JPH059299A - Slurry composition - Google Patents

Abstract

PURPOSE:To obtain a slurry composition having a high glass transition temperature and excellent flame retardancy, chemical resistance, toughness, and blending compatibility with other resins. CONSTITUTION:A slurry composition formed by dispersing a powdery aromatic sulfide/sulfone polymer (PPSSS) having repeating units represented by formula [-phi-SO2-phi-S-phi-S-] (wherein-phi-denotes a p-phenylene group) alone, or a resin mixture of the PPSSS and other powdery resin, such as polyphenylene sulfide, polyarylate, polybutylene terephthalate or polyphenylene oxide, in a dispersing medium, e.g., a mixture of water and propylene glycol. A coating material containing the slurry composition. A prepreg for molding formed by impregnating a glass fiber with the slurry composition.

Description

Detailed Description of the Invention

[0001]

The present invention is based on an aromatic sulfide / sulfone polymer which is an amorphous polymer having a high glass transition temperature (Tg) and excellent heat resistance, flame retardancy and mechanical properties. And a slurry composition. The slurry composition is used as a coating composition such as a coating material or a lining material such as a rust preventive / corrosion preventive material for a metal surface, or a molding prepreg obtained by further impregnating a fiber base material with the slurry composition, It is used as a molding material for electric / electronic parts, automobile parts, sports equipment, etc.

[0002]

2. Description of the Related Art In recent years, a wide variety of polymeric materials have been developed, among which high heat resistance and glass transition temperature (Tg) are high.
A variety of engineering plastics having the following are attracting attention. Amorphous engineering plastics such as polycarbonate (hereinafter abbreviated as PC), polyarylate (hereinafter abbreviated as PAr) and polysulfone (hereinafter abbreviated as PSF) are used for various purposes due to their high impact resistance and heat resistance. There is. However, since these resins are inferior in flame retardancy and chemical resistance, there is a problem in using them as coating materials for coating. Further, since the adhesiveness to a fiber base material such as glass fiber is poor, there is a problem that mechanical properties are rather deteriorated even when used as a matrix resin of a composite material.

Further, as an amorphous engineering plastic having a relatively high flame retardance, a general formula (-φ-
SO 2 -φ-S-) (wherein -φ- represents a p-phenylene group. The same shall apply hereinafter), polyphenylene sulfide sulfone (hereinafter P
(Abbreviated as PSS) is disclosed in JP-B-53-25880. Since this resin has a high Tg, it has excellent mechanical properties and electrical properties at high temperatures, but it has poor chemical resistance to aromatic or ketone organic solvents such as toluene and acetone. There was a problem.

Further, polyphenylene sulfide (hereinafter abbreviated as PPS), which is a crystalline polymer having a repeating unit represented by the general formula (-φ-S-), is also adhesive to a fiber base material such as glass fiber. Is known to be inferior to. Furthermore, the random copolymer and block copolymer of PPS and PPSS (Japanese Patent Laid-Open No. 63-13066) are already known. However, in the case of the random copolymer, the variation of the properties of the obtained polymer was very large, and it was very difficult to reduce the variation. Further, in the case of the block copolymer, there is a problem that the elastic modulus remarkably lowers and softens at the glass transition temperature Tg (80 to 90 ° C.) of PPS or higher.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in order to solve the problems of each resin as described above, and found that the aromatic sulfide / sulfone polymer having a high glass transition temperature (Tg). Can be used for coating paints and molding prepregs, and has various physical properties such as flame retardancy, chemical resistance, toughness, heat resistance, and adhesion to fiber base materials. It was found that the above was also excellent, and the present invention was completed.

[0006]

That is, the present invention provides a general formula [-φ-SO ₂ -φ-S-φ-S-] (provided that -φ-
Represents a p-phenylene group. ) A slurry composition obtained by mixing an aromatic sulfide / sulfone polymer having a repeating unit represented by (4) and a dispersion medium, and optionally other miscible resins, or a coating composition using these slurry compositions The present invention relates to a paint, and further to a molding prepreg obtained by impregnating a fiber base material with the slurry composition.

