, for example, by polymerizing one or more monomers m1, any one or both of one or more monomers m2 and monomer m3 used as needed.

[0056] During the polymerization, a radical polymerization initiator is preferably used. As the radical polymerization initiator, a compound having a temperature of 0 to 100 °C at a half-life of 10 hours is preferred, and a compound having a temperature of 20 to 90 °C is particularly preferred. Examples include azo compounds (such as azobisisobutyronitrile), non-fluorine-based diacyl peroxides (such as diisobutyryl peroxide, dioctanoyl peroxide, benzoyl peroxide, lauroyl peroxide, etc.), peroxydicarbonates (such as diisopropyl peroxydicarbonate), peresters (such as tert-butyl peroxyneopentanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxyacetate, etc.), fluorine-containing diacyl peroxides (such as Compound 2), and inorganic peroxides (such as potassium persulfate, sodium persulfate, ammonium persulfate, etc.). (Z(CF2) r COO)2···Formula 2 In Formula 2, Z is a hydrogen atom, a fluorine atom or a chlorine atom, and r is an integer from 1 to 10.

[0057] During the polymerization, a chain transfer agent can also be used. As the chain transfer agent, examples include Compound 3, Compound 4, alcohols (such as methanol, ethanol, etc.), chlorofluorocarbons (such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, etc.), hydrocarbons (such as pentane, hexane, cyclohexane, etc.), and thiols (such as tert-dodecyl mercaptan, n-octadecyl mercaptan, etc.). R 1 I2…Formula 3 R 2 IBr···Formula 4 In Formula 3, R 1 is an alkylene or polyfluoroalkylene having 2 or more carbon atoms. In Formula 4, R 2 is an alkylene or polyfluoroalkylene having 1 to 16 carbon atoms.

[0058] R 1 、R 2 Among them, the polyfluoroalkylene can be linear or branched. As R 1 、R 2 ,perfluoroalkylene is preferred. As Compound 3, examples include 1,4-diiodoperfluorobutane, 1,2-diiodoperfluoroethane, 1,3-diiodoperfluoropropane, 1,5-diiodoperfluoropentane, and 1,6-diiodoperfluorohexane. Among them, 1,4-diiodoperfluorobutane is preferred. Examples of Compound 4 include 1-iodo-4-bromoperfluorobutane, 1-iodo-4-bromoperfluorobutane, 1-iodo-6-bromoperfluorhexane, and 1-iodo-8-bromoperfluorooctane.

[0059] Iodine compounds such as Compound 3 and Compound 4 can function as chain transfer agents. Therefore, if each monomer is copolymerized in the presence of an iodine compound, an iodine atom can be bonded to the terminal of the main chain of the fluorine-containing elastomer B. In the case of obtaining a fluorine-containing elastomer B having a branched chain, an iodine atom can also be bonded to the terminal of the branched chain in the same manner.

[0060] Examples of the polymerization method include emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. From the viewpoint of easily adjusting the number-average molecular weight and copolymer composition of the fluorine-containing elastomer B and improving productivity, emulsion polymerization in which monomers are polymerized in the presence of an aqueous medium and an emulsifier is preferred.

[0061] As the radical polymerization initiator used in emulsion polymerization, a water-soluble initiator is preferred. Examples of the water-soluble initiator include: a redox initiator composed of persulfuric acid, hydrogen peroxide, a water-soluble organic peroxide, an organic initiator, or a combination of persulfuric acid or hydrogen peroxide and a reducing agent; an inorganic initiator of a system in which a small amount of iron, ferrous salt, silver sulfate, etc. coexist in the redox initiator. Examples of persulfuric acid include ammonium persulfate, sodium persulfate, and potassium persulfate. Examples of the water-soluble organic peroxide include disuccinic peroxide, diglycidic peroxide, and tert-butyl hydroperoxide. Examples of the organic initiator include 2,2'-azobis(2-methylpropionamidine) dihydrochloride. Examples of the reducing agent include sodium bisulfite and sodium thiosulfate.

[0062] In the emulsion polymerization method, an elastomer latex is obtained by polymerizing monomers in the presence of an aqueous medium, an emulsifier, and a radical polymerization initiator. A pH regulator can also be used during monomer polymerization.

[0063] (Other Components) Examples of other components include inorganic fillers, polymer fillers, plasticizers, and flame retardants. The other components can be used alone or in combination of two or more.

[0064] Examples of the inorganic filler include glass fiber, carbon fiber, graphite, graphene, carbon nanotube, gypsum fiber, mica, talc, glass flake, wollastonite, potassium titanate, aluminum borate, boron nitride, aluminum nitride, calcium carbonate, magnesium oxide, tin oxide, silicon oxide (silica), titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, clay, white carbon, carbon black, inorganic pigment, molybdenum disulfide, metal powder, magnetic material, and zeolite.

[0065] Examples of the glass fiber include chopped fiber, milled fiber, and flat glass fiber having an irregular cross-section. In addition, from the viewpoint of electrical properties, glass fiber having a low dielectric constant can also be used. Examples of the carbon fiber include PAN-based carbon fiber, pitch-based isotropic carbon fiber, and pitch-based anisotropic carbon fiber. For the shape of the carbon fiber, chopped fiber and milled fiber can be selected according to the required physical properties.

