JP2016027147A - Polyphenylene sulfide composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide composition which comprises a polyphenylene sulfide and a fluorine resin and can produce a molded product having excellent tensile strength and to provide a molded product of the composition.SOLUTION: There is provided a polyphenylene sulfide composition which comprises a polyphenylene sulfide (A) and a fluorine-containing copolymer (B) having at least one reactive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, wherein the reactive functional group is derived from at least one selected from the group consisting of a monomer used for the production of a main chain of the fluorine-containing copolymer (B), a chain transfer agent and a polymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to a polyphenylene sulfide composition and a molded article.

Polyphenylene sulfide (hereinafter also referred to as “PPS”) is known as a resin having excellent heat resistance, solvent resistance, electrical properties, mechanical strength, dimensional stability, flame retardancy, and the like. It is used for electronic equipment parts materials, automotive parts materials, chemical equipment parts materials, and other functional parts materials.
While PPS is excellent in the above-mentioned properties, it has poor toughness and is fragile. Therefore, in general, inorganic fillers such as glass fiber and carbon fiber are blended with PPS. However, even if an inorganic filler is added to PPS, the toughness is insufficient and impact resistance is low compared to other engineering plastics.

In order to improve impact resistance, a method of blending another polymer having excellent flexibility with PPS has also been proposed. However, when other polymers are blended, the heat resistance, flame retardancy, chemical resistance, etc. inherent to PPS are reduced.
On the other hand, Patent Document 1 discloses a PPS composition having excellent impact resistance while maintaining the heat resistance, flame retardancy, and chemical resistance of PPS by blending a specific fluorine-containing graft polymer with PPS. Is obtained. For example, Patent Documents 2 and 3 disclose that a fluororesin is blended with PPS.

JP 09-263676 A International Publication No. 98/21277 Japanese Patent Laid-Open No. 11-269383

  However, as a result of studies by the present inventors, it has been found that the molded articles of the compositions described in Patent Documents 1 to 3 have low tensile strength.

  An object of this invention is to provide the polyphenylene sulfide composition which can manufacture the molded article which contains PPS and a fluororesin, and is excellent in tensile strength, and the molded article of this composition.

The present invention has the following configuration.
[1] Polyphenylene sulfide (A) and fluorine-containing, which can be melt-molded and has at least one reactive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group A copolymer (B), and the reactive functional group is selected from the group consisting of monomers, chain transfer agents, and polymerization initiators used in the production of the main chain of the fluorine-containing copolymer (B). The polyphenylene sulfide composition is derived from at least one selected from the group consisting of:
[2] The polyphenylene sulfide composition according to [1], wherein the reactive functional group comprises an acid anhydride residue which is the carbonyl group-containing group.
[3] The polyphenylene sulfide according to [1] or [2], wherein the content of the reactive functional group is 500 or more per 1 × 10 ⁶ main chain carbon atoms of the fluorine-containing copolymer (B). Composition.
[4] The polyphenylene sulfide (A) and the fluorine-containing copolymer (B) are contained at (A) / (B) = 99/1 to 60/40 (volume ratio), [1] to [3 ] The polyphenylene sulfide composition of any of.
[5] The fluorine-containing copolymer (B) is a copolymer containing at least the reactive functional group derived from the monomer used for the production of the main chain of the fluorine-containing copolymer (B). The main chain is a structural unit (b1) based on tetrafluoroethylene, a structural unit (b2) based on a monomer having the reactive functional group and a polymerizable unsaturated bond, and a structural unit based on another monomer. The polyphenylene sulfide composition according to any one of [1] to [4], comprising (b3).
[6] The polyphenylene sulfide composition according to any one of [1] to [5], further comprising an inorganic filler (C).
[7] The polyphenylene sulfide composition according to [6], wherein the inorganic filler (C) includes at least carbon fiber.
[8] A molded product obtained by molding the polyphenylene sulfide composition according to any one of [1] to [7].
[9] The molded product according to [8], which is an injection molded product.
[10] The molded product according to [8] or [9], wherein the molded product has a portion having a thickness of 1.5 mm or less.

  ADVANTAGE OF THE INVENTION According to this invention, the polyphenylene sulfide composition which contains PPS and a fluororesin, and is excellent in tensile strength, and the molded article of this composition can be provided.

The PPS composition of the present invention is a composition containing PPS (A) and a fluorine-containing copolymer (B) that can be melt-molded.
In the present specification, the “structural unit” means a unit based on the monomer formed by polymerization of the monomer. The structural unit may be a unit directly formed by a polymerization reaction or a unit in which a part of the unit is converted into another structure by treating the polymer.
“Monomer” means a compound having a polymerizable unsaturated bond, that is, a polymerization-reactive carbon-carbon double bond. “Fluorine-containing monomer” means a monomer having a fluorine atom in the molecule, and “non-fluorine-containing monomer” means a monomer having no fluorine atom in the molecule.
“Main chain” refers to a portion having the maximum number of carbon atoms in a carbon chain formed by polymerization of monomers.

[PPS (A)]
PPS (A) is a polymer containing 70 mol% or more of a structural unit represented by the following formula (a1) (hereinafter also referred to as “structural unit (a1)”) in 100 mol% of all structural units. . In PPS (A), the content of the structural unit (a1) is preferably 80 mol% or more. When the content of the structural unit (a1) is out of the above range, the degree of crystallinity is lowered and the mechanical properties are lowered.

  PPS (A) may have another structural unit (a2) having an arylene sulfide structure in a range of 30 mol% or less in 100 mol% of all the structural units. The content of the other structural unit (a2) is preferably 20 mol% or less. Examples of the other structural unit (a2) include units represented by the following formulas. PPS (A) may have 1 type of other structural units (a2), or may have 2 or more types.

In the formula, R ^S represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxy group, or a carboxylate metal base.

  PPS (A) can be produced by a known polymerization method. Among these, a method in which sodium sulfide and p-dichlorobenzene are reacted at least in an amide solvent such as N-methylpyrrolidone and dimethylacetamide and a sulfone solvent such as sulfolane is preferable. At this time, an alkali metal carboxylate such as sodium acetate or lithium acetate may be added to adjust the degree of polymerization.

  It is known that PPS has a molecular structure that is linear and has no branching or cross-linking structure and a structure that has a branching or cross-linking structure based on the production method. In the present invention, PPS obtained by any production method can be used, but a linear structure having no branch is preferable in terms of mechanical strength.

  As PPS (A), in addition to those washed after polymerization, those treated with an aqueous solution containing acid such as hydrochloric acid or acetic acid, water-organic solvent mixed solution, etc., or treated with a salt solution such as ammonium chloride Etc. can also be used.

  PPS (A) has a melt flow rate (hereinafter also referred to as “MFR”) measured at a temperature of 297 ° C. and a load of 2.16 kgf (21.17 N) of 0.1 to 500 g / 10 minutes. 1 to 300 g / 10 min is more preferable. If the MFR is equal to or higher than the lower limit of the above range, the fluidity at the time of molding the PPS composition is excellent. Suitable for.

