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WO1999021929A1 - Composition de matiere de revetement - Google Patents

Composition de matiere de revetement Download PDF

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Publication number
WO1999021929A1
WO1999021929A1 PCT/JP1998/004784 JP9804784W WO9921929A1 WO 1999021929 A1 WO1999021929 A1 WO 1999021929A1 JP 9804784 W JP9804784 W JP 9804784W WO 9921929 A1 WO9921929 A1 WO 9921929A1
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WO
WIPO (PCT)
Prior art keywords
resin
group
formula
coating
coating composition
Prior art date
Application number
PCT/JP1998/004784
Other languages
English (en)
Japanese (ja)
Inventor
Haruhiko Mohri
Yasushi Yonei
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO1999021929A1 publication Critical patent/WO1999021929A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • Hatsuho relates to a paint composition that can prevent the attachment of stains such as rain streaks.
  • silane compounds are used as dewatering agents when dispersing polymers or pigments, but most silane compounds are used during production. Can react with water, and the paints produced from them have little effect on improving the antifouling and stainability. There is no such thing.
  • W094 / 0670, WO95 / 02645 Japanese Patent Publication No. 7-148540, JP-A-7-102211, JP-A-7-136584, JP-A-7-173432, JP-A-7-8250, JP-T Japanese Patent Application Laid-Open No. 7-09435 and Japanese Patent Application Laid-Open No. 7-601184 each disclose techniques using a gay compound.
  • the purpose of the present invention is to form a coating film that is excellent in antifouling and adhesion, and does not accumulate and accumulate atmospheric contamination and rain streaks.
  • the purpose is to provide such a paint composition at a relatively low cost. Disclosure of the invention
  • gallium-containing compounds that are (B) Resin for paint
  • the present invention relates to a coating composition comprising the composition.
  • the number average molecular weight of the compound containing a gayne is 2000 to 5000 in terms of GPC (polystyrene conversion).
  • At least one of the organic groups R in the silicon-containing compound (A) is H (CF 9 ) 2 CH 2 —, H (CH ⁇ ⁇ CH n — or CF 3 CF
  • it is 2 CH 9 —
  • X in the amino compound (A) is a methyl group.
  • At least one of R is a methylene group, and the number of methyl groups occupying in all organic groups R (CH 3 Z total R) is 0.2 to 0.8. Is preferred.
  • the coating resin (B) may be a homopolymer of futivinylidene, a copolymer of a solvent-soluble fuzivinylidene or a copolymer of vinylidene fluoride. It is preferably a water-soluble polymer dispersion, and the coating resin (B) is a hydroxyl- and / or carboxy-group-containing solvent-soluble fluoropolymer.
  • a coating composition which is a polyethylene copolymer and contains (C) a hardening agent and / or a curing catalyst. Best form to carry out the invention
  • the coating composition of the present invention requires (A) a silicon-containing compound containing no or less than 5% by weight of a fluorine-containing compound and (B) a coating resin. (C) It consists of a curing agent and Z or a curing catalyst.
  • the silicon-containing compound (A) acts as an antifouling agent. That is, when the alkoxy group bonded to the silicon constituting the silicon-containing compound (A) is applied as a paint, it gathers on the surface of the coating film. In addition, it is decomposed and desorbed by the action of rainwater and the like to remove contaminants adhered to the surface of the coating film.
  • the co-condensation product of the trialkyloxysilane of the above formula (1) and tetraalkyloxysilane of the formula 2) or the oligomer thereof and the formula It may be the reaction product with alcohol of (3).
  • a feature of the present invention is that, even when the silicon-containing compound (A) does not contain a fluorine atom or contains a fluorine atom, it is less than 5% by weight, and is preferable. Is 3% by weight or less.
  • X is a hydrogen atom, methyl, ethynole, propyl
  • R is methyl, ethyl, propyl.
  • the tetraalkyloxysilane of the formula (2) may be a 1 to 20-mer, preferably a 1 to 10-mer.