[0066] Examples of the carbon black include furnace black, acetylene black, pyrolytic carbon black, and channel black, etc. Among them, furnace black is preferred. Examples of the furnace black include HAF-LS carbon, HAF carbon, HAF-HS carbon, FEF carbon, GPF carbon, APF carbon, SRF-LM carbon, SRF-HM carbon, MT carbon, etc., and MT carbon is preferred.

[0067] The shape of the inorganic filler is not particularly limited and may be fibrous, plate-like, or particulate (including spherical). From the viewpoints of mechanical properties and friction and wear characteristics, fibrous is preferred. In applications where isotropy of the formed body is required, plate-like inorganic fillers and particulate inorganic fillers are preferred. The size of the inorganic filler is not particularly limited. Depending on the use of the formed body, inorganic fillers of any size from nano-size to micron-size to millimeter-size can be used.

[0068] Examples of the polymer filler include liquid crystal polymer, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyester elastomer, polyacrylate, polycaprolactone, phenoxy resin, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 46, aromatic polyamide, polyamide elastomer, polyphenylene ether, polytetrafluoroethylene, acrylonitrile-butadiene-styrene copolymer (ABS resin), polymethyl methacrylate, polypropylene, polyethylene, polybutadiene, butadiene-styrene copolymer, ethylene-propylene-diene monomer (EPDM), styrene-butadiene block copolymer, butadiene-acrylonitrile copolymer, acrylic rubber, styrene-maleic anhydride copolymer, styrene-phenylmaleimide copolymer, ethylene / acrylic acid / glycidyl methacrylate copolymer, silicone elastomer, aramid. Among them, polytetrafluoroethylene is applicable to the case where the dielectric constant and the tangent of the dielectric loss angle of the formed body are decreased.

[0069] Examples of the plasticizer include phthalate and adipate. As flame retardants, examples include aluminum hydroxide, magnesium hydroxide, magnesium carbonate, antimony trioxide, sodium antimonate, antimony pentoxide, phosphonitrile compounds, phosphate esters (triphenyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, tolylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc.), ammonium polyphosphate, melamine polyphosphate·melem·melam, red phosphorus, molybdenum compounds, boric acid compounds, polytetrafluoroethylene.

[0070] When the resin composition further contains an inorganic filler as another component, the proportion of the inorganic filler is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass in total of the polyarylene sulfide resin A and the fluorine-containing elastomer B. When the proportion of the inorganic filler is above the lower limit value within the above numerical range, the characteristics of the inorganic filler are likely to be exhibited. When the proportion of the inorganic filler is below the upper limit value within the above numerical range, moldability, stress crack resistance, and impact resistance are likely to be exhibited.

[0071] (Preferred mode of the resin composition) The melt viscosity μ of the polyarylene sulfide resin A A and the melt viscosity μ of the fluorine-containing elastomer B B The melt viscosity ratio (μ A / μ B ) is preferably 0.3 or more, more preferably 0.3 to 1.7, still more preferably 0.5 to 1.4, and particularly preferably 0.7 to 1.2. μ A / μ B When it is above the lower limit value within the above numerical range, the difference in melt viscosity between the polyarylene sulfide resin A and the fluorine-containing elastomer B is likely to be reduced. Therefore, the fluorine-containing elastomer B is likely to be dispersed in the polyarylene sulfide resin A in the form of fine particles. As a result, a resin composition excellent in moldability can be easily obtained. In addition, a molded article excellent in stress crack resistance can be easily obtained. μ A / μ B When it is below the upper limit value within the above numerical range, the combination of the polyarylene sulfide resin A and the fluorine-containing elastomer B can be easily selected and determined, and raw materials can be easily obtained.

[0072] To make μ A / μ B within the above numerical range, preferably μ A is 100 to 1500 Pa·s and μ B is 100 to 1500 Pa·s, more preferably μ A is 300 to 400 Pa·s and μ B is 300 to 300 Pa·s. As μ AThe polyphenylene sulfide resin A within the above numerical range includes, for example, products QC-160 and QC-200 of Solvay Specialty Polymers. As μ B The fluorine-containing elastomer B within the above numerical range includes, for example, the fluorine-containing elastomer B1 used in the following examples.

[0073] The melt viscosity μ of the resin composition is preferably 100 to 1000 Pa·s, more preferably 200 to 500 Pa·s, and further preferably 300 to 420 Pa·s. If the melt viscosity μ of the resin composition is above the lower limit value within the above numerical range, it is easy to apply the resin composition to heat forming. If the melt viscosity μ of the resin composition is below the upper limit value within the above numerical range, the fluidity during heat forming is high, and the formability of the resin composition is more excellent.

[0074] The melt flow rate MFR of the polyphenylene sulfide resin A A and the melt flow rate MFR of the fluorine-containing elastomer B B The ratio (MFR A / MFR B ) is preferably 300 or less, more preferably 0.05 to 200, further preferably 0.1 to 100, and particularly preferably 0.2 to 10. MFR A / MFR B If it is above the lower limit value within the above numerical range, it is easy to select and determine the combination of the polyphenylene sulfide resin A and the fluorine-containing elastomer B, and it is easy to obtain raw materials. MFR A / MFR B If it is below the upper limit value within the above numerical range, it is easy to reduce the difference in melt viscosity between the polyphenylene sulfide resin A and the fluorine-containing elastomer B. Therefore, the fluorine-containing elastomer B is easily dispersed in the polyphenylene sulfide resin A in the form of fine particles. As a result, it is easy to obtain a molded article with excellent stress cracking resistance. Moreover, it is easy to obtain a resin composition with excellent formability.