[Fluorine-containing copolymer (B)]
The fluorine-containing copolymer (B) contained in the PPS composition of the present invention is a copolymer that can be melt-molded. “Melting is possible” means exhibiting melt fluidity.
The fluorine-containing copolymer (B) capable of melt molding is a temperature at which the MFR is 0.1 to 1000 g / 10 min at a temperature higher than the melting point of the copolymer under a load of 49 N by 20 ° C. or more. Is preferably present, more preferably at a temperature of 0.5 to 100 g / 10 minutes, and more preferably at a temperature of 1 to 30 g / 10 minutes. Preferably, it is most preferable that a temperature of 5 to 20 g / 10 min exists. When the MFR is not less than the lower limit of the above range, the fluidity of the PPS composition is more excellent, and when it is not more than the upper limit of the above range, the mechanical strength of the PPS composition is more excellent. In addition, as temperature at the time of measuring MFR, 297 degreeC or 372 degreeC is normally employ | adopted according to melting | fusing point of a copolymer.

  MFR is a measure of the molecular weight of the fluorinated copolymer (B). When the MFR is large, the molecular weight is low, and when it is small, the molecular weight is large. The molecular weight of the fluorine-containing copolymer (B) can be adjusted by the production conditions of the fluorine-containing copolymer (B). For example, if the polymerization time is shortened during the polymerization of the monomer, the molecular weight tends to decrease and the MFR tends to increase. Moreover, when the fluorine-containing copolymer obtained by the polymerization reaction is heat-treated, a crosslinked structure is formed, the molecular weight tends to increase, and the MFR tends to decrease.

The fluorine-containing copolymer (B) used in the present invention includes the monomer used for the production of the main chain of the fluorine-containing copolymer (B), the chain transfer agent used for the production of the main chain, and the production of the main chain. It has a reactive functional group derived from at least one selected from the group consisting of polymerization initiators used in the above.
In this specification, the reactive functional group is at least one selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group.
When the fluorine-containing copolymer (B) has a reactive functional group derived from one of the monomers, chain transfer agents, and polymerization initiators used in the production of the main chain, the fluorine-containing copolymer The tensile strength of the PPS composition containing the copolymer (B) is excellent. For example, when a fluorine-containing copolymer having a reactive functional group derived from the monomer used for producing the side chain instead of the main chain, that is, a graft polymer is used, the tensile strength of the PPS composition is insufficient. . The reason is considered as follows.
A reactive functional group derived from at least one selected from the group consisting of a monomer used in the production of the main chain, a chain transfer agent used in the production of the main chain, and a polymerization initiator used in the production of the main chain Any of the fluorine-containing copolymers (B) can be produced by a polymerization reaction in one polymerization tank. On the other hand, the above graft polymer usually produces a main chain by a polymerization reaction in a polymerization tank and then reacts with a compound having a reactive functional group in another step (grafting step) to form a side chain ( (Graft chain). In this case, since a thermal history is added in the grafting step, the obtained graft polymer tends to have a low molecular weight. Therefore, the PPS composition containing such a graft polymer has insufficient tensile strength. The fluorinated copolymer (B) is preferably a copolymer having no graft chain introduced in a separate step.

As will be described in detail later, when the reactive functional group of the fluorine-containing copolymer (B) is derived from the monomer used for the production of the main chain of the fluorine-containing copolymer (B), the fluorine-containing copolymer The polymer (B) can be produced by the following method (1). In this case, the reactive functional group is present in a unit based on the monomer formed by polymerization of the monomer during the production of the main chain.
Method (1): A monomer having a reactive functional group is used when the main chain of the fluorine-containing copolymer is produced by a polymerization reaction.

When the reactive functional group possessed by the fluorine-containing copolymer (B) is derived from the chain transfer agent used for the production of the main chain of the fluorine-containing copolymer (B), the fluorine-containing copolymer (B ) Can be produced by the following method (2). In this case, the reactive functional group exists as a terminal group at the main chain terminal of the fluorine-containing copolymer (B).
Method (2): A main chain of the fluorinated copolymer is produced by a polymerization reaction using a chain transfer agent that generates a radical having a reactive functional group.

When the reactive functional group possessed by the fluorine-containing copolymer (B) is derived from the polymerization initiator used for the production of the main chain of the fluorine-containing copolymer (B), the fluorine-containing copolymer (B ) Can be produced by the following method (3). In this case, the reactive functional group exists as a terminal group at the main chain terminal of the fluorine-containing copolymer (B).
Method (3): The main chain of the fluorinated copolymer is produced by a polymerization reaction using a polymerization initiator such as a radical polymerization initiator that generates radicals having reactive reactive groups.

  The reactive functional group possessed by the fluorine-containing copolymer (B) is contained in two or more of the monomers, chain transfer agents, and polymerization initiators used in the production of the main chain of the fluorine-containing copolymer (B). When derived, the fluorine-containing copolymer (B) can be produced by using two or more of the methods (1) to (3) in combination.

The fluorinated copolymer (B) preferably has at least a carbonyl group-containing group as a reactive functional group.
The carbonyl group-containing group is a group containing a carbonyl group (—C (═O) —) in the structure. For example, a group containing a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxyl group, a haloformyl group , An alkoxycarbonyl group, an acid anhydride residue and the like. Among these, an acid anhydride residue is preferable because a PPS composition having more excellent tensile strength can be easily obtained.

As a hydrocarbon group, a C2-C8 alkylene group etc. are mentioned, for example. In addition, carbon number of this alkylene group is carbon number in the state which does not contain a carbonyl group. The alkylene group may be linear or branched.
The haloformyl group is represented by —C (═O) —X (where X is a halogen atom). Examples of the halogen atom in the haloformyl group include a fluorine atom and a chlorine atom, and a fluorine atom is preferable. That is, the haloformyl group is preferably a fluoroformyl group (also referred to as a carbonyl fluoride group).
The alkoxy group in the alkoxycarbonyl group may be linear or branched and is preferably an alkoxy group having 1 to 8 carbon atoms, particularly preferably a methoxy group or an ethoxy group.

The content of the reactive functional group in the fluorinated copolymer (B) is preferably 500 or more and more than 600 with respect to 1 × 10 ⁶ main chain carbon atoms of the fluorinated copolymer (B). More preferably, 800 or more are particularly preferable. The content of the reactive functional group in the fluorinated copolymer (B) is preferably 10,000 or less, and preferably 5,000 or less with respect to 1 × 10 ⁶ main chain carbon atoms of the fluorinated copolymer (B). More preferred is 3000 or less.
The tensile strength of the PPS composition containing this fluorine-containing copolymer (B) is more excellent as content of a reactive functional group is more than the said lower limit. When the content of the reactive functional group is not more than the above upper limit, the balance between heat resistance and tensile strength of the PPS composition containing the fluorine-containing copolymer (B) is excellent.