  • R be methyl, ethyl, propyl, or butyl.
  • R CH 3 or C 9 H
  • the condensation ratio of the formula (1) and the Z formula (2) is 1/3 to 20, preferably 1/5 to 15, in terms of the mole ratio of a gay atom unit.
  • the ratio of equation (1) increases, the surface lyophilicity tends to be insufficient.
  • At least one of R is a methyl group, and the number of methyl groups occupied by all the organic groups R.
  • (CH 3 / all R) is 0.2 to 0.8, especially 0.35 to 0.65, it is superior in the initial lyophilicity, and as a result, the initial It is possible to improve the antifouling adhesion property of the product.
  • the fluorine-containing compound (A) containing a fluorine atom is represented by the formula (1), the formula (2) and / or the low R in the formula (3). At least one of them is a group containing a fluorine atom (R f ).
  • R f is a monovalent fluorinated organic group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom. Specific examples include H (CF 2 ) m CH 0 , F (CF 2 ) m CH o CH 0 (m is 2 to 10), and particularly water-decomposability. From H (CF.) 2 CH 2 — and H (CF 2 ) 4 CH. Short-chain phenolic alkyl groups, such as CF 3 CF 2 CH 2 , etc., are preferred.
  • R f may be introduced as at least one of R in the formula (1) or the formula (2).
  • the fact that the fluorine content in the silicon-containing compound (A) is less than 5% by weight is based on the formula (1) and the formula (2). This can be easily achieved if the non-fluorine system is a fluorine-containing alcohol including the alcohol of the formula (3).
  • the non-fluorine system is a fluorine-containing alcohol including the alcohol of the formula (3).
  • the reaction ratio of the formula (1), the formula (2) and the formula (3) is different depending on which compound has a fluorine atom introduced therein.
  • it is an alkoxysilane non-fluorine system of the formula (1) and the formula (2), and the fluorine-containing alcohol is used as the formula (3).
  • the fluorine content in the raw material mixture should be considered.
  • the non-fluorine-based formula (1) is a co-condensate with a fluorine atom-containing alcohol with a molar ratio of 1Z3 to 20 per unit of a silicon atom in formula (2).
  • the weight fraction of the fluorine atom in the fluorine-containing alcohol is 0.:! It should be charged so that it is 30%, usually 1-10%.
  • the production of the silicon-containing compound (A) is carried out according to the formulas (1) and (2).
  • the alcohol of formula (3) may be mixed with the formula (2), which may be an oligomer. However, it can be obtained by heating in the presence of a catalyst.
  • a mixture of the formulas (1) and (2) in the formula (2) may be an oligomer. Heating may be carried out in the presence of a catalyst, and if necessary, a distillation operation may be carried out. Then, heating may be carried out by adding the phenol compound of the formula (3).
  • the catalyst includes, for example, hydrochloric acid, sulfuric acid, acetic acid, paranorenens olenoic acid, ammonia, trimethylamine, triethylamine, and the like.
  • Min triplamine, 1, 8 — diaza bicyclo (5, 4, 0) ⁇ decene 1-7 (DBU), (1) 1 snow, ° Tin, 4 — N, N — Dimethylaminopyrimidine, Monoethanolamine, Triethanolamine, ⁇ , ⁇ , ⁇ ' , ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ t — Butoxy, sodium ethoxide, hydroxylated tetramethylammonium, ammonium hydrogen sulfate tetramethylammonium , water Acid
  • reaction solvent examples include methanol, ethanol, and isoprono. No-nore, n-butano-no-re, t-butano-no-no-re, octano-no-re, 2, 2, 2, 2-trif-no-re-hole Etano-no-re, 2, 2, 3 , 3,3 — phenolic and other phenolic alcohols, tetrahydrofuran, 1,4-dioxane, tetra Ethers such as hydroxysilane, acetone, acetic acid 2-ketones / esters such as methoxyethyl, N, N-dimethyl Norehole amide, N, N—Dimethylacetamide, N—Methylacetate amide, N—Methinolepyrrolidon, Polio Amides such as oxazoline, acetic acid, trifluoroacetic acid, power oleonic acids such as F (CF ⁇ ) g C00
  • 2,2,2-Trifluorene Nono, 2,2,3,3,3—Pentafluoroethanol, Tetrahydrofuran , 1, 4 — Zoxan, tetrahydropyran is preferred. If phenol is used as the reaction solvent, it is preferable to distill the alcohol after the co-condensation by distillation or the like from the viewpoint of inhibiting the curing reaction. It is better.
