DE4206996A1 - Block polyphenylene sulphide sulphone polyphenylene sulphide ketone copolymer - used in resin compsn., fibre, film or paste, esp. for coating or prepreg - Google Patents

Abstract

Block copolymers (I) have polyphenylene sulphide sulphone (PPSS) segment and a polyphenylene sulphide ketone (PPSK) segment and a flow of 1-900 g/10 min. at 370 deg.C 5 kg load. USE/ADVANTAGE - (I) is used in resin compsns. contg. (I) and miscible resin(s) (II) i.e. polyamides, thermoplastic polyesters, polysulphones, PPO, PEEK, polyether-imides, polyether-ketones, polyacrylates, completely aromatic polyesters, polycarbonates, alpha-olefin copolymers, styrene copolymers, hydrogenated conjugated diene copolymers, ABS and phenoxy, fluorinated, epoxy, phenolic and furan resin and/or esp. PPS, PPSS and/or PPSK; and in filled resin compsns. contg. (I) and opt. (II). (I) and mixts. of (I) with miscible PPS, PPSS and/or PPSK resin(s) are claimed for use as melt-spun fibres, melt-formed films, including oriented films, or as resin pastes in a dispersion medium esp. for producing coatings and prepregs. (I) and compsns. contg. (I) have excellent resistance to heat, chemicals and weathering and excellent softness, water absorption and flame retardancy. They are used for injection moulding, pressing, extrusion etc. to electrical and electronic components, car parts, sliding parts, building materials, technical materials, e.g. in engineering, air, space and sea transport, sports articles, bag filters, grids, nonwoven fabrics, aircraft interiors, reinforcing fibres for concrete industrial films, magnetic tapes, films for laminates etc

Description

The present invention relates to a block copolymer comprising a Polyphenylene sulfide sulfone segment and a Polyphenylene sulfide ketone segment includes and an improved has thermal stability; a resin containing the same Composition; and uses of these, as well as in particular a fiber, a film and a slurry composition made up of the block copolymer or the composition thereof becomes. It also refers to a block copolymer, that can be used as a molding compound in injection molding Compression molding, extrusion and the like to make moldings from to deliver various external shapes that are well usable are as electrical or electronic parts, auto parts, Sliding or sliding parts and as other different parts in the fields of construction, engineering, aviation, Space travel, marine etc .; a resin composition that the Block copolymer contains improved properties regarding thermal stability, chemical resistance, softness, Water absorption, weather resistance and flame retardant effect has, and which can be used as a molding compound for electrical or electronic parts, auto parts, articles for the Interior fittings, sporting goods, etc .; a fiber that comes from the Block copolymer or a resin composition available therefrom that excels in chemical resistance, flame retardant effect and dimensional stability, the greatly improved properties with respect to  Has toughness, thermal resistance and dimensional stability, and which is therefore well applicable in the areas that thermal stability, chemical resistance, flame retardant Effect, etc. require such. B. as a bag filter, grid, non- Woven fabric, aircraft interior components, reinforcing fibers for Concrete, etc .; made a film including a film from the block copolymer or a resin composition thereof, which is excellent in chemical resistance, flame retardant effect and dimensional stability and greatly improved properties in terms has thermal stability and toughness and is therefore good can be used in the fields of thermal resistance, chemical resistance and flame retardancy require, like, e.g. B. as industrial films, magnetic tapes and films for Laminates; and a slurry composition that is prepared by dispersing the block copolymer or a resin Composition from it in a liquid medium, the one improved adhesion, improved compatibility with Additive polymers and improved heat resistance and is therefore usable as an anti-rust and anti-corrosive Coating agent or as fiber material for metals and as impregnation material to prepregs for electrical or to provide electronic parts, auto parts and sporting goods.

Polyarylene sulfide resins (hereinafter abbreviated: PAS) inferior in weather resistance and Adhesive power. They are very brittle, they lack Impact resistance and softness, but they stand out through thermal stability, chemical resistance, electrical insulating properties, flame retardant effect and dimensional stability. Such drawbacks have been identified as The main reason for the limited application of these resins specified. To overcome these disadvantages of PAS or others Resins with the excellent characteristics of PAS  A variety of proposals have been made to equip Mix PAS with other polymers.

However, none of the PAS resin Mixes achieved the main goal of mixing because each of the known PAS resins have a poor affinity for resin components or the heat resistance of PAS when mixed with others Resin is reduced. For example, polymer blends of polyphenylene sulfide (hereinafter abbreviated as PPS), which on is most typical of the known PAS resins, and other resins in JP-B-54-39 856, U.S. Patent 40 21 596, JP-B-56-34 032, (the The term "JP-B" used here means "tested Japanese Patent Publication "), U.S. Patent 45 28 346, JP-A-53-57 255, JP-A-59-2 13 758 and JP-A-59-1 55 461 (the term used here "JP-A" stands for "unchecked published Japanese Patent application ") disclosed. However, the mixing insufficient improvements in PPS with respect to Achieve impact strength or softness, and in some Cases were rather reductions in these properties due to poor compatibility with the resins caused.

In US-A-41 02 875 it is disclosed that phenylene sulfide sulfone (hereinafter abbreviated as PPSS) Difficulty with Molding presses because of its weak fluidity at high Temperatures. Although PPSS is not crystalline and therefore has a relatively high glass transition temperature there is a decrease at high temperatures of 220 ° C or higher in mechanical strength and is consequently in the Application to areas that have thermal resistance in one require such temperature range, limited. To this Overcoming disadvantage has been attempted using PPSS heat-stable resins to mix, but the resulting Polymer blends were unsuitable because they  due to insufficient compatibility no improvement heat resistance.

Polyphenylene sulfide ketone (hereinafter abbreviated as PPSK), disclosed in U.S. 47 34 470, but has a high thermal resistance, has a glass transition temperature of only 140 ° C, and therefore there is a lack of maintenance of the Rigidity at high temperatures. PPSK also tends to Melt kneading to gel formation, resulting in a deteriorates shape stability, and is in practical use Not easy to use.

On the other hand, known block copolymers include PPSS Contain segments, a block copolymer made of PPSS and an amorphous aromatic sulfone as disclosed in JP-A-61-72 020 and a block copolymer of PPSS and PPS, as in US-A- 47 34 470 is disclosed. These techniques are aimed at one Improving the mechanical characteristics of PPSS and especially impact strength. Molded parts made of PPSS Block copolymers are accordingly not produced always have sufficient thermal resistance and are in limited their application.

Furthermore, a block copolymer has a PPS segment and a PPSS segment and which is described in US-A-49 60 841, improved affinity for resin components, however, it is still unsatisfactory in terms of thermal stability. From US-A-49 60 806 and JP-A-2-1 33 428 a block copolymer is known which has a PPS segment and a PPSK segment contains, but not enough softness and Impact resistance due to poor affinity Has resin components.

An object of the present invention is to provide a To provide PPSS / PPSK block copolymer that is improved  has thermal stability while the excellent Characteristics that are inherent to PPSS and PPSK are retained.

Another object of the present invention is to provide a highly functional PAS resin composition, which, if desired, may contain fillers in the resin components have an improved affinity or Have compatibility, so that excellent characteristics of the PAS resins, such as thermal stability and chemical Resistance to be fully exploited while the Inadequacies of impact strength, softness, Weather resistance, etc. of the PAS resins can be compensated.

Another object of the present invention is a PAS fiber from the PPSS / PPPSK block copolymer or a resin To provide a composition that is free of the Disadvantages associated with PPS fibers or PPSK fibers is excellent in terms of thermal stability, chemical Resistance, flame retardant effect and dimensional stability, which have a high glass transition temperature as well as a high one Has tensile strength, and that in terms of affinity other polymers and in terms of dimensional stability has excellent properties.

In addition, it is an object of the present invention to PPSS / PPSK block copolymer or resin film To provide a composition thereof, which is free of Disadvantages associated with PPS films or PPSK films, which has improved toughness as well as thermal Stability, chemical resistance, dimensional stability and shows flame retardant effectiveness.

Finally, there is another object of the present Invention in a slurry composition from the PPSS / PPSK Block copolymer or a resin composition thereof  which is capable of providing excellent properties such as dimensional stability, chemical resistance, flame retardant To give effectiveness and thermal stability, and the excellent adhesiveness and adhesive properties Has compatibility with admixtures, the Composition when in a coating formulation is used, can be applied thickly, or when used in Compression molding used by prepregs is excellent Has adhesion on a fibrous basis.

The inventors have made extensive investigations to to find a polymer suitable for block copolymerization PPSS is suitable, and also excellent thermal Has stability, and as a result, it was found that a Block copolymer by copolymerization of PPSK and PPSS can be manufactured. Thus they came to the present one Invention.

The present invention relates to a block copolymer a PPSS segment and a PPSK segment (hereinafter referred to as PPSS / PPSK) contains, wherein the block copolymer has improved thermal stability and a Flowability (hereinafter abbreviated as MI) from 1 to 900 g / 10 min at 370 ° C under a load of 5 kg.

The present invention further relates to a resin Composition, the PPSS / PPSK and at least one miscible Contains resin or a filler.

The present invention further relates to a fiber and a Film made from PPSS / PPSK or a resin composition made of it getting produced.

The PPSS segment, part of PPSS / PPSK of the present invention, is a polymer with a repeating unit of the formula (Φ-SO ₂ -Φ-S-), in which Φ represents a phenylene group (the same applies in the further text). The polymer preferably has a molecular weight such that it has an inherent viscosity η _inh. in the range from 0.05 to 1.0, measured at 30 ° C. in a 0.5 g / 100 ml polymer solution in a 3: 2 ratio (by weight) of phenol and 1,1,2,2- Tetrachloroethane mixed solvent. η _inh. is denoted by the following equation: η _in.h = [ln (η / η ₀ )] / c, where (η / η ₀ ) is a relative viscosity η _rel. , and c is a polymer concentration. The polymer can be produced, for example, by a polymerization reaction between a dihalogenated aromatic sulfone and an alkali metal sulfide in an organic amide solvent. In this regard, reference may be made to US Pat. No. 4,102,875.

PPSS used in the synthesis of PPSS / PPSK contains for example a terminal chlorophenyl group ((Cl-Φ-). Die Production of PPSS with terminal chlorophenyl group can e.g. B. take place so that in the polymerization described above the dihalogenated aromatic sulfone for example in 5 mol% excess over the alkali metal sulfide is used. In this regard, reference may be made to U.S. Patent 4,301,274 will.

The PPSK segment, which is part of PPSS / PPSK, is a polymer with a repeating unit of the following formula (-Φ-CO- Φ-S-). The polymer preferably has a reduced viscosity η _red. in the range from 0.2 to 2, measured at 25 ° C. in a 0.5 g / 100 ml polymer solution in 98% sulfuric acid. η _red. is calculated according to the following equation: η _red. = (η / η ₀ -1Φ) / c, where η / η _{0 is} a relative viscosity and c is a polymer concentration. The polymer can be produced, for example, by a polymerization reaction between a dihalobenzophenone and an alkali metal sulfide in an organic amide solvent. This is described in US-A-47 16 212 and in US-A-48 73 283.

The block copolymer of the present invention will for example by reaction of the end group of PPSS and that manufactured by PPSK. When using PPSS with terminal Chlorophenyl group it is therefore necessary to remove the end group from PPSK into a group reactive to a chlorophenyl group convert, for example in a sodium sulfide group (NaS-). PPSK with a terminal NaS group can be obtained, for example when the polymerization reaction described above with an excess (1 to 20 mol%) of the sodium sulfide component against the dihalobenzophenone component.

The copolymerization of PPSS and PPSK can be carried out in the presence of a binding agent, such as. B. a dihalogenated aromatic Sulfones or sodium sulfide as a third component be performed. So the end product is a block copolymer is, as intended, a monomer that can be PPSS or PPSK supplies, are polymerized in the presence of the other polymer.

To get the block copolymer in good yield, it is very advantageous if the total number of reactive end groups of PPSS and PPSK are the same. However, if the number of End groups of one of the PPSS components are those of the other exceeds the unreacted after the reaction Homopolymer component only by fractionation or extraction are removed so as to produce the block copolymer produced isolate.