  The reactive functional group content of the fluorinated copolymer (B) can be easily adjusted within the above range by employing the above-described method (1) to produce the fluorinated copolymer (B).

  The content of the reactive functional group can be measured by a method such as nuclear magnetic resonance (NMR) analysis or infrared absorption spectrum analysis. For example, as described in JP 2007-314720 A, a structural unit having a reactive functional group in all the structural units constituting the fluorinated copolymer (B) using a method such as infrared absorption spectrum analysis. Is obtained, and the content of the reactive functional group can be calculated from the ratio.

  As described above, the fluorinated copolymer (B) is at least one selected from the group consisting of monomers, chain transfer agents, and polymerization initiators used for the production of the main chain of the fluorinated copolymer (B). Among them, the fluorine-containing copolymer (B) having a reactive functional group derived from a species and having a reactive functional group derived from a monomer in the main chain is preferable. As described above, the fluorine copolymer (B) can be produced by the above method (1). According to the method (1), the content of the reactive functional group can be easily controlled, and therefore a fluorine-containing copolymer (B) capable of producing a PPS composition having excellent tensile strength is easily obtained.

(Fluorine-containing copolymer (B) having a reactive functional group derived from a monomer in the main chain)
As the fluorine-containing copolymer (B) having a reactive functional group derived from a monomer in the main chain, the main chain is a structural unit (b1) based on tetrafluoroethylene (hereinafter also referred to as “TFE”); A copolymer having a structural unit (b2) based on a monomer having a reactive functional group and a polymerizable unsaturated bond and a structural unit (b3) based on another monomer is preferable.
The structural unit (b3) is a unit that does not correspond to either the structural unit (b1) or the structural unit (b2). As described later, the structural unit (b3α) is based on a fluorinated monomer (excluding TFE). ) And a structural unit (b3β) based on a non-fluorinated monomer (excluding a monomer having a reactive functional group and a polymerizable unsaturated bond). As the structural unit (b3), the structural unit (b3α) is preferable from the viewpoint of heat resistance of the PPS composition.

As the monomer constituting the structural unit (b2), a cyclic hydrocarbon monomer having an acid anhydride residue as a reactive functional group is preferable.
Examples of the cyclic hydrocarbon monomer include itaconic anhydride (hereinafter also referred to as “IAH”), citraconic anhydride (hereinafter also referred to as “CAH”), and 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as “hydrocarbonic anhydride”). , Also referred to as “NAH”), and maleic anhydride. These may be used alone or in combination of two or more.
Among the above, at least one selected from the group consisting of IAH, CAH, and NAH is preferable. When at least one selected from the group consisting of IAH, CAH, and NAH is used, the acid can be used without using a special polymerization method (see JP-A-11-19312) required when maleic anhydride is used. A fluorine-containing copolymer (B) containing an anhydride residue can be easily produced.
Among IAH, CAH, and NAH, NAH is preferable because a fluorine-containing copolymer (B) that can produce a PPS composition having more excellent tensile strength can be easily obtained. NAH has a stable molecular structure, is not easily decomposed by heat or moisture in the air when kneaded with PPS (A), and is easily dispersed by PPS (A), thus producing a PPS composition with superior tensile strength. Can do.

Of the structural unit (b3), the fluorine-containing monomer forming the structural unit (b3α) is preferably a fluorine-containing compound having one polymerizable double bond. For example, vinyl fluoride, vinylidene fluoride (hereinafter referred to as “VdF”). ), Trifluoroethylene, chlorotrifluoroethylene (hereinafter also referred to as “CTFE”), hexafluoropropylene (hereinafter also referred to as “HFP”) and the like, but excluding TFE. CF ₂ = CFOR ^f1 (where R ^f1 is a perfluoroalkyl group having 1 to 10 carbon atoms and may contain an oxygen atom between carbon atoms), CF ₂ = CFOR ^f2 SO ₂ X ¹ (where R ^f2 is ¹ carbon atom) may contain an oxygen atom between carbon atoms 10 perfluoroalkylene group, X ¹ is a halogen atom or a hydroxyl group.), C ^{_{2 = CFOR f3 CO 2 X 2}} ( provided that ^{R f3} is also good perfluoroalkylene group contain an oxygen atom between carbon atoms at 1 to 10 carbon atoms, ^{X 2} is a hydrogen atom or an alkyl group having 3 or less carbon atoms.), CF _{2 = CF (CF 2) p} OCF = CF 2 ( where p is 1 or ^{_{2.), CH 2 = CX}} 3 (CF 2) q X 4 ( provided that ^{X 3} is a hydrogen atom or a fluorine atom, q is from 2 10 And X ⁴ is a hydrogen atom or a fluorine atom.) And perfluoro (2-methylene-4-methyl-1,3-dioxolane).

Among these fluorine-containing monomers, at least one selected from the group consisting of VdF, CTFE, HFP, CF ₂ = CFOR ^f1 , and CH ₂ = CX ³ (CF ₂ ) _q X ⁴ is used in terms of improving heat resistance. CF ₂ = CFOR ^f1 and HFP are more preferable.
As CF ₂ = CFOR ^f1 , CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F, etc. CF ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”) is preferable.
As CH ₂ = CX ³ (CF ₂ ) _q X ⁴ , CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ ═CF (CF ₂ ) ₃ H, CH ₂ ═CF (CF ₂ ) ₄ H and the like, and CH ₂ ═CH (CF ₂ ) ₄ F or CH ₂ ═CH (CF ₂ ) ₂ F are preferable.
A fluorine-containing monomer may be used individually by 1 type, or may be used 2 or more types.

Of the structural unit (b3), the non-fluorine-containing monomer forming the structural unit (b3β) is preferably a non-fluorine-containing compound having one polymerizable double bond, such as olefins having 3 or less carbon atoms such as ethylene and propylene. And vinyl esters such as vinyl acetate.
A non-fluorine-containing monomer may be used individually by 1 type, or may use 2 or more types.
Of these, ethylene, propylene, and vinyl acetate are preferable, and ethylene is particularly preferable.