Aromatic Sulfide / Sulfone Polymerization of the Invention
The body (hereinafter abbreviated as PPSSS) is represented by the above general formula.
Repeating structural unit [-φ-SO₂ -Φ-S-φ-S
-] (Provided that -φ- represents a p-phenylene group).
It is a polymer having 90 mol% or more. Structures other than the above formula
The unit is mainly formed in the synthesis process (-φ-SO₂ −
φ-S-) and (-φ-S-). In addition, for each aromatic ring
Is F, Cl, Br, CH ₃ , COOH, NH₂ , OH,
CN, NO₂ Substituents such as may be introduced.

The melt viscosity of the PPSSS is in the range of ^{5 to} 10 ⁵ poise. Especially when used for paints, 5
-10 ⁴ poise, preferably 10-5 x 10 ³ poise, and when used for pre-preg, 50-10
^{It is 5} poise, preferably 100 to ⁵ × 10 ⁴ poise. Further, the glass transition temperature (Tg) is 140 ° C. or higher,
It is particularly preferably 150 ° C. or higher. The viscosity is 27
The value of the dynamic viscosity [η '] at 0 ° C, 10 rad / sec,
Tg is a value measured by a scanning differential calorimeter (DSC) at a heating rate of 10 ° C./min.

In the present invention, the PPSSS is preferably used in powder form. The particle size is such that 80% or more of the total weight is in the range of 10 to 400 mesh, preferably 20 to 300 mesh. When the particle size is in this range, processing such as mixing and dispersion processing and painting is easy and workability is excellent.

The PPSSS is disclosed in JP-A-59-81335.
It can be manufactured according to the synthetic method disclosed in Japanese Patent Publication No. 61-200127 and other synthetic methods. For example, 4,4'-dihalodiphenyl sulfone and p-dimercaptobenzene are used as raw materials, an organic amide solvent or an aliphatic or aromatic sulfone which is an aprotic polar solvent is used as a solvent, and an alkali metal salt such as In the presence of at least one selected from carbonates, hydroxides and bicarbonates, substantially equimolar amounts of p-dimercaptobenzene and 4,4'-at a temperature in the range of 200 to 400 ° C. It can be synthesized by polycondensation with dihalodiphenyl sulfone.

The starting monomers used are p-dimercaptobenzene (HS-φ-SH) and the general formula (X ¹ -φ-
SO ₂ -φ-X ² ) (wherein X ¹ and X ² in the formula represent a halogen atom, and they may be the same or different). It is a sulfone. Specific examples of the 4,4'-dihalodiphenyl sulfone include 4,4'-dichlorodiphenyl sulfone, 4,4'-dibromodiphenyl sulfone and 4,4 '.
-Difluorodiphenyl sulfone and the like. Of these, 4,4'-dichlorodiphenyl sulfone is easily available and its use is preferable from the industrial viewpoint. Further, these monomers may be used alone or in combination of two or more kinds.

Among the solvents used, the organic amide-based solvent is hexamethylphosphoric triamide (HMPA),
N-methylpyrrolidone (NMP), N-cyclohexylpyrrolidone (NCP), tetramethylurea (TM)
U), dimethylformamide (DMF), dimethylacetamide (DMA) and the like. Aliphatic or aromatic sulfonic solvents have the general formula _{^{(R 1 -SO 2 -R 2)}} ( where, R ¹ and R ² in the formula is an aliphatic residue or an aromatic residue, they are identical or different May also be R
¹ and R ² may be directly bonded by a carbon-carbon bond or may be bonded via a hetero atom such as an oxygen atom), and specifically, dimethyl sulfone ( DMS), diethyl sulfone (DES), sulfolane, diphenyl sulfone (DPS), methylphenyl sulfone (MPS), dibenzothiophene oxide, 4
-Phenylsulfenyl biphenyl and the like.

Alkali metal salts used, such as carbonates,
Examples of the hydroxide compound and bicarbonate include sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. These salts may be used alone or in combination of two or more. Of these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are particularly preferable.

A preferred embodiment of the synthetic method will be described.
First, in at least one solvent selected from aliphatic sulfones, aromatic sulfones, and organic amide solvents, at least one selected from the required amount of alkali metal carbonate, hydroxide compound, or bicarbonate. The seed alkali metal salt and p-dimercaptobenzene and 4,4'-dihalodiphenyl sulfone are added. The solvent is usually used in the range of 10 to 1000 parts by weight per 100 parts by weight of p-dimercaptobenzene and 4,4'-dihalodiphenyl sulfone.

