JPH0436191B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyphenylene sulfide composition for paints that can be coated thickly. Paints based on polyphenylene sulfide (hereinafter abbreviated as PPS) take advantage of their excellent heat resistance, chemical resistance, abrasion resistance, electrical insulation properties, etc., and are used as rust prevention and anticorrosion materials for metal surfaces. It is used in various fields for various purposes. When applying PPS-based paint,
Generally, slurry paint is applied and after drying, 285
The method used is heat treatment at ~480°C to melt the PPS particles and form a uniform coating. However, there is a limit to the film thickness that can be applied in one process with such paints; if the thickness exceeds 30 to 50 μm, the molten resin will aggregate and cause a repelling phenomenon, making it impossible to obtain a film with a uniform thickness. . A coating film for the purpose of rust prevention and corrosion protection usually requires a film thickness of several hundred μm, but
Currently, such paints must be coated several times to several dozen times. USP 3,894,983 has proposed an attempt to add fine powders such as bentonite, kaolinite, zeolite, and clay to improve this drawback, but the film thickness that can be applied in one process is limited to about 150 μm. , it is still difficult to say that it is sufficient. As a result of intensive research into PPS paints that produce a thick coating film in one process, the present inventors found that it is possible to achieve this by adding 0.01 to 5 parts by weight of a thermosetting resin as a solid content to 100 parts by weight of PPS. The present invention was achieved by discovering that. That is, in the present invention, the solid content of the thermosetting resin is 0.01 to 100 parts by weight (hereinafter abbreviated as "parts") of PPS.
Provided is a PPS composition for paint, characterized in that it contains 5 parts. Since the composition of the present invention contains a thermosetting resin compared to conventional paints containing bentonite, etc., a crosslinked structure is already formed before the PPS is melted into a paint film by heating, and the PPS particles It is possible to form a thick film due to the effect of preventing agglomeration when melted. According to the composition of the present invention, several steps can be performed in one step.
It is possible to obtain a coating film with a thickness of mm, and it is amazing that a thick coating film can be obtained without the need for overcoating as in conventional methods, and is extremely effective in shortening the coating process. The PPS used in the present invention has the general formula

Those containing 70 mol% or more of the structural unit represented by the formula are preferable, and the amount thereof is 70 mol%.
If it is less than that, it is difficult to obtain a coating composition with excellent properties. In addition, as a copolymer component, if it is less than 30 mol%, it is a meta bond.

[Formula] Ortho bond

[Formula] Ether bond

[Formula] Sulfone bond

[Formula] biphenyl join

[Formula] Substituted phenyl sulfide bond

[Formula] where R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal base of a carboxylic acid), trifunctional bond