When the structural unit (b3) of the fluorine-containing copolymer (B) having a reactive functional group derived from a monomer in the main chain is the structural unit (b3α), the structural unit (b1), the structural unit (b2), With respect to the total molar amount with the structural unit (b3α), the structural unit (b1) is 80 to 99.69 mol%, the structural unit (b2) is 0.01 to 0.5 mol%, and the structural unit (b3α ) Is preferably 0.3 to 19.99 mol%, the structural unit (b1) is 90 to 99.58 mol%, the structural unit (b2) is 0.02 to 0.3 mol%, The unit (b3α) is more preferably 0.4 to 9.98 mol%, the structural unit (b1) is 97.5 to 99.5 mol%, and the structural unit (b2) is 0.05 to 0.00. It is particularly preferable that the structural unit (b3α) is 3 mol% and 0.45 to 2.45 mol%.
When the structural unit (b3) of the fluorine-containing copolymer (B) having a reactive functional group derived from a monomer in the main chain is the structural unit (b3β), the structural unit (b1), the structural unit (b2), With respect to the total molar amount with the structural unit (b3β), the structural unit (b1) is 50 to 99.69 mol%, the structural unit (b2) is 0.01 to 1.0 mol%, and the structural unit (b3β ) Is preferably 0.3 to 49.99 mol%, the structural unit (b1) is 52 to 69.98 mol%, the structural unit (b2) is 0.02 to 1.0 mol%, The unit (b3β) is more preferably 30 to 47.98 mol%, the structural unit (b1) is 53 to 64.95 mol%, and the structural unit (b2) is 0.05 to 0.8 mol%. The structural unit (b3β) is particularly preferably 35 to 46.95 mol%.

  The molar ratio of the structural unit (b3α) to (b3β) in the structural unit (b3) is such that when the total of the structural unit (b3α) and the structural unit (b3β) is 100 moles, the structural unit (b3β) / The structural unit (b3α) is preferably 0/100 to 100/0, and more preferably 70/30 to 90/10.

When the content of each structural unit is within the above range, the fluorine-containing copolymer (B) is excellent in heat resistance and chemical resistance, and the tensile strength of the PPS composition containing the same is further improved.
In particular, when the content of the structural unit (b2) is within the above range, the amount of the acid anhydride residue of the fluorine-containing copolymer (B) becomes an appropriate amount, and PPS (A) and the fluorine-containing copolymer are contained. The compatibility with the polymer (B) is excellent, and the tensile strength of the PPS composition is more excellent.

  The content of each structural unit can be calculated by melting NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the fluorine-containing copolymer (B).

The structural unit constituting the main chain of the fluorinated copolymer (B) is composed of the structural unit (b1), the structural unit (b2), and the structural unit (b3), and the structural unit (b2) is one acid anhydride. When based on a cyclic hydrocarbon monomer having a product residue and a polymerizable unsaturated bond, the content of the structural unit (b2) is the total mole of the structural unit (b1), the structural unit (b2), and the structural unit (b3). 0.01 mol% with respect to the amount means that the content of acid anhydride residues in the fluorine-containing copolymer (B) is 1 × 10 ⁶ carbon atoms in the main chain of the fluorine-containing copolymer (B). Is equivalent to 100. The content of the structural unit (b2) is 5 mol% with respect to the total molar amount of the structural unit (b1), the structural unit (b2), and the structural unit (b3). The fluorine-containing copolymer (B) This corresponds to the content of acid anhydride residues in the fluorine-containing copolymer (B) being 50,000 with respect to 1 × 10 ⁶ main chain carbon atoms.
When the structural unit (b2) is a unit based on a cyclic hydrocarbon monomer having an acid anhydride residue and a polymerizable unsaturated bond, the fluorine-containing copolymer (B) contains one of the cyclic hydrocarbon monomers. Part is hydrolyzed, and as a result, a structural unit based on a dicarboxylic acid (itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.) corresponding to the acid anhydride residue is contained. There is. When the structural unit based on this dicarboxylic acid is contained, content of this structural unit shall be contained in a structural unit (b2).

Preferable specific examples of the fluorine-containing copolymer (B) include TFE / PPVE / NAH copolymer, TFE / PPVE / IAH copolymer, TFE / PPVE / CAH copolymer, TFE / HFP / IAH copolymer. , TFE / HFP / CAH copolymer, TFE / VdF / IAH copolymer, TFE / VdF / CAH copolymer, TFE / CH ₂ ═CH (CF ₂ ) ₄ F / IAH / ethylene copolymer, TFE / _{CH 2 = CH (CF 2)} 4 F / CAH / ethylene _{copolymer, TFE / CH 2 = CH (} CF 2) 2 F / IAH / ethylene _{copolymer, TFE / CH 2 = CH (} CF 2) 2 F / CAH / ethylene copolymer and the like.

(Fluorine-containing copolymer (B) having a reactive functional group derived from a chain transfer agent in the main chain)
The fluorine-containing copolymer (B) having a reactive functional group derived from a chain transfer agent in the main chain is a copolymer having a reactive functional group derived from the chain transfer agent as an end group of the main chain, The main chain may not have the structural unit (b2), but preferably has the structural unit (b1), the structural unit (b2), and the structural unit (b3).

  For the production of the fluorine-containing copolymer (B) having a reactive functional group derived from a chain transfer agent in the main chain, a chain transfer agent that generates a radical having a reactive functional group is used as the chain transfer agent. Examples of the chain transfer agent include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like, and among them, acetic anhydride having an anhydride residue is preferable.

(Fluorine-containing copolymer (B) having a reactive functional group derived from a polymerization initiator in the main chain)
The fluorine-containing copolymer (B) having a reactive functional group derived from the polymerization initiator in the main chain is a copolymer having a reactive functional group derived from the polymerization initiator as an end group of the main chain, The main chain may not have the structural unit (b2), but preferably has the structural unit (b1), the structural unit (b2), and the structural unit (b3).

  In the production of the fluorine-containing copolymer (B) having a reactive functional group derived from the polymerization initiator in the main chain, a radical polymerization initiator that generates a radical having a reactive functional group is used as the polymerization initiator. Examples of the radical polymerization initiator include di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, t-butyl peroxyisopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and the like. Is mentioned.

(Production method of fluorine-containing copolymer (B))
The specific method for polymerizing the fluorinated copolymer (B) is not particularly limited, but bulk polymerization; organics such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, alcohols and hydrocarbons Solution polymerization using a solvent; suspension polymerization using an aqueous medium and, if necessary, an appropriate organic solvent; emulsion polymerization using an aqueous medium and an emulsifier may be mentioned. Among them, solution polymerization is preferable.

At the time of polymerization, a polymerization initiator such as a radical polymerization initiator can be used.
When producing a fluorine-containing copolymer (B) having a reactive functional group derived from a polymerization initiator in the main chain, it is necessary to use a polymerization initiator that generates a radical having a reactive functional group. is there. On the other hand, a fluorine-containing copolymer (B) having a reactive functional group derived from a monomer in the main chain and a fluorine-containing copolymer (B) having a reactive functional group derived from a chain transfer agent in the main chain are produced. In some cases, a polymerization initiator may or may not be used. When used, any polymerization initiator may be used.

As the radical polymerization initiator, an initiator whose half-life is 10 hours is preferably 0 to 100 ° C, and more preferably an initiator whose temperature is 20 to 90 ° C.
Specific examples of the radical polymerization initiator other than the previously exemplified radical polymerization initiator (radical polymerization initiator generating a radical having a reactive functional group) include azo compounds such as azobisisobutyronitrile, isobuty Non-fluorinated diacyl peroxides such as ril peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate, tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxy Peroxyesters such as acetate, compounds represented by (Z (CF ₂ ) _r COO) ₂ (wherein Z is a hydrogen atom, a fluorine atom or a chlorine atom, and r is an integer of 1 to 10), etc. Fluorine-containing diacyl Hydroperoxide, potassium persulfate, sodium persulfate, inorganic peroxides such as ammonium persulfate.