The dihalogenated aromatic sulfone that the PPSS- Segment forms, includes bis (4-chlorophenyl) sulfone, bis (4- bromophenyl) sulfone and bis (4-fluorophenyl) sulfone.  

The dihalobenzophenone, which forms the PPSK segment, suitably includes 4,4'-dichlorobenzophenone, 4,4'- Difluorobenzophenone and 4,4'-dibromobenzophenone.

The alkali metal sulfides preferably include lithium sulfide and Sodium sulfide. The alkali metal sulfide can pass through in situ Reaction between an alkali metal hydrogen sulfide and one Alkali metal hydroxide can be produced.

The solvents used in the copolymerization reaction Can preferably be used include polar organic Solvents that work at temperature and below Pressure conditions of the copolymerization essentially liquid are. Specific examples of such solvents are amides, Urea derivatives and lactams, e.g. B. formamide, acetamide, N- Methylformamide, N.N-dimethylformamide, N, N-dimethylacetamide, 2- Pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ε- Caprolactam, N-methyl-ε-caprolactam, hexamethylphosphoramide, Tetramethyl urea and 1,3-dimethyl-2-imidazolidinone; Sulfones, such as B. Sulforan and Dimethylsulforan; Nitriles, e.g. B. Benzonitrile; Ketones such as methylphenyl ketone; Polyethylene glycols, as well as mixtures thereof. Aprotic are particularly preferred organic polar solvents such as amines, lactams and sulfones.

This organic solvent is used in 2-20 times the amount the weight of the polymer components used.

The fact that the product described above Copolymerization reaction is a block copolymer in which a PPSS segment and a PPSK segment are chemically linked, can by extracting the product with a mixture of Phenol and tetrachloroethane in the ratio (by weight) 3: 2 and 98% sulfuric acid can be confirmed, the former being a good solvent for PPSS and the latter for PPSK  represents. Examination of the extracts showed that none of the Extracts contained the respective homopolymer.

The PPSS / PPSK ratio in the copolymerization system can be changed, depending on the Characteristics that are sought. Generally there is one molar PPSS / PPSK ratio in the range of 1: 99/99: 1, preferably 5: 90/95: 10, and more preferably from 30: 70/70: 30 If it is less than 1/99, the effects that be contributed by PPSS, such as B. Maintaining the Stiffness does not appear at approximately 150 to 200 ° C, and if it exceeds 99/1, the effects caused by PPSK be contributed such. B. thermal stability and mechanical characteristics do not emerge. In one Case may be those envisaged by the present invention Effects cannot be achieved.

PPSS / PPSK according to the present invention has an MI of 1 to 900 g / 10 min at 370 ° C under a load of 5 kg. PPSS / PPSK, which has an MI value of not more than 100 g / 10 min has, is particularly suitable for compression molding. PPSS / PPSK, whose MI is over 100 g / 10 min depends on End use, also usable.

The resin composition according to the present invention has essentially (a) PPSS / PPSK and (b) at least one with PPSS / PPSK miscible resin and / or a filler.

While the ratio of PPSS to PPSK in PPSS / PPSK, which may be mixed with other miscible resins, changes depending on the type of mixed resin or the end use the composition is subject to the PPSS Segments in PPSS / PPSK usually in the range of 20 to 80 mol% and preferably in the range of 25 to 75 mol%. Is the Share of the PPSS segment in this area, PPSS / PPSK shows  especially excellent compatibility with other resins and the resulting composition has improved thermal stability and improved heat resistance.

PPSS / PPSK which can be used in the resin composition may contain unreacted PPSS and PPSK homopolymers that were present in the copolymerization system for producing PPSS / PPSK, as long as the effects of the present invention are not deteriorated. PPSS / PPSK must also not contain more than 30 mol%, and preferably not more than 10 mol%, of other polyarylene sulfide (PAS) components as the copolymerization component. PAS components that can be incorporated into PPSS / PPSK include those that have a divalent aromatic residue as an arylene group, such as. B. p-phenylene, m-phenylene, o-phenylene, 2,6-naphthalene, 4,4'-biphenylene, or a divalent aromatic radical containing at least 2 aromatic rings with 6 carbon atoms, e.g. B. (-Φ-O-Φ-), (-Φ-CH ₂ -Φ-), and (-Φ-C (CH ₃ ) ₂ -Φ. Each of the aromatic rings of these aromatic radicals can with F, Cl, Br, CH ₃ , etc. may be substituted.

PPSS / PPSK, for use in the resin composition, has a dynamic viscosity coefficient (η ′) in the range from 50 to 10 ⁵ poise, and preferably from 100 to 50,000 poise, measured at a melting point + 20 ° C. and 10 rad / sec.

The miscible resins that can be mixed with PPSS / PPSK include known PAS resins, e.g. B. PPS, PPSK and PPSS; such as other admixtures that are used as conventional PAS resin composites are known, for example polyamide resins (hereinafter abbreviated to PA), thermoplastic polyester resins, Polysulfone resins (hereinafter abbreviated to PSF), polyphenylene oxides (hereinafter abbreviated PPO), polyetherimide resins (hereinafter abbreviated PEI), polyether ketones (hereinafter abbreviated PEK), Polyetheretherketone (hereinafter abbreviated to PEEK), polyarylate  Resins (hereinafter abbreviated to PAr), the entire aromatic Polyester resins, polycarbonate resins (hereinafter abbreviated to PC), Phenoxy resins, α-olefin copolymers, styrene copolymers, Hydrogenation products of copolymers of conjugated dienes, ABS Resins, Fluorine Resins, Epoxy Resins, Phenolic Resins and Furan resins. Of these mixed resins, PPS, PPSK and PPSS preferably used.

PA that can be used in the resin composition includes various known polyamide resins such as e.g. B. those by polycondensation between a dicarboxylic acid (e.g. oxalic acid, adipic acid, suberic acid, sebacic acid, Terephthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid) and a diamine (e.g. ethylenediamine, pentamethylenediamine, Hexamethylene diamine, decamethylene diamine, 1,4-cyclohexyl diamine, m- Xylenediamine) can be prepared; those by polymerization a cyclic lactam (e.g. caprolactam, laurolactam) be won; as well as those obtained by copolymerization of a cyclic lactams with a salt of a dicarboxylic acid and a diamine. Among them are nylon 6, nylon 66, nylon 46, nylon MXD6 (m-xylenediamine-adipic acid copolymer), Nylon 6.10, Nylon 66 / 6.10, Nylon 6/66, Nylon 12, Nylon 11 and Nylon 6 / 6T (caprolactam-terephthalic acid-hexamethylenediamine- Copolymer), preferred; Nylon 6, Nylon 66, Nylon 46, and Nylon MXD6 are particularly preferred. These polyamide resins can either individually or in combination of two or more of which are used. PA has thermal Stability, softness and impact resistance excellent Properties, but it has poor flame retardant Effectiveness and it contributes to a decrease in strength Water absorption by. The resin composition, the PPSS / PPSK and PA contains, eliminates such disadvantages of PA.

The thermoplastic polyester resins used in the resin Composition that can be used include those made from  a dicarboxylic acid or an ester-forming derivative thereof (e.g. terephthalic acid, isophthalic acid, orthophthalic acid, Naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, Diphenylene ether dicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, Adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, Dodecanedicarboxylic acid, cyclohexanedicarboxylic acid and dimeric acid) and a glycol component (e.g. ethylene glycol, Porpylene glycol, butanediol, pentanediol, neopentyl glycol, Hexanediol, octanediol, decanediol, cyclohexanedimethanol, Hydroquinone, bisphenol A, 2,2-bis (4-hydroxyethoxyphenyl) propane, Xylene glycol, polyethylene ether glycol, Polytetramethylene ether glycol and an aliphatic Polyester oligomer with a hydroxyl group at both ends) be preserved. Polyesters are usually used, which have an intrinsic viscosity (η) in the range from 0.3 to 1.5 dl / g, measured at 30 ° C in one of phenol and tetrachloroethane in Ratio (by weight) 6: 4 mixed solvent.

The polyesters can be used as a comonomer component Hydroxycarboxylic acid (e.g. glycolic acid, hydroxybutyric acid, Hydroxybenzoic acid, hydroxyphenylacetic acid and Naphthylglycolic acid) or a lactone compound (e.g. Propiolactone, butyrolactone, valerolactone and caprolactone) or, insofar as thermoplastic properties are preserved, a polyfunctional ester-forming component (e.g. Trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, Trimellitic acid, trimesic acid and pyromellitic acid included.

The polyesters may also contain as a comonomer component a halogenated aromatic compound with a halogen atom (e.g. chlorine, bromine) on the aromatic ring, an ester-forming group (a carboxyl group or a hydroyl group), e.g. B. Dicarboxylic acid, dibromoterephthalic acid, tetrabromophthalic acid and tetrachloroterephthalic acid and as diols 1,4-dimethylol tetrabromobenzene, tetrabromobisphenol A and tetrabromobisphenol A-ethylene oxide adduct are contained. Preferred polyester resins are:
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, poly (ethylene · butylene · terephthalate), poly (cyclohexanedimethylene terephthalate), poly (butylene · tetramethylene terephthalate) and a 2,2-bis (β-hydroxyethoxy tetrabromophenyl) propane butane Copolymer. Thermoplastic polyesters have relatively well-balanced characteristics in terms of sliding properties, thermal stability, impact resistance, weather resistance and the like, but a further improvement in thermal stability is desirable. It was also emphasized that a blend of polyester and PPS caused a sharp decrease in dynamic characteristics such as. B. the impact resistance suffers. The composition of PPSS / PPSK and the polyester resin shows improvements in this point.

Is PSF that can be used in the resin composition a polyarylene compound in which an arylene unit in regular or irregular shape with an ether bond and a sulfone bond. Common PSF resins include those of the structural formulas listed below (a) to (r), and preferably those of structural formulas (a) or (f). These polymers can be either homopolymers or block copolymers be. The block copolymers contain a block copolymer of (a) and (b), a block copolymer of (f) and a polyarylate, and a block copolymer (f) and a polycarbonate.

In the following formulas, -Df- stands for 3.6- Benzofuranylene group, -Np- for a 2,7-naphthylene group, -Ph- for a phenyl group and n is an integer of 10 upwards.  

(a) (-Φ-O-Φ-SO₂-) _n
(b) (-Φ-Φ-SO₂) ₂
(c) (-SO₂-DF-SO₂-Φ-O-Φ-) _n
(d) (-Np-SO₂-Φ-O-Φ-) _n
(e) (-SO₂-Φ-O-Φ-SO₂-Φ-CH₂-Φ-) _n
(f) (-Φ-C (CH₃) ₂-Φ-O-Φ-SO₂-Φ-O-) _n

(h) (-O-Φ-CH₂-Φ-O-Φ-SO₂-Φ-) _n
(i) (-O-Φ-O-Φ-SO₂-Φ-) _n
(j) (-O-Φ-CO-Φ-O-Φ-SO₂-Φ-) _n
(k) (-O-Φ-C (Ph) ₂-Φ-O-Φ-SO₂-Φ-) _n
(l) (-O-Φ-O-Φ-O-Φ-SO₂-Φ-) _n )
(m) (-O-Φ-SO₂-Φ-O-Φ-CF₂-Φ-) _n
(n) (-O-SO₂-Φ-Φ-SO₂-Φ-O-Φ-O-Φ-C (CH₃) ₂-Φ-O-) _n
(o) (-Φ-SO₂-Φ-O-Φ-SO₂-Φ-O-Φ-C (CH₃) ₂-Φ-O-) _n
(p) (-Φ-SO₂-Φ-O-Φ-SO₂-Φ-) _n
(q) (-Φ-Φ-O-Φ-SO₂-Φ-O-) _n
(r) (-Φ-O-Φ-SO₂-Φ-Φ-SO₂-) _n

PPO that can be used in the resin composition also called polyphenylene ether (hereinafter abbreviated PPE) and can be made by polycondensation of one or several monocyclic phenols of the formula (I):  

in which R _{1 represents} a lower alkyl group having 1 to 3 carbon atoms; R ₂ and R ₃ each represent a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms;
PPO can be either a homopolymer or a copolymer.

Examples of the monocyclic phenol of the formula (I) are: 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2- Methyl 6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6- propylphenol, m-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3- propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol, 2- Propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6- Trimethylphenol, 2,3,6-triethylphenol, 2,3,6-tripropylphenol, 2,6-dimethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol.

Examples of PPO made from these monocyclic phenols obtained include poly (2,6-dimethyl-1,4-phenylene) ether, Poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4- phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, Poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6- propyl-1,4-phenylene) ether, a 2,6-dimethylphenol / 2,3,6- trimethylphenol copolymer, a 2,6-dimethylphenol / 2,3,6- triethylphenol copolymer, a 2,6-diethylphenol / 2,3,6- trimethylphenol copolymer, a 2,6-dipropylphenol / 2,3,6- trimethylphenol copolymer, a styrene-grafted poly (2,6- Dimethyl-1,4-phenylene) ether copolymer and a styrene-grafted 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer. Under these  PPO resins are poly (2,6-dimethyl-1,4-phenylene) ether and a 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer preferred.

PEI, which can be used in the resin composition, is a polymer with a repeating unit of the formula (II):

wherein -O-Q₁-O in the 3- or 4-position and the 3'- or 4'- Position is bound; Q₁ represents a substituted or unsubstituted divalent aromatic group of the formulas (III), (IV) or (V) represents:

wherein Q 'individually represents an alkyl group having 1 to 6 carbon atoms, an aryl group or a halogen atom; m represents 0 or an integer from 1 to 4; and Q ₃ represents -O-, -S-, -CO-, -SO ₂ -, -SO- an alkylene group with 1 to 6 carbon atoms, an alkylidene group with 1 to 6 carbon atoms or a cycloalkylene group with 4 up to 8 carbon atoms;
Q ₂ stands for an aromatic hydrocarbon group with 6 to 20 carbon atoms or its halogenated derivative, which contains 1 to 6 carbon atoms in the alkyl part, for an alkylene group with 2 to 20 carbon atoms, for a cycloalkylene group with up to 20 Carbon atoms, a poly (diorganosiloxane) with an alkylene terminal which contains 2 to 8 carbon atoms in the terminal alkylene group, or for an aromatic group of the formula (V).

Is PEK that can be used in the resin composition a tough and crystalline thermoplastic aromatic Polyether ketone, which is a repeating unit of the formula (VI):

(-Φ-CO-Φ-O-) (VI)

and / or a repeating unit of the formula (VII):

(-Φ-O-Φ-CO-Φ-) (VII)

either alone or in combination with others Repeating units, and that a limit viscosity in of not less than 0.7.

The repeating units, in addition to those of the formulas (VI) and (VII) can occur, include those of the formulas (VIII) to (XI):  

(-Φ-A-Φ-O-Φ-CO-Φ-) (VIII)

in which A represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO- or a divalent hydrocarbon group,

(-Φ-CO-Φ-O-Φ-CO-Φ-O-) (IX)

(-Φ-O-Φ-SO₂-Φ-O-) (X)

in which Y and Y ', which may be the same or different, each represent -CO- or -SO ₂ -; Ar 'represents a divalent aromatic group; n stands for 0, 1, 2 or 3; and the oxygen atom in the subunit -O-Φ- is in the o- or p-position with respect to Y or Y '.

PAr that can be used in the resin composition is a polyester resin synthesized from a bisphenol or a Derivative thereof and a dibasic acid or derivative from that. Examples of common bisphenols are 2,2-bis (4- hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, 4,4'- Dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-3,3'- dichlorodiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-  ditromphenyl) propane and 2,2-bis (4-hydroxy-3,5- dichlorophenyl) propane and 2,2-bis (4-hydroxyphenyl) propane, called bisphenol A, which is particularly advantageous.

Examples of common dibasic acids include aromatic dicarboxylic acids, e.g. B. isophthalic acid, Terephthalic acid, bis (4-carboxy) diphenyl, bis (4- carboxyphenyl) ether, bis (4-carboxyphenyl) sulfone, bis (4- carboxyphenyl) carbonyl, bis (4-carboxyphenyl) methane, bis (4- carboxyphenyl) dichloromethane, 1,2- or 1,1-bis (4- carboxyphenyl) ethane, 1,2- or 2,2-bis (4-carboxyphenyl) propane, 1,2 or 2,2-bis (4-carboxyphenyl) -1,1-dimethylpropane, 1,1- or 2,2-bis (4-carboxyphenyl) butane, 1,1- or 2,2-bis (4- carboxyphenyl) pentane, 3,3-bis (4-carboxyphenyl) heptane and 2,2- Bis (4-carboxyphenyl) heptane; as well as fatty acids, e.g. B. oxalic acid, Adipic acid, succinic acid, malonic acid, sebacic acid, Glutaric acid, azelaic acid and suberic acid. Mixtures of Isophthalic acid, terephthalic acid or their derivatives particularly advantageous.

All of the aromatic polyesters used in the resin Are known to be used as a composition liquid, crystal clear polymers and are made by Polycondensation of aromatic diols such as B. Hydroquinone and aromatic dicarboxylic acids such as. B. terephthalic acid or Hydroxycarboxylic acid, such as. B. p-hydroxybenzoic acid. Specific examples of this include polyesters with the following Structural elements I to III, structural elements I, III and IV, and the structural elements I and V and mixtures thereof.

PC that can be used in the resin composition includes homogeneous PC and PC copolymers, mainly have at least one bisphenol component selected is made of hydroquinone, resorcinol, dihydroxydiphenyl, Bis (hydroxyphenyl) alkane, bis (hydroxyphenyl) cycloalkane, Bis (hydroxyphenyl) sulfide, bis (hydroxyphenyl)) ketone, Bis (hydroxyphenyl) ether, bis (hydroxyphenyl) sulfoxide, Bis (hydroxyphenyl (sulfone and α, α′-bis (hydroxyphenyl) diisopropylbenzene, each of which is an alkyl May contain a group or a halogen atom at the core.

Specific examples of preferred bisphenol compounds are 4,4-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4- Bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4- hydroxyphenyl) cyclohexane, α, α′-bis (4-hydroxyphenyl) -p- diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2- Bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4- hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4- hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4- hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2- mercaptan, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α, α′- Bis-3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2- Bis (3,5-dichloro-4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4- hydroxyphenyl) propane. 2,2-bis (4- hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4- hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4- hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane.  

Preferred are PC resins which preferred those mentioned above Bisphenol compounds included as a main component. Particularly preferred PC resins are polymers that are exclusive 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (3,5-dimethyl-4- contain hydroxyphenyl) propane and copolymers which contain 2,2-bis (4- hydroxyphenyl) propane and one of the other preferred bisphenol Connections included.

PC can be made by known methods, e.g. B. by esterification in the molten state between one Bisphenol and a diphenyl carbonate or by a two- Phase interface polymerization of a bisphenol and Phosgene.

PSF, PPO, PEI, PEK, PAr and PC each have a high Glass transition temperature and excellent mechanical Characteristics such as B. Impact resistance, but they are lower valuable in their malleability and chemical resistance. Furthermore, PPO and PEI each suffer one when mixed with PPS strong reduction of their dynamic characteristics such as B. Impact strength. The resin Composition can be solved according to the present invention.

ABS resins used in the resin composition can be graft copolymers obtained by polymerizing two or more monomers from the group of the vinyl cyanide compounds, aromatic vinyl compounds and acrylic compounds in Be prepared in the presence of a conjugated diene rubber. If desired, ABS resins can contain copolymers made by Polymerization of two or more monomers selected from Vinyl cyanide compounds, aromatic vinyl compounds and Acrylic compounds. The conjugated servant Rubber includes polybutadiene, butadiene-styrene copolymer and a Butadiene-acrylonitrile copolymer. The vinyl cyanide compounds include acrylonitrile and methacrylonitrile. The aromatic  Vinyl compounds contain styrene, vinyl toluene, dimethyl styrene and chlorostyrene and the particularly preferred α-methylstyrene. The acrylic compounds include acrylic acid, methacrylic acid, Methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and Hydroxyethyl acrylate.

α-olefin copolymers that can be used in the resin composition include copolymers of at least two α-olefin monomers and copolymers of an α-olefin monomer and other copolymerizable monomers. Examples of the α-olefin are ethylene, propylene, butene-1, isobutene, pentane-1, 4-methylpentene-1 and hexane-1. The other copolymerizable monomers include butadiene, vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, acrylonitrile, styrene, vinyl ether and unsaturated dicarboxylic acids (e.g. acrylic acid, methacrylic acid, maleic acid). Ionomers containing a copolymer with a carboxyl group to which a metal ion, e.g. B. Na⁺ and Zn ^{++ is} introduced, can also be used as an α-olefin copolymer. Of these α-olefin copolymers, ethylene copolymers are preferred.

The styrene copolymers that can be used in the resin composition include a styrene homopolymer and copolymers of styrene and one or more other copolymerizable monomers, such as. B. Styrene derivatives (e.g. α-methylstyrene, dimethylstyrene, Chlorostyrene), unsaturated carboxylic acids (e.g. acrylic acid, Methacrylic acid, maleic acid, maleic anhydride), Acrylic acid esters (e.g. methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate); as well as vinyl monomers (e.g. Vinyl acetate, vinyl ether).

The hydrogenation product of a conjugated diene copolymer, which is useful in the resin composition includes a Hydrogenation product of a homopolymer from a diene monomer (e.g. butadiene, pentadiene) or a copolymer containing a diene  Has monomer and other copolymerizable monomers, such as e.g. B. those listed above for styrene copolymers, e.g. B. styrene derivatives, unsaturated carboxylic acids, acrylic acid esters, Vinyl monomers etc.

The in the resin composition of the present invention Phenoxy resins that can be used are thermoplastic polyether resins with high molecular weight, none at both ends Have epoxy groups. They are synthesized from bisphenol A and epichlorohydrin as the main starting materials. Also too The phenoxy resins include thermoplastic polyether resins that have no epoxy group at both ends, and the by the reaction between a diol compound, such as. B. one dihydric phenol, a bisphenol compound (for example bisphenol F, tetrachlorobisphenol), Diphenolic acid, a condensate of bisphenol and p- Xylene dichloride, and an epoxy compound, e.g. B. epichlorohydrin, Butadiene oxide, glycidic compounds can be synthesized.

The fluorine-containing resins which are used in the resin Compositions that can be used include synthetic ones High polymers that contain a fluorine-containing repeating unit have and copolymers thereof. Typical examples of fluorine Resins containing are polytetrafluoroethylene, Polychlorotrifluoroethylene, a tetrafluoroethylene hexafluoropropylene copolymer, a tetrafluroethylene perfluoroalkyl vinyl ether copolymer, polyvinylidene fluoride, Polyvinyl fluoride, a tetrafluoroethylene-ethylene copolymer and additionally fluorine rubber, e.g. B. a vinylidene fluoride hexafluoropropylene copolymer.

The epoxy resins used in the resin composition can preferably include (1) epoxy resins which are produced by Reaction of an active hydrogen compound, the one phenolic hydroxyl group, a carboxyl group, an amino  Group or an amide group (e.g. bisphenol A, two valuable phenols, phenolic novolaks, terephthalic acid, Methacrylic acid, aniline, p-phenylenediamine and sulfonamide) with Epichlorohydrin can be obtained, for example, as a Reaction product of bisphenol A and epichlorohydrin, one Glycidether of a phenol or cresol novolak and one Glycide esters of an organic acid (e.g. phthalic acid, Methacrylic acid); (2) epoxy resins that are oxidized in liquid phase of compounds that have a double bond included with z. B. hydrogen peroxide, peracetic acid, etc., are produced, for example as oxidation products olefinic compounds, butadiene, soy or one Esters thereof and of oleic acid or an ester thereof a peracid; and (3) epoxy resins produced by air oxidation of Compounds containing a double bond, e.g. B. styrene oxide getting produced. Among these, epoxy resins from Bisphenol type and epoxy novolak resins preferred.

The compounding ratio of PPSS / PPSK and the above described admixing resins in the resin composition of the present invention varies depending on the type of Mixing resins and the end use of the composition. If the Composition PPSS / PPSK and PPSK or PPSS contains, has the Composition 3 to 100 parts by weight, and preferably 10 to 100 parts by weight of PPSS / PPSK and 1 to 97 parts by weight, and preferably 10 to 90 parts by weight of PPSK or 1 to 60 Parts by weight, and preferably 10 to 40 parts by weight of PPSS on. If the PPSS / PPSK content falls in the range of 3 to 100 Parts by weight, the composition shows an excellent Compatibility. Epoxy resins are used in an amount of 0.1 to 10 Parts by weight and preferably from 0.2 to 5 parts by weight per 100 parts by weight of PPSS / PPSK used. α-olefin copolymers, Styrene copolymers, hydrogenation products from copolymers conjugated dienes or phenoxy resins are used in an amount of  1 to 100 parts by weight, preferably 2 to 80 parts by weight Parts by weight per 100 parts by weight of PPSS / PPSK used. Resin compositions containing the other resins usually 95 to 5 parts by weight of PPSS / PPSK and 5 to 95 Parts by weight of other resin and preferably 90 to 10 Parts by weight of PPSS / PPSK and 10 to 90 parts by weight of other Resin on.

If necessary, the resin composition of the present Invention further fibrous or particulate fillers included to further improve thermal stability, dynamic characteristics and dimensional stability to reach. Suitable fibrous fillers include glass fiber, Carbon fiber, silane glass fiber, boron fiber, whisker, Potassium titanium, asbestos, carborundum, aramid fiber, ceramic Fiber and metallic fiber. Suitable particulate Fillers are, for example, silicates, carbonates, sulfates and Metal oxides. Specific examples of these particulate Fillers are barium sulfate, calcium sulfate, kaolin, clay, Pyrophylite, bentonite, sericite, zeolite, rock mica, Nepheline synite, talc, attapulgite, wollastonite, PMF, ferrite, Calcium silicate, calcium carbonate, magnesium carbonate, dolomite, Antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, Molybdenum dioxide, graphite, lithium carbonate, gypsum, glass balls, Glass balloons, silica. These fillers can either used individually or in combination of two or more will. The fillers that are to be installed can be used with Silane or titanium are commonly treated as adhesives can be used for fillers.

The amount of fillers added varies depending on the on the type of filler or the end use of the Composition. It is generally in the range from 10 to 300 parts by weight and preferably from 30 to 200 Parts by weight for fibrous fillers and from 2 to 100  Parts by weight and preferably from 5 to 80 parts by weight particulate fillers, both based on 100 Parts by weight of the resin components.

The resin composition of the present invention may further contain other additives in such small quantities that the effects of the present invention do not deteriorate will. Common additives include release agents (e.g. Polyethylene wax), dyes (e.g. various pigments), Heat stabilizers, antioxidants, ultraviolet Stabilizers, blowing agents, flame retardant additives, agents, that support the flame retardant effect of additives, Rust preventives, silicate adhesives (e.g. aminosilane, Epoxysilane) and titanate adhesive. Examples of suitable ones Heat stabilizers include basic compounds, e.g. B. Hydroxides, oxides or aromatic carboxylic acid salts of metals Group IIa, excluding magnesium and aromatic Carboxylic acid salts, carbonates, hydroxides, phosphates or borates Group Ia metals, calcium hydroxide or oxide and Barium hydroxide or oxide are particularly preferred. Examples for suitable antioxidants, disabled phenolic Compounds, Disabled Amine Compounds, and Phosphorus Compounds, with trivalent phosphorus compounds preferred are. Examples of suitable rust preventives include Carbonates of the alkali metals, e.g. B. lithium and potassium and oxides or carbonates of the metals of groups IIa and IIb, for example magnesium, calcium and zinc, zinc oxide and Zinc carbonate are particularly advantageous.

The composition according to the present invention can can be produced by a known method. The Raw materials can, for example, in a mixing machine, e.g. B. a tumble mixer and a Henschel mixer and then melt kneaded and pelletized in one Single or double screw extruders at 230 ° C to 420 ° C  will. The raw materials can be in a suitable Solvents are mixed and the resulting resinous Substance is melt kneaded in an extruder for granulation. The resinous substance can with PPSS / PPSK and a thermoplastic resin are melt mixed.

So much for the resins to be mixed in a mushy Dispersants are soluble, they have any shape that can be solved, e.g. B. the form of pellets. But if they do are insoluble or poorly soluble, they must be ground be so that at least 80% of the total weight of particles exist that have a particle size between 10 and 400 mesh, and preferably between 20 and 300 mesh. The Block copolymer according to the present invention and the resin Compositions from them can be used as molding compounds, not only in injection molding or molding to electrical or to supply electronic parts, but also for Extrude to fibers, foils, films, tubes or pipes manufacture, blow molding and transfer molding.

The fiber according to the present invention can be used in Melt spinning from PPSS / PPSK or a resin Composition from PPSS / PPSK and other miscible resin getting produced. If necessary, routes and Connect heat curing. The melt spinning process is carried out by filling the resin into an extruder, which is equipped with a conventional spinneret, the resin a temperature in the range of 290 to 380 ° C and preferably is extruded from 300 to 360 ° C, the extruded thread in a deduction ratio (a ratio of winding Speed to spinning speed) from 1 to 5000 and preferably 5 to 3000 is wound. It is recommended fluctuations in temperature during melt spinning the nozzle surface and the temperature as well as the humidity to reduce the spinning shaft to a minimum. The  The temperature and the humidity of the spinning shaft can decrease Setting the temperature or the speed of the cooling air etc. can be controlled.

In addition to melt spinning using a spiral, the resin can be Spinning process according to US-A-41 35 903 can be spun. This Spinning process can be done even with PPSS / PPSK, which has a melt viscosity in the range of 50 to 200 poise having.

The spun thread produced in the melt spinning process shows a birefringence of not more than 5 · 10 ^-2 , and particularly advantageously of not more than 1 · 10 ^-2 .

It is convenient to put some lubrication under before winding Use a suitable lubricant. Suitable lubricants are oil based on dibasic Acid ester or sulfur-containing aromatic ester.

If necessary, the spun threads can be stretched around the Degree of orientation, degree of crystallinity, etc. increase and improve the strength and the like. The Stretching is usually done in several stages, and the number of stretching stages will be according to the need fixed. For example, in the case of a two-tier Stretching the first stage, which is the improvement of the Degree of orientation is used at a temperature of 120 to 250 ° C carried out at a stretch ratio of 1.5 to 16; the second stage of stretching is used to heat harden the Ripple and is at a temperature in the range of the temperature used in the previous step is up to 320 ° C at a stretch ratio of 0.8 to 2 carried out. in the In the case of a three-stage stretch, the first stage becomes 120 up to 200 ° C with a stretch ratio of 1.5 to 10 carried out; the second stage at 180 to 250 ° C at one  Stretch ratio of 2 to 10; and the third stage in one Temperature in the temperature range based on the temperature of the previous step up to 320 ° C with a stretch Ratio from 0.8 to 2.

Heating means for stretching or heat curing the fiber include one Hot roller, a hot air oven, a warm water bath, a steam bath and an infrared heater.

Zone stretching can be used for local stretching of the spun fiber be applied either alone or as one of the stages of multi-stage stretching described above. Zone stretching will carried out at a stretching temperature of 120 to 250 ° C, the stretch ratio being 50 to 95% of the highest possible Stretch ratio is and neither to the final break nor leads to fraying.

The stretching process can be carried out directly in series with the stage of Spinning.

The film according to the present invention can be made from PPSS / PPSK or a resin composition of PPSS / PPSK and other miscible resins using melt molding techniques including T-die extrusion, blown film extrusion with one Annular gap nozzle and hot pressing can be obtained. The film can be stretched uniaxially or biaxially, whereby heat hardening connects to a high strength stretched film receive. The biaxial stretching can either be sequential or be carried out simultaneously.

Preferably, the film can be extruded from PPSS / PPSK or a composition obtained from an extruder which has a T nozzle or an annular gap nozzle, at a temperature of 280 to 380 ° C; the film can go through too Pressing of PPSS / PPSK or a combination thereof  Heating to 280 to 380 ° C made by a hot press will. The film is used to produce stretched films quenched immediately after extrusion or hot molding, to get a film with low crystallinity, which then depending on the end use by means of a stretching device z. B. Stretching rollers and a single-axis or two-axis tensioning machine is stretched, namely at a temperature of 120 to 250 ° C. at a stretch ratio of 1.5 to 10. The stretched film is then subjected to heat curing at a temperature of 140 to Subjected to 350 ° C for a period of 1 to 3000 sec on the stretched film, or in some cases in bulk State a voltage is applied. The stretch ratio during heat curing with or without applied voltage is 0.8 to 2.

The film of the present invention has a thickness of not more than 2 mm, and preferably not more than 1 mm. Where a composition of PPSS / PPSK and other resins or Fillers used for film production, the Composition preferably used in the form of pellets uniform by kneading the raw materials beforehand in a kneading machine, e.g. B. an extruder.

The slurry composition according to the present invention comprises PPSS / PPSK or a resin composition thereof as well as a Dispersing medium. Examples of suitable dispersing media include water; Alcohols, e.g. B. ethanol, propanol, isopropanol Ethylene glycol, diethylene glycol, propylene glycol and glycerin; Hydrocarbons, e.g. B. hexane, pentane, benzene, toluene and Petroleum ether; Esters, e.g. B. methyl acetate, ethyl acetate and Benzoic acid esters; Ketones, e.g. B. methyl ethyl ketone, 2-heptanone and Cyclohexanone; as well as mixtures thereof. Of these, preferred Water and polyhydroxy alcohols, e.g. B. ethylene glycol, Diethylene glycol, propylene glycol and glycerin. Where a resin Composition is used, the PPSS / PPSK and an admixture  Resin containing is used, a solvent can be used for solution of the admixing resin in combination with these dispersants be used as long as the dispersibility of PPSS / PPSK is not reduced.

If desired, the slurry composition of the present Invention contain inorganic fillers, e.g. B. alumina, Silicon oxide, zirconium oxide, glass balls, titanium oxide, ferrite, Mica, magnesium oxide, zinc oxide and graphite; and lubricants, such as fluorine-containing resins and molybdenum compounds. To the Can improve dispersibility or stability of the pulp the slurry composition further various surfactants Contain means and means to accelerate networking. Examples of the surfactants include anionic surfactants, e.g. B. carboxylic acid salts, Sulfuric acid esters of higher alcohols, amide-bound sulfur acid esters, ester-bound ester salts, amide-bound Sulfonates, alkylallylsulfonates, ester-linked sulfonates and Phosphoric acid ester salts; cationic surfactants, e.g. B. quaternary ammonium salts, ether-linked quaternaries Ammonium salts, ester-bound quaternary ammonium salts, amide bound quaternary ammonium salts, amine salts, ester-bound Amine salts, ether-bonded amine salts, amide-bonded amine Salts and pyrridine salts; as well as non-ionic surfactants Agents, for example of the ether type, ester type, amine condensate Type, amide condensate type and polyethyleneimine type. examples for Means to accelerate the crosslinking are polyhydroxybenzene, p-aminophenol, ammonium persulfate, aluminum phosphate and Mercaptoalkylbenzene derivatives.

If the slurry composition of the invention in prepregs used include the fibrous foundations of prepregs short or long fibers, e.g. B. glass fiber, carbon fiber, Silane glass fiber, silicon dioxide fiber, aramid fiber, boron fiber, Alumina fiber, ceramic fiber, asbestos fiber, metal fiber  as well as wiskers and woven fabrics of this fiber. This fibrous Basics can be used in combination. in the glass fiber and carbon fiber are generally used. For special applications such as B. sporting goods, aramid Fiber, boron fiber, etc. are also used. The amount of The fibrous base used is usually though depending on the end use and the type or shape of the fiber, changes, in the range of 20 to 400 parts by weight and preferably from 30 to 300 parts by weight, per 100 Parts by weight of the resin components. With the amount of fibrous The basis that lies in this area is the pulp Composition impregnated satisfactorily in the base, to achieve a sufficient reinforcing effect. in the the rest of the fibrous bases listed above can be in shape short fibers in a slurry composition of the present Invention are dispersed, namely for a coating Recipe as described below.

The fiber reinforced prepregs can be made using the slurry Composition and fibrous base are made namely z. B. after that described in JP-A-60-38 433 Method or by another known method including paper making techniques. If desired, known dispersants, binders and Coagulants are used.

Where the slurry composition of the present invention as Coating recipe is used, the slurry Composition on various objects made of metal, glass, Ceramic, etc. applied in a known manner and for a predetermined time to be heated to a temperature in the Range between the melting point of PPSS / PPSK and one Temperature is up to 150 ° C higher than that Melting point. Before coating, a primer can be applied to the Surface of the article to be coated.  

If desired, the slurry composition can include pigments, Heat stabilizers, ultraviolet stabilizers, Contain rust preventives and the like Effects of the present invention cannot be worsened.

The present invention is described in more detail below Illustrated with reference to examples, it is self-evident understands that the present invention is not limited thereby shall be. All parts, percentages and ratios refer on the weight, unless otherwise stated.

EXAMPLE 1

• a) Synthesis of PPSS with terminal chlorophenyl group:
  9.90 kg of N-methylpyrrolidone, 3.28 kg (25.0 mol) of sodium sulfide-2.7 hydrate, 10 g of sodium hydroxide and 7.18 kg (25.0 mol) of bis () were placed in a 50-liter autoclave. p-chlorophenyl) sulfone added, and the mixture was heated to 220 ° C in a nitrogen atmosphere, then stirred at this temperature for 6 h.
  A solution of 360 g (1.25 mol) of bis (p-chlorophenyl) sulfone in 1 kg of N-methylpyrrolidone was added to the mixture, and the mixture was then allowed to react for 1 hour. The reaction vessel was cooled and the contents removed, washed several times with hot water and Acteon and filtered. The filter cake was dried at 80 to 150 ° C under reduced pressure to obtain 5.89 kg (95%) of a light brown polymer. The polymer had an inherent viscosity η _inh. 0.25, determined according to the method described above.
• b) Synthesis of PPSK with terminal NaS:
  A 50 liter autoclave was charged with 14.70 kg of N-methylpyrrolidone, 4.82 kg (36.8 mol) of sodium sulfide 2,7 hydrate and 18 g (0.45 mol) of sodium hydroxide, the mixture was stirred for about Heated in a nitrogen atmosphere to 190 ° C with stirring, whereby 800 ml of water were distilled off. The reaction system was cooled to 100 ° C, 8.75 kg (35.0 mol) of 4,4'-dichlorobenzophenone and 3.50 kg of N-methylpyrrolidone were added. The mixture was then allowed to react at 240 ° C. for 3 hours. After cooling the reaction vessel and sampling part of the contents, the mixture was filtered. The filter cake was washed three times with boiling water and then twice with acetone and dried at 120 ° C., whereby a polymer was obtained as a pale gray-brown powder (yield: about 94%). The polymer had a reduced viscosity (η _red. ) Of 0.45, determined by the previously described method.
• c) Synthesis of the block copolymer (PPSS / PPSK):
  In an autoclave were 1.50 kg of PPSS with a terminal chlorophenyl group (prepared as described under (a) above), 3.80 kg of PPSK with terminal NaS (prepared as described under (b) above) and 6.00 kg of N-methylpyrrolidone filled. After cleaning with nitrogen, the autoclave was sealed, the contents were heated to 205 ° C. and left to react for 3 h at this temperature. After the autoclave had cooled, the contents were filtered. The filter cake was washed twice with N-methylpyrrolidone and then three times with boiling water. The resulting solid was dried at 120 ° C. for 5 hours in order to obtain 2.38 kg of polymer as a pale brown powder.

10 g of the polymer obtained were extracted into 100 ml 98% sulfuric acid dispersed. It was found that in Extract no PPSK was included. On the other hand, 2.38 kg Polymer twice with 10 kg portions of one made from phenol and Tetrachloroethane in a 3: 2 mixed solvent ratio  washed and extracted, and then the Solvent replaced by acetone. The second extraction no PPSS homopolymer was fractionated at all, the last extracted PPSS homopolymer fell in an amount of only 30 g at.

For comparison purposes, those were as described above manufactured PPSS and PPSK only mixed, and the Mixture was fractionated in the manner described above. PPSS and PPSK were recovered quantitatively.

These results prove that this is after that described above Extraction treatment polymer obtained a chemical The reaction product of PPSS and PPSK is, for example, a Block copolymer. PPSS / PPSK obtained in this way was Designated PPSS / PPSK (A). PPSS / PPSK (A) had MI (370 ° C, 5th kg load) of 872 g / 10 min.

The infrared absorption spectrum of PPSS / PPSK (A) shows no absorption peak other than the characteristic absorptions by PPSS and PPSK.

An infrared absorption spectrum of a mere mixture of PPSS and PPSK was prepared separately in order to determine the respective intensity of the absorption characteristics of PPSS and PPSK at 620 cm ^-1 and 920 cm ^-2, respectively. Then, a work diagram for the peak intensity ratio at 920 cm was created ^-1 [absorption intensity at 920 cm ^-1 / (absorption intensity at 920 cm ^-1 + absorption intensity at 620 cm ^-1)] above the PPSK- mixing ratio.

Using the absorption diagram, it was found that the PPSK content in PPSS / PPSK (A) is 40 mol%, derived from the peak-intensity ratio at 920 cm ^{-1 of} the IR spectrum of PPSS / PPSK (A).

PPSS / PPSK (A) was additionally determined by elemental analysis examined. As a result, a sulfur content of 21.51% detected. From the fact that the theoretical sulfur Salary as for a structural formula

- (Φ-SO₂-Φ-S) _0.6 - (Φ-CO-Φ-S) _0.4 -

is calculated to be 21.52%, the PPSK content was in the Block copolymer of 40 mol% confirmed.

The crystallization behavior of PPSS / PPSK (A) on cooling after melting in a nitrogen atmosphere, was by means of a differential scanning calorimeter "DSC 200" (manufactured at Seiko Senshi Kogyo K.K.). As a result, a Crystallization peak for the crystalline polymer segment, i.e. H. for the PPSK segment, at 280 ° C (cooling rate: 20 ° C / min) observed.

These results also confirm that the one obtained above Copolymerization reaction product is a block copolymer in which a PPSS segment and PPSK segment are chemically linked.

An amorphous sample was obtained by quenching the molten one Block copolymer made. The sample was placed in a nitrogen Atmosphere heated at a heating rate of 20 ° C / min. As a result the glass transition temperature Tg and the melting point Tm of 205 ° C or 340 ° C found.

PPSS / PPSK (A) had a dynamic viscosity coefficient [η ′] of 70 Pa · s, measured at the melting point + 20 ° C (i.e. at 360 ° C) and 10 rad / s.  

PPSS / PPSK (A) was in a twin screw extruder with a Melt-kneaded diameter of 30 mm at 320 to 380 ° C to To produce pellets. The pellets were injection molded Process at a prescribed resin temperature of 320 to 380 ° C and a mold temperature of 150 ° C supplied to To produce test pieces. MI, flexural strength and Shrinkage factor was determined according to ASTM D-1238 (370 ° C, 5 kg Load) ASTM D-790 or ASTM D-955 measured. The received Results are shown in Table 1 along with those described above shown analytical results.

COMPARATIVE EXAMPLE 1

The PPSS and PPSK homopolymers as described in Example 1 synthesized were mixed such that a PPSK Proportion of 40 mol% was obtained; the mixture was in the examined in the same way as described in Example 1. The Results obtained are shown in Table 1.

COMPARATIVE EXAMPLES 2 AND 3

Both the PPSS homopolymer and the PPSK homopolymer as described in Example 1 were synthesized in the same manner as described in Example 1. The received Results are shown in Table 1. From the results of Example 1 with regard to the Results of Comparative Examples 1 to 3 as shown in Table 1 are shown that PPSS / PPSK (A) are a higher Tg and / or higher Tm and higher Flexural strength than that of PPSS homopolymer, PPSK- Homopolymer or the mere mixture of PPSS and PPSK, which makes an improved thermal stability and an improved mechanical strength can be proven. Beyond that PPSS / PPSK (A) a reduced shrinkage factor, the higher indicates dimensional stability.  

EXAMPLE 2

A polymerization mixture of PPSK with terminal NaS was prepared in the same manner as in Example 1, except that 5.30 kg (36.8 mol) of sodium benzoate was added together with sodium sulfide. A part of the product was taken as a sample and a H _red. of 0.70.

Then PPSS with terminal chlorophenyl group (η _inh .: 0.38) was prepared in the same manner as described in Example, except that 1.65 kg (25.0 mol) of lithium acetate was added together with the monomers.

A reaction vessel was terminated with 1.50 kg of PPSS Chlorophenyl group, 14.01 kg of the polymerization mixture of PPSK with terminal NaS and 4.00 kg of N-methylpyrrolidine loaded, and after cleaning with nitrogen, the The reaction vessel is tightly closed. The mixture was 5 hours allowed to react for long at 210 ° C and then in the same Way, as in Example 1, worked up to unreacted Remove PPSS and PPSK and finally 4.13 kg one gray-brown polymer (referred to as PPSS / PPSK (B)).

The PPSK content in PPSS / PPSK (B) was 72 mol% after the Determination from the IR absorption spectrum.

Test samples were made in the same manner as in Example 1 and the physical properties in measured in the same way as in Example 1. The obtained Results are shown in Table 1.  

EXAMPLE 3

PPSS / PPSK (C) was presented in the same way as in Example 2, except that the amount of PPSK polymerization mixture was changed to 1.50 kg. The yield of PPSS / PPSK (C) was 1.73 kg. A PPSK content in PPSS / PPSK (C) of 21 mol% found by determination from the IR spectrum.

Test samples were made in the same manner as in Example 1 manufactured, and the physical properties were in the measured in the same way as in Example 1. The received Results are shown in Table 1.  

Table 1

EXAMPLE 4

PPSS / PPSK (D), which has a PPSK content of 50 mol% and an MI of 63g / 10 min was done in the same manner prepared as in Example 1, except that 3.00 kg PPSS as synthesized in Example 1 and 11.41 kg the PPSK polymerization mixture as described in Example 1 was used.

80 parts of PPSS / PPSK (D) were mixed with 20 parts of PPSS as synthesized in Example 1, and the mixture was kneaded and pelletized in the same manner as in Example 1. The pellets were subjected to an injection molding process to prepare test samples, and heat distortion temperature and bending strength were measured in accordance with ASTM D-648 (18.6 kg / cm ² load) and ASTM D-790, respectively. The measurement results are shown in Table 2 below.

EXAMPLES 5 TO 8

PPSS / PPSK (D), produced according to Example 4, PPSS and / or PPSK homopolymers, both obtained Example 1, commercially available PPS ("Ryton P-4" manufactured by Phillips Petroleum Co.) and glass fiber ("CS-03 MA 419") by Asahi Fiber Glass Co., Ltd.) according to the in Table 2 compounding ratio mixed. It test samples were made, and the physical Properties were measured in the same way as in Example 4 given. The results obtained are in Table 2 listed.

COMPARATIVE EXAMPLE 4

The PPSS and PPSK homopolymers manufactured by Example 1, and glass fiber as used in Example 6  became dry according to the compounding ratio Table 2 mixed, and the physical properties measured in the same manner as in Example 4. The Results obtained are shown in Table 2.

EXAMPLE 9

60 parts PPSS / PPSK (B) made in Example 2 and 40 Parts of the same glass fiber as used in Example 6 were mixed dry. The physical Properties were measured in the same way as in Example 4 described. The results obtained are in Table 2 shown.

EXAMPLE 10

50 parts of PPSS / PPSK (C), produced according to Example 3, 10 Parts of PPSK powder, obtained according to Example 2, 10 parts of one commercially available polyethersulfone resin ("VICTREX 200P, manufactured by ICI Japan Co., Ltd.) and 30 parts thereof Glass fiber as used in Example 6 were mixed. The physical properties were in the determined in the same way as in Example 4. The obtained Results are shown in Table 2.

EXAMPLE 11

PPSS with an inherent viscosity η _inh. of 0.18 was synthesized in the same manner as in Example 1. The resulting PPSS was reducted with a polymerization mixture, the PPSK with a reduced viscosity η _. of 0.30, copolymerized to produce a composition containing 80% PPSS / PPSK with a PPSK content of 56 mol% and 20% PPSK homopolymer. MI of the resulting composition was 240.

40 parts of the PPSS / PPSK composition prepared above were mixed with 30 parts of the glass fiber as described in Example 5 was used, and with 30 parts commercially available Calcium carbonate mixed. The physical properties were measured in the same manner as in Example 4. The Results obtained are shown in Table 2.  

Table 2

As can be seen in Table 2, the block copolymer resin Composition of the present invention, even if it is is compounded with glass fiber, a high Heat distortion temperature and improved bending strength, especially at a high temperature. So that becomes a excellent thermal stability as well as a excellent mechanical strength.

EXAMPLE 12

PPSS with terminal chlorophenyl group (η _inh .: 0.18), produced in the same manner as in Example 1, except that the reaction temperature was changed to 180 ° C., and PPSK with terminal NaS (η _red. 0.26) Prepared in the same manner as in Example 1, except that the reaction temperature was changed to 230 ° C, were copolymerized to give PPSS / PPSK with a PPSK content of 45 mol%, an MI of 430 g / 10 min, a Tg of 203 ° C and a Tm of 342 ° C.

EXAMPLE 13

PPSS with terminal chlorophenyl group (η _in.h : 0.13) synthesized in the same manner as in Example 12, except that the reaction time was changed in 3 h, and PPSK with terminal NaS (η _red .: 0.22 ), prepared in the same manner as in Example 12, except that the reaction time was changed in 1.5 hours, were copolymerized to give PPSS / PPSK with a PPSK content of 38 mol%, an MI of 740 g / 10 min, to obtain a Tg of 208 ° C and a Tm of 336 ° C.

EXAMPLE 14, COMPARATIVE EXAMPLE 5 AND REFERENCE EXAMPLES 1 AND 2

PPSS / PPSK (A) made according to Example 1 was mixed with modified PPO ("NORYL 534J-801" made by General Electric Co.) in a ratio of 1: 1, and the mixture was made at 350 ° C to produce pellets melt kneaded. Test samples were produced from the pellets by injection molding. The molding properties of the resin compound (pellets) and the appearance of the resulting molded parts were satisfactory. The impact resistance test was carried out in accordance with ASTM D-256 on a rod sample which had a cross section of 3.2 × 3.2 mm ² . The bending test was carried out according to ASTM D-790 with a tape-shaped sample that was 10 mm wide, 2 mm thick and 30 mm long. The puncture test was carried out by a penetrometer ("TMA-SS120C", manufactured by Seiko Denshi Kogyo KK). 1 mm diameter of the sample, heating rate 5 ° C / min. and 5 g load.

For comparison, a resin composition called PPS ("B- 600 "manufactured by Dai-Nippon Ink & Chemicals, Inc.) and modified PPO (NORYL 534J-801) in the above described way examined. Furthermore, too Reference purposes PPSS / PPSK (A) or PPS (B-600) also alone examined. The composition of Comparative Example 5 gave satisfactory shape properties, but it led to molded parts with non-uniform and poor appearance. The results obtained are shown in Table 3.

The inventors tried a mixture of PPSK and to mix modified PPO, but due to considerable Gel formation failed to form the mixture.

The fracture cross-section of each sample after the Izod test was viewed under a scanning electron microscope (SEM). The  Sample from Example 14 showed a uniformly dispersed one System of particles with a size of about 1 to 10 µm, while the comparative example is an uneven dispersed system of spherical particles one Particle size of about 10 to 50 microns showed.

EXAMPLES 15 AND 16

It became a resin composition in the same way as prepared in Example 14, except that the mixing ratio from PPSS / PPSK to modified PPO in 7: 3 (example 15) or 3: 7 (Example 16) was changed. The composition was by means of Izod impact test and bending test in the same way as described in Example 14, examined. The results obtained are in Table 3 shown. In any case, the shape properties were as well Satisfactory appearance of molded articles.

EXAMPLE 17 AND COMPARATIVE EXAMPLE 6

PPSS / PPSK (A), modified PPO (NORYL 534J-801) and Glass fiber (cut glass spun threads) ("CS 06 MA 404", manufactured by Asahi Fiber Glass Co., Ltd.) according to the ratio given in Table 3 mixed. The weight ratio of the total resin Components to fiber was set to 6: 4.

The resulting resin composition was in the same Way as described in Example 14, the Impact resistance test according to Izod and the bending test subjected to a heat distortion test carried out. For comparison purposes, a resin Composition made in the same manner as above, except that PPSS / PPSK was replaced by PPS (B-600), examined. The results obtained are in Table 3 shown.  

Table 3

EXAMPLES 18 TO 20 AND COMPARATIVE EXAMPLES 7 TO 9

A resin composition, the PPSS / PPSK (A) and a Additive polymer selected from polyethersulfone (PES) ("VICTREX PES-4100" manufactured by ICI Co.) in accordance with the compounding Relationship established. The composition was in the examined in the same way as described in Example 14. Pellets were made at a temperature of 350 to 360 ° C melt kneaded. In any case, the shape properties were and the appearance of the molded parts is satisfactory. The Results obtained are shown in Table 4.

For comparison, a resin composition, the PPS (B 600) and each contained one of the admixtures, in examined in the same way. As a result, everyone showed Comparative compositions satisfactory shape properties, however, they led to molded articles with poor appearance and low compatibility.

EXAMPLES 21 TO 24

A resin composition containing PPSS / PPSK (A) and PES (Victrex PES-4100) or PEI (ULTEM 1000) was tested in the same manner as described in Examples 15 and 16. In any case, the molding properties and the appearance of the molded parts were satisfactory. The results of the tests are shown in Table 4.

EXAMPLES 25 TO 30 AND COMPARATIVE EXAMPLES 10 AND 11

PPSS / PPSK (A) was made with PAr ("U Polymer U100") by Unitika Ltd.) or PC ("IUPILON S-2000") by Mitsubishi Gas Chemical Industries Ltd.) accordingly mixed the compounding ratio given in Table 5 and the resulting resin composition was in the evaluated in the same manner as in Example 14. The Shape properties and the appearance of the molded parts were in satisfactory in every case. For comparison, PPS (B-600) used instead of PPSS / PPSK. The results of the Evaluations are given in Table 5.  

Table 5

In addition, samples containing PAr were in 20% Sodium hydroxide immersed, samples containing PC were immersed in acetone, both for about 50 hrs To investigate solvent resistance. With a PPSS / PPSK to a PAr ratio of 4: 6, the flexural strength was 90 MPa. With a PPS to PAr ratio of 4: 6, the Flexural strength 46 MPa. With a PPSS / PPSK to PC ratio 1: 1 or 3: 7 the weight gain rate was 1.05% and 1.07%, respectively, and the bending strength was 70 MPa and 75 MPa, respectively. Accordingly, the weight gain rate was one PPS to PC ratio of 1: 1 or 3: 7 1.13% or 1.18% and the bending strength was 35 MPa and 25 MPa, respectively. At a PPS to PC ratio of 3: 7, the sample was at a Solvent attack brittle.

EXAMPLES 31 TO 34 AND COMPARATIVE EXAMPLES 12 AND 13

PPSS / PPSK (A) was made with nylon 66 ("UBE nylon 2026D", manufactured by Ube Industries, Ltd.) or Nylon 46 ("JSR Nylon 46 "manufactured by DMS) in that shown in Table 6 below specified compounding ratio mixed, and the resulting resin composition was in the same Manner as in Example 14 and Comparative Example 5, examined. The shape characteristics and the appearance of the Molded parts were satisfactory in every case. To the For comparison, PPS (B-600) was used instead of PPSS / PPSK. The comparative composition was satisfactory Shape properties, but the ones made from it Molded parts had a pearl-like and inferior quality Appearance. The results of the tests are in Table 6 shown.

The fracture cross section of the test sample from Example 31 and Comparative example 12 was viewed using SEM. In the Sample from Example 31 was no dispersed particles of  1 µm or larger is observed while the sample of Comparative Example 12 an unevenly dispersed system of spherical particles in the size range from 3 to 20 µm showed.

The sample from Example 33 (ratio PPSS / PPSK to nylon 66: 3: 7) was immersed in warm water at 70 ° C for 50 h. Water absorption and flexural strength were measured. The Weight gain through water absorption was 2.2% and that Flexural strength was 88 MPa. With a ratio of PPS to Nylon 66 of 3: 7, the water absorption was 3.8% and that Flexural strength was 54 MPa.

EXAMPLE 35 AND COMPARATIVE EXAMPLE 14

PPSS / PPSK (A), nylon 66 ("UBE nylon 2026D") and glass fiber were compounded according to Table 6. The resulting resin Composition was examined in the same way as described in Example 17. The ratio of the total resin Component to fiber was set to 6: 4. For comparison PPS (B-600) was used instead of PPSS / PPSK. The Results of the tests are shown in Table 6.  

Table 6

EXAMPLES 36 TO 39 AND COMPARATIVE EXAMPLES 15 AND 16

PPSS / PPSK (A) was made with PBT ("PLANAC BT-128") by Dai-Nippon Ink & Chemicals, Ind.) or PET ("Mitsui PET J-125 ", manufactured by Mitsui PET Co., Ltd.) accordingly mixed the compound ratio given in Table 7. For comparison, PPS (B-600) was used instead of PPSS / PPSK used. The resulting resin composition was shown in in the same manner as in Example 14. Those Compositions that have a ratio of PPSS / PPSK or PPS to PBT or PET of 1: 1 were also Test examined. The compositions of Examples 36 to 39 were satisfactory on their Shape characteristics and in terms of the appearance of the Molded parts. The comparative compositions were satisfactory in terms of their shape characteristics, however the molded parts contained a pearl-like and inferior appearance. The results of the investigations are shown in Table 7.

EXAMPLE 40 AND COMPARATIVE EXAMPLE 17

PPSS / PPSK (A) or, for comparison purposes, PPS (B-600) with PBT (PLANAC BT-128) and glass fiber according to the Compounding ratio of Table 7 mixed. The relationship the total resin components to glass fiber was 6: 4. The Results of the tests are shown in Table 7.  

Table 7

EXAMPLES 41 TO 45 AND COMPARATIVE EXAMPLES 18 TO 22

PPSS / PPSK (A) was made with a blend polymer selected from polyethylene (PE) ("SHOLEX F-5010" manufactured by Showa Denko KK) an ionomer ("HIMILAN 1707" manufactured by Mitsui-De Pont Polychemical Co.), a phenoxy resin ("UCAR Phenoxy PKHH" manufactured by Union Carbite Co.), a hydrogenated styrene / butadiene rubber (SBR) ("TUFTEC M193G" manufactured by Asahi Chemical Industry Co., Ltd.) and polyvinylidene fluoride (PVdF ) ("NEOFLON PVDF VP-810" manufactured by Daikin Kogyo Co., Ltd.) and glass fiber mixed according to the compounding ratio shown in Table 8. For comparison purposes, PPSS / PPSK was replaced by PPS (B-600). The resulting resin composition was examined in the same manner as described in Example 14 or 17 (puncture test was not carried out). All of the compositions of the examples had satisfactory molding properties to produce molded articles with a satisfactory appearance. The comparative resin compositions were satisfactory in terms of molding properties, but the molded articles made therefrom had a non-uniform and poor appearance. The results of the tests are given in Table 8.

EXAMPLE 46

A resin composition of 100 parts of PPSS / PPSK (A) and 2 parts of an epoxy resin ("EPICLON N-965" manufactured by Dai-Nippon Ink & Chemicals Inc.) was prepared in the same manner as in Example 14. described, examined. The sample had an Izod impact strength of 25 kg · cm / cm ² , a bending deflection of 5.2% and a bending strength of 130 MPa.

EXAMPLE 47

PPSS / PPSK (A) was processed in the melt spinning process at a temperature of 350 ° C., a spinning rate of 1200 g / hr and a winding speed of 450 m / min. The spun thread had a diameter of 28 µm and birefringence of 3 · 10 ^-3 . The filament was drawn in a heating furnace at 250 ° C (Tg + 25 ° C) with a draw ratio of 10 and then at 280 ° C and with a draw ratio of 1.1 to obtain a drawn fiber . The stretching should be done in a stable manner without causing breakage.

The tensile strength was determined in accordance with ASTM D-638. The resulting fiber had a tensile strength of 65 kg / mm ² , a Young's modulus of 12 GPa at 35 ° C and of 10 GPa at 150 ° C and a Tm (DSC peak) of 334 ° C.

COMPARATIVE EXAMPLE 23

A fiber was made in the same manner as described in Example 47, except that PPSS / PPSK was replaced with PPS ("RYTON GR-01" manufactured by Phillip Petroleum). The melt spinning process was carried out at 320 ° C and the stretching at 115 ° C (Tg of PPS + 25 ° C) and 250 ° C. The thread could be drawn up to a draw ratio of 8 at a draw temperature of 100 ° C. For a stable draw, it was necessary to keep the draw ratio at 6. The spun thread had a diameter of 28 µm and a birefringence of 4 · 10 ^-3 . The drawn fiber had a tensile strength of 50 kg / mm ² , a Young's modulus of 8.8 GPa at 35 ° C and 1.3 GPa at 150 ° C and a Tm (DSG peak) of 287 ° C.

Furthermore, an attempt to use PPSK with a dynamic failed Viscosity coefficient (η ′) of 150 Pa · s, measured at 370 ° C and 10 rad / s, a melt spinning process at a Subject to spinning temperature of 370 ° C. The attempt resulted because of the strong gel formation, even if that Deduction ratio was reduced, just for breaking.

EXAMPLE 48 AND COMPARATIVE EXAMPLE 24

Each of the spun threads used in Example 47 and in Comparative Example 23 was obtained had a young Modulus of 8.4 GPa or 6.4 GPa at 35 ° C and of 8.1 GPa or 0.86 GPa at 150 ° C.

EXAMPLE 49

The spun yarn obtained in Example 47 was drawn at 150 ° C, 210 ° C and then at 280 ° C with a draw ratio of 2.5, 6 and 1.0, respectively. The stretching could be done in a stable manner without causing breakage. The resulting fiber had a tensile strength of 70 kg / mm ² and a Young's modulus of 14 GPa at 35 ° C and of 13 GPa at 150 ° C.

EXAMPLE 50

A resin mixture containing PPSS / PPSK (A) and PPS (RYTON GR-01) in a ratio of 7: 3 was subjected to a melt spinning process in the same manner as described in Example 47. The spun yarn was drawn in the same manner as described in Example 49. The spun thread had a diameter of 30 microns and a birefringence of 4 · 10 ^-3 . The drawn fiber had a tensile strength of 62 kg / mm ² and a Young's modulus of 9.3 GPa at 35 ° C and 7.6 GPa at 150 ° C.

EXAMPLE 51

The fibers made in Examples 47 and 49 were in petrol, oil, acetone, toluene and 20% sodium hydroxide soaked for 10 days, but it kicked in nowhere corrosion. As a match to the fibers was brought, the fire went out immediately, what the shows self-extinguishing properties.

EXAMPLE 52 AND COMPARATIVE EXAMPLE 25

PPSS / PPSK (A) was melt-pressed at 350 ° C using a Hot press and cooled by a cooling press to a Obtain film with a thickness of about 150 microns. The film was then heat treated at 150 ° C for about 10 min subject. The resulting film had a Tm (DSC peak) of 332 ° C. A strip 1 cm wide and 5 cm long became cut from the film, and it became the Young module E 'at 35 ° C and measured at 150 ° C. E 'at 35 ° C was 2.9 GPa and E 'at 150 ° C was 2.0 GPa.

For comparison, a film from PPS (RYTON GR-01) was made in the manufactured in the same manner as described above, except that  the melt pressing was carried out at 320 ° C. The film was examined in the same manner as above. The Comparative film had an E ′ of 2.5 GPa at 35 ° C and 0.32 GPa at 150 ° C and a Tm (DSC peak) of 281 ° C.

It was thus proven that PPSS / PPSK is one compared to PPS has significantly improved heat resistance.

EXAMPLE 53 AND COMPARATIVE EXAMPLE 26

PPSS / PPSK (A) was placed in an extruder equipped with a T die (Diameter 40 mm) was filled, at 350 ° C melt extruded and quenched by chill rolls to make one Obtain film with a thickness of about 200 microns. The film was stretched biaxially at 150 ° C at the same time a stretch ratio of approximately 2.4 in each direction a biaxial stretching machine (manufactured by Iwamoto Seisakusho). Then the film was thermoset at 280 ° C for about 5 min without applying voltage to one to produce stretched film of a thickness of approx. 35 µm.

The resulting film was tested in a tensile test, in a tear test, in a heat-shrink test and measurements of E 'were carried out at 35 ° C and 150 ° C. The tensile test was carried out on a 5 mm wide and 3 cm long film strip at a drawing speed of 5 mm / min. 19357 00070 552 001000280000000200012000285911924600040 0002004206996 00004 19238. The tear test was carried out on a 3 cm wide and 10 cm long film strip with a 5 mm deep notch, which was formed at 90 ° C., at a tear speed of 10 mm / min. The heat-shrink test was carried out using a 10 x 10 cm square sample with a cross at its center made up of two 8 cm long intersecting lines in the same directions of biaxial stretching. The sample was held in a thermostat at 250 ° C for about 5 minutes to cause percent shrinkage. It was found that the film had a tensile strength of 16 kg / mm ² , a tensile modulus of elasticity of 410 kg / mm ³ , a tensile strength of 12 kg, a percentage shrinkage of 0.4% and an E ′ of 3, 8 GPa at 35 ° C and 3.6 GPa at 150 ° C.

For comparison purposes, a film was made from PPS (RYTON GR-01) in the same manner as described above, except that the temperatures of the melt pressing, stretching and thermosetting were changed to 320 ° C, 110 ° C and 250 ° C, respectively, and in examined in the same way as above. The film had a tensile strength of 14 kg / mm ² , a tensile modulus of 370 kg / mm ² , a tensile strength of 4 kg, a percentage shrinkage of 10% and E 'of 3.3 GPa at 35 ° C and of 0.63 GPa at 150 ° C.

It can be seen that the film made of PPSS / PPSK is extraordinary improved properties in terms of tearability, Resistance to heat shrinkage and heat resistance.

Each of the films made above had one Degree of crystallization of not more than 10%, determined by means of X-ray diffractometer and there was no diffraction peak observed.

EXAMPLE 54

The unstretched film obtained in Example 52 was uniaxially stretched with a stretch ratio of about 5 and the same type as described in Example 53, thermoset. A uniaxially stretched film with a thickness of approximately 40 μm was obtained. Samples were cut from the film along the stretch direction. The film had a tensile strength of 18 kg / mm ² , a tensile modulus of 450 kg / mm ² , a tensile strength of 14 kg and an E 'of 4.2 GPa at 35 ° C and 4.1 GPa at 150 ° C.

EXAMPLE 55

PPSS / PPSK (A) and PSS (Lyton GR-01) were mixed at a compounding ratio of 7: 3 and the resulting gompound was pressed under pressure into metal tools (film thickness before stretching: 300 µm) and biaxially at one Stretch ratio of 1.6 in the same manner as described in Example 53, stretched to obtain an 80 µm thick stretched film. The resulting stretched film had a tensile strength of 16 kg / mm ² , a tensile modulus of elasticity of 0.8% and an E ′ of 3.5 GPa at 35 ° C and of 3. GPa at 150 ° C.

The film had a degree of crystallization of no more than 10%, determined-by means of an X-ray diffractometer, and it was no clear diffraction peak was observed.

EXAMPLE 56

Each of the films obtained in Examples 52 and 53 was made each in petrol, oil, acetone, toluene and 20% Sodium hydroxide soaked for 10 days, but it occurred no corrosion at all. If a match to the When fibers were brought out, the fire went out immediately, which the proves self-extinguishing properties.

EXAMPLE 57

• a) Synthesis of PPSS with terminal chlorophenyl group: 1980 g of N-methylpyrrolidone, 388 g were placed in a 101 autoclave Sodium hydrogen sulfate 1,2 hydrate (NaSH), 200 g Sodium hydroxide and 1436 g bis (p-chlorophenyl) sulfone filled. The mixture was at 200 ° C for 6 h in one Leave the nitrogen atmosphere to the reaction.  
• A solution of 72 g of bis (p- chlorphenyl) sulfone in 200 g of N-methylpyrrolidone and the mixture was kept at 200 ° C. for a further hour Leave reaction. So a porridge made from PPSS terminal chlorophenyl group.
• b) Synthesis of PPSK with terminal NaS:
  A 10 liter autoclave was charged with 1980 g of N-methylpyrrolidone, 388 g of sodium hydrogen sulfide-1,2-hydrate, 200 g of sodium hydroxide and 1436 g of 4,4'-dichlorobenzophenone, the mixture was stirred at 230 ° C. for 6 hours in one Nitrogen atmosphere reacted. 72 g of 4,4′-dichlorobenzophenone and 200 g of N-methylpyrrolidone were also added to the reaction system. The mixture was then left to react at 210 ° C. for 1 h, in order then to obtain a slurry of PPSK with terminal NaS:
• c) Synthesis of PPSS / PPSK (E):
  The slurry of PPSS with terminal chlorophenyl group obtained according to (a) and the slurry of PPSK obtained according to (b) with terminal NaS were introduced into an autoclave and the mixture was left to react at a temperature of 230 ° C. for 3 h. The reaction product was purified in a known manner, whereby a block copolymer (referred to as PPSS / PPSK (E)) with a PPSK content of 50 mol% was obtained. PPSS / PPSK (E) had a 7 m (DSC peak) of 340 ° C, a Tg of 205 ° C, a dynamic viscosity coefficient (η ′) of 100 Pa · s, measured at 360 ° C and 10 rad / s.

PPSS / PPSK (E) was classified using a 30 mesh screen and a 200 mesh screen.  

EXAMPLE 58

20 g of PPSS / PPSK was placed in a synthetic resin jar (E), prepared in Example 57, 100 g propylene glycol and 150 g of glass beads, then the mixture was mixed using a Paint shaker dispersed for about 2 hours to make a pulp to manufacture. This slurry was each made on a tintype Plate and an aluminum plate applied, at 100 ° C for Dried for 30 min and oven dried at 420 ° C for 1 h Films of a thickness of 50 µm, 100 µm and 300 µm in thickness form. Each of the films was smooth and smooth and showed no limpness (cissing).

On the 50 km thick film on the tintype plate were Lines are drawn to draw 1mm x 1mm squares and the plate is then subjected to the cellophane tape lifting test subject. As a result, it was found that none Square was lifted off. In all the following examples and Comparative examples were the lifting test with a 50 microns thick film performed.

COMPARATIVE EXAMPLE 27

An applied and oven dried film was placed in the prepared in the same way as described in Example 58, except that PPS ("B-100" manufactured by Dai-Nippon Ink & Chemicals, Ind.) Was used instead of PPSS / PPSK and that the oven drying was carried out at 360 ° C. A 50 µm thick film was relatively even and smooth while that Porridge coating to form a 100 µm thick film had a lobbed appearance and failed to get an even one To form coating film. Withdrawal test, about 40% subtracted from the squares.

The PPS used (B-100) had a DSG 7 m of 285 ° C and a dynamic viscosity coefficient [η ′] of 20 Pa · s  at 305 ° C and 10 rad / s. According to PPSS / PPSK PPS also classified using a 20 mesh screen and a 200 mesh sieve.

COMPARATIVE EXAMPLE 28

Coated and oven dried films were made in the same Way as in Comparative Example 27, except that PPS made with 2% of a phenolic resin ("PLYOPHEN J-325" by Dai-Nipppon Inks% Chemicals, Ind .; Solids content: 60%) was compounded. The films were only shown on the Tintype plate formed. It was not observed that the Coatings were lobed, but the resulting films had a rough surface and thread holes in places. About 50% of the squares were removed in the lift-off test.

EXAMPLE 59

In a bottle made of synthetic resin, 20 g of PPSS / PPSK (E), 60 g water, 1 g non-ionic surfactant Medium ("TRITON X-100", manufactured by Rohm & Haas C.), 30 g propylene glycol and 150 g glass balls filled, the mixture was dispersed for 2 h using a paint shaker to make a porridge. The resulting porridge was on applied a Ferrotpyie plate and under the same Conditions as oven-dried as described in Example 58 to form films of 50 µm and 30 µm thickness. Every film was even and smooth. No square was found in the withdrawal test deducted.

COMPARATIVE EXAMPLE 29

There were applied and oven-dried films in the prepared in the same manner as in Example 59, except that PPS (B-100) was used instead of PPSS / PPSK. The pulp showed a lumpiness when coating and none of the  resulting films were coated evenly. At the Withdrawal test about 50% of the squares were subtracted.

EXAMPLE 60

In a bottle made of synthetic resin, 10 g of PPSS / PPSK (E), 10 g PPS (B-100), 60 g water, 1 g TRITON X-100, 30 g Propylene glycol and 150 g glass balls filled. The mixture was dispersed by means of a paint shaker for 2 h to make a To get porridge. This porridge was made on a tintype Plate applied, and oven dried, among the same conditions as described in Example 58, so Produce films of 50 µm, 100 µm and 300 µm in thickness. Everyone Film was smooth and smooth. None was in the withdrawal test Subtracted square.

EXAMPLE 61

Applied and oven dried films were made in the same Way as made in Example 58 except that a compound 15 g PPSS / PPSK (E) and 5 g poly (2,6- dimethyl-1,4-phenylene) ether as PPO (classified with 30 mesh and 200 mesh sieves) and that the slurry only on one Tintype plate for a dry thickness of 50 µm or 300 µm was applied. The porridge showed good affinity Resins, and the resulting film had a uniform and smooth surface and good looks. Withdrawal test no square was subtracted.

COMPARATIVE EXAMPLE 30

Applied and oven dried films were made according to the example 61 except PPS instead of PPSS / PPSK has been used. The resulting films were not evenly and due to the bad affinity between inferior to the resins. In the withdrawal test, approximately 60% of the  Subtracted squares.

EXAMPLE 62

Applied and oven dried films were made in the same manner as in Example 58, except that a compound was used, the 18 g PPSS / PPSK (E) and 2 g PE (SHOLEX F-5010) contained and that by means of 30 mesh and 100 mesh-seven was classified, and that the porridge only on one Tintype plate for a dry thickness of 50 µm or 300 µm was applied. The porridge showed good affinity for resins and the resulting film was smooth and smooth Surface and good looks. The withdrawal test was almost not subtracted any of the squares.

EXAMPLE 63

The 300 μm film obtained in Example 58 was in each case Soaked petrol, oil, acetone and toluene for 10 days, however no corrosion was found at all.

EXAMPLE 64 AND COMPARATIVE EXAMPLE 31

A slurry composition of 500 g PPSS / PPSK (E), 750 g water, 150 g propylene glycol and 3 g TRITON X-100 was divided into 8 parts. Each of the porridge portions and a substantially equal proportion by weight of glass beads were placed in a bottle made of synthetic resin, the contents were moved by means of a paint shaker for about 1 hour. The resulting slurry was impregnated into a glass fiber mat ("SWIRL MAT", manufactured by Asahi Fiber Glass Go., Ltd .; basis weight: 450 g / m ² ) with a resin to glass fiber ratio of 3: 2 and dried in an oven, to get prepregs. Some prepregs were pressed under pressure at 360 ° C and 5 kg / cm ² to obtain a laminate.

For comparison, a laminate was made in the same way except that PPS was used instead of PPSS / PPSK.

Each sample was tested for flexural strength and interlaminar shear strength in accordance with JIS K7055 and JIS K7057, respectively. The sample of Example 64 had a flexural strength of 26 kg / mm ² and an interlaminar shear strength of 2.6 kg / mm ² . The comparative laminate had a bending strength of 17 kg / mm ² and an interlaminar shear strength of 1.6 kg / mm ² .

The fracture cross section of each sample was taken under the SEM examined. It was found that the sample from Example 64 satisfactory adhesion between the resin and the Had fiber while the sample of Comparative Example 31 showed a detachment of the fiber from the resin.

EXAMPLES 65 TO 68

A prepreg was produced in the same way as in Example 64, except that PPSS / PPSK (E) through a resin The composition was replaced, the PPSS / PPSK (E) and a Additive polymer from the group PPS (DIC · PS B-600), PEEK (VITREX PEEK 4506), PES (VITREX PES-4100) and PPO (NORYL 534 J-801) in a compounding listed in Table 9 Ratio contained. The resulting prepreg was in examined in the same manner as described in Example 64 and additionally determines the heat deformation temperature. The Results obtained are shown in Table 9. All Resins used were 30 mesh and 200 mesh mesh-seven have been classified.  

Table 9

Since the block copolymer according to the present invention has chemically bonded PPSS segments and PPSK segments and thus from a mere mixture of PPSS and PPSK differs, it has a crystalline polymer structure and a high melting point. This gives it a excellent thermal stability.

The resin composition comprising such a block copolymer contains, is characterized by thermal resistance and Compatibility with and admixed with significant improvements in mechanical Characteristics such as B. Impact resistance and chemical Resistance. Surprisingly, the composition has one low shrinkage factor and provides a very molded parts  high dimensional accuracy. Based on these The composition is suitable for advantageous characteristics as a molding material in various shapes and Manufacturing areas, e.g. B. in injection molding or Compression molding to electrical and electronic parts produce, for example, connecting means, plates for printed circuits and seals; Auto parts, e.g. B. Light reflectors and electrical parts; Components for the Interior construction of buildings, aircraft and automobiles; Sporting goods, e.g. B. tennis rackets, skis, golf club shafts and fishing rods; acoustic materials, e.g. B. Attachments for Speakers, back panels for stringed instruments; such as Precision parts, e.g. B. parts of office automation systems, Cameras and clocks; as well as when extruding into one closed tool or deep drawing to Manufacture composite panels and lines.

The PPSS / PPSK fiber according to the present invention shows excellent chemical properties Resistance, dimensional stability and flame retardant Effect as well as with regard to mechanical characteristics, especially with regard to the modulus of elasticity and Tensile strength at high temperatures.

In view of these excellent characteristics, the Fiber, for example, can be used for briefcases, nets, non-woven cloth, clothing, parts for interior fittings of aircraft and as reinforcing fiber for concrete.

The PPSS / PPSK film according to the present invention draws toughness, heat shrink resistance and heat resistance as well as chemical resistance and flame retardant effect. The improvements will be in particular clearly in the elastic modulus, the toughness and resistance to heat shrinkage at temperatures around 150 ° C. Accordingly, there are a variety of for the film  Applications, e.g. B. as magnetic tapes, photographi cal films, condenser films, plates for printed scarf cables, electrical and electronic films, insulating Films, protective films for industrial use, printers films, speaker bags, decorative films in buildings, Automobiles and airplanes, stamp foils, trays, containers and separation membranes.

The slurry composition that the block copolymer of the present containing invention is excellent in terms of Heat resistance, corrosion resistance, chemical resistance, di dimensional stability, flame retardant effect, resistance to Wear, adhesion and compatibility with admixtures and is suitable for paints, coatings, binders, Adhesives and impregnation slurries for prepregs. For example shows the porridge composition as a coating recipe in Compared to conventional PPS coating materials improves adhesion and compatibility with admixing resins on and provides a thick coating in a single coating process Layer with a smooth surface. The porridge composition for Impregnation shows improved adhesion to the fibrous Basis and thus delivers satisfactory prepregs. Dement speaking, the porridge composition is suitable for use in areas that have heat resistance, flame retardant effect, di dimensional stability, chemical resistance and the like other. It is e.g. B. as a coating formulation to form Corrosion-resistant or protective surface films for different parts of the petrochemical industry or other chemical industries, such as pipes on oil fields, valves, stirring blades, joints and pump wheels; as a binder for pipe linings or fire-resistant Blocks; and as a prepreg for press molding, electrical and electronic parts, parts for aircraft or automobiles, Manufacture building materials and sporting goods.  

While the invention is in detail above and with reference to FIG special exemplary embodiments have been described noted that various within the invention Changes and modifications can be made without the essence and scope of the invention to be left.

Claims (28)

1. Block copolymer which is a polyphenylene sulfide sulfone Segment and a polyphenylene sulfide ketone segment and a flowability of 1 to 900 g / 10 min, measured at 370 ° C under a load of 5 kg. 2. Resin composition, which is essentially one Block copolymer comprising a polyphenylene sulfide sulfone segment and has a polyphenylene sulfide ketone segment and one Flow from 1 to 900 g / 10 min, measured at 370 ° C under a load of 5 kg, and at least one contains miscible resin. 3. A resin composition according to claim 2, in which the Miscible resin is selected from the group consisting of Polyphenylene sulfide sulfones, polyphenylene sulfide ketones, Polyphenylene sulfides, polyamides, thermoplastic polyesters, Polysulfones, polyphenylene oxides, polyether ether ketones, Polyetherimides, polyether ketones, polyacrylates, the whole aromatic polyesters, polycarbonates, phenoxy resins, α-olefin copolymers, styrene copolymers, hydrogenation products from Copolymers of conjugated dienes, ABS resins, fluorine-containing Resins, epoxy resins, phenolic resins and furan resins. 4. A resin composition according to claim 2, in which the miscible Resin is selected from the group consisting of Polyphenylene sulfides, polyphenylene sulfide sulfones and  Polyphenylene sulfide ketones. 5. Resin composition according to claim 2, in which the miscible resin a mixture of at least one resin, selected from the group consisting of polyphenylene sulfides, Polyphenylene sulfide sulfones and polyphenylene sulfide ketones, and other miscible resin. 6. Resin composition, which is a block copolymer, the one Polyphenylene sulfide sulfone segment and a Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg, and contains a filler. 7. A resin composition according to claim 2, in which a filler is also included. 8. A resin composition according to claim 3, in which a filler is also included. 9. A resin composition according to claim 4, in which a filler is also included. 10. A resin composition according to claim 5, in which a filler is also included. 11. Fiber made by melt spinning a Block copolymer comprising a polyphenylene sulfide sulfone segment and has a polyphenylene sulfide ketone segment and one Flow from 1 to 900 g / 10 min, measured at 370 ° C under a load of 5 kg. 12. Fiber made by melt spinning a resin Composition which is essentially a block copolymer which is a Polyphenylene sulfide sulfone segment and a  Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg, and at least one miscible resin contains. 13. Fiber made by melt spinning a resin Composition which is essentially a block copolymer which is a Polyphenylene sulfide sulfone segment and a Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg, has at least one miscible resin, selected from the group consisting of polyphenylene sulfides, Polyphenylene sulfide sulfones and polyphenylene sulfide ketones, contains. 14. Film made by melt molding a Block copolymer comprising a polyphenylene sulfide sulfone segment and a Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg. 15. Film made by melt molding a resin Composition which is essentially a block copolymer which is a Polyphenylene sulfide sulfone segment and a Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg, and at least one miscible resin contains. 16. Film made by melt molding a resin Composition which is essentially a block copolymer which is a Polyphenylene sulfide sulfone segment and a Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg, and at least one miscible resin  selected from the group consisting of polyphenylene sulfides, Polyphenylene sulfide sulfones and polyphenylene sulfide ketones contains. 17. The film of claim 14, wherein the film is a stretched one Film is. 18. The film of claim 15, wherein the film is a stretched one Film is. 19. The film of claim 16, wherein the film is a stretched one Film is. 20. Resin paste composition made by Disperse a block copolymer containing a Polyphenylene sulfide sulfone segment and a Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg, in a dispersion medium. 21. Porridge composition made by Disperse a resin composition that is essentially a Block copolymer comprising a polyphenylene sulfide sulfone segment and a Has polyphenylene sulfide ketone segment and flowability from 1 to 900 g / 10 min, measured at 370 ° C under one Load of 5 kg, and at least one miscible resin contains, in a dispersing medium. 22. Resin paste composition made by Essentially dispersing a resin composition a block copolymer comprising a polyphenylene sulfide sulfone segment and has a polyphenylene sulfide ketone segment and one Flow from 1 to 900 g / 10 min, measured at 370 ° C under a load of 5 kg, and at least one miscible resin selected from the group consisting of  Polyphenylene sulfides, polyphenylene sulfide sulfones and Contains polyphenylene sulfide ketones in a dispersing medium. 23. Resin slurry composition according to claim 20 for formation a coating layer. 24. Resin slurry composition according to claim 21 for formation a coating layer. 25. Resin slurry composition according to claim 22 for formation an overcoat layer. 26. A resinous slurry composition according to claim 20 for formation a prepreg. 27. A resinous slurry composition according to claim 21 for formation a prepreg. 28. A resinous slurry composition according to claim 22 for formation a prepreg.