[Formula] etc. may be contained within a range that does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 10 mol% or less. In particular, when trifunctional or more functional phenyl, biphenyl, natylsulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less. The PPS used in the present invention preferably has an intrinsic viscosity in α-chlornaphthalene at 206°C (0.2 g of polymer in 100 c.c. of α-chlornaphthalene) of 0.08 to 0.3. If the intrinsic viscosity is less than 0.08, the coating film strength will not be sufficient due to the low molecular weight of the polymer, and if it exceeds 0.3, the fluidity when melted will be low and a uniform coating film will not be formed. Regarding the particle size of PPS, it is preferable that 80% or more of the total weight is within the range of 10 to 500 mesh. More preferably, the particle size is within the range of 30 to 200 meshes, accounting for 80% or more of the total weight. If the particle size is smaller than 500 meshes, it will be difficult for the air bubbles inside to come out during melting, while if it is larger than 10 meshes, uneven coating will occur, and not only will the appearance be poor, but the strength of the coating will also decrease. . The thermosetting resin used in the present invention includes one or more selected from the group consisting of phenolic resins, amino resins, epoxy resins, diallyl phthalate resins, and unsaturated polyester resins, including phenolic resins and amino resins. is preferred. The phenolic resin used in the present invention refers to all conventionally known resol type and novolac type unmodified and modified phenolic resins, such as phenol, cresol, xylenol, resorcinol, alkylphenol, bisphenol, etc. Monovalent or polyvalent phenols and aldehydes such as formaldehyde, paraformaldehyde, furfural, hexamethylenetetramine, etc., acidic substances such as organic acids and inorganic acids, amines,
Novolac type or resol type resins obtained by reacting basic substances such as alkalis or their salts as catalysts, and at any stage of the production of these resins and molding materials, rosin, ester gum, vegetable oil, synthetic rubber, alcohols, It includes all those modified by conventionally known methods using epoxy compounds, aniline, melamine, lignin, coumaron indene resins, hydrocarbon resins, etc. Examples of amino resins include urea, thiourea, dicyandiamide, melamine, benzoguanamine,
Urea formalin resin, melamine formalin resin, which is made by reacting an amino compound such as aniline or toluenesulfonamide with formaldehyde,
Guanamine resin, etc. Epoxy resin is a compound that has two or more epoxy resins in one molecule, and is a resin synthesized from epichlorohydrin, bisphenol A, and various novolacs, an alicyclic epoxy resin, or a resin that imparts flame retardant function. This includes a wide range of epoxy resins into which halogen atoms such as bromine and chlorine are introduced. For example, 2,2-bis(4'-hydroxy phenyl)propane diglycidyl ether, bis(4-hydroxy phenyl)methane.
Polyglycidyl ethers of polyhydric phenols such as diglycidyl ether, phenol formaldehyde condensates, cresol formaldehyde condensates, and poly(β-methylglycidyl) ethers, phthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acids, etc. Polyglycidyl esters and poly(β-methylglycidyl) esters, triglycidyl isocyanurate, N,
Examples include N-glycidyl derivatives such as N'-diglycidyl-5,5-dimethyl hydantoin. Further, a curing agent is usually used in combination with the epoxy resin. Examples of the curing agent include amine curing agents such as diaminodiphenylmethane, diaminophenyl sulfone, and metaphenylenediamine; phthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride; Acid anhydride curing agents, phenol novolac curing agents, etc. are used. As the diallyl phthalate resin, a prepolymer of diallyl phthalate or diallyl isophthalate and a monomer that reacts with the prepolymer, such as styrene or (meth)acrylic acid ester, and a curing catalyst are used. In addition, unsaturated polyester resin is a condensation product of a polyfunctional acid and a polyfunctional alcohol and has an unsaturated double bond, and is generally made from a saturated dibasic acid, a polyhydric alcohol, or an unsaturated dibasic acid by a conventional method. Although it refers to what can be obtained, it is not particularly limited, and so-called unsaturated epoxy esters, unsaturated epoxy urethanes, etc. can also be used. For example, isophthalic acid, orthophthalic acid, phthalic anhydride, succinic acid, adipic acid, sebacic acid, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, chlorendic acid, maleic acid and piperylene adduct, etc. saturated acids, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, adducts of bisphenol A with ethylene oxide or propylene oxide, 1,3-butanediol, 1,4- Unsaturated polyester and vinyl obtained by reacting polyhydric alcohols such as butanediol, 1,6-hexanediol, and glycerin, and unsaturated dibasic acids such as maleic anhydride, fumaric acid, and itaconic acid at 160 to 240°C Typical examples include monomers such as styrene, methyl methacrylate, ethyl methacrylate, methyl acrylate, acrylonitrile, and the like. The above thermosetting resins are usually used alone, but two or more types can also be used in combination. Further, any of the above thermosetting resins may be used, but when the paint is used in the form of a slurry, it is preferable to use a resin that can be uniformly dispersed or dissolved in the dispersion medium, for example, using water as the dispersion medium. Phenol resins and amino resins are suitable. The composition of the present invention contains 0.01 to 5 parts of thermosetting resin as a solid content, preferably 0.1 parts to 100 parts of PPS.
~4 parts are added. If the amount is less than 0.01 part,
There is no agglomeration prevention effect when melting PPS to form a coating film, and if the amount exceeds 5 parts, the density of the crosslinked structure becomes too high, so when PPS is melted, a uniform coating film cannot be formed. The coating composition of the present invention is preferably in the form of a slurry, and the dispersion medium used in this case is water; alcohols such as ethanol, propanol, i-propanol, ethylene glycol, propylene glycol, and glycerin; hexane, pentane,
Hydrocarbons such as benzene, toluene, and petroleum ether are used, but water and higher alcohols such as ethylene glycol, propylene glycol, and glycerin are preferred. In addition, if necessary, fibers such as glass fiber, carbon fiber, ceramic fiber, organic fiber, etc., and inorganic filling such as alumina, silica, zirconia, glass beads, glass flakes, titania, ferrite, mica, magnesia, zinc oxide, graphite, etc. Lubricant agents, fluororesins, molybdenum compounds, surfactants as slurry dispersion stabilizers, and PPS crosslinking accelerators such as polyhydroxybenzene, para-aminophenol, ammonium persulfate, aluminum phosphate, and mercaproalkylbenzene derivatives.
It can be used by containing it in. Furthermore, pigments, heat stabilizers, ultraviolet stabilizers, rust preventives, etc. may be used within the scope of the purpose of the present invention. Furthermore, polyamide, polyester, polycarbonate, polyacetal,
Other polymers such as polysulfone, polyethersulfone, polyphenylene oxide, polyimide, polyamideimide, furan resins, etc. may also be used in the composition of the present invention. The coating composition of the present invention is applied to a base material such as metal, glass, or ceramic according to a conventional method.
A coating film is formed by heating to ~480°C for a predetermined period of time.
Incidentally, prior to painting, it is also possible to undercoat the surface to be painted with an appropriate primer. The composition of the present invention has good heat resistance, corrosion resistance, and abrasion resistance, and a thick coating film can be obtained in one coating process, so it can be used in areas where heat resistance, corrosion resistance, and abrasion resistance are required. Suitable for surface coating. It is especially suitable for corrosion-resistant and protective coatings of oil field pipes, valves, fittings, stirring blades, pump impellers, and other parts in the petrochemical and chemical industries. Examples are shown below. In the examples, all percentages are by weight. Example 1 100 parts of Ryton V-1 (manufactured by Philips Co., Ltd., polyphenylene sulfide), 2 parts of Plyophen J-325 (manufactured by Dainippon Ink Chemical Industries, Ltd., phenol resin, solid content 60%), titanium oxide 40 copies, Wednesday
100 parts of propylene glycol, and 2 parts of Triton X-100 (manufactured by Rohm & Haas, nonionic surfactant) were added and mixed in a ball mill for 24 hours to obtain a uniform slurry. Next, it was applied to a soft steel plate that had been cleaned with a solvent using an applicator, dried at 80°C, and then baked at 370°C. As shown in Table 1,
The composition of the present invention can be coated in one coat even if the coating thickness is 300 μm. Comparative Example 1 A slurry was obtained in the same manner as in Example 1 except that Plyophen J-325 was not used, and then baked to obtain a coating film. However, during the baking process, repellency and uneven coating occurred due to agglomeration of PPS. Comparative Example 2 A baked coating film was obtained in the same manner as in Example 1 except that the amount of Plyophen J-325 added was changed from 2 parts to 10 parts. An ink test revealed that the paint film was not airtight.