The amount of the alkali metal atom in the alkali metal salt is 1. per mol of p-dimercaptobenzene.
It is used in a proportion of 6 to 2.4 gram atom.
It is preferable to use anhydrous ones of these alkali metal salts, but those having crystal water or bound water should be distilled off from the polymerization system by simple distillation or distillation using an azeotropic solvent. Can be used. Further, these alkali metal salts can be divided and added to the polymerization system. For example, when the reaction is charged, the amount of the alkali metal atom is added in such a ratio that it becomes 2 gram atom per mol of p-dimercaptobenzene, and when the polymerization reaction proceeds to some extent, p-dimercaptobenzene 1 is further added as the alkali metal atom. The method is to add 0.4 gram atom of alkali metal salt per mole.

4,4'-dihalodiphenyl sulfone and p
-The proportion of dimercaptobenzene used must be substantially equimolar, usually 1 mole of the former and 0.
It is selected in the range of 95 to 1.20 mol, the latter being 1.0
A slight excess, such as 1-1.10 moles, gives higher molecular weight polymers.

Next, the mixture of the above-mentioned solvent, alkali metal salt and monomer is heated in an atmosphere of an inert gas such as nitrogen or argon to 100 to 400 ° C., preferably 150 to 300.
The polymerization reaction is carried out in the temperature range of ° C. To avoid local heating that causes side reactions such as decomposition reactions, do not raise the temperature rapidly, but raise the temperature stepwise or gradually to keep the polymerization reaction system as uniform as possible. You should devise it. . The reaction time is 1 to 20 hours, preferably 3 to
15 hours. In a reaction at a high temperature where the decomposition reaction and the polymerization reaction compete with each other, the reaction time may be set short.

The polymerization reaction is carried out by using a suitable terminal stopper such as a monofunctional or polyfunctional halide, specifically methyl chloride, methyl iodide, tert-butyl chloride, 4,
It can be stopped by adding 4'-dichlorobenzophenone, p-nitrochlorobenzene, monomer 4,4'-dihalodiphenyl sulfone, etc. to the reaction system at the above-mentioned polymerization temperature. This makes it possible to obtain a polymer having a thermally stable alkyl group, aromatic halogen group, or aromatic group at the terminal.

To recover the polymer, at the end of the reaction, the reaction mixture is first heated under reduced pressure or normal pressure to distill off only the solvent, and then the bottom solid is treated with a solvent such as water, acetone, methyl ethyl ketone or alcohols. It can be performed by washing once or twice or more, and then neutralizing, washing with water, filtering and drying. Further, as another method, after the reaction is completed, water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons are added to the reaction mixture,
A solvent such as an aromatic hydrocarbon or an aliphatic hydrocarbon (which is soluble in the used polymerization solvent and is a non-solvent for at least the produced polymer) is added as a precipitating agent to form the polymer. It can also be carried out by settling and filtering it, washing and drying it. The "washing" in these cases can be carried out in the form of extraction. Further, after the reaction is completed, the reaction solvent or a low-molecular weight polymer equivalent thereto is dissolved in the reaction mixture, for example, a sulfone-based or amide-based solvent other than the reaction solvent is added and stirred, and then filtered to remove the low-molecular weight polymer. After that, it can be also carried out by washing once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, and then neutralizing, washing with water, filtering and drying.

The PPSSS according to the present invention is thermally crosslinked by heating in the presence of oxygen. Utilizing this property, a low-molecular weight polymer can be synthesized and thermally crosslinked to increase the molecular weight, and then used. Further, if the thermal crosslinking is hindered when a high molecular weight polymer is used, zinc oxide, carbonate, hydroxide compound, hydroxide compound, oxide, carbonate of Group IIA of the Periodic Table of Elements. It is also possible to add and use a heat stability improver such as an aromatic carboxylic acid salt.

As the other resin miscible with PPSSS, known resins can be used, but the following resins are particularly preferable.