  • the obtained co-condensate does not contain a silane group from the viewpoint of surface hydrophilicity.
  • the compound containing a compound (A) has a number-average molecular weight measured by GPC (converted to polystyrene using tetrahydrofuran as a solvent). Is preferably from 2000 to 5000, particularly preferably from 2500 to 3500, from the viewpoints of surface hydrophilicity, storage stability of the compound containing silicon and appearance of the coating film.
  • the compounding amount of the silicon-containing compound (A) is 0.1 to 60 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the coating resin (B). If the amount is less than 0.1 parts by weight, the anti-staining property tends to decrease.If the amount exceeds 80 parts by weight, the coating film cracks and the compatibility with the resin increases. Degradation may occur.
  • the coating composition of the present invention comprises (A) the above-mentioned specified compound containing a compound acting as an antifouling agent, (B) a coating resin, and (C) a curing agent, if necessary. And / or curing catalyst power, which imparts to the coating film, such as excellent antifouling adhesion properties, low electrification properties, and anti-fog properties.
  • the resin for coating (B) is, for example, a solvent-soluble, hydroxyl- and / or carboxyl-containing phenolic olefin resin.
  • Polymer Acrylic Polyol Resin, Acrylic Silicone Resin, Inorganic Material, Independent Weight of Fushidani Vinylidene Not Having a Functional Group Aqueous or copolymerized polymer, composite aqueous dispersion of fusidani vinylidene copolymer and acrylyl copolymer, or phenolic lipstick An aqueous dispersion of a vinyl ether copolymer is preferred.
  • the fluoroolefin copolymer having a hydroxyl group and / or a carboxy group for example, Japanese Patent Publication No. Sho 60-21686 , JP-A-3-121107, JP-A-4-27961, JP-A-4-28707, JP-A-2-2322221, etc.
  • the number average molecular weight (according to GPC) of the copolymer is from 1,000 to 100,000, preferably from 1,500 to 30,000. No. If the molecular weight is less than 100, the curability and weather resistance tend to be insufficient, and if the molecular weight exceeds 100, there is a problem in workability and paintability. There is a tendency to occur.
  • the hydroxyl value of this copolymer is from 0 to 200 (mg KOH / g), preferably from 0 to 150 (mg KOH / g). If it exceeds 200 (mg K0H / g), there is a tendency to cause a problem in the flexibility of the coating film.
  • the acid value is from 0 to 100 (mg KOH / g), and more preferably from 0 to 50 (mg KOH). If it exceeds 100 (mg KOH / g), there is a tendency that a problem occurs in the flexibility of the coating film.
  • one of the copolymers has a hydroxyl group or a carboxyl group from the viewpoints of anti-staining property, anti-staining property, and anti-staining property.
  • a solvent soluble tetrafluoroethylene copolymer may also be used.
  • copolymer examples include Zefflu manufactured by Daikin Industries, Ltd., Lumifuron manufactured by Asahi Glass Co., Ltd., and Central Glass Co., Ltd. Marketed products such as Cefral Co., Ltd., Finknet by DINKI INK CHEMICAL INDUSTRIES CO., LTD., And ZAFLON by Toa Kasei Co., Ltd. are available. .
  • the acrylic polyol resin a known resin can be used.
  • the resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group.
  • the hydroxyl value of the acrylpolyol resin is 0 to 200 (mgKOH / g), and 0 to: L00 (mgKOHZg) is preferable. If it exceeds 200 (mg KOH / g), there is a tendency to cause a problem in the flexibility of the coating film.