[0075] To make MFR A / MFR B within the above numerical range, preferably MFR A is 1 to 200 g / 10 min and MFR B is 2 to 170 g / 10 min, more preferably MFR A is 3 to 150 g / 10 min and MFR B is 5 to 100 g / 10 min. As the polyphenylene sulfide resin A within the above numerical range of MFR A includes, for example, products QC-160 and QC-200 of Solvay Specialty Polymers. As MFR BThe fluorine-containing elastomer B within the above numerical range may be exemplified by the fluorine-containing elastomer B1 used in the following examples.

[0076] The melt flow rate of the resin composition: MFR is preferably 1 g / 10 min or more, more preferably 3 to 180 g / 10 min, still more preferably 5 to 150 g / 10 min, and particularly preferably 10 to 100 g / 10 min. If the melt flow rate of the resin composition is at or above the lower limit value within the above numerical range, the fluidity during heat forming is high, and the formability of the resin composition is more excellent. If the melt flow rate of the resin composition is at or below the upper limit value within the above numerical range, it is easy to moderately maintain the melt viscosity during heat forming.

[0077] When the resin composition is formed into a test piece with a thickness of 4.0 mm, the tensile strength is preferably 30 MPa or more, more preferably 35 MPa or more, still more preferably 40 MPa or more. When the tensile strength is at or above the above lower limit value, the mechanical properties of the formed body are excellent. The upper limit value of the tensile strength is not particularly limited.

[0078] When the resin composition is formed into a test piece with a thickness of 4.0 mm, the tensile elongation is preferably 8% or more, more preferably 10% or more, still more preferably 15% or more. When the tensile elongation is at or above the above lower limit value, the mechanical properties of the formed body are excellent. The upper limit value of the tensile elongation is not particularly limited.

[0079] When the resin composition is formed into a test piece with a thickness of 4.0 mm, the flexural strength is preferably 50 MPa or more, more preferably 70 MPa or more, still more preferably 75 MPa or more. When the flexural strength is at or above the above lower limit value, the mechanical properties of the formed body are excellent. The upper limit value of the flexural strength is not particularly limited. The upper limit value of the flexural strength is, for example, 133 MPa.

[0080] When the resin composition is formed into a test piece with a thickness of 4.0 mm, the flexural modulus is preferably 1800 MPa or more, more preferably 2000 MPa or more, still more preferably 2200 MPa or more. When the flexural modulus is at or above the above lower limit value, the mechanical properties of the formed body are excellent. The upper limit value of the flexural modulus is not particularly limited. The upper limit value of the flexural modulus is, for example, 4000 MPa.

[0081] When the resin composition is formed into a test piece with a thickness of 4.0 mm, the Izod impact strength at 23°C is preferably 18 J / m or more, more preferably 28 J / m or more, still more preferably 40 J / m or more. When the Izod impact strength at 23°C is at or above the above lower limit value, the impact resistance of the formed body at room temperature is excellent. The upper limit value of the Izod impact strength at 23°C is not particularly limited, for example, NB (No break).

[0082] (Method for manufacturing resin composition) The resin composition of the present invention can be manufactured, for example, by melt-kneading a polyarylene sulfide resin A, a fluorine-containing elastomer B, and other components used as needed. When other components are included in the resin composition, the other components can be added when the polyarylene sulfide resin A and the fluorine-containing elastomer B are melt-kneaded, or can be added after the polyarylene sulfide resin A and the fluorine-containing elastomer B are melt-kneaded.

[0083] From the viewpoint of easy operation when preparing the composite, the fluorine-containing elastomer B before melt-kneading is preferably in the form of granules. The number average particle diameter of the fluorine-containing elastomer B before melt-kneading is preferably 10 mm or less, more preferably 8 mm or less, and still more preferably 6 mm or less. When the number average particle diameter of the fluorine-containing elastomer B before melt-kneading is below the above upper limit value, the transportability by the screw during melt-kneading is stable.

[0084] The volume ratio of the polyarylene sulfide resin A to the fluorine-containing elastomer B during melt-kneading is the same as the volume ratio of the polyarylene sulfide resin A to the fluorine-containing elastomer B in the resin composition. When the volume ratio of the polyarylene sulfide resin A and the volume ratio of the fluorine-containing elastomer B are within the above ranges, the appearance of the strands obtained during melt-kneading is less rough. As a result, the molding processability of the obtained granules (resin composition) is excellent. In addition, when the sum of the volume ratio of the polyarylene sulfide resin A and the volume ratio of the fluorine-containing elastomer B is within the above range and the volume ratio of the polyarylene sulfide resin A is within the above range, it is easy to exhibit molding processability, stress crack resistance, and impact resistance.

[0085] As the melt-kneading device, devices having various melt-kneading functions can be cited. As the melt-kneading device, a single-screw extruder or a twin-screw extruder having a screw with a high kneading effect is preferred, a twin-screw extruder is more preferred, and a twin-screw extruder having a screw with a high kneading effect is particularly preferred. As a screw with a high kneading effect, a screw that has a sufficient kneading effect on the melt-kneading object and does not apply excessive shear force can be selected. As the melt-kneading device, a LABOPLASTOMILL kneader (manufactured by Toyo Seiki Seisaku-sho, Ltd.) can be cited.

[0086] As a method for supplying the polyarylene sulfide resin A and the fluorine-containing elastomer B to the melt-kneading device, the polyarylene sulfide resin A and the fluorine-containing elastomer B can be premixed and then supplied to the melt-kneading device, or the polyarylene sulfide resin A and the fluorine-containing elastomer B can be supplied to the melt-kneading device separately.