PPS, polyphenylene sulfide ketone (hereinafter abbreviated as PPSK), PPSS and polyarylene sulfide which is a block copolymer thereof (hereinafter PA).
Abbreviated as S) resin (excluding PPSSS); polyamides such as nylon 6, nylon 66, nylon 46, nylon 12, nylon MXD6 (copolymer obtained from metaxylene diamine and adipic acid); polyethylene; Terephthalate, polybutylene terephthalate, poly (cyclohexane dimethylene terephthalate)
Thermoplastic polyester represented by: (-φ-SO
₂₋ ), (−φ−O−φ−SO ₂ −), (−φ−C (CH
_{3) 2 -φ-O-φ} -SO 2 -) polyethersulfone having repeating units such as, polyaryl sulfone, polysulfone; (- φ-CO-φ -O -), (- φ-O-
φ-CO-φ-O-) and other polyetherketones having repeating units, polyetheretherketone; 2,6-
Polyphenylene oxide, which is a polymer of di-substituted phenol or a polymer of 2,6-substituted phenol and polyhydric phenol; polycarbonate; polyarylate; homopolymers and copolymers of ethylene, propylene, butylene and pentene monomers. Α-Olefin copolymers which are copolymers or copolymers of these monomers with butadiene, isoprene, (meth) acrylic acid ester, (meth) acrylonitrile, etc .; hydrogenated styrene / butadiene rubber and other conjugated diene-based copolymers Hydrogenated product; Styrene copolymer; ABS resin, MB
ABS resins such as S resins and AES resins; polyetherimides; phenoxy resins; fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride; epoxy resins. These may be modified with an acid or the like.

The addition rate to PPSSS varies depending on the resin used and the purpose for which it is used, and therefore cannot be specified unconditionally, but when epoxy resin is used, it is usually 0.1 to 30 parts by weight, preferably 100 parts by weight of PPSSS. , 0.5-
When 20 parts by weight uses an α-olefin copolymer, a conjugated diene-based copolymer, a styrene copolymer, or a phenoxy resin, it is 1 to 100 parts by weight, preferably 2 to 80 parts by weight. Other resins such as PAS-based resin are 5 to 2
00 parts by weight, preferably 8 to 150 parts by weight. In particular, the PPSSS is particularly excellent in affinity with PPS and the like, so that its combined use is preferable. In such a combination, PP
Improvement of toughness of S and softening above Tg, or PPS / P
In addition to the effect of improving softening of the block copolymer such as PSS and PPS / PPSK in a high temperature region, the physical properties such as chemical resistance and heat resistance of PPSSS can be further improved.

The form of the resin to be blended may be pellets or the like as long as it can be dissolved in the dispersion medium of the slurry, and the shape is not particularly limited, but in the case of a resin that does not dissolve or is difficult to dissolve Must be in powder form.
For the same reason as PPSSS, the particle size in this case is in the range of 10 to 400 mesh, preferably 20 to 300 mesh for 80% or more of the total weight.

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; hydrocarbons such as hexane, pentane, benzene, toluene and petroleum ether; methyl acetate, ethyl acetate,
Esters such as benzoic acid ester; methyl ethyl ketone, 2-heptanone, ketones such as cyclohexanone and the like, and mixtures thereof can be used, but preferably water and ethylene glycol, diethylene glycol, propylene glycol, It is a polyvalent alcohol such as glycerin. In addition, when mixed with other resin, it is possible to mix and use a solvent in which the resin is dissolved within a range in which the dispersibility of the block copolymer powder is not deteriorated.

The slurry composition may optionally contain
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. Further, in order to improve the dispersibility and stability of the slurry, for example, carboxylate, higher alcohol sulfate ester salt, amide bond sulfate ester salt, ester bond ester salt, amide bond sulfonate, alkylallyl sulfonate, Anionic surfactants such as ester-bonded sulfonates or phosphoric acid ester salts, quaternary ammonium salts, ether-bonded fourth
Cationic surfactants such as ammonium salt, quaternary ammonium salt with ester bond, quaternary ammonium salt with amide bond, amine salt, amine salt with ester bond, amine salt with ether bond, amine salt with amide bond or pyridinium salt, ether type, ester type A nonionic surfactant such as a condensation type with an amine, a condensation type with an amide or a polyethyleneimine type; polyhydroxybenzene,
A crosslinking promoter such as para-aminophenol, ammonium persulfate, aluminum phosphate, and a mercaptoalkylbenzene derivative can be contained and used.

When the slurry composition of the present invention is used in a molding prepreg, the fiber base material is carbon fiber, glass fiber, silane glass fiber, silica fiber, ceramic fiber, aramid fiber, boron fiber, alumina fiber or asbestos fiber. , Metal fibers, short fibers such as whiskers, long fibers, and woven fabrics, and these can be used in combination. Generally, glass fibers and carbon fibers are preferably used, but in special applications such as sports equipment, in addition to these, aramid fibers and boron fibers are used.
The mixing ratio of the fiber base material cannot be specified unconditionally because it varies depending on the purpose of use, the type of fiber, the shape of the fiber, etc.
0 parts by weight, preferably 30 to 300 parts by weight are used. In such a range, it penetrates well into the fiber base material and a preferable reinforcing effect is obtained. It is also possible to disperse and use these fibrous base materials in a slurry used for paints. In this case, usually short fibrous fibers are used.