  • the acid value of the acrylic polyol resin is from 0 to: L00 (mgKOH / g), and more preferably from 0 to 50 (mgKOH / g). . If it exceeds 100 (mg KOH / g), there is a tendency that a problem occurs in the flexibility of the coating film.
  • acrylic resin are Dynal made by Mitsubishi Rayon Co., Ltd. and Acrylic made by Dainippon Ink Chemical Industry Co., Ltd. It is possible to use commercial products such as Dick, Hitaroid manufactured by Hitachi Chemical Co., Ltd., and a hoster manufactured by Mitsui Toatsu Chemicals, Inc.
  • acrylic silicone resin examples include a hydroxyl group silicone monomer and a hydroxyl group-containing monomer or other polymerizable unsaturated monomer. It only needs to be polymerized with the body.
  • the acrylic silicone resin may have a force II water-decomposable silyl group, hydroxyl group, or epoxy group.
  • acrylic silicone resins examples include Zemlack, manufactured by Kane-Fuchi Ridakaku Industry Co., Ltd., and Kryama, manufactured by Sanyo Chemical Industry Co., Ltd. Commercial products can be used.
  • the inorganic material examples include non-fluorine-containing non-hydrolyzable group-containing metals (such as Si, Ti, and A1), and non-fluorine-containing non-fluorine-containing metals.
  • Non-fluorine-containing non-hydrolyzable group-containing metals such as Si, Ti, and A1
  • non-fluorine-containing non-fluorine-containing metals such as Si, Ti, and A1
  • Gunze Industries Co., Ltd. launched Ecotone, Nihon Gosei Gum Co., Ltd.'s glass power, Tobebe
  • a fluorine resin having no functional group Japanese Patent Publication No. 43-10363, Japanese Patent Application Laid-Open No. 3-28206, Japanese Patent Publication No.
  • the homopolymers and copolymers of Futsidani vinylidene described in each official gazette and the like are exposed, and the resin having the above-mentioned functional group is used as a resin. It can also be rendered.
  • a resin having no functional group it is not always necessary to use a curing agent or a hard catalyst in the coating composition of the present invention. .
  • the composite aqueous dispersion of the above-mentioned fluorinated vinylidene copolymer and acrylyl copolymer for example, JP-A-3-7784 and Japanese Unexamined Patent Publication No. Hei 8-12201 has been elaborated.
  • Examples of commercially available products include Zeffle manufactured by Daikin Industries, Ltd., and Japan. Floren made by Synthetic Rubber Industry Co., Ltd. is required.
  • aqueous dispersion of the above-mentioned phenolic vinous vinyl-vinyl ether copolymer for example, Japanese Unexamined Patent Publication No. 3-372252 is described.
  • Some of the products sold are Lumifront manufactured by Asahi Glass Co., Ltd., and Fumino manufactured by Ink Chemicals Co., Ltd. of Japan. You will be able to get more information.
  • the coating composition of the present invention may contain a hardening agent and a curing catalyst, as long as the present invention does not impair the antifouling adhesion property.
  • the curing agent examples include an isocyanate compound, a block isocyanate compound, a melamine resin, a dibasic acid, and a non-hydrated water.
  • Degradable group-containing silane compounds, epoxy resins, or acid anhydrides can be used, but from the viewpoints of weather resistance, acid resistance, and rain resistance, it is possible to use iso- Lock isocyanate and epoxy resin are preferred.
  • the above-mentioned isocyanate compound and block isocyanate compound are, for example, 2,41 tri-range isocyanate.
  • the mixing ratio of the resinate and the resin for paint is preferably 0.5 to 5.0 in terms of NC0 to 0H (molar ratio), and more preferably 0.8 to 1.2. Is more preferred. Also, if the iso- nate is of a moisture-hardening type, it is preferred that the strength be 1.1 to 1.5 force.