[0087] When other components are included in the resin composition, the other components may be premixed with either the polyarylene sulfide resin A or the fluorine-containing elastomer B and then supplied to the melt-kneading apparatus, or may be supplied to the melt-kneading apparatus separately from the polyarylene sulfide resin A and the fluorine-containing elastomer B. Further, the other components may be added after melt-kneading the polyarylene sulfide resin A and the fluorine-containing elastomer B.

[0088] The melt-kneading is preferably carried out until particles of the fluorine-containing elastomer B having an average dispersed particle diameter of less than 10 μm are dispersed in the polyarylene sulfide resin A. For example, the average dispersed particle diameter of the particles of the fluorine-containing elastomer B having less than 10 μm can be dispersed in the polyarylene sulfide resin A by appropriately adjusting the melt viscosity ratio (μ A / μ B ), the melt-kneading temperature, the extrusion shear rate, and the residence time of the object to be melt-kneaded in the melt-kneading apparatus.

[0089] The melt-kneading temperature is preferably set according to the polyarylene sulfide resin A and the fluorine-containing elastomer B. The melt-kneading temperature is preferably 200 to 450 °C, more preferably 240 to 400 °C, still more preferably 250 to 350 °C, and particularly preferably 280 to 330 °C. When the melt-kneading temperature is at or above the lower limit value within the above numerical range, the fluorine-containing elastomer B is easily dispersed in the polyarylene sulfide resin A, and coarse particles of the fluorine-containing elastomer B are not likely to remain. When the melt-kneading temperature is at or below the upper limit value within the above numerical range, thermal decomposition of the fluorine-containing elastomer B is not likely to be promoted, and heat resistance is improved. Moreover, the particle diameter of the fluorine-containing elastomer B will not be too small.

[0090] The extrusion shear rate during melt-kneading is preferably set according to the melt viscosity of the object to be melt-kneaded at the melt-kneading temperature. The extrusion shear rate during melt-kneading is preferably 3 to 2500 s -1 , more preferably 10 to 2000 s -1 , still more preferably 15 to 1500 s -1 . When the extrusion shear rate is at or above the lower limit value within the above numerical range, the fluorine-containing elastomer B is easily dispersed in the polyarylene sulfide resin A, and coarse particles of the fluorine-containing elastomer B are not likely to remain. When the extrusion shear rate is at or below the upper limit value within the above numerical range, the particle diameter of the fluorine-containing elastomer B will not be too small.

[0091] The residence time of the object to be melt-kneaded in the melt-kneading apparatus is preferably 10 to 290 s, more preferably 20 to 240 s, still more preferably 30 to 210 s. When the residence time of the object to be melt-kneaded in the melt-kneading apparatus is at or above the lower limit value within the above numerical range, the fluorine-containing elastomer B is easily dispersed in the polyarylene sulfide resin A, and large particles of the fluorine-containing elastomer B are not likely to remain. When the residence time is at or below the upper limit value within the above numerical range, thermal decomposition of the fluorine-containing elastomer B is not likely to be promoted.

[0092] The melt-kneading is preferably carried out in the substantially absence of a crosslinking agent and a crosslinking aid. Carrying out the melt-kneading in the substantially absence of a crosslinking agent and a crosslinking aid means that the fluorine-containing elastomer B in the resin composition is melt-kneaded in the substantially non-crosslinked state. Whether the fluorine-containing elastomer B in the resin composition is substantially non-crosslinked can be confirmed by the value of the flexural modulus of the resin composition. When the fluorine-containing elastomer B is substantially crosslinked, the fluorine-containing elastomer B loses its flexibility and thus the flexural modulus exceeds 3.7 GPa. When carrying out the melt-kneading in the substantially absence of a crosslinking agent and a crosslinking aid, the flexibility of the fluorine-containing elastomer B in the resin composition can be ensured, and the impact resistance of the molded article can be improved.

[0093] However, the melt-kneading can also be carried out in the presence of a crosslinking agent and a crosslinking aid. In the case of carrying out the melt-kneading in the presence of a crosslinking agent and a crosslinking aid, the crosslinking agent and the crosslinking aid can be used in an amount within the range capable of ensuring the thermoplasticity of the resin composition.

[0094] (Mechanism of action) In the resin composition of the present invention described above, the fluorine-containing elastomer B having terminal functional groups is dispersed in the polyarylene sulfide resin A and the average dispersed particle diameter of the fluorine-containing elastomer B is less than 10 μm. Therefore, a molded article excellent in stress crack resistance can be obtained, and the resin composition has excellent moldability.

[0095] (Use) The resin composition of the present invention can be made into a powder form and used as a coating material. Examples of the use as a coated article are those described in International Publication No. 2015 / 182702. In addition, the resin composition of the present invention can also be used as an additive for a fiber-reinforced resin molded article and a matrix resin for a prepreg. The reinforcing fibers used for the fiber-reinforced resin molded article and the prepreg are not particularly limited. Various inorganic fibers, various metal fibers, and various organic fibers can be used.

[0096] <Molded article> The molded article of the resin composition of the present invention is obtained by molding the resin composition of the present invention. Since the molded article of the present invention can exhibit the properties of PAS resin, it can be applied to various uses required for PAS resin. In addition, since the molded article of the present invention has particularly excellent stress cracking resistance and impact resistance, it can be applied to various uses that require these properties.