The prepreg can be produced from the slurry composition and the fiber base material by a known method such as the method described in JP-A-60-38433 or the papermaking method. At this time, known dispersants, binders, aggregating agents and the like can be used as necessary.

On the other hand, when used as a coating material, the slurry composition is applied to a material to be coated such as various metals, glass and ceramics by a conventional method, and the melting point of the polymer to the melting point plus 15
Heat at 0 ° C. for a predetermined time to form a coating film. Prior to coating, the surface to be coated may be undercoated with an appropriate primer.

In the slurry composition of the present invention, a small amount of a releasing agent such as polyethylene wax, a coloring agent such as various pigments, a phosphorus compound or a hindered phenol compound, etc. may be used within a range not departing from the object of the present invention. It is possible to add antioxidants, heat stabilizers, UV stabilizers, foaming agents, flame retardants, flame retardant aids, rust inhibitors, silane coupling agents such as aminosilane and epoxysilane, and titanate coupling agents. is there. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds and the like, but trivalent phosphorus compounds are preferable. As the heat resistance stabilizer, hydroxides, oxides and aromatic carboxylates of Group IIa metals of the periodic table excluding magnesium, and aromatic carboxylates, carbonates and hydroxides of Group Ia metals of the periodic table, Phosphates, borates and the like can be mentioned, but among them, hydroxides of calcium and barium are preferable. Examples of the rust preventive include carbonates of alkali metals such as lithium and potassium, oxides and carbonates of metals belonging to Group IIa and b of the periodic table such as magnesium, calcium and zinc. Among them, zinc oxide and carbonate Zinc or the like is preferably used.

[0031]

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

[Synthesis Example 1] 4,4'-dichlorodiphenyl sulfone 287.17 g (1.00 mol) and p-dimercaptobenzene 149.34 g were placed in a stainless steel (titanium lining) 2 liter autoclave equipped with a synthetic stirring blade of PPSSS. (1.05 mol), anhydrous potassium carbonate 145.12 g (1.05 mol) and diphenyl sulfone 700 g were charged, the system was sufficiently replaced with nitrogen while stirring, and then the temperature was raised to 200 ° C. over 3 hours,
Hold for 5 hours. After this, anhydrous potassium carbonate 7.3g
(0.05 mol) was added, the temperature was raised to 250 ° C., and the temperature was maintained for 2 hours. Then blow methyl chloride at this temperature for 20 minutes, cool, grind, and then twice with acetone and 2 times with warm water.
Washed once with acetone and once with acetone
φ-SO ₂ -φ-S-φ-S-] (where -φ- is p
Represents a phenylene group. ), To obtain 340.0 g of an amorphous polymer (PPSSS).

The melt viscosity of this PPSSS was 950 poise, Tg was 171 ° C., and the result of elemental analysis was C H OS measurement value (%) 60.5 3.2 9.1 26.7 theoretical value (%). It was 60.67 3.40 8.99 26.94. The particles were sized with 30 mesh and 200 mesh.

The melt viscosity of the obtained polymer was measured by a rheometrics viscoelasticity measuring device (RDS-II) at 270 ° C. and a dynamic viscosity [η ′] of 10 rad / sec. And the glass transition point (Tg) is DS manufactured by Seiko Denshi.
The measurement was performed using C200 under the conditions of a sample amount of about 5 mg and a heating rate of 10 ° C./min.

[Synthesis Example 2] Synthesis of block copolymer composed of PPS and PPSS N-methylpyrrolidone (NM) was placed in a 10 L autoclave.
P) 1980 g, sodium hydrosulfide 1.2 hydrate (N
aSH) 388 g, sodium hydroxide (NaOH) 200 g, bis (p-chlorophenyl) sulfone 143
6 g was charged and reacted at 200 ° C. for about 6 hours under a nitrogen atmosphere. Furthermore, bis (p-chlorophenyl) sulfone 7
2g and NMP200g were added, and it was made to react at 200 degreeC for 1 hour, and the terminal chloro group type PPSS reactant slurry was obtained.