  • the above-mentioned melamin resin includes, for example, the strength of the melamin resin, and the methylolated polymer obtained by squeezing the melamin into the mouth.
  • Min tree month, melody, and alcohol are classified into alcohol, such as methanol, ethanol, butyl, and so on.
  • the power that can be used to derive the alkinoleate and melamine resin is not limited to these.
  • Examples of the acid anhydride include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrous anhydride.
  • Examples include, but are not limited to, dicarboxylic acid, succinic anhydride, anhydrous maleic acid, and the like.
  • fumaric acid succinic acid, adipic acid, azelinic acid, cenocinic acid, dodecanedioic acid, 1,2-cyclohexyl Dibasic acids such as rudicarboxylic acid are also used as curing agents.
  • the curing agent is used in an amount of 100 parts by weight or less, preferably 5 to 40 parts by weight, per 100 parts by weight of the coating resin (B).
  • Curing catalysts include, for example, organic tin compounds, organic acid phosphoric acid esters, organic titanate conjugates, acid phosphoric acid esters and a Reactant with min, saturated or unsaturated polyvalent Carboxylic acid or its anhydride, organic sulfonate, amide-based conjugate, aluminum chelate, titanium conjugate It can be used for chelate compounds, zirconium compounds, etc.
  • organic tin compounds include dibutyl tin glaurate, dibutyl tin maleate, and dioctinole tin.
  • mallet, dibutyls jiacetate, etc. are required.
  • organic acid phosphoric acid ester examples include:
  • organic titanium compounds include, for example, tetrabutyl titanate, tetraisopropinolate titanate, and tritium titanate. Titanate esters such as ethanol monoamine titanate are exposed.
  • examples of the above-mentioned amide-based compounds include, for example, petitamine, octylamine, dibutylamine, and monomono.
  • chelate compounds include aluminum tris (ethyl acetate acetate) and anoluminium tris (ethyl acetate).
  • Acetate Acetate Gil Conteum Tetrax (Acetate Acetate)
  • Jiso Propoxy Business (Acetate) (Ruacet acetate) Titanium, etc.
  • One hardening catalyst may be used, or two or more hardening catalysts may be used in combination.
  • Preferred hardening catalysts include organic tin compounds and anoluminum metal chelate compounds.
  • the combination of the resin for coating and the hardener and / or hardener catalyst is not particularly limited.
  • a combination that is not preferred is the one that is as follows.
  • stiffening agents such as isopropylate compounds and blockisoate anilide compounds Or melamine resin, and as a stiffening agent when it has a carboxinole group, it may be melamine resin or epoxy resin. It is a compound.
  • a hardening catalyst can also be used.
  • the curing catalyst is used in an amount of 50 parts by weight or less, preferably 0.0001 to 10 parts by weight, based on 100 parts by weight of the coating resin (B).
  • an organic solvent can be mixed into the coating composition.
  • organic solvent examples include charcoal such as xylene, toluene, sonolesso 100, solubeso 150, and hexane.
  • Hydrogen solvents methyl acetate, ethyl acetate, ethyl acetate, ethylene glycol acetate monomethyl ether, ethyl alcohol glycol Monomethyl ether, ethylene glycol monobutyrate, monoethyl alcohol ft, monoethylene glycol ft acid Monoethyl ether, diethylene glycol monoethyl ether, diethyl acetate acetate monobutyl ether, ethyl acetate Ester-based solvents such as glycol alcohol, diethyl acetate glycol, dimethyl ether, dimethyl ether, etc.
  • the fluorinated solvent a liquid at room temperature is desired, and trichlorofluorophenol, tetrachlorofluorene, etc. Tan, trichlorene trifluorene, jibromote rafurorotan, HCFC-123 HCFC-141 b HCFC-225, jikuroro Safluorocyclobutane, Tetraclorohexafluorobutane, Perfluoropentane, 0 — Fluoro mouth , One-fluoroheptane, perfluorooctane, and the like, but the above-mentioned compounds containing a gay compound, resin for paints, and curing agents It is desirable to simultaneously contain a fluorine atom, a chlorine atom, and a carbon atom in order to dissolve the HCFC-123 HCFC. — 141 b HCFC — 225, Tetrachloro is preferred.