[0097] The molding method is not particularly limited. Various molding methods can be applied. Examples include melt molding methods and lamination molding methods. As the melt molding method, examples include injection molding methods, extrusion molding methods, and compression molding methods (thermoforming methods). As the injection molding method, examples include conventional injection molding methods, high-speed injection molding methods, multi-color molding methods, co-injection molding methods, injection compression molding methods, gas-assisted injection molding methods, foam injection molding methods (MUCELL), hot and cold molding methods using a rapidly heated mold, insert molding methods, in-mold insert injection molding methods, etc.

[0098] As the extrusion molding method, examples include film forming methods using a T-die, tube forming methods using a circular die, profile extrusion molding methods, melt spinning methods, and float forming methods for forming hollow parts. According to the extrusion molding method, multi-layer molded articles with two or more layers and multi-layer fibers with a core-sheath structure can be obtained.

[0099] The compression molding method is a method of thermoforming a single-layer or multi-layer sheet. As the lamination molding method, 3D printing and molding methods called additive manufacturing are widely used. For example, fused deposition modeling and selective laser sintering can be cited.

[0100] Since the conventional polyarylene sulfide resin has poor processability in molding, especially cracks are likely to occur on the molded article during extrusion molding. In contrast, the resin composition of the present invention has excellent processability in molding, so cracks are not easily generated on the molded article during extrusion molding. Therefore, considering that the resin composition of the present invention is suitable for the extrusion molding method, an extruded molded article is preferably used as the molded article.

[0101] The barrel temperature of the extruder is preferably 300 to 420 °C, more preferably 330 to 370 °C. The die temperature is preferably 350 to 420 °C, more preferably 350 to 380 °C. When the temperature is within the above numerical range, the frictional stress between the molten resin and the die is reduced, and the surface smoothness of the extruded molded article is improved. Moreover, the resin decomposition caused by the thermal history during molding is suppressed, and the surface smoothness of the extruded molded article is improved. The extrusion shear rate of the extruder is preferably 3 to 2500 s -1 , more preferably 10 to 1000 s -1 , further preferably 10 to 100 s -1 . The residence time of the resin composition in the extruder is preferably 10 to 1000 seconds, more preferably 60 to 500 seconds.

[0102] The molded article of the present invention can also be used in the form of a composite body that is compounded or laminated with other materials other than the molded article of the present invention. Examples of other materials include metals, glasses, plastics, and rubbers. Examples of plastics include the substances described in International Publication No. 2015 / 182702, liquid crystal polymers, polyaryl ketones, polyether sulfones, polyphenyl sulfones, polyacetals, polyurethanes, and polyamides. Examples of polyamides include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6 / 66 copolymer, polyamide 6 / 66 / 610 copolymer, polyamide MXD6, polyamide 6T, polyamide 9T, and polyamide 6 / 6T copolymer.

[0103] Examples of the form and use of the molded article and the composite body include the housing (outer shell) of a portable electronic device, a coupling member of a portable electronic device, a sliding member, a three-dimensional circuit member, a gear, an actuator, a piston, a bearing, a valve, an aircraft interior material, a bipolar plate, a heat exchanger, a bushing, a pipeline (for fuel, etc.), a hose, a tank, a seal, a cable, an insulating coating material for wires (cables, electric cables, etc.), a film, a sheet, a bottle, a fiber, etc.

[0104] Examples of portable electronic devices include mobile phones, portable terminals, laptop computers, tablet computers, radios, cameras, camera accessories, watches, calculators, music players, global positioning system signal receivers, portable game consoles, hard disks, portable recording devices, portable playback devices, and portable radio signal receivers.

[0105] Examples of the form of the housing of a portable electronic device include the back cover, front cover, antenna housing, frame, and backbone of the portable electronic device. The housing can be a member composed of a single part of the molded article of the present invention or a member composed of multiple parts. Here, the backbone is a part on which components of a portable electronic device such as electronics, microprocessors, screens, keyboards, keypads, antennas, and battery sockets are installed. When the housing is located inside the portable electronic device, the housing may not be visible from the outside of the portable electronic device, or may be partially visible from the outside of the portable electronic device. A housing such as a cover for protecting and supporting the internal structure may be exposed to the outside of the portable electronic device.

[0106] As forms of coupling members for portable electronic devices, there may be mentioned snap connectors between a circuit board, a microphone, a speaker, a display, a battery, a cover, an electrical connector, an electronic connector, a hinge, an antenna, a switch, and a game pad (switchpad) of a portable electronic device. The coupling members can be applied to portable electronic devices such as mobile phones, portable terminals (PDAs), music storage devices, eavesdropping devices, portable DVD players, electrical multimeters, portable electronic game machines, portable personal computers (e.g., laptop computers, etc.).

[0107] The three-dimensional circuit member is a member formed by forming a circuit pattern on the surface of a resin member formed in a three-dimensional shape, and can be used as an antenna member for a portable electronic device or a member for in-vehicle electronic equipment. As a method for forming the circuit pattern, a laser direct structuring (LDS) method can be used, in which electroplating treatment is performed after laser-etching the circuit pattern.