Next, NMP 3 was placed in a 10 L autoclave.
10 g, NaSH 597.5 g, and NaOH 308
G was charged, the temperature was raised while allowing water to flow out, and dehydration treatment was performed. Then, the autoclave was sealed, and at 220 ° C.,
P-dichlorobenzene 1029 was added to this dehydrated system.
g and NMP 700 g were added under pressure, and the mixture was further reacted at a temperature of 260 ° C. for 2 hours to obtain a terminal sodium sulfide group type PPS reactant slurry.

The above PPSS reactant slurry and PPS reactant slurry were charged into an autoclave and reacted at 220 ° C. for 3 hours, the reaction product was filtered off, hot water, methanol,
After washing and purification with acetone, a block copolymer (PPS / PPSS) having a PPSS portion of 50 parts by weight was obtained. The melting point of PPS / PPSS determined by a scanning differential calorimeter (DSC) was 270 ° C., and the viscosity at 290 ° C. was about 800 poise. In addition, sizing was performed with 30 mesh and 200 mesh.

[Synthesis Example 3] Synthesis of PPSS A PPSS slurry was synthesized and purified in the same manner as in Synthesis Example 2 to obtain PPSS. The melt viscosity of PPSS at 270 ° C. was about 800 poise. 30 mesh and 2
The particles were sized with a 00 mesh.

[Example 1] PPSSS 20 in powder form
g, propylene glycol 100 g and glass beads 1
50 g was put in a polybin and dispersed and mixed for about 2 hours with a paint conditioner to obtain a slurry. The obtained thriller was coated on a photographic ferro plate and an aluminum plate, respectively, dried at 100 ° C. for 30 minutes, and then baked at 330 ° C. for about 1 hour to give a thickness of 50 μm, 100 μm.
A coating film with a thickness of 300 μm was obtained. All the films were coating films having a uniform smoothness without repellency.

When a 100 μm coating film was burned using a gas burner, the fire was extinguished and the self-extinguishing property was observed. A 100 μm coating film was placed in a high temperature tank of 150 ° C. and held for 1 hour, then the coating film was taken out and the hardness of the coating film was immediately examined. However, the ballpoint pen did not scratch it.

Further, a 300 μm coating film was immersed in acetone for 1 day to examine the weight change. The weight increase rate by immersion was about 1%, but no cracks were observed. Further, the same examination was conducted when toluene was used instead of acetone, but almost the same result was obtained.

Example 2 PPSSS 20 g, water 60
g, Triton X-100 (Rome & Haas, nonionic surfactant) 1 g, propylene glycol 30 g
And 150 g of glass beads were placed in a polybin and dispersed and mixed for 2 hours with a paint conditioner to obtain a slurry.
The slurry thus obtained was treated under the same conditions as in Example 1 at 50 μm and 10 μm.
Coating films of 0 μm and 300 μm were prepared. The coating film was formed only on the ferro plate. All were uniform and smooth coating films. Further, the same test as in Example 1 was conducted, but the same result was obtained.

Comparative Example 1 PPS / obtained in Synthesis Example 2
A coating film was prepared by using the PPSS block copolymer in the same manner as in Example 1, and the same examination was performed. The coating film was uniform. The flame retardancy test gave similar results, but the coating film held at 150 ° C was easily scratched with a pole pen.

Comparative Example 2 PPSS obtained in Synthesis Example 3
Was used to prepare a coating film in the same manner as in Example 1. The coating film was uniform. The 300 μm coating film was immersed in acetone for 1 day, and the weight change was examined. The weight increase rates were all about 20%, and cracks were generated on the coating film surface. Further, the same examination was performed when toluene was used instead of acetone, but almost the same result was obtained.

[Example 3] 10 g of PPSSS and PPS
10 g of water, 60 g of water, Triton X-100 (Rom &
1 g of nonionic surfactant manufactured by Haas Co., 30 g of propylene glycol and 150 g of glass beads were put in a polybin and dispersed and mixed with a paint conditioner for 2 hours.
A slurry was obtained. A coating film of 100 μm was prepared from the obtained slurry by the same method as in Example 1. The coating film was formed only on the ferro plate, and the baking temperature of the coating film was 360 ° C. All were uniform and smooth coating films. It was immersed in gasoline, oil, etc. for 10 days and in acetone, toluene for 1 day, but was not attacked at all.