Check for the presence of [Table].
Example 2 In Example 1, Plyophen J-325 2
A slurry-like composition was obtained in the same manner except that 1 part of Betsucamin APM (manufactured by Dainippon Ink and Chemicals, melamine formalin resin, solid content 80%) was used. When baking was performed in the same manner as in Example 1,
A uniform coating film with a film thickness of 440 μm and good airtightness was obtained. Example 3 1.5 parts of Epiclon 800 (manufactured by Dainippon Ink Chemical Industries, Ltd., epoxy resin) to 100 parts of Ryton V-1,
0.2 parts of triethylenetetramine, 50 parts of zirconia,
100 parts of ethanol and 50 parts of ethylene glycol were added and mixed in a ball mill for 1 hour to obtain a uniform slurry. This was applied by spraying onto a test mild steel plate that had been cleaned with a solvent, dried at 60°C, and baked at 350°C, resulting in a uniform coating film with a thickness of 210 μm and good airtightness. Example 4 100 parts of Ryton V-1 and Polylyte PB-220
(manufactured by Dainippon Ink Chemical Industries, Ltd., unsaturated polyester resin), 10 parts of glass flakes, and 120 parts of toluene were added and mixed with a stirrer to obtain a uniform slurry. It was spray-painted on a mild steel plate for testing that had been cleaned with solvent, dried at 80°C, and baked at 360°C. The resulting coating film had a uniform thickness of 230 μm and good airtightness. Comparative Example 3 In Example 1, 252 parts of Plyophen J-3 was replaced with furan resin (Assyuland Co., Ltd., Chemretsu).
A slurry composition was obtained in the same manner except that the amount was changed to 3 parts (201: resin content 45%). When baking was performed in the same manner as in Example 1, the film thickness was
A coating film of 310 μm was obtained, but the airtightness was poor according to the ink test. In addition, repellency and uneven coating occurred during the baking process, resulting in an incomplete coating film. Therefore, this product has no practical utility as a thick coating composition.

Claims (1)

[Claims] 1 For 100 parts by weight of polyphenylene sulfide,
It is characterized by containing 0.01 to 5 parts by weight of one or more thermosetting resins selected from the group consisting of phenolic resins, amino resins, epoxy resins, diaryl phthalate resins, and unsaturated polyester resins as a solid content. Polyphenylene sulfide composition for paints.