[0108] As uses of pipelines, hoses, tanks, seals, and cables, there may be mentioned the uses described in International Publication No. 2015 / 182702. In addition, as uses of pipelines and hoses, there may be mentioned pipelines for drilling energy resources such as petroleum, natural gas, and shale oil. As a use of an insulating coating material for electric wires, there may be mentioned an insulating coating material for electric wires for motor coils or flat copper wires, particularly for flat conductors in drive motors of hybrid electric vehicles (HEVs) and electric vehicles (EVs). As a form of the insulating coating material for the flat conductor, a film is preferred. As a use of an insulating coating material for electric wires, there may be mentioned an insulating coating material for downhole cables for drilling energy resources (such as petroleum, natural gas, and shale oil), etc. Among them, an insulating coating material for downhole cables for oil production is preferred. As uses of films and sheets, there may be mentioned: speaker diaphragms, plates for trauma and fractures, insulating papers (such as insulating papers for motors) for various electrical insulating adhesive tapes, sealing tapes for petroleum and natural gas pipelines, release films.

[0109] A wire or a film having the molded body of the present invention as an insulating member is one of the preferred use examples. This is because when the resin composition of the present invention is extrusion-molded to manufacture a wire or a film, cracks are less likely to occur in the extrusion-molded body. In addition, the coating layer of the film or the wire also has the advantage of excellent stress cracking resistance.

[0110] In the case where the molded article is a film, examples of its uses include a speaker diaphragm having a film, a film for wire coating, a flexible printed circuit board, a rigid substrate, a heat-resistant roller for OA equipment, and a film for impregnating other fiber composites. In addition, thin film capacitors can also be cited. Insulating tapes for fixing components of electrolytic capacitors such as aluminum and tantalum. The film thickness is preferably 1 to 100 μm, more preferably 2 to 80 μm, and further preferably 5 to 50 μm. If the film thickness is above the lower limit value within the above numerical range, the strength of the film is improved. If the thickness of the film is below the upper limit value within the above numerical range, the operability of the film is improved. In the case where the molded article is a tube, examples of its uses include a medical catheter having a pipeline, wire coating, and piping for an analytical device. In the case where the molded article is a fiber, examples of its uses preferably include protective clothing and various filters. As injection molded products, examples include capacitor cases, battery cases, power storage packages such as LIBs, and in particular, cover packages are also preferred examples of uses.

[0111] The above describes several embodiments, but each embodiment is presented only as an example and does not limit the scope of the present invention. Each embodiment described in this specification can be changed within the scope of achieving the effects of the present invention, and can be combined with the features described in other embodiments within the scope where it can be implemented. Examples

[0112] The following presents examples to describe the embodiments in more detail. However, the present invention is not limited to the following description. Examples 1 to 8 are examples. Examples 9 to 13 are comparative examples.

[0113] <Measurement methods, evaluation methods> (Average dispersed particle size) The resin composition was compression molded at 320 °C to form a pressed sheet (size 130 mm × 130 mm × 1 mm thick). After freeze-drying the pressed sheet, it was cut with a cutter, and its cross-section was observed with SEM (JSM-IT700HR manufactured by JEOL Ltd., magnification 5000 times). The maximum diameter of 100 randomly selected regions (dispersed particles) was measured from the SEM image, and the arithmetic mean of the maximum diameters of each region was taken as the average dispersed particle size. The substance in each region was confirmed by energy dispersive X-ray spectroscopy (EDS) of JSM-IT700HR manufactured by JEOL Ltd. for the fluoropolymer (fluorine-containing elastic copolymer or fluororesin).

[0114] (Melt viscosity (μ, μ A , μ B )) Using a capillary rheometer (manufactured by Toyo Seiki Seisaku-sho, Ltd., capillary length L: 10 mm, capillary inner diameter r: 1.0 mm, piston diameter D: 9.55 mm), the melt viscosity at a temperature of 320 °C and a shear rate of 122 s -1 was determined.

[0115] (Melt flow rate of the resin composition: MFR) It was determined using a melt indexer (manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature of 297 °C and a load of 21 N in accordance with JIS K 7210-1:2014 (corresponding to the international standard ISO 1133-1:2011).

[0116] (Melt flow rate of polyarylene sulfide resin A: MFR A ) It was determined using a melt indexer (manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature of 297 °C and a load of 21 N in accordance with JIS K 7210-1:2014 (corresponding to the international standard ISO 1133-1:2011).

[0117] (Melt flow rate of fluorine-containing elastomer B: MFL B ) It was determined using a melt indexer (manufactured by Techno Seven Co., Ltd.) under the conditions of a temperature of 297 °C and a load of 21 N in accordance with JIS K 7210-1:2014 (corresponding to the international standard ISO 1133-1:2011).

[0118] (Mooney viscosity (ML 1+10 , 121 °C)) It was measured using an SMV-201 (manufactured by Shimadzu Corporation) at 121 °C in accordance with JIS K6300-1:2000 (corresponding to the international standards ISO 289-1:2005 and ISO 289-2:1994).

[0119] (Storage elastic modulus G’) It was measured using an RPA2000 (manufactured by Alpha Technologies) under the conditions of 100 °C and 50 cpm in accordance with ASTM D6204.

[0120] (Fabrication of injection-molded article) The granular resin composition was pre-dried at 200 °C for 3 hours. Subsequently, the resin composition was injection-molded using an injection molding machine (manufactured by FANUC Corporation, ROBOSHOT α-50) at a barrel temperature of 380 °C and a mold temperature of 170 °C to obtain an injection-molded article with a thickness of 4.0 mm.