PPS is B-1 manufactured by Dainippon Ink and Chemicals, Inc.
00 was used. As the PPS, granular ones were used, and sizing was performed with 30 mesh and 200 mesh.

Example 4 PPSSS of 10 g and polyarylate (PAr) of 10 g were slurried in the same manner as in Example 1 and a coating film of 100 μm was formed on a ferro plate. The affinity between the resins was good, and the coating film obtained was uniform and had a good surface appearance and was smooth. Irradiation was carried out for about 200 hours with a sunshine super long life weather meter (manufactured by Suga Test Instruments Co., Ltd.), and the brightness before and after irradiation was measured. Lightness 55 to 4
Changed to 6. PPSSS coating (100μ of Example 1
(in m) was from 54 to 30, and the addition of PAr resulted in a coating having further improved weather resistance.

As PAr, U polymer U-100 manufactured by Unitika Ltd. was used. A powdery material was used and sizing was performed with 30 mesh and 200 mesh. For the measurement of the lightness, a minute flat curved surface photometer manufactured by Nippon Denshoku Co., Ltd. was used.

[Examples 5 and 6] PPSSS 10g, polybutylene terephthalate (PBT) 10g (Example 5) and PPSSS 15g, polytetrafluoroethylene (PTFE) 5g (Example 6) were used. The same examination was performed. In the case of PTFE, the coating film was baked at 360 ° C. Coating is 300
Ferro plates having a thickness of μm were prepared. Example 5 (in the case of PBT) was used to measure the friction coefficient for steel.
Was 0.2 and Example 6 (in the case of PTFE) was 0.15. The coefficient of friction of the 300 μm coating of Example 1 is 0.
4 and the addition of PBT and PTFE provided a coating film with further improved slidability.

The PBT used was Planac BT-128 manufactured by Dainippon Ink and Chemicals, and the PTFE used was Polyflon TFE M-31 manufactured by Daikin Industries. Using powdery ones, respectively, sizing was performed with 30 mesh and 200 mesh.

The friction coefficient is 500 mm / m when a sample piece having a cross-sectional area of 5 × 5 cm ² is cut and a load of 700 g is applied.
Calculated from the force required to slide on steel at a speed of in.

Example 7, Comparative Example 3 PPSSS 50
0 g, 750 g of water, 150 g of propylene glycol, and 3 g of Triton X-100 were divided into 8 parts, glass beads having a weight approximately equal to that of the slurry were put in a polybin, and the mixture was stirred for about 1 hour with a paint conditioner to obtain a slurry. After impregnating the glass fiber mat with the slurry, it was dried in an oven to obtain a prepreg. Several pieces of the obtained prepreg were press-molded at 280 ° C. and 5 Kg / cm ² to prepare sample pieces. The ratio of resin to glass fiber was 7: 3 by weight.

When the bending strength and the interlaminar shear strength were measured, the bending strength was 30 kg / mm ² , and the interlaminar shear strength was 3.2 Kg.
It was / mm ² .

Further, as Comparative Example 3, the same examination was carried out for the case where the PPS / PPSS block copolymer obtained in Synthesis Example 2 was used. Flexural strength 20 Kg / mm ^2, interlaminar shear strength was 2.4 Kg / mm ²

As the glass mat, a swirl mat (450 g / m ² ) manufactured by Asahi Fiber Glass Co., Ltd. was used.

The bending strength is JIS (K7055).
The interlaminar shear strength was in accordance with JIS (K7057).

[Examples 8 to 12, Comparative Example 4] PPSSS
And PPS, polyphenylene oxide (PPO), polyether sulfone (PES), nylon 66, polycarbonate (PC) are blended as shown in Table-1, and a sample piece is prepared in the same manner as in Example 7 to obtain bending strength. And the interlaminar shear strength test was performed. The press molding temperature was 320 ° C. in Example 8, 340 ° C. in Examples 9 and 10, and Examples 11 and 1
2 was 300 ° C. Further, as a comparative example, the same examination was conducted for the case of PPS alone. The results are shown in Table-1.

PPS is B- manufactured by Dainippon Ink and Chemicals, Inc.
600, PPO is General Electric's Noril 534J-8, PES is ICIC's VICTREX PES-3600, nylon 6
6 is UBE nylon 2026D made by Ube Industries, P
As C, Iupilon S-2000 manufactured by Mitsubishi Gas Chemical Co., Inc. was used. Each polymer uses a granular one,
The particles are sized with 30 mesh and 200 mesh.