  • the blending ratio of the paint resin and the alcohol-based solvent is 150 parts by weight with respect to 100 parts by weight of the paint resin, which indicates curability and appearance of the coating film. From 1 to 25 parts by weight Is even more preferred.
  • the coating composition of the present invention further includes, for example, a pigment, a pigment dispersant, a thickener, a leveling agent, a defoaming agent, a film-forming auxiliary, an ultraviolet absorber, HALS, anti-glazing agent, filler, colloidal silica, anti-fungal agent, silane coupling agent, anti-skinning agent, antioxidant, flame retardant,
  • a pigment for example, a pigment, a pigment dispersant, a thickener, a leveling agent, a defoaming agent, a film-forming auxiliary, an ultraviolet absorber, HALS, anti-glazing agent, filler, colloidal silica, anti-fungal agent, silane coupling agent, anti-skinning agent, antioxidant, flame retardant,
  • Additives can also be incorporated.
  • the coating composition of the present invention is suitable for coating materials such as metals, ceramics, plastics, cement, wood, and old coatings. Then, if necessary, the undercoat layer and the intermediate coat layer can be provided, and the coating can be performed. There are no particular restrictions on the method of painting, such as the mouth-coating method, spraying method, brush-coating method, roller method, flow-coating method, and date. Bing method can be adopted.
  • the thickness of the coating film is usually from l to 100 zm, preferably from l to 50 ⁇ m.
  • the articles coated with the coating composition of the present invention may be used for, for example, waterproof sheets for construction, waterproof sheets for tunnels, and agricultural vinyls.
  • HCF 2 CF 9 CH was added to 100 g of a co-condensate of methyltrimethoxysilane and ethyl silicate 40 synthesized in the same manner as in Synthesis Example 1. OH was added thereto, and the mixture was heated under reflux for 1 hour. Then, low boiling components such as methanol and ethanol were distilled off using a rectification column to obtain 106 g of a product.
  • the number average molecular weight by GPC was 3,300, and the fluorine content measured by elemental analysis was 4.8% by weight.
  • Zeffl LC-1974 White paint (Paint consisting of vinylidene fluoride copolymer and acryl resin manufactured by Daikin Industries, Ltd .: Resin solid content 30%) Then, 100 parts by weight (hereinafter referred to as “parts”) of the above and 150 parts of butylacetate are mixed, and 12.0 parts of the silicon-containing compound obtained in Synthesis Example 1 is added thereto. After stirring well, the coating composition of the present invention was obtained. This paint composition was pre-painted (spray coating) using a fluorine paint (white) as an undercoat paint (film thickness 50 // m). Luminium plates (7 x 15 x 0.5 cm) were painted, dried at room temperature for 1 week, and coated with a 40 m film thickness. The following tests were performed. The results are shown in Table 1.
  • the antifouling stain adhesion and appearance were evaluated. did . That is, the antifouling property was measured by measuring the difference (AL *) between the initial lightness of the coated plate and the lightness after exposure, and setting the AL * force, ', 0 or less than 0 to A , B when less than 1 to 2, C when less than 2 to 4, D when less than 4 to 6, and E when more than 6.
  • AL * the difference between the initial lightness of the coated plate and the lightness after exposure
  • bias refers to a phenomenon in which a coating film becomes wave-like after painting and drying, and the thickness of the coating film is not constant.
  • a coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • LC-1941 in Table 1 is Zeffl LC—941 manufactured by Daikin Industries, Ltd., and it means that it is a copolymer of Fuzihi vinylidene and an acrylic resin. It is a varnish for paint.