[0121] (Tensile strength, elongation at break) For the injection-molded body, use TENSILON (manufactured by A&D Co., Ltd., model: RTF-1350). Measure the tensile strength and elongation at break according to JIS K7161 (corresponding to the international standard ISO 527-1:2012) under the conditions of the rated capacity of the load cell: 10 kN, the distance between chucks: 115 mm, and the speed: 50 mm / minute.

[0122] (Flexural strength, flexural modulus of elasticity) Cut out test pieces with a length of 80 mm and a width of 10 mm from the injection-molded body. For the test pieces, use TENSILON (manufactured by A&D Co., Ltd., RTF-1350) to measure the flexural modulus of elasticity and flexural strength according to JIS K7171 (corresponding to the international standard ISO 527-1:2012) under the conditions of the rated capacity of the load cell: 10 kN, the distance between supports: 64 mm, and the speed: 2 mm / minute.

[0123] (Izod impact strength) Cut out test pieces with a length of 80 mm and a width of 10 mm from the injection-molded body, and make a notch at the position where the height of the test piece is 40 mm. For the test pieces, use a cantilever test device (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to measure the Izod impact strength under the conditions of the hammer capacity: 2.75 J, the hammer load: 13.97 N, the distance from the axis to the center of gravity: 10.54 cm, and the distance from the axis to the impact point: 33.5 cm. The measurement is carried out at 23°C.

[0124] (Manufacture of insulated wire) As the flat conductor, use a flat copper wire (oxygen-free copper, height 1.5 mm × width 2.3 mm) manufactured by FCM Co., Ltd. Coat the periphery of the flat copper wire with an extrusion molding of the resin composition to obtain an insulated wire. When coating, use a wire extrusion molding machine equipped with the following wire extruder, screw, wire die crosshead, wire pulling machine, and coiling machine to obtain an insulated wire with a wire diameter thickness accuracy of ±0.03 mm. The extrusion molding conditions are the die head temperature: 350°C, and the barrel temperature: 280 - 350°C. · Wire extruder: MS30-25 extruder manufactured by IKG Co., Ltd. · Screw: Full-thread type manufactured by IKG Co., Ltd., L / D = 24 (L is the length from the start of the screw thread ridge under the hopper opening to the front end, D is the screw diameter, which is 30 mm) · Wire die crosshead: Manufactured by UNITEC Co., Ltd., maximum conductor diameter: 3 mm, maximum die hole diameter: 20 mm · Wire drawing machine, coiling machine: Manufactured by Sei Seisakusho Co., Ltd.

[0125] (Stress cracking resistance) Bend and deform the insulated wire in the edge width direction and the plane width direction respectively. The deformation angle is 90 ± 10°. Then, visually observe the coating of the insulated wire and evaluate the stress cracking resistance according to the following criteria. A: No cracks will occur on the coating during deformation in any bending direction in the edge width direction and the plane width direction. B: Cracks will occur on the coating when deforming in at least one bending direction.

[0126] (Preparation of evaluation film) Pre-dry the resin composition at 200 °C for 3 hours. Using a single-screw extruder (manufactured by Tanabe Plastic Machinery Co., Ltd., VS-30) and a 150 mm wide T-die, extrude and form the resin composition at a barrel temperature of 280 - 350 °C, a die temperature of 320 °C, a rotation speed of 6 rpm, and a drawing speed of 1.0 m / minute, and make it pass through a metal roller maintained at 145 °C to obtain an evaluation film with a thickness of 5 μm.

[0127] (Forming processability) Visually observe the surface of the evaluation film and evaluate the forming processability according to the following criteria. A: Neither pinholes nor necking phenomena occur on the evaluation film. B: At least one of pinholes and necking phenomena occurs on the evaluation film.

[0128] (MIT) According to ASTM D2176, press and form the resin composition with a pressing plate at 320 °C to obtain a pressed sheet with a thickness of 0.23 mm. Cut out test pieces with a width of 12.5 mm, a length of 130 mm, and a thickness of 0.23 mm from the pressed sheet. Use a MIT bending test device (manufactured by Toyo Seiki Seisakusho Co., Ltd., MIT-DA) to bend the test pieces under the conditions of a temperature of 23 °C, a humidity of 50% RH, a load of 12.25 N, a bending angle of 135 degrees to the left and right, and a bending frequency of 175 times per minute, and calculate the number of times until the test pieces break (MIT bending life). The more the number of times, the better the bending resistance. In the case of more than 10,000 times, the number is recorded as > 10,000 and the test is aborted.

[0129] <Material> (Polyarylene sulfide resin) · Polyarylene sulfide resin A1: Polyphenylene sulfide (linear, product of Solvay Specialty Polymers "160P", MFR A : 17 g / 10 min, melt viscosity μ A: 358 Pa·s, specific gravity: 1.34 g / cm 3 )。 · Polyphenylthioether resin A2: Polyphenylene sulfide (linear, product "MA-520" of Solvay Specialty Polymers, MFR A : 55.0 g / 10 min, melt viscosity μ A : Not measured, specific gravity: 1.34 g / cm 3 )。

[0130] (fluorine-containing elastomer) · Fluorine-containing elastomer B1: TFE unit: P unit = 56:44, a fluorine-containing elastomer having iodine atoms as terminal functional groups at 0.4 mass% relative to the mass of the fluorine-containing elastomer, MFR B : 27.9 g / 10 min, melt viscosity μ B : 354 Pa·s, specific gravity: 1.55 g / cm 3 , Mooney viscosity (ML 1+10 , 121 °C): 50, storage elastic modulus G': 250). · Fluorine-containing elastomer B2: TFE unit: P unit = 56:44, a fluorine-containing elastomer without terminal functional groups, melt viscosity μ B : 1726 Pa·s, specific gravity: 1.55 g / cm 3 , Mooney viscosity (ML 1+10 121 °C): 100, storage elastic modulus G': 390).

[0131] (inorganic filler) · MgO: Magnesium oxide.

[0132] <Example 1> After mixing polyphenylthioether resin A1 and fluorine-containing elastomer B1 at the volume ratio shown in Table 1, they were fed from the hopper at the base end of the screw of a twin-screw extruder (manufactured by Technovel Corporation, KZW32TW-45MG-NH(-1500), screw diameter: 32 mm Φ, L / D: 45) at a flow rate of 15.0 kg / hour. Under the conditions of screw rotation speed: 200 rpm, set temperatures of the barrel, die head and head: C1 = 340 °C, C2 = 360 °C, C3 = 370 °C, C4 = 370 °C, C5 = 370 °C, C6 = 370 °C, AD = 350 °C, H = 360 °C, the strands extruded from the die head were air-cooled and cut with a granulator to obtain the resin composition particles. When it was difficult to form strands, water-cooling was used instead of air-cooling, and the resin composition particles were obtained by cutting with a granulator. The evaluation results are shown in Table 1.

[0133] <Examples 2 - 4> A resin composition was obtained in the same manner as in Example 1, except that the volume ratio of the polyarylene sulfide resin A1 to the fluorine-containing elastomer B1 was changed as shown in Table 1. In Example 4, 0.7 parts by mass of MgO was mixed with respect to 100 parts by mass of the total mass of the polyarylene sulfide resin A1 and the fluorine-containing elastomer B1 before being fed into the twin-screw extruder. The evaluation results are shown in Table 1.

[0134] <Examples 5 to 8> A resin composition was obtained in the same manner as in Examples 1 to 4, except that the polyarylene sulfide resin A2 was used instead of the polyarylene sulfide resin A1. In Example 8, 0.7 parts by mass of MgO was mixed with respect to 100 parts by mass of the total mass of the polyarylene sulfide resin A2 and the fluorine-containing elastomer B1 before being fed into the twin-screw extruder. The evaluation results are shown in Table 1.

[0135] <Examples 9 to 11> A resin composition was obtained in the same manner as in Examples 1 to 3, except that the fluorine-containing elastomer B2 was used instead of the fluorine-containing elastomer B1. The evaluation results are shown in Table 1.

[0136] <Examples 12, 13> A resin composition was obtained in the same manner as in Example 1, except that the polyarylene sulfide resin A1 and the polyarylene sulfide resin A2 were used separately without using the fluorine-containing elastomer. The evaluation results are shown in Table 1.

[0137] Table 1

[0138] The evaluation results of the stress crack resistance and the moldability of Examples 1 to 4 were superior to those of Examples 9 to 11 using the fluorine-containing elastomer B2 without terminal functional groups. It was confirmed that by using the fluorine-containing elastomer B having terminal functional groups and making the average dispersed particle diameter of the fluorine-containing elastomer B less than 10 μm, the moldability of the resin composition was excellent and the stress crack resistance of the molded article was excellent. Examples 5 to 8 in which the type of the polyarylene sulfide resin A was changed are also expected to have excellent stress crack resistance and moldability.

[0139] Regarding the impact resistance, the Izod impact strength of Examples 1 to 4 was higher than that of Example 12. And the Izod impact strength of Examples 5 to 8 was higher than that of Example 13. It was confirmed that in any of Examples 1 to 8, as the volume ratio of the fluorine-containing elastomer B increased, the Izod impact strength increased. Industrial applicability

[0140] According to the resin composition of the present invention, a molded article having excellent stress crack resistance can be obtained. Moreover, the resin composition of the present invention has excellent moldability. The molded article of the present invention has excellent stress crack resistance. The composite of the present invention has a molded body with excellent stress crack resistance. The wire or film of the present invention has an insulating member with excellent stress crack resistance.

[0141] This application claims priority based on Japanese Patent Application No. 2022-194180 filed on December 5, 2022, and incorporates by reference the entire content of the Japanese application cited in this application.

Claims

1. A resin composition comprising a polyarylene sulfide resin A and a fluorine-containing elastomer B having terminal functional groups. The volume ratio of the polyarylene sulfide resin A to the fluorine-containing elastomer B is from 99:1 to 50:

50. The fluorine-containing elastomer B is dispersed in the polyarylene sulfide resin A. The average dispersion particle size of the fluorine-containing elastomer B is less than 10 μm.

2. The resin composition according to claim 1, wherein, The melt viscosity μ of the polyarylene sulfide resin A A and the melt viscosity μ of the fluorine-containing elastomer B B has a melt viscosity ratio of 0.3 or more.

3. The resin composition according to claim 1, wherein, The terminal functional group is at least one selected from an iodine atom, an epoxy group, and an acid anhydride group.

4. The resin composition according to claim 1, wherein The volume ratio of the polyarylene sulfide resin A to the fluorine-containing elastomer B is from 95:5 to 50:

50.

5. The resin composition according to claim 1, wherein, The melt viscosity μ of the resin composition is 300 to 420 Pa·s.

6. A molded article of the resin composition according to any one of claims 1 to 5.

7. A composite body formed by compounding or laminating the molded article according to claim 6 with other materials other than the molded article.

8. A wire or film having the molded article according to claim 6 as an insulating member.

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