[0059]

[Table 1]

[Examples 13 to 17] PPSSS was added to PB
T, polyethylene, ionomer, hydrogenated styrene / butadiene rubber (SBR), and epoxy resin were blended as shown in Table 2, and the same examination as in Example 7 was conducted. The results are shown in Table-2. In the case of PBT (Example 13), the friction coefficient was measured and found to be 0.24. The friction coefficient of PPSSS of Example 7 was 0.35, and the sliding property was improved by the addition of PBT.

[0061] Polyethylene is Showrex MO-32 manufactured by Showa Denko KK, Ionomer is Himilan 1707 manufactured by Mitsui DuPont Chemical Co., SBR is Tuftics M193G manufactured by Asahi Kasei, and epoxy resin is Dainippon Ink and Chemicals. Epicron N-695 manufactured by the company was used. Each of the resins used is a granular one, and is divided into 30 mesh and 200 mesh.

[0062]

[Table 2]

[Embodiment 18] PPSSS and PTFE are 7
For the case of 3 and the resin and glass fiber 6: 4,
A sample was prepared in the same manner as in Example 7 and a friction test was conducted. The friction coefficient was 0.16.

Example 19 A sample piece was prepared in the same manner as in Example 7 when PPSSS and PAr were set to 6 to 4 and resin and glass fiber were set to 7 to 3, and bending test and interlaminar shear strength were performed. And a weather resistance test was conducted. Bending strength is 34 (Kg / mm ² ), interlayer shear strength is 4.2 (Kg / mm ² ),
The brightness changed from 60 to 50. The brightness of Example 7 is 58.
From 34 to 34, the weather resistance was improved by the addition of PAr. In addition, the weather resistance test is a sunshine super long life weather meter (manufactured by Suga Test Instruments Co., Ltd.)
Then, irradiation was performed for about 200 hours, and the same method as in Example 4 for measuring the brightness before and after irradiation was used.

[0065]

The slurry composition of the present invention has a high glass transition temperature and is excellent in flame retardancy, chemical resistance, toughness, blend compatibility, etc., and is suitable for coating, coating, prepreg and the like. It can be suitably used as a slurry composition. When used as a paint for painting, for example, conventional PP
Compared to S-based paint, flexibility, adhesiveness, blend compatibility are improved, and a thick coating film with good smoothness of the coating surface can be applied. Further, when a prepreg is prepared, it is possible to obtain a suitable molded product because of excellent mechanical properties such as adhesion between the resin and the fiber base material and bending strength. Therefore, for example, oil field pipes in the petrochemical industry, other chemical industries, valves, stirring blades, joints, pump impellers, coatings and lining pipes for surface coating film formation such as corrosion resistance / protective coating of other parts, It can be used as a binder for refractory bricks, or as a pre-preg for press molding used for various electric / electronic parts, aircraft / automobile parts, various building materials, sports equipment, and the like.

Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location B29K 81:00 105: 06 C08L 81:00 (72) Inventor Takahiro Kawabata 1551 Rokuzaki, Sakura City, Chiba Prefecture Town 9-202 (72) Inventor Yoshifumi Noto 2982-1, Mamuro, Urawa City, Saitama Prefecture

Claims (5)

[Claims] 1. A general formula [-φ-SO ₂ -φ-S-φ-S
-] (However, -φ- represents a p-phenylene group.) A slurry composition comprising an aromatic sulfide / sulfone polymer having a repeating unit represented by the formula and a dispersion medium. 2. (A) General formula [-φ-SO ₂ -φ-S-
[phi] -S-] (where-[phi] -represents a p-phenylene group), an aromatic sulfide / sulfone polymer having a repeating unit represented by (B), another resin miscible with (C) dispersion A slurry composition comprising a medium. 3. As (B) other miscible resin, polyamide, thermoplastic polyester, polysulfone, polyphenylene oxide, polyarylene sulfide resin, polyether ketone, polyetherimide, polyarylate, polycarbonate, phenoxy resin, α The slurry composition according to claim 2, wherein at least one resin selected from an olefin copolymer, a hydrogenated product of a conjugated diene copolymer, a fluororesin, and an epoxy resin is used. 4. A coating composition comprising the slurry composition according to claim 1, 2 or 3. 5. A molding prepreg obtained by impregnating a fiber base material with the slurry composition according to claim 1.