  • Zeffl GK-500 White paint (Daikin Industries, Ltd., a solvent-soluble fluorinated fluorinated copolymer butylene acetate solution: resin solid component 30 %) 100 parts and 150 parts of butyric acetate are mixed, and the mixture is mixed with Taken D-140 N (Isophorone ISO, manufactured by Takeda Pharmaceutical Co., Ltd.). 12.9 parts (NCO / OH-1.0) with the compound-based curing agent and dibutyltin dilaurate (12.0 parts) , And the mixture was thoroughly stirred to obtain a coating composition of the present invention. This coating composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 A coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a coating composition for comparison was prepared in the same manner as in Example 1 except that each component shown in Table 1 was used, and evaluated in the same manner as in Example 1.
  • Comparative Example 6 LF-200 (a hydroxyl group-containing solvent-soluble fluorine resin) manufactured by Asahi Glass Co., Ltd. was used as the resin. The results are shown in Table 1.
  • a coating composition which is effective in preventing adhesion of rain streaks and the like, and which can maintain the appearance of a coating film stably for a long period of time. It can be provided at a low price.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de matière de revêtement bon marché, susceptible de former des films pouvant maintenir un effet de protection contre les taches ainsi qu'une apparence excellente, de manière stable sur une durée prolongée. La composition comporte (A) un co-condensat constitué d'un composé représenté par la formule générale (1): XSi(OR)3, et d'un composé représenté par la formule générale (2): Si(OR)4 ou d'un oligomère de celui-ci (X étant hydrogène ou un alkyle en C1-C5, et les R étant chacun indépendamment un groupe organique monovalent en C1-C10 contenant éventuellement de l'oxygène, de l'azote ou du fluor) qui présente une teneur en fluor inférieure à 5 % en poids, le cas échéant; et (B) une résine de revêtement.
PCT/JP1998/004784 1997-10-29 1998-10-21 Composition de matiere de revetement WO1999021929A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP29717497A JPH11131020A (ja) 1997-10-29 1997-10-29 塗料用組成物
JP9/297174 1997-10-29

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WO1999021929A1 true WO1999021929A1 (fr) 1999-05-06

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JP2002129110A (ja) * 2000-10-31 2002-05-09 Asahi Glass Co Ltd 水性塗料用組成物
JP2002138251A (ja) * 2000-11-01 2002-05-14 Asahi Glass Co Ltd 水性塗料用組成物
JP2003020450A (ja) * 2001-07-09 2003-01-24 Nippon Paint Co Ltd 耐汚染性塗料組成物および塗膜形成方法
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JPS63243174A (ja) * 1987-03-30 1988-10-11 Sumitomo Chem Co Ltd 高純度シリカ被膜形成用塗布液
JPH06136321A (ja) * 1991-10-17 1994-05-17 Agency Of Ind Science & Technol ポリウレタン・シリカハイブリット体の製造方法及びアルコールゾル溶液
JPH0812922A (ja) * 1993-07-14 1996-01-16 Asahi Glass Co Ltd 屋外物品表面を処理する方法
JPH09111120A (ja) * 1995-10-17 1997-04-28 Agency Of Ind Science & Technol アルコール性シリカゾル組成物とそれを用いたプラスチック基材の表面改質方法
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* Cited by examiner, † Cited by third party
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JPS63243174A (ja) * 1987-03-30 1988-10-11 Sumitomo Chem Co Ltd 高純度シリカ被膜形成用塗布液
JPH06136321A (ja) * 1991-10-17 1994-05-17 Agency Of Ind Science & Technol ポリウレタン・シリカハイブリット体の製造方法及びアルコールゾル溶液
JPH0812922A (ja) * 1993-07-14 1996-01-16 Asahi Glass Co Ltd 屋外物品表面を処理する方法
JPH09111120A (ja) * 1995-10-17 1997-04-28 Agency Of Ind Science & Technol アルコール性シリカゾル組成物とそれを用いたプラスチック基材の表面改質方法
JPH10110078A (ja) * 1996-10-09 1998-04-28 Daikin Ind Ltd 含フッ素樹脂水性分散体組成物

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