During the polymerization, a chain transfer agent can be used.
When producing a fluorine-containing copolymer (B) having a reactive functional group derived from a chain transfer agent in the main chain, it is necessary to use a chain transfer agent that generates a radical having a reactive functional group. is there. On the other hand, a fluorine-containing copolymer (B) having a reactive functional group derived from a monomer in the main chain and a fluorine-containing copolymer (B) having a reactive functional group derived from a polymerization initiator in the main chain are produced. In some cases, a chain transfer agent may or may not be used, and when used, any chain transfer agent may be used.

  Specific examples of the chain transfer agent other than the chain transfer agent (chain transfer agent generating a radical having a reactive functional group) exemplified above include alcohols such as methanol and ethanol, 1,3-dichloro-1,1 , 2,2,3-pentafluoropropane, chlorofluorohydrocarbons such as 1,1-dichloro-1-fluoroethane, and hydrocarbons such as pentane, hexane, and cyclohexane.

As the solvent used in the solution polymerization, perfluorocarbon, hydrofluorocarbon, chlorohydrofluorocarbon, hydrofluoroether or the like is used. As for carbon number, 4-12 are preferable.
Specific examples of the perfluorocarbon include perfluorocyclobutane, perfluoropentane, perfluorohexane, perfluorocyclopentane, and perfluorocyclohexane.
Specific examples of the hydrofluorocarbon include 1-hydroperfluorohexane and the like.
Specific examples of the chlorohydrofluorocarbon include 1,3-dichloro-1,1,2,2,3-pentafluoropropane.
Specific examples of the hydrofluoroether include methyl perfluorobutyl ether and 2,2,2-trifluoroethyl 2,2,1,1-tetrafluoroethyl ether.

The polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.
When polymerizing a fluorine-containing copolymer (B) having a structural unit (b2) based on a cyclic hydrocarbon monomer having an acid anhydride residue and a polymerizable unsaturated bond, the acid anhydride residue and the polymerizable unsaturated bond are polymerized. The concentration during the polymerization of the cyclic hydrocarbon monomer having the above is preferably 0.01 to 5 mol%, more preferably 0.1 to 3 mol%, and most preferably 0.1 to 2 mol% with respect to all monomers .
When the concentration of the monomer is in the above range, the polymerization rate during production is moderate, and when the concentration of the monomer is too high, the polymerization rate tends to decrease.
During the polymerization, as the cyclic hydrocarbon monomer having an acid anhydride residue and a polymerizable unsaturated bond is consumed in the polymerization, the consumed amount is continuously or intermittently supplied into the polymerization tank, It is preferable to maintain the concentration within the above range.

[PPS composition]
The PPS composition of the present invention preferably contains PPS (A) and the fluorinated copolymer (B) at (A) / (B) = 99/1 to 60/40 (volume ratio). The volume ratio between the PPS (A) and the fluorine-containing copolymer (B) is more preferably 95/5 to 70/30, and particularly preferably 90/10 to 75/25. When the volume ratio is within the above range, a PPS composition having better tensile strength can be obtained.

The PPS composition of the present invention preferably contains an inorganic filler (C) as an optional component other than PPS (A) and the fluorinated copolymer (B).
Examples of the inorganic filler (C) include inorganic fillers such as glass fiber, carbon fiber, graphite, carbon, metal oxide, and natural earth. An inorganic filler (C) may be used individually by 1 type, or may use 2 or more types. As the inorganic filler (C), glass fiber and carbon fiber are preferable from the viewpoint of easy availability. Carbon fiber is particularly preferable from the viewpoint of impact resistance.

The shape of the glass fiber and the carbon fiber is not particularly limited, but preferably has an average length of 0.05 to 10 mm and an average thickness of 1 to 50 μm.
The average length and average thickness can be measured by various methods. In this specification, 1000 fibers (samples) were observed with a microscope at a magnification of 70 times, and the average was calculated using image processing software. Adopt value.
The length is the total length in the longitudinal direction of the fiber, and the thickness is the maximum diameter of the surface perpendicular to the longitudinal direction of the fiber. If the surface is a perfect circle, the maximum diameter is the diameter of the circle, and if the surface is a shape other than a true circle, the diameter is the diameter of a perfect circle circumscribing the surface.

  As for content of an inorganic filler (C), 10-200 mass parts is preferable with respect to a total of 100 mass parts of PPS (A) and a fluorine-containing copolymer (B). If the content of the inorganic filler (C) is not less than the lower limit of the above range, the effect of improving the impact resistance of the PPS composition is sufficiently obtained, and if it is not more than the upper limit of the above range, a melt molding machine Can be melt-kneaded well.

  The PPS composition of the present invention includes an organic pigment, a metal soap, a surfactant, an ultraviolet absorber, a lubricant, a silane coupling agent, an organic compound (for example, an organic monomer, a polymerization agent) as an optional component other than the inorganic filler (C). Organic oligomers having a degree of 50 or less.

  The PPS composition of the present invention is obtained by melt-kneading PPS (A), a fluorine-containing copolymer (B), an inorganic filler (C) blended as necessary, etc. with a melt molding machine to form a pellet. It is preferable to manufacture by a molding method.

  As the melt molding machine, an extrusion molding machine is preferable, and a biaxial extrusion molding machine is particularly preferable. Molding of pellets with an extruder is performed by melt-kneading PPS (A), a fluorine-containing copolymer (B), an inorganic filler (C) blended as necessary, etc. with an extruder, It is performed by extruding a strand from a die, cooling the strand, and cutting it into an appropriate length with a cutter or the like.

The temperature of the PPS composition during melt-kneading is preferably 280 to 400 ° C, particularly preferably 300 to 350 ° C. The temperature of the die is preferably 300 to 350 ° C, particularly preferably 300 to 340 ° C.
The strand is usually cooled using air, warm water or the like, and it is preferable to use warm water of 20 to 50 ° C.

  There is no particular limitation on the method of feeding each component into the extruder. Even if all the components contained in the PPS composition are blended and fed from the hopper, a part of all the components are blended and fed from the hopper. The rest may be loaded at an appropriate position between the hopper and the die. For example, when blending the inorganic filler (C), the PPS (A) and the fluorine-containing copolymer (B) are blended and introduced from the hopper, and the inorganic filler (C) is placed between the hopper and the die. It is preferable to feed at an appropriate position (side feed). According to the method of introducing the inorganic filler (C) by side feed, for example, when the inorganic filler (C) is fibrous, the inorganic filler (C) is prevented from being excessively shortened by being kneaded. it can.

The PPS composition of the present invention contains PPS (A) having a specific reactive functional group derived from at least one selected from the group consisting of a monomer, a chain transfer agent and a polymerization initiator in the main chain. Since the fluorine copolymer (B) is blended, the tensile strength is excellent.
Further, PPS (A) has a property that characteristics such as rigidity change when exposed to a high temperature, and therefore, there is a tendency that inconvenience such as dimensional change is likely to occur due to molding or the like. On the other hand, the PPS composition of the present invention in which the fluorine-containing copolymer (B) is blended has reduced rigidity change due to exposure to high temperatures. Specifically, when the storage elastic modulus of the PPS composition of the present invention is G1, and the storage elastic modulus after exposure of the PPS composition at 250 ° C. for 1 hour is G2, G2 / G1 is 1.0 or more. Less than 2.5. G2 / G1 is preferably 1.0 or more and less than 2.3, and more preferably 1.0 or more and less than 2.2. The storage elastic modulus is measured by the method described later.

[Molding]
The molded article of the present invention can be obtained by molding the above-described PPS composition by various molding methods. As the molding method, for example, conventionally known methods such as injection molding (including injection compression molding), extrusion molding, coextrusion molding, blow molding, inflation molding, transfer molding, and coating can be employed.
Among them, the PPS composition of the present invention is excellent in strength even when it is molded by injection molding or the like, which tends to cause a decrease in strength when formed into a molded product because a large shearing force is applied during molding. That is, an injection molded product obtained by molding the PPS composition of the present invention has high strength.

  Further, the molded product of the present invention has high strength even if it has a thin portion. For example, even if a portion having a thickness of 1.5 mm or less, more specifically 1.0 mm or less, has high impact strength. In addition, it is preferable that the molded article of this invention is 0.01 mm or more in thickness.

  Examples of applications of molded products include sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, Electrical and electronic parts represented by tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc. Audio / video equipment such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark), compact discs, digital video discs, etc. Products, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, Machine-related parts typified by cleaning jigs, motor parts, lighters, typewriters, etc., optical equipment typified by microscopes, binoculars, cameras, watches, etc., precision machine-related parts, tap faucets, mixed water Water-related parts such as stoppers, pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, and water meter housings, valve alternator terminals, alternator connectors, IC regulators, potentiometers for light dials Base, exhaust gas valve, etc. Various valves, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle Position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor , Starter switch, starter relay, wire harness for transmission, window washer nozzle, air Control panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, fuel tank, Examples include automobile / vehicle-related parts such as an ignition device case, a vehicle speed sensor, and a cable liner, medical products, and other various uses.

In addition, the PPS composition of the present invention can be used for insulating films, connectors, sockets, relay cases, switches, coil bobbins, capacitors, optical pickups, printed boards, etc., for example, components that are soldered by reflow method. It can also be used as a material. For such applications, the fluorine-containing copolymer (B), as the above structural units _(b3), the copolymer having the structural units based on CF 2 = CFOR ^f1 are preferred.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.
Copolymerization composition of fluorine-containing copolymer (B), content of reactive functional group, melting point and MFR, MFR of PPS (A), storage elastic modulus of PPS composition, tensile strength of molded product, Izod impact test value Was measured by the following method.

[Fluorine-containing copolymer (B)]
(1) Copolymer composition The copolymer composition was determined by melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis.
(2) Content of reactive functional group By the following infrared absorption spectrum analysis, the ratio of the repeating unit based on NAH which has a reactive functional group in a fluorine-containing copolymer (B) was calculated | required.
The fluorine-containing copolymer (B) was press-molded to obtain a 200 μm film. In the infrared absorption spectrum, the absorption peak in the structural unit based on NAH in the fluorine-containing copolymer appears at 1778 cm ⁻¹ . The absorbance of the absorption peak was measured, and the proportion (mol%) of the structural unit based on NAH was determined using the molar absorption coefficient of NAH of 20810 mol ⁻¹ · l · cm ⁻¹ .
Then, when the ratio for example a (mol%), the number of main chain reactive functional groups to the number 1 × 10 ⁶ carbon (acid anhydride ^{residues), [a × 10 6/100} ] Pieces and calculation Is done.
(3) Melting point (° C)
Using a differential scanning calorimeter (DSC apparatus) made by Seiko Electronics, the melting peak when the fluorine-containing copolymer (B) was heated at a rate of 10 ° C./min was recorded, and the temperature corresponding to the maximum value (° C. ) As the melting point (Tm).
(4) MFR (g / 10 min)
MFR of the fluorine-containing copolymer (B) is a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 372 ° C. and 5 kgf (49 N), which is 20 ° C. higher than the melting point, using a melt indexer manufactured by Techno Seven. From this, the mass (g) of the fluorine-containing copolymer (B) flowing out for 10 minutes (unit time) was measured and used as MFR.
When a TFE-ethylene copolymer is used as the fluorine-containing copolymer (B), the nozzle is 2 mm in diameter and 8 mm in length under a load of 297 ° C. and 5 kgf (49 N), which is 20 ° C. higher than the melting point. The mass (g) of the fluorinated copolymer (B) flowing out for 10 minutes (unit time) was measured and used as MFR.
The MFR of PPS (A) was measured in the same manner as the fluorinated copolymer (B) except that the measurement conditions were 297 ° C. and 2.16 kgf (21.17 N) load.

[PPS composition and molded product]
(1) Storage elastic modulus (MPa)
(1-1) Preparation of sample The PPS composition was press-molded with a melt hot press manufactured by Tester Sangyo Co., Ltd. to obtain a 0.25 mm thick sheet. The pressing conditions were a processing temperature of 340 ° C., a preheating of 10 minutes, a pressure of 10 MPa, and a pressing time of 3 minutes.
A sample (α) was obtained by cutting out a strip-like sample having a length of 30 mm, a width of 5 mm, and a thickness of 0.25 mm from the obtained sheet.
The obtained sheet was placed in an oven at 250 ° C. for 60 minutes, allowed to cool to room temperature, and a sample of a strip (30 mm in length, 5 mm in width, 0.25 mm in thickness) cut out from the sheet (β ).
(1-2) Measurement The storage elastic modulus is a value measured at 250 ° C. by dynamic viscoelasticity measurement. Specifically, using the dynamic viscoelastic device “DMS6100” manufactured by SII, the sample was set to a tensile mode and a grip width of 20 mm, and the temperature was increased from 25 ° C. at a temperature increase rate of 2 ° C./min to reach 250 ° C. The storage elastic modulus at the time was measured. The frequency was 1 Hz.

(2) Tensile strength (MPa)
(2-1) Preparation of Sample (Press-Molded Product) The PPS composition was press-molded with a melt hot press machine manufactured by Tester Sangyo Co., Ltd. to obtain a 0.25 mm thick sheet. The pressing conditions were a processing temperature of 340 ° C., a preheating of 10 minutes, a pressure of 10 MPa, and a pressing time of 3 minutes. A dumbbell test piece according to ASTM D638 Type V was cut out from the sheet.
(2-2) Preparation of Sample (Injection Molded Product) A PPS composition was injection molded at a molding temperature of 320 ° C. with a FUNUC injection molding machine (FUNUC 30A), and a dumbbell specimen conforming to ASTM D638 Type IV having a thickness of 3 mm. Was made.
(2-3) Measurement Using a tensile compression tester “Strograph R-2” manufactured by Toyo Seiki Co., Ltd., test conditions of a load of 100 kgf (981 N), a pulling speed of 5 mm / min, and a distance between marked lines: 7.62 mm Tensile properties (tensile strength) were measured.
In addition, the measurement about a sample (injection molded product) was performed in the following Example 2 and Comparative Example 2.

(3) Izod impact test (3-1) Preparation of sample (Izod test piece) The PPS composition was injection molded at a molding temperature of 340 ° C. with an injection molding machine (FUNUC 30A and α50C) manufactured by FUNUC, and the thickness was 3 mm. Molded pieces having a length of 127 mm, a width of 12.7 mm, and a thickness of 1 mm, a length of 100 mm, and a width of 50 mm were obtained. Thereafter, the molded product was cut into a shape having a length of 60 mm, a width of 12 mm, a thickness of 3 mm, and a length of 60 mm, a width of 12 mm, and a thickness of 1 mm. Furthermore, a notch was made in the central portion in the length direction so that the width was 10 mm, and a test piece shape was produced. These are referred to as “injection molded product (3 mm)” and “injection molded product (1 mm)” in Tables 2 and 3.
Further, the PPS composition was press-molded with a melt hot press machine manufactured by Tester Sangyo Co., Ltd. to obtain a 1 mm thick sheet. The pressing conditions were a processing temperature of 300 ° C., a preheating of 10 minutes, a pressure of 10 MPa, and a pressing time of 3 minutes. Thereafter, the sheet obtained was cut into a shape having a length of 60 mm, a width of 12 mm, and a thickness of 1 mm. Furthermore, a notch was made in the central portion in the length direction so that the width was 10 mm, and a test piece shape was produced. This is referred to as “press-formed product (1 mm)” in Tables 2 and 3.
(3-2) Measurement The Izod impact test was performed using an “impact tester” manufactured by Toyo Seiki Co., Ltd. The hammer used for the measurement had a capacity of 10 kg-cm, a hammer weight of 1.002 kg, a distance from the axis to the center of gravity of 5.85 cm, and a distance from the axis to the impact point of 35.7 cm. Measurement ambient temperature is room temperature.

(Production Example 1) Production of fluorinated copolymer (B-1) A fluorinated copolymer (B-1) was produced by the above method (1) as follows.
TFE forming the structural unit (b1), NAH forming the structural unit (b2) (“Hymic Anhydride”, manufactured by Hitachi Chemical Co., Ltd.), and CF ₂ ═CFO (CF ₂ ) forming the structural unit (b3) _{Using 3} F (perfluoropropyl vinyl ether, manufactured by Asahi Glass Co., Ltd.) (hereinafter referred to as “PPVE”), a fluorinated copolymer (B-1) was produced as follows.
First, 369 kg of 1,3-dichloro-1,1,2,2,3-pentafluoropropane (AK225cb, manufactured by Asahi Glass Co., Ltd.) (hereinafter referred to as “AK225cb”) and 30 kg of PPVE are degassed in advance. The polymerization volume with a stirrer having an inner volume of 430 L was charged. Next, the inside of the polymerization tank was ripened and heated to 50 ° C., and further charged with 50 kg of TFE, the pressure in the polymerization tank was increased to 0.89 MPa / G. “0.89 MPa / G” indicates that the gauge pressure is 0.89 MPa. The same applies hereinafter.
Furthermore, a polymerization initiator solution in which (perfluorobutyryl) peroxide ((CF ₃ CF ₂ CF ₂ COO) ₂ ) was dissolved in AK225cb at a concentration of 0.36% by mass was prepared, and the polymerization initiator solution was added to the polymerization tank. Polymerization was carried out while continuously adding 3 L of 1 at a rate of 6.25 mL per minute. Further, TFE was continuously charged so that the pressure in the polymerization tank during the polymerization reaction was maintained at 0.89 MPa / G. Further, a solution in which NAH was dissolved in AK225cb at a concentration of 0.3% by mass was continuously charged in an amount corresponding to 0.1 mol% with respect to the number of moles of TFE charged during the polymerization.
8 hours after the start of polymerization, when 32 kg of TFE was charged, the temperature in the polymerization tank was lowered to room temperature, and the pressure was purged to normal pressure. The obtained slurry was solid-liquid separated from AK225cb, and the solid content was dried at 150 ° C. for 15 hours to obtain 33 kg of a fluorinated copolymer (B-1). The specific gravity of the fluorine-containing copolymer (B-1) was 2.15.
From the results of melt NMR analysis, fluorine content analysis, and infrared absorption spectrum analysis, the copolymer composition of the fluorine-containing copolymer (B1) is the structural unit (b1) based on TFE / the structural unit (b2) based on NAH. The structural unit (b3) based on / PPVE was 97.9 / 0.1 / 2.0 (mol%).
Moreover, the content of the reactive functional group (acid anhydride group) of the fluorinated copolymer (B-1) is 1 × 10 ⁶ main chain carbon atoms of the fluorinated copolymer (B-1). It was 1000 pieces.
The melting point of the fluorinated copolymer (B-1) was 300 ° C., and the MFR under a load of 372 ° C. and 49 N higher than the melting point by 20 ° C. was 17.6 g / 10 min.

(Fluorine-containing copolymer (B-2))
As the fluorine-containing copolymer (B-2), a TFE-perfluoro (alkyl vinyl ether) copolymer containing no reactive functional group (hereinafter also referred to as “PFA”) (product name “Fluon PFA 63P” manufactured by Asahi Glass Co., Ltd.). )). The melting point of the fluorine-containing copolymer (B-2) was 300 ° C., and the MFR under a load of 372 ° C. and 49 N higher than the melting point by 20 ° C. was 12.8 g / 10 min.

(Fluorine-containing copolymer (B-3))
As the fluorine-containing copolymer (B-3), a TFE-ethylene copolymer (product name “Fluon LM-ETFE AH-2000” manufactured by Asahi Glass Co., Ltd.) containing a reactive functional group was used. The melting point of the fluorinated copolymer (B-3) was 245 ° C., and the MFR under a load of 297 ° C. and 49 N, which is 20 ° C. higher than the melting point, was 23 g / 10 min.

(Fluorine-containing copolymer (B-4))
As the fluorine-containing copolymer (B-4), a TFE-ethylene copolymer containing no reactive functional group (manufactured by Asahi Glass Co., Ltd., product name “Fluon LM-ETFE LM-730AP”) was used. The melting point of the fluorinated copolymer (B-4) was 225 ° C., and the MFR under a load of 297 ° C. and 49 N, which is 20 ° C. higher than the melting point, was 24 g / 10 min.

(PPS (A-1))
The product name “MA520” manufactured by DIC Corporation was used as the PPS. PPS (A-1) was a linear type (linear structure), and the MFR under a load of 297 ° C. and 2.16 kgf (21.17 N) was 57.7 g / 10 min.

(PPS (A-2))
The product name “LD-10” manufactured by DIC was used as PPS. PPS (A-2) had an MFR under a load of 297 ° C. and a load of 2.16 kgf (21.17 N) of 55 g / 10 min.

(Carbon fiber)
A product name “Kureka Chop M-201S” manufactured by Kureha Co., Ltd. was used as the carbon fiber. The average fiber length of the carbon fibers was 0.15 mm, and the average fiber diameter was 14.5 μm.

[Example 1]
PPS (A-1) and fluorine-containing copolymer (B-1) are supplied to the base end of a screw of a twin screw extruder (manufactured by Technobel) so as to have a volume ratio shown in Table 1, and the temperature is 300 The mixture was melt-kneaded under the condition of ° C. to obtain a PPS composition (1) as a kneaded product.
Table 1 shows the measurement results of tensile strength and storage elastic modulus.

[Example 2]
A PPS composition (2) was obtained in the same manner as in Example 1 except that the volume ratio of PPS (A-1) to the fluorinated copolymer (B-1) was changed to the values shown in Table 1. .
Table 1 shows the measurement results of tensile strength and storage elastic modulus.

[Comparative Example 1]
PPS (A-1) and fluorine-containing copolymer (B-2) are supplied to the base end of a screw of a twin screw extruder (manufactured by Technobel) so as to have a volume ratio shown in Table 1, and the temperature is 300 The mixture was melt-kneaded under the condition of ° C. to obtain a PPS composition (3) as a kneaded product.
Table 1 shows the measurement results of tensile strength and storage elastic modulus.

[Comparative Example 2]
A PPS composition (4) was obtained in the same manner as in Comparative Example 1, except that the volume ratio of PPS (A-1) to the fluorine-containing copolymer (B-2) was changed to the values shown in Table 1. .
Table 1 shows the measurement results of tensile strength and storage elastic modulus.

[Reference Example 1]
Table 1 shows the results of measuring the storage elastic modulus of PPS (A-1).

[Example 3]
PPS (A-2) and fluorine-containing copolymer (B-3) are supplied to the base end of the screw of a twin-screw extruder (manufactured by Technobel) at a volume ratio shown in Table 2, and the temperature is 340 ° C. The mixture was melt-kneaded under the above conditions to obtain a PPS composition (5) as a kneaded product.
Table 2 shows the measurement results of the Izod impact test.

[Comparative Example 3]
A PPS composition (6) was obtained in the same manner as in Example 3, except that the fluorinated copolymer (B-3) was changed to the fluorinated copolymer (B-4).
Table 2 shows the measurement results of the Izod impact test.

[Example 4]
At the base end of the screw of the twin-screw extruder (manufactured by Technobel), carbon fibers were added so that the volume ratio of PPS (A-2) and the fluorinated copolymer (B-1) shown in Table 3 was obtained. Were supplied so that the mass ratio was as shown in FIG. 1, and melt-kneaded at a temperature of 340 ° C. to obtain a PPS composition (7) as a kneaded product. The mass ratio of carbon fibers is the mass ratio of carbon fibers in 100 parts by mass of the PPS composition.
Table 3 shows the measurement results of the Izod impact test.

[Comparative Example 4]
A PPS composition (8) was obtained in the same manner as in Example 4 except that the fluorinated copolymer (B-1) was changed to the fluorinated copolymer (B-2).
Table 3 shows the measurement results of the Izod impact test.

  As shown in Table 1, the molded products (injection molded products and press molded products) obtained by molding the PPS compositions (1) and (2) of the examples were excellent in tensile strength. Further, when Example 2 and Comparative Example 2 are compared, in Example 2, the tensile strength of the press-molded product and the injection-molded product is comparable, whereas in Comparative Example 2, the injection-molded product is more than the press-molded product. The tensile strength of was poor. From this, it was found that the strength reduction was suppressed even when the PPS composition (2) of Example 2 was molded by a method such as injection molding in which a large shear force was applied during molding.

  As shown in Table 2, the molded product (press molded product, injection molded product) obtained by molding the PPS composition (5) of the example is superior in impact resistance to the molded product of the composition (6) of the comparative example. ing. In particular, it was found that the injection molded product has high impact resistance even at a thickness of 1 mm.

  As shown in Table 3, the molded product (press molded product, injection molded product) obtained by molding the PPS composition (7) of the example to which carbon fiber was added as an inorganic filler was molded from the composition (8) of the comparative example. Excellent impact resistance compared to products. In particular, it was found that the injection molded product has extremely high impact resistance even at a thickness of 1 mm.

  The PPS composition of the present invention is molded and can be used for various applications such as medical products, machine parts, automobile parts, and electric / electronic parts.

Claims (10)

Polyphenylene sulfide (A),
And a fluorine-containing copolymer (B) having at least one reactive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. ,
The reactive functional group is derived from at least one selected from the group consisting of a monomer, a chain transfer agent, and a polymerization initiator used in the production of the main chain of the fluorine-containing copolymer (B). A polyphenylene sulfide composition.   The polyphenylene sulfide composition according to claim 1, wherein the reactive functional group comprises an acid anhydride residue that is the carbonyl group-containing group. 3. The polyphenylene sulfide composition according to claim 1, wherein the content of the reactive functional group is 500 or more with respect to 1 × 10 ⁶ main chain carbon atoms of the fluorine-containing copolymer (B).   The polyphenylene sulfide (A) and the fluorine-containing copolymer (B) are contained in a ratio (A) / (B) = 99/1 to 60/40 (volume ratio). The polyphenylene sulfide composition according to Item.   The fluorine-containing copolymer (B) is a copolymer containing at least the reactive functional group derived from the monomer used for the production of the main chain of the fluorine-containing copolymer (B), The main chain is a structural unit (b1) based on tetrafluoroethylene, a structural unit (b2) based on a monomer having the reactive functional group and a polymerizable unsaturated bond, and a structural unit (b3) based on another monomer. The polyphenylene sulfide composition according to any one of claims 1 to 4, comprising:   Furthermore, the polyphenylene sulfide composition as described in any one of Claims 1-5 containing an inorganic filler (C).   The polyphenylene sulfide composition according to claim 6, wherein the inorganic filler (C) contains at least carbon fiber.   A molded article formed by molding the polyphenylene sulfide composition according to any one of claims 1 to 7.   The molded article according to claim 8, which is an injection molded article.   The molded product according to claim 8 or 9, wherein the molded product has a portion having a thickness of 1.5 mm or less.