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WO2012036183A1 - Composition de revêtement résistante à la contamination ayant une excellente durabilité - Google Patents

Composition de revêtement résistante à la contamination ayant une excellente durabilité Download PDF

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Publication number
WO2012036183A1
WO2012036183A1 PCT/JP2011/070932 JP2011070932W WO2012036183A1 WO 2012036183 A1 WO2012036183 A1 WO 2012036183A1 JP 2011070932 W JP2011070932 W JP 2011070932W WO 2012036183 A1 WO2012036183 A1 WO 2012036183A1
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WO
WIPO (PCT)
Prior art keywords
component
acid
group
coating
resin
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2011/070932
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English (en)
Japanese (ja)
Inventor
松田　英樹
武司 内田
正人 中水
眞弘 林
裕也 三好
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Filing date
Publication date
Application filed by Kansai Paint Co Ltd filed Critical Kansai Paint Co Ltd
Priority to JP2012534027A priority Critical patent/JP5840132B2/ja
Publication of WO2012036183A1 publication Critical patent/WO2012036183A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/02—Polysilicates

Definitions

  • the present invention relates to a stain-resistant coating composition that can form a coating film having excellent stain resistance retention over time mainly against rainwater and the like, particularly a stain-resistant coating composition suitable for forming a top coating film on a coated metal plate,
  • the present invention relates to a method for forming a coating film excellent in rainwater stain resistance using a stain-resistant coating composition, and a coated metal plate on which a cured coating film is formed from the stain-resistant coating composition.
  • outdoor base materials for example, buildings, display objects, guard fences, appliances, machines, etc.
  • outdoor paints excellent in weather resistance for the purpose of decoration or protection.
  • paints used outdoors include polyurethane resin-containing paints, fluororesin-containing paints, silicon resin-containing paints, acrylic resin-containing paints, polyester-containing paints, and the like, but these paints are exposed outdoors.
  • the surface of the coated material is easily soiled by the influence of dust, iron powder, rain (acid rain), sunlight, and the like, and the appearance of the coating film is deteriorated.
  • the applicant of the present invention is an organic solvent-based coating composition (1) containing a hydroxyl group-containing fluororesin and an amino resin crosslinking agent as a reaction-curable organic resin, or a hydroxyl group-containing fluororesin and / or a hydroxyl group-containing
  • a paint comprising an organic solvent-containing paint composition (2) containing an acrylic resin and a (blocked) polyisocyanate compound crosslinking agent as a reaction-curable organic resin, and a tetraalkyl silicate and / or a condensate thereof.
  • the top coating composition of Patent Document 1 has insufficient resistance to contamination against rainwater, such as rain streak stains, when used outdoors, and is resistant to rainwater, etc. even in the initial stage of outdoor use. Contamination was not sufficient.
  • a stain-resistant coating composition that suppresses the adhesion of substances that cause dirt and has good stain removal
  • a polyester resin (b) a crosslinking agent, and (c) a polyester containing a hydroxyl group or a carboxyl group
  • a stain-resistant coating composition mainly composed of a modified polysiloxane compound and / or a polyether-modified polysiloxane compound containing a hydroxyl group or a carboxyl group, and (d) fluororesin particles (Patent Document 2). reference).
  • thermosetting resin composition comprising an amino resin, (C) an alkoxysilane compound, and (D) a curing catalyst has been proposed.
  • a coating film having a gloss less than semi-gloss 60 ° gloss is about 50 or less
  • the stain resistance and the corrosion resistance were insufficient.
  • the present invention relates to a stain-resistant paint composition capable of forming a coating film excellent in stain resistance and corrosion resistance retention against rainwater and the like, and in particular, a stain-resistant paint suitable for forming a top coat film of a glossy coated metal plate having a semi-gloss or less. It is to provide a composition.
  • a resin containing a polyester resin component containing a specific hydroxyl group-containing polyester resin and a melamine resin component containing a butyl etherified melamine resin A coating composition containing a specific organosilicate and / or its condensate component and a fluorine atom-containing non-aqueous dispersion type resin component in the binder (especially, gloss less than semi-gloss (60 ° gloss is about 50 or less)) It was found that a coating film excellent in retention of contamination resistance against rain water and the like can be formed, and the present invention has been completed.
  • the present invention includes the following inventions: Item 1, (A) A polyester resin component containing 50 to 100% by mass of a hydroxyl group-containing polyester resin (A1) having a number average molecular weight of 5000 to 30000 and a hydroxyl value of 5 to 100 mgKOH / g as a solid content, A polyester resin component obtained by a reaction of (a1) a polybasic acid component and (a2) an alcohol component; (B) a melamine resin component containing 30 to 100% by mass of butyl etherified melamine resin (B1) as a solid content, (C) Organosilicate represented by the following general formula and / or its condensate component: General formula: (R 1 ) n —Si— (OR 2 ) 4-n [Wherein, R 1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group which may be substituted with an epoxy group or a mercapto group, R 2 is an alkyl group having 1 to 6 carbon atom
  • component (D) a coating composition containing a fluorine atom-containing non-aqueous dispersion type resin, Based on the total solid content of component (A) and component (B), The content of the component (C) is 1 to 20% by mass, Component (D) content is 5-30% by mass An antifouling paint composition characterized by the above.
  • the fluorine atom-containing non-aqueous dispersion resin (D) is obtained by copolymerizing a polymerizable unsaturated monomer in a mixed liquid of a fluorine atom-containing dispersion stabilizer (D1a) and an organic solvent (D1b).
  • D1a fluorine atom-containing dispersion stabilizer
  • D1b organic solvent
  • Item 2 The antifouling paint composition according to Item 1, which is a non-aqueous dispersion type resin that can be prepared by forming polymer particles (D1c) insoluble in the liquid.
  • the fluorine atom-containing dispersion stabilizer (D1a) is a polymer obtained by copolymerizing a polymerizable unsaturated monomer containing a fluoroalkyl group-containing (meth) acrylate and / or a fluoroolefin The antifouling paint composition described in 1.
  • the total content of the alicyclic polybasic acid (a1-1) in the polybasic acid component (a1) is the total amount of the polybasic acid component (a1).
  • Item 2 The antifouling paint composition according to Item 1, which is in the range of 50 to 100 mol% based on
  • the polyester resin component (A) is 50 to 90% by mass, and the melamine resin component (B) is solid.
  • Item 5 The antifouling paint composition according to any one of Items 1 to 3, which is contained in an amount of 10 to 50% by mass.
  • Item 6 The contamination-resistant paint composition according to any one of Items 1 to 4, further comprising a matting agent (E).
  • Item 7 A step of forming a primer coating with a chromium-free primer coating on one side or both sides of a metal plate, and a top coating with at least one of the primer coatings with a stain-resistant coating composition according to Item 1.
  • a method of forming a coating film comprising a step of forming a coating film.
  • Item 8 A step of forming a primer coating with a chromium-free primer coating on one or both surfaces of a metal plate, and a top coating with a stain-resistant coating composition according to Item 1 on at least one of the primer coatings
  • the antifouling paint composition of the present invention comprises a resin binder containing a polyester resin component containing a specific hydroxyl group-containing polyester resin and a melamine resin component containing a butyl etherified melamine resin, a specific organosilicate and / or condensation thereof.
  • the coating film with the stain resistant coating composition of the present invention can form a coating film having excellent anti-staining property against rainwater etc., particularly when the coating film is semi-glossy or glossy. Although it is not clear, I think as follows.
  • anti-staining paints that combine fluorine atom-containing polymers and silicate compounds (silicone compounds) with the aim of synergistic action of water repellency and oil repellency due to the characteristics of fluorine atoms and hydrophilization with the generated silanol.
  • fluorine atom-containing polymers and silicate compounds silicone compounds
  • the antifouling component in the antifouling coating composition of the present invention is an organosilicate and / or a condensate component thereof, and a fluorine atom-containing non-aqueous dispersion type resin component, and a fluorine atom-containing polymer and a silicate compound are used in combination. Is.
  • the fluorine atom-containing non-aqueous dispersion type resin component is a polymer particle in a form in which it is dispersed in an insoluble state in an organic solvent containing a dispersion stabilizer.
  • a fluorine atom-containing polymer and a silicate compound silicate compound
  • both the fluorine atom-containing component and the silicate component are uniformly present on the surface of the coating film. This is considered to be because a good distribution state is obtained.
  • a glossy film that is less than semi-glossy with a matting agent, etc. has a more uneven surface shape, better water wetting, and is exposed to more severe conditions regarding hydrolysis resistance. Therefore, when the conventional polyester paint system is used, the deterioration of the painted surface (choking, etc.) is accelerated, and the appearance is not good.
  • the coating film obtained by the stain-resistant coating composition of the present invention is highly resistant to stains by fully exhibiting the synergistic effect of water repellency, oil repellency due to the characteristics of fluorine atoms and hydrophilization due to the generated silanol. Since it is excellent, it is considered that excellent appearance and stain resistance retention can be exhibited as compared with conventional polyester paint systems.
  • the antifouling paint composition of the present invention comprises the following polyester resin component (A), melamine resin component (B), organosilicate and / or its condensate component (C), and fluorine atom-containing non-aqueous dispersion. It is a coating composition containing a mold resin component (D).
  • the polyester resin component (A) comprises the following hydroxyl group-containing polyester resin (A1) in a solid content of 50 to 50% based on the total solid content of the polyester resin component (A). Contains 100% by mass.
  • the hydroxyl-containing polyester resin (A1) which is an essential component of the polyester resin component (A), is usually an esterification reaction or ester with the following polybasic acid component (a1) and alcohol component (a2). It can be produced by an exchange reaction.
  • polybasic acid component (a1) a compound usually used as a polybasic acid component in the production of a polyester resin can be used.
  • polybasic acid component (a1) for example, an alicyclic polybasic acid (a1-1), an aliphatic polybasic acid (a1-2), an aromatic polybasic acid (a1-3), etc. should be used. Can do.
  • the alicyclic polybasic acid (a1-1) is generally a compound having one or more alicyclic structures (for example, 4 to 6 membered rings) and two or more carboxyl groups in one molecule, An acid anhydride and an esterified product of the compound.
  • Examples of the alicyclic polybasic acid (a1-1) include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid.
  • Alicyclics such as acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid
  • Polyhydric carboxylic acids; anhydrides of these alicyclic polyvalent carboxylic acids; lower alkyl esterified products of these alicyclic polyvalent carboxylic acids herein, “lower alkyl” in this specification means, for example, carbon number 1 Refers to about 5 alkyls).
  • the alicyclic polybasic acid (a1-1) can be used alone or in combination of two or more.
  • 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-Cyclohexene-1,2-dicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic anhydride can be preferably used.
  • 1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid anhydride can be particularly preferably used from the viewpoint of hydrolysis resistance.
  • the total content of the alicyclic polybasic acid (a1-1) is selected from the viewpoints of hydrolysis resistance and stain resistance of the polybasic acid component (a1). Based on the total amount, it is preferably in the range of 50 to 100 mol%, particularly 70 to 100 mol%, more particularly 80 to 100 mol%.
  • the aliphatic polybasic acid (a1-2) is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, an esterified product of the aliphatic compound, and the like.
  • succinic acid glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, octadecanedioic acid, citric acid, etc.
  • Carboxylic acid anhydrides of these aliphatic polyvalent carboxylic acids; lower alkyl esterified products of these aliphatic polyvalent carboxylic acids.
  • the aliphatic polybasic acid (a1-2) can be used alone or in combination of two or more.
  • a dicarboxylic acid having an alkyl chain having 4 to 18 carbon atoms examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, and octadecanedioic acid.
  • adipic acid can be preferably used.
  • the aromatic polybasic acid (a1-3) is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, an esterified product of the aromatic compound, and the like.
  • aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, and pyromellitic acid
  • Carboxylic anhydrides lower alkyl esterified products of these aromatic polycarboxylic acids.
  • the aromatic polybasic acid (a1-3) can be used alone or in combination of two or more.
  • examples of the acid component include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed Fatty acids such as oil fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid Examples thereof include monocarboxylic acids such as acid, cyclohexane acid, and 10-phenyloctadecanoic acid; hydroxycarboxylic acids such as lactic acid, citric acid, 3-hydroxybutanoic acid, and 3-hydroxy-4-ethoxybenzoic acid
  • Fatty acid (a3) is a monovalent carboxylic acid of a linear hydrocarbon, such as coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid Fatty acids such as paulownia oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, etc. it can.
  • the said fatty acid can be used individually or in combination of 2 or more types.
  • the iodine value is a numerical value serving as an index representing the degree of unsaturation of the compound, and is represented by the number of g of iodine absorbed by 100 g of the sample.
  • the measurement can be performed according to the standard of JIS K 5421.
  • coconut oil fatty acid lauric acid, myristic acid, palmitic acid, stearic acid, especially coconut oil fatty acid can be suitably used as the fatty acid (a3).
  • the alcohol component (a2) a polyhydric alcohol having two or more hydroxyl groups in one molecule can be suitably used.
  • the polyhydric alcohol include alicyclic diol (a2-1), aliphatic diol (a2-2), and aromatic diol (a2-3).
  • the alicyclic diol (a2-1) is generally a compound having one or more alicyclic structures (for example, 4 to 6 membered rings) and two hydroxyl groups in one molecule.
  • Examples of the alicyclic diol (a2-1) include dihydric alcohols such as 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, and the like.
  • Examples include polylactone diols to which a lactone compound such as ⁇ -caprolactone is added, and these can be used alone or in combination of two or more.
  • the aliphatic diol (a2-2) is generally an aliphatic compound having two hydroxyl groups in one molecule.
  • Examples of the aliphatic diol (a2-2) include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3-butane.
  • the aromatic diol (a2-3) is generally an aromatic compound having two hydroxyl groups in one molecule.
  • Examples of the aromatic diol (a2-3) include ester diol compounds such as bis (hydroxyethyl) terephthalate; alkylene oxide adducts of bisphenol A, and these are used alone or in combination of two or more. be able to.
  • polyhydric alcohols other than the alicyclic diol (a2-1), aliphatic diol (a2-2), and aromatic diol (a2-3) include polyglycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol.
  • Ether diol compounds glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol And trihydric or higher alcohols such as polylactone polyol compounds obtained by adding a lactone compound such as ⁇ -caprolactone to these trihydric or higher alcohols.
  • trivalent or higher alcohols can be suitably used from the viewpoint of increasing the molecular weight and improving the reactivity of the modification reaction with the fatty acid (a3) when the fatty acid (a3) is used.
  • trihydric or higher polyhydric alcohol examples include glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol and the like.
  • trimethylolpropane is particularly preferable.
  • the total content of the trihydric or higher polyhydric alcohol in the alcohol component (a2) is 10 to 70 mol%, particularly 20%, based on the total amount of the alcohol component (a2). It is preferably in the range of ⁇ 65 mol%, more preferably in the range of 30 ⁇ 60 mol%.
  • Examples of the alcohol component (a2) other than the polyhydric alcohol include monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, and 2-phenoxyethanol; propylene oxide, butylene oxide, and synthetic highly branched saturated fatty acids.
  • An alcohol compound obtained by reacting a monoepoxy compound with an acid such as glycidyl ester (trade name “Cardura E10” manufactured by HEXION Specialty Chemicals) and the like can be used as necessary.
  • the production of the hydroxyl group-containing polyester resin (A1) is not particularly limited, and can be performed according to a usual method.
  • the acid component having the polybasic acid component (a1) as an essential component and the alcohol component (a2) are reacted in a nitrogen stream at 150 to 250 ° C. for 5 to 10 hours to produce an esterification reaction or a transesterification reaction. Can be manufactured.
  • the acid component and alcohol component (a2) may be added at once, or may be added in several portions. Moreover, after synthesize
  • a catalyst may be used to promote the reaction.
  • known catalysts such as dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, and tetraisopropyl titanate can be used.
  • the hydroxyl group-containing polyester resin (A1) can be modified with a fatty acid, a monoepoxy compound, a polyisocyanate compound or the like during the preparation of the resin, or after the esterification reaction or the transesterification reaction.
  • fatty acid examples include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor An oil fatty acid, safflower oil fatty acid, etc. can be mentioned.
  • a glycidyl ester of a synthetic highly branched saturated fatty acid (trade name “Cardura E10” manufactured by HEXION Specialty Chemicals) can be suitably used.
  • polyisocyanate compound examples include aliphatic diisocyanate compounds such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6 Alicyclic diisocyanate compounds such as diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate; lysine Organic polyisocyanate such as triisocyanate or higher polyisocyanate such as triisocyanate As such, or an adduct of each of these organic polyisocyanate
  • the number average molecular weight of the hydroxyl group-containing polyester resin (A1) is from 5,000 to 30,000, particularly from 7,000 to 25,000, more particularly from 10,000 to 20,000, from the viewpoints of the processability and smoothness of the resulting coating film. It is preferable to have
  • the number average molecular weight and the weight average molecular weight are values obtained by converting the number average molecular weight and the weight average molecular weight measured using a gel permeation chromatograph (GPC) based on the molecular weight of standard polystyrene. is there.
  • GPC gel permeation chromatograph
  • HLC8120GPC trade name, manufactured by Tosoh Corporation
  • TSK-gel G4000 HXL “TSK-gel G3000 HXL ”
  • Four TSK-gel G2500 HXL ”and“ TSK-gel G2000 HXL ” (trade names, all manufactured by Tosoh Corporation) were used.
  • Mobile phase tetrahydrofuran, measuring temperature 40 ° C., flow rate 1 mL / min, detector RI Can be measured under the following conditions.
  • the hydroxyl value of the hydroxyl group-containing polyester resin (A1) is from 5 to 100 mgKOH / g, particularly from 10 to 90 mgKOH / g, more particularly from 40 to 80 mgKOH / g, from the viewpoint of curability of the resulting coating film. It is preferable to have a valence.
  • the acid value of the hydroxyl group-containing polyester resin (A1) is preferably in the range of 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, from the viewpoints of processability and water resistance.
  • Adjustment of the number average molecular weight, the hydroxyl value, and the acid value of the hydroxyl group-containing polyester resin (A1) is, for example, an acid component (polybasic acid component (a1) having the polybasic acid component (a1) as an essential component and as necessary.
  • the equivalent ratio (COOH / OH) of the carboxyl group in the acid component containing the polybasic acid component (a1) as an essential component to the hydroxyl group in the alcohol component (a2) is generally 0.5 to 0.98. It is preferable to be within the range.
  • the hydroxyl group-containing polyester resin (A1) preferably has a glass transition temperature in the range of 0 to 50 ° C., preferably 10 to 40 ° C., from the viewpoint of the hardness and workability of the resulting coating film.
  • the glass transition temperature (Tg) is a value (glass transition temperature) measured by differential thermal analysis (DSC).
  • the hydroxyl group-containing polyester resin (A1) is an oil in the range of 3 to 30%, preferably 5 to 20%, from the viewpoint of the weather resistance of the resulting coating film. It is preferred to have a length.
  • the oil length is a mass% of the fatty acid component (a3) with respect to the total amount of the acid component and the alcohol component (a2) having the polybasic acid component (a1) and the fatty acid (a3) as essential components as essential components. .
  • polyester resin component (A) a polyester resin (A2) other than the hydroxyl group-containing polyester resin (A1) can also be included.
  • the polyester resin (A2) is a polyester resin obtained by an esterification reaction or transesterification reaction of an acid component and an alcohol component (a2) having the polybasic acid component (a1) as an essential component by a conventional method.
  • the acid component and alcohol component (a2) having the component (a1) as essential components those exemplified for the hydroxyl group-containing polyester resin (A1), and the method exemplified for the hydroxyl group-containing polyester resin (A1) Similarly, it can be manufactured.
  • the solid content of the hydroxyl group-containing polyester resin (A1) is 50 to 100% by mass from the viewpoint of stain resistance of the resulting coating film. Is within the range. It is preferably in the range of 60 to 100% by mass, more preferably 70 to 100% by mass.
  • the melamine resin component (B) contains the following butyl etherified melamine resin (B1) in a solid content of 30 to 100% by mass with respect to the total solid content of the melamine resin component (B). .
  • butyletherified melamine resin is a methylolated melamine resin that is an addition reaction product (either a monomer or a multimer) of melamine and an aldehyde component such as formaldehyde or paraformaldehyde. It is a melamine resin obtained by etherifying a part or all of the methylol groups therein with n-butyl alcohol or isobutyl alcohol.
  • the butyl etherified melamine resin includes a melamine resin obtained by etherifying some or all of the methylol groups in the methylolated melamine resin with n-butyl alcohol, a melamine resin etherified with isobutyl alcohol, n-butyl alcohol and Any melamine resin etherified with isobutyl alcohol is included.
  • the number average molecular weight of the butyl etherified melamine resin is preferably in the range of 800 to 8000, particularly preferably in the range of 1000 to 5000, from the viewpoint of the processability and stain resistance of the resulting coating film.
  • the butyl etherified melamine resin (B1) can be used alone or as a mixture of two or more.
  • butyl etherified melamine resin (B1) examples include, for example, Uban 20SE, Uban 225 (all of which are trade names, manufactured by Mitsui Chemicals, Inc.), Super Becamine J820-60, Super Becamine L-117- 60, Super Becamine L-109-65, Super Becamine 47-508-60, Super Becamine L-118-60, Super Becamine G821-60 (all of which are manufactured by DIC Corporation, trade name), etc. Can be mentioned.
  • melamine resin component (B) As the melamine resin component (B), a melamine resin (melamine resin (B2)) other than the butyl etherified melamine resin (B1) can be included.
  • a methylol group in a methylolated melamine resin which is an addition reaction product of melamine and an aldehyde component such as formaldehyde or paraformaldehyde (which may be either a monomer or a multimer).
  • Melamine resin partly or entirely etherified with one or more alcohols other than n-butyl alcohol and isobutyl alcohol, n-butyl alcohol and / or isobutyl alcohol, and other than n-butyl alcohol and isobutyl alcohol Mention may be made of melamine resins etherified with one or more alcohols.
  • alcohols other than n-butyl alcohol and isobutyl alcohol used for etherification include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, 2-ethylbutanol and 2-ethylhexanol.
  • Specific examples of the melamine resin (B2) include melamine resin etherified with methyl alcohol (methyl etherified melamine resin), melamine resin etherified with methyl alcohol and butyl alcohol (methyl / