JPH04279663A - Polyarylene sulfide-based resin slurry composition - Google Patents

Abstract

PURPOSE:To obtain a polyarylene sulfide-based resin slurry composition suitable for coating such as coating material or lining material and molding prepreg, having excellent heat resistance, chemical resistance and corrosion resistance and improved adhesiveness and blend compatibility. CONSTITUTION:One or more block copolymers selected from a block copolymer comprising a polyphenylene sulfide part and a polyphenylene sulfide sulfone part, a block copolymer comprising polyphenylene sulfide part, a polyphenylene sulfide ketone part, and a block copolymer comprising a polyphenylene sulfide sulfone part and a polyphenylene sulfide ketone part, and optionally another resin, are dispersed into a dispersion medium (e.g. water, ethanol or propylene glycol). The prepared slurry composition is processed into a coating compound and the slurry composition is impregnated into a fiber base to give molding prepreg.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is based on a polyarylene sulfide resin that has excellent chemical resistance, electrical insulation, dimensional stability, flame retardancy, etc., and has excellent adhesive properties, blend compatibility, and heat resistance. The present invention relates to an improved slurry composition. The slurry composition can be used as a coating composition such as a coating material or a lining material such as rust-proofing and anti-corrosion material for metal surfaces, and can also be used as a molding composition obtained by impregnating a fiber base material with the slurry composition. Prepreg is used in various fields, including as a molding material for electrical and electronic parts, automobile parts, sports equipment, etc.

0002

[Prior Art] Paints and prepregs are based on polyphenylene sulfide (hereinafter referred to as PPS), which is an engineering plastic with excellent heat resistance, chemical resistance, hydrothermal properties, electrical insulation, dimensional stability, etc. It is already well known and is attracting attention as a coating material for special purposes that requires heat resistance, chemical resistance, etc., and as a material for press molding.

However, since this resin has poor adhesive properties, when used as a paint, there are problems such as poor adhesion to the coating substrate and the inability to apply thick coatings, and when used as a prepreg for molding, it is difficult to bond to the fiber base material. Each has its own problems, such as poor adhesion. Furthermore, when used in combination with other polymers, the blend compatibility is poor, resulting in problems such as poor appearance and deterioration of strength. As a method to improve such drawbacks, for paints, USP 3,894,983
Attempts have been made to add fine powders of bentonite, kaolinite, zeolite, clay, etc., and phenolic resins have been attempted in JP-A-60-206873, etc., but satisfactory results have not yet been obtained. In addition, JP-A-57
Publication No. 90044 discloses a paint made of a mixture of PPS and polysulfone, but the appearance of the resulting paint film was not satisfactory. In addition, in prepreg, we use coupling agents such as silane, chromium, and titanate, which are conventionally used in thermosetting resins, and adhesive resins such as polyurethane and epoxy resins as processing agents. I am using it, but I am not getting enough results.

[0004]Although PPS has a melting point of 285°C, which is extremely high heat resistance for a plastic material, it may be insufficient depending on the purpose of use, or its glass transition temperature (Tg) is 80 to 90°C. There is also the problem that the elastic modulus decreases rapidly in the relatively low temperature range of .degree. C. and exceeds Tg.

[0005]

[Problems to be Solved by the Invention] The present inventors have developed a material that has properties equivalent to the excellent properties of PPS such as dimensional stability, chemical resistance, flame retardancy, etc., and has heat resistance, adhesiveness, A slurry composition that has excellent blend compatibility, and can be expected to have effects such as, for example, when used as a paint, it can be applied thickly, and when used as a prepreg for molding, it has excellent adhesion to fiber base materials. We conducted a study to obtain the following.

[0006]

[Means for Solving the Problems] The present invention provides (A) a block copolymer (hereinafter abbreviated as PPS/PPSS) consisting of a polyphenylene sulfide moiety (PPS) and a polyphenylene sulfide sulfone moiety (hereinafter abbreviated as PPSS).
, a block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide ketone (hereinafter abbreviated as PPSK) moiety (hereinafter abbreviated as PPS/PPSK), and a block copolymer consisting of a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety (hereinafter abbreviated as PPS/PPSK). A polyarylene sulfide system consisting of a resin base consisting of one type of block copolymer selected from PPSS/PPSK), optionally containing (B) one or more other resins, and (C) a dispersion medium. A resin slurry composition, further a slurry composition using the slurry composition,
Alternatively, the present invention relates to a molding prepreg obtained by impregnating a fiber base material with the slurry composition.

[0007] PPS/PPSS is mainly (-φ-
It is a block copolymer consisting of a part whose repeating unit is S-) (PPS part) and a part whose repeating unit is (-φ-SO2 -φ-S-) (PPSS part), and PPS/PPSK is , mainly (-φ-S-)
The repeating unit is mainly (-φ-CO-
The part where φ-S-) is the repeating unit (PPSK part)
It is a block copolymer consisting of PPSS/PPSK
is mainly composed of (-φ-SO2 -φ-S-) as a repeating unit and (-φ-CO-φ-S-
) is a block copolymer consisting of repeating units. (However, -φ- is a p-phenylene group, and the same will be expressed hereinafter.)

[0008] PPS/PPSS is Japanese Patent Application Laid-Open No. 1150/1986.
No. 30, JP-A No. 63-278935, and various other manufacturing methods. For example, a terminal chlorphenylene group type PPSS obtained by reacting sodium sulfide and bis(p-chlorophenyl)sulfone in N-methylpyrrolidone (NMP),
Examples include a method of producing a block copolymer by heating in NMP terminal sodium sulfide group type PPS obtained by reacting sodium sulfide and p-dichlorobenzene in NMP.

[0009] PPS/PPSK is disclosed in Japanese Patent Application Laid-Open No. 2-13342.
It can be obtained by the manufacturing method shown in Publication No. 8 and various other manufacturing methods. For example, sodium sulfide and dichlorobenzophenone are combined with N-methylpyrrolidone (NM
P) terminal chlorphenylene group type PP obtained by reaction in
SK, sodium sulfide and p-dichlorobenzene in N
Examples include a method in which a block copolymer is produced by heating a terminal sodium sulfide group type PPS obtained by reacting in MP in NMP.

[0010] PPSS/PPSK is, for example, a terminal chlorphenylene group type PPSS obtained by reacting sodium sulfide and bis(p-chlorophenyl) sulfone in N-methylpyrrolidone (NMP), and sodium sulfide and bis(p-chlorophenyl)sulfone. Examples include a method of producing a block copolymer by heating terminal sodium sulfide group type PPSK obtained by reacting dichlorobenzophenone with NMP in NMP.

[0011] The block copolymer may contain homopolymers of PPS, homopolymers of PPSS, homopolymers of PPSK, PPS, PPSS, PPS
A random copolymer made of K or the like may be included as long as it does not impair the effects of the present invention. Also,
The block copolymer contains 30 mol% or less of a polyarylene sulfide moiety whose repeating unit is represented by the general formula (-Ar-S-) as a component other than that which may be included from the manufacturing perspective.
It may be contained as long as it is preferably 10 mol% or less. The polyarylene sulfide moiety has an arylene group (-Ar-) of 2 such as m-phenylene, o-phenylene, 2,6-naphthalene, 4,4'-biphenylene, etc.
aromatic residue, or (- φ − O− φ −)
, (−φ − CO −φ − ) , (−
φ − CH2 − φ −) , ( − φ − S
O2 − φ −) , (− φ − C(CH3)2
- φ -) etc., and each aromatic ring also contains F.
, Cl, Br, CH3, and other substituents are included.

In the present invention, the block copolymer used is in powder form. The particle size is 1 or more than 80% of the total weight.
A material within the range of 0 to 400 mesh, preferably 20 to 300 mesh is used. If the particle size is larger than 10 mesh, the dispersibility will decrease, and if the particle size is smaller than 400 mesh, air bubbles will easily enter the coating film and the adhesion between the resin and the fibers will decrease, which is not preferable.

The melt viscosity of the above block copolymer is the melting point plus 20°C, or if it is amorphous, the glass transition temperature plus 100°C, and the dynamic viscosity [η'] at 10 rad/sec. , 5 to 5×104 poise. When used for paint, 5 to 104 poise, preferably 1
When using 0 to 5000 poise for prepreg, 50 to 105 poise, preferably 100 poise.
~5×104 poise is used.

[0014] The proportion of each repeating unit in the block copolymer cannot be unconditionally defined because it varies depending on the purpose of use, etc., but the proportion of each repeating unit is 20 to 80 mol%.
, preferably 30 to 70 mol%. Other than this, favorable characteristics as a block copolymer are not exhibited.

In the present invention, the block copolymer may be used alone, but it may also be used when other resins are mixed with the block copolymer for the purpose of imparting excellent properties that other resins have. , suitable paints and prepregs with good compatibility can be obtained. As other resins that can be used, any of the various resins described in known literature regarding polyarylene sulfide resins can be used, but polyarylene sulfide resins such as PPS, PPSS, and PPSK are preferably used. Homopolymers or copolymers of monomers such as ethylene, propylene, butylene, and pentene, and various copolymers of these monomers with butadiene, isoprene, styrene, (meth)acrylic esters, (meth)acrylonitrile, etc. α-polyolefin copolymer which is a polymer;
Nylon 6, Nylon 66, Nylon 46, Nylon 1
Thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate; polycarbonates based on bisphenols obtained by reaction with diphenyl carbonate or phosgene; bisphenols such as bisphenol A Polyarylate preferably synthesized from a derivative and a dibasic acid such as isophthalic acid, terephthalic acid or a derivative thereof; (-φ-SO2-),
(-φ-O-φ-SO2-), (-φ-C(CH3)2
Polysulfone, polyethersulfone, polyarylsulfone having repeating units such as -φ-O-φ-SO2-); (-φ-CO-φ-O-), (-φ-O-φ-C
Polyetherketone, polyetheretherketone having repeating units such as O-φ-O-); polyphenylene which is a polymer of 2,6-disubstituted phenol or a polymer of 2,6-substituted phenol and polyhydric phenol Oxide; polyetherimide; polyamideimide; polyimide; phenoxy resin; epoxy resin; phenolic resin;
It is a furan resin. These may be modified with acid or the like.

[0016] The mixing ratio of these resins and the block copolymer cannot be unconditionally defined because it varies depending on the type of resin used and the purpose of use, but the ratio to 100 parts by weight of the block copolymer is as follows: 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight
parts by weight, when using an α-polyolefin copolymer or phenoxy resin, 1 to 100 parts by weight, preferably 2 to 8 parts by weight.
0 parts by weight, otherwise 5 to 200 parts by weight, preferably 8 to 150 parts by weight. Furthermore, by adding a block copolymer to a polyarylene sulfide resin such as PPS, it is also possible to improve adhesion, blend compatibility, etc., which are disadvantageous. In this case, the block copolymer is added in an amount of 1 part by weight or more, preferably 2 parts by weight or more, based on 100 parts by weight of the polyarylene sulfide resin. There are no particular restrictions on the upper limit of usage. In addition, when the resin to be blended dissolves in the slurry dispersion medium, it may be in the form of pellets, for example, as long as it is soluble, and there is no particular restriction on the shape; In the case of difficult resins, it is necessary to make them into powder form. In this case, the particle size is such that 80% or more of the total weight is 10% for the same reason as for block copolymers.
~400 mesh, preferably 20-300 mesh.

The dispersion medium used in the slurry composition of the present invention includes water; ethanol, propanol, i-propanol, ethylene glycol, diethylene glycol,
Alcohols such as propylene glycol and glycerin; hexane, pentane, benzene, toluene, petroleum
Hydrocarbons such as esters; esters such as methyl acetate, ethyl acetate, and benzoate; ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone; and mixtures thereof can be used. Preferably, water and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin. Furthermore, when mixing with other resins, it is possible to mix and use solvents in which the resins used are dissolved within a range that does not reduce the dispersibility of the block copolymer powder.

[0018] The slurry composition also contains, if necessary,
It is possible to add inorganic fillers such as alumina, silica, zirconia, glass beads, titania, ferrite, mica, magnesia, zinc oxide, and graphite, and oil lubricants such as fluororesins and molybdenum compounds. In order to improve the dispersibility and stability of the slurry, for example, carboxylates, higher alcohol sulfate ester salts, amide bond sulfate ester salts, ester bond ester salts, amide bond sulfonates, alkylaryl sulfonates, Anionic surfactants such as ester-bonded sulfonates or phosphate ester salts, quaternary ammonium salts, ether-bound quaternary
Cationic surfactants such as ammonium salts, ester-bonded quaternary ammonium salts, amide-bonded quaternary ammonium salts, amine salts, ester-bonded amine salts, ether-bonded amine salts, amide-bonded amine salts, or pyridinium salts, ether type, ester type , surfactants such as condensation type with amine, condensation type with amide, or nonionic surfactants such as polyethyleneimine type; polyhydroxybenzene;
A crosslinking accelerator such as para-aminophenol, ammonium persulfate, aluminum phosphate, and mercaptoalkylbenzene derivatives can be included and used.

When the slurry composition of the present invention is used for prepreg, examples of the fiber base material include glass fiber, carbon fiber, silane glass fiber, silica fiber, aramid fiber, boron fiber, alumina fiber, ceramic fiber, asbestos fiber, and metal. Examples include short fibers such as fibers, whiskers, long fibers, and woven fabrics, and these can be used in combination. Generally, glass fibers and carbon fibers are preferably used, but in addition to these, aramid fibers, boron fibers, etc. are used for special purposes such as sports equipment. The blending ratio of the fiber base material cannot be unconditionally defined as it varies depending on the purpose of use, type of fiber, shape of the fiber, etc., but usually,
20 to 400 parts by weight per 100 parts by weight of the resin component,
Preferably it is 30 to 300 parts by weight. In this range, the penetration into the fiber base material is good and a preferable reinforcing effect can be obtained. Incidentally, these fiber base materials can also be used by being dispersed in a slurry used for paint, and in this case, short fibers are usually used.

Prepreg can be produced from a slurry composition and a fiber base material by a known method such as the method described in JP-A-60-38433 or the papermaking method. At this time, it is possible to use a known dispersant, binder, flocculant, etc., if necessary.

On the other hand, when used as a coating material, the slurry composition is applied to various materials to be coated such as metals, glass, ceramics, etc. according to the usual guidelines, and heated for a predetermined period of time from the melting point of the block copolymer to 150° C. above the melting point. Use as a coating film. In addition,
Prior to painting, it is also possible to prime the surface to be painted with a suitable primer.

[0022] Furthermore, within the scope of the purpose of the present invention,
Pigments, heat stabilizers, UV stabilizers, rust preventives, etc. can also be used.

[0023]

[Examples] Examples will be shown below, but the present invention is not limited thereto.

[Reference Example 1] (Synthesis example of PPS/PPSS) N-methylpyrrolidone (
NMP) 1980g, sodium hydrosulfide hemihydrate (
NaSH) 388g, sodium hydroxide (NaOH)
200g, bis(p-chlorophenyl)sulfone 14
36 g was charged and reacted at 200° C. for 6 hours under a nitrogen atmosphere. Furthermore, bis(p-chlorophenyl)sulfone 7
2 g and 200 g of NMP were added and reacted at 200° C. for 1 hour to obtain a slurry of a PPSS reactant having a terminal chloro group.

Next, add NMP 3 to a 10L autoclave.
100g, NaSH 597.5g, and NaOH3
After charging 08g of p-dichlorobenzene to the dehydrated system at 220°C, the autoclave was heated and dehydrated while water was flowing out.
29g and 700g of NMP were press-fitted, and then 26g of NMP was added.
The reaction was carried out at a temperature of 0° C. for 2 hours to obtain a PPS reactant slurry having terminal sodium sulfide groups.

[0026] The above PPSS reactant slurry and PPS reactant slurry were charged into an autoclave, reacted at 220°C for 3 hours, and purified by a known method until the PPSS portion was 50%
Parts by weight of a block copolymer (PPS/PPSS) were obtained. PPS/PPS determined by scanning differential calorimeter (DSC)
The melting point of S is 270°C, 290°C, 10 rad/s
The dynamic viscosity at EC was 800 poise. Also, PP
S/PPSS was sized with 30 mesh and 200 mesh.

[Example 1] 20 g of PPS/PPSS,
100g propylene glycol and 150 glass beads
Put g in a plastic bottle and add about 2 g with paint conditioner.
A slurry was obtained by dispersion mixing for hours. The resulting thriller
was coated on a photographic ferro plate and an aluminum plate, dried at 100°C for 30 minutes, and then baked at 360°C for about 1 hour to obtain a thickness of 50 μm and 100 μm.
, a coating film of 300 μm was obtained. All films were uniform and smooth coatings without any repelling phenomenon. Ferro board 50
Scratches were made in a checkerboard pattern at 1 mm intervals on the μm coating film, and a cellophane tape peeling test was performed. It did not peel off at all. In addition, all peeling tests in the following examples and comparative examples were performed using 50μ
A coating film of m was used.

[Comparative Example 1] In the case of using PPS, a paint was formed by the same method as in Example 1 to form a coating film. The coating film with a thickness of 50 .mu.m was relatively uniform and smooth, but the coating with a thickness of 100 .mu.m or more showed a repelling phenomenon and it was not possible to obtain a uniform coating film. In addition, in the peel test, about 40% of the film was peeled off.

[0029] As the PPS, B-100 manufactured by Dainippon Ink and Chemicals Co., Ltd. was used. Melting point measured by DSC is 285
The dynamic viscosity at 305°C and 10 rad/sec was 200 poise. Similar to CPPS, particle sizing is performed using 30 mesh and 200 mesh.

[Comparative Example 2] Phenol resin (Prior resin)
Fen J-325, manufactured by Dainippon Ink Chemical Industries, Ltd. Solid content 6
A paint film was prepared in the same manner as in Comparative Example 1 except that 2% by weight of PPS was added. still,
The coating film was created only on the Ferro board. Although no repelling phenomenon was observed, the surface of the coating film was rough with pinholes here and there, and no smoothness was observed. Further, in the peel test, about 50% of the film was peeled off.

[Example 2] 20 g of PPS/PPSS,
60 g of water, 1 g of Triton X-100 (manufactured by Rohm & Haas, nonionic surfactant), propylene glycol
30 g of glass beads and 150 g of glass beads were placed in a polyethylene bottle and dispersed and mixed with paint conditioner for 2 hours to obtain a slurry. The obtained slurry was heated to 50 μm under the same conditions as in Example 1.
A coating film of 300 μm was prepared. Incidentally, the coating film was created only on the Ferro board. All coatings were uniform and smooth. In addition, no peeling occurred in the peeling test.

[Comparative Example 3] PPS was made into a paint using the same method as in Example 3, and a coating film was formed on a ferro plate. All films showed a repelling phenomenon and the coating layers were non-uniform. In the peel test, about 50% peeled off.

[Examples 3 and 4] PPS/PPSS 10
g and PPS 10 g (Example 3) and PPS/PPSS
5g and 15g of PPS (Example 4), respectively, and 60g of water.
, 1 g of Triton Obtained. The obtained slurry was heated to 50 μm and 10 μm under the same conditions as in Example 1.
Coating films of 0 μm and 300 μm were created. Incidentally, the coating film was created only on the Ferro board. All coatings were uniform and smooth. In the peel test, no peeling occurred in any case.

[Example 5, 6, 7] PPS/PPSS
15g of polyphenylene oxide (PPO) (Example 5), polyethersulfone (PES) (Example 6),
Nylon 66 (N66) (Example 7) The same study as in Example 1 was conducted for the case where each weight was 5 g. still,
Coating films of 50 μm and 300 μm were prepared on Ferro plates. The resins had good affinity with each other, and the resulting coating film was uniform, had a good surface appearance, and was smooth. Furthermore, no peeling occurred in the peeling test.

[0035] PPO is poly(2,6-dimethyl-1
, 4-phenylene) ether, PES is I.C.
VICTREX PES-3600p manufactured by Ai Co., Ltd.
Nylon 66 is Vydyne 22 manufactured by Monsanto.
H was used. Each powder was used and sized using 30 mesh and 200 mesh.

[Comparative Examples 4 and 5] Similar studies as in Examples 5 and 6 were carried out using PPS. In either case, the resins had poor affinity with each other, and the resulting coating films were non-uniform and of very poor quality. In addition, in the peel test, Comparative Example 4 showed about 60%, and Comparative Example 5 about 20%.
peeled off.

[Example 8, 9] PPS/PPSS 18
The same study as in Example 1 was conducted in the case where g was 2 g each of polyethylene (Example 8) and ionomer (Example 9). Incidentally, coating films of 50 μm and 300 μm were prepared on Ferro plates. The affinity of the resin was good, and the resulting coating film was uniform, had a good surface appearance, and was smooth. Further, in the peel test, almost no peeling occurred.

[0038] As the polyethylene, Shorex F-5010 manufactured by Showa Denko Co., Ltd. was used, and as the ionomer, Himilan 1707 manufactured by DuPont Mitsui Chemicals was used. In addition, each particle is sized with 30 mesh and 100 mesh.

[Comparative Example 6] The same study as in Example 8 was conducted using PPS. The resins had poor affinity with each other, and the resulting coating film was non-uniform and poor quality.

[Reference Example 2] (Synthesis example of PPS/PPSK) 1980 g of NMP, N
388 g of aSH, 200 g of NaOH, and 1436 g of 4,4'-dichlorobenzophenone were charged, and the mixture was reacted at 230° C. for 6 hours under a nitrogen atmosphere. Furthermore, 72 g of 4,4'-dichlorobenzophenone and 200 g of NMP were added and reacted at 210°C for 1 hour to form PPS with chlorine terminal group.
A K reactant slurry was obtained.

Next, add NMP 3 to a 10L autoclave.
100g, NaSH 597.5g, and NaOH3
After charging 08g of p-dichlorobenzene to the dehydrated system at 220°C, the autoclave was heated and dehydrated while water was flowing out.
29g and 700g of NMP were press-fitted, and then 26g of NMP was added.
The reaction was carried out at a temperature of 0° C. for 2 hours to obtain a PPS reactant slurry having terminal sodium sulfide groups.

[0042] The above PPSK reactant slurry and PPS reactant slurry were charged into an autoclave, reacted at 230°C for 3 hours, and purified by a known method until the PPSK portion was 50%
Parts by weight of a block copolymer (PPS/PPSK) were obtained. The melting point of PPS/PPSK determined by DSC is 335°C,
Tg is 120°C, 355°C, 10rad/sec
The dynamic viscosity was 700 poise. Also, PPS
/PPSK was sized with 30 mesh and 200 mesh.

[Examples 10 to 15] Similar studies as in Examples 1, 2, 3, 5, 6, and 8 were conducted using PPS/PPSK. However, the baking temperature was 420°C. All coating films were uniform, had a good appearance, and were smooth. Furthermore, in the peel test, almost 100% of the coating films did not peel off.

[Reference Example 3] (Synthesis example of PPSS/PPSK) In a 10 L autoclave, 1980 g of N-methylpyrrolidone (NMP), 388 g of sodium hydrosulfide hemihydrate (NaSH), and sodium hydroxide (NaOH) were placed in a 10 L autoclave.
), 200 g of bis(p-chlorophenyl)sulfone 1
436 g was charged and reacted at 200° C. for 6 hours under a nitrogen atmosphere. Further, 72 g of bis(p-chlorophenyl)sulfone and 200 g of NMP were added and reacted at 200° C. for 1 hour to obtain a slurry of a PPSS reactant having terminal chlorphenyl groups.

[0045] NMP 1980 in a 10L autoclave
g, 388 g of NaSH, 200 g of NaOH, 4,4'
1436 g of -dichlorobenzophenone was charged and reacted at 230° C. for 6 hours under a nitrogen atmosphere. Furthermore, 4,4′
72 g of -dichlorobenzophenone and 200 g of NMP were added and reacted at 210° C. for 1 hour to obtain a slurry of a terminal sodium sulfide group type PPSK reactant.

[0046] The above PPSS reactant slurry and PPSK reactant slurry were charged into an autoclave and heated at 230°C for 3
The PPSK portion was reacted for 5 hours and purified by a known method.
0 parts by weight of a block copolymer (PPSS/PPSK) was obtained. The melting point of PPSS/PPSK determined by DSC is 34
0℃, Tg is 205℃, 360℃, 10rad/
The dynamic viscosity in sec was 1000 poise. In addition, PPSS/PPSK was sized with 30 mesh and 200 mesh.

[Examples 16-20] PPSS/PPSK
The same study as in Examples 1, 2, 3, 5, and 8 was conducted using the following. However, the baking temperature was 420°C. All coating films were uniform, had a good appearance, and were smooth. Furthermore, in the peel test, almost 100% of the coating films did not peel off.

[Example 22] Examples 1, 3, 10, 16
The resulting 300 μm coating film was immersed in gasoline, oil, acetone, and toluene for 10 days, but was not attacked at all.

[Example 23, Comparative Example 7] PPS/PPS
S 500g, water 750g, propylene glycol 15
0 g and 3 g of Triton X-100 were divided into 8 parts, glass beads of approximately the same weight as the slurry were placed in a polyethylene bottle, and the mixture was stirred with a paint conditioner for about 1 hour to obtain a slurry. After the glass fiber mat was impregnated with the slurry, it was dried in an oven to obtain a prepreg. Several pieces of the obtained prepreg were press-molded at 320°C and 5Kg/cm2,
A sample piece was created. The ratio of resin to glass fiber was 6:4 in weight percent. Bending strength and interlaminar shear strength were measured. The bending strength was 28 kg/mm2, and the interlaminar shear strength was 3.6 kg/mm2. In addition, as a comparative example, P
A similar study was conducted when PS was used. Bending strength is 1
7Kg/mm2, interlaminar shear strength 1.6Kg/mm2
Met. The fracture surface of the sample piece was examined using a scanning electron microscope (S
When observed by EM), the adhesion between the resin and the fibers was good in the Examples, but the fibers in the Comparative Examples were in a state where they had completely slipped out from the resin.

[0050] As the glass mat, Swirl Mat (450 g/m2) manufactured by Asahi Fiberglass Co., Ltd. was used. Further, the bending test was conducted in accordance with JIS (K7055), and the interlaminar shear strength was conducted in accordance with JIS (K7057).

[Example 24, 25] PPS/PPSK (
The same study as in Example 23 was conducted using Example 24) and PPSS/PPSK (Example 25). Note that the press molding temperature was 360°C. Bending strength is 28K each
g/mm2 and 26 Kg/mm2, and the interlaminar shear strengths were 3 Kg/mm2 and 2.6 Kg/mm2, respectively. Furthermore, SEM observation of the fractured surface showed that the adhesion between the fiber and the resin was good. Furthermore, ASTM (D-648, load 18.6Kg
The heat distortion temperature was measured according to 2008/cm2) and was 310°C and 313°C, respectively, compared to 270°C for PPS.

[Examples 26 to 30, Comparative Examples 7 to 10] PPS/PPSS and each resin were blended in the proportions shown in Table 1, and the same study as in Example 23 was conducted. Furthermore, as a comparative example, a similar study is being conducted on the case where PPS is used instead of PPS/PPSS. The results are shown in Table-1.

[0053] Furthermore, polybutylene terephthalate (PBT
) used Planac BT-128 manufactured by Dainippon Ink. All resins were sized with 30 mesh and 200 mesh.

[0054]

[Table 1]

[Examples 31 to 38] PPS/PPSS and each resin were blended in the proportions shown in Table 2, and Example 24
A similar study was conducted. The results are shown in Table-2.

[0056] Furthermore, polyether ether ketone (PEE
K) is VICTREX PE manufactured by I.C.I.
EK380 was used. All resins are 30 mesh and 200 mesh.
The particles were sized using a mesh.

[0057]

[Table 2]

[0058]

[Effects of the Invention] The slurry composition of the present invention has excellent heat resistance, corrosion resistance, chemical resistance, dimensional stability, flame retardancy, abrasion resistance, adhesiveness, and blend compatibility, and is suitable for painting and coating. It can be suitably used as a slurry for binders, adhesives, prepregs, etc. For example, when used as a coating composition, it has improved adhesion and blend compatibility compared to conventional PPS paints, and a thick coating with good surface smoothness can be obtained in one application. It is possible. Furthermore, when a prepreg is created, the adhesion between the resin and the fiber base material is improved, making it possible to obtain a suitable molded product. Therefore, as a material in fields where properties such as heat resistance, flame retardance, dimensional stability, and chemical resistance are particularly required,
Suitably used. For example, oil field pipes, valves, stirring blades in the petrochemical industry and other chemical industries, etc.
As a paint for forming surface coatings such as corrosion-resistant and protective coatings on joints, pump impellers, and other parts, as a binder for lining pipes, firebricks, etc., as well as for various electrical and electronic parts, aircraft and automobile parts, It can be used as a prepreg for press molding, etc. used for various building materials, sports equipment, etc.

Claims (5)

[Claims] Claim 1: (A) A block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety, a block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, and a block consisting of a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety. A polyarylene sulfide resin slurry composition comprising at least one block copolymer selected from the group consisting of copolymers and (B) a dispersion medium. (A) A block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety, a block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, and a block consisting of a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety. At least one block copolymer selected from the group consisting of copolymers, (B) at least one other resin, and (C
) A polyarylene sulfide resin slurry composition containing a dispersion medium. 3. The polyarylene sulfide resin slurry composition according to claim 2, wherein a polyarylene sulfide resin other than the component (A) is used as the other resin. 4. A coating composition comprising the polyarylene sulfide resin slurry composition according to claim 1, 2 or 3. 5. A prepreg for molding comprising a fiber base material impregnated with the polyarylene sulfide resin slurry composition according to claim 1, 2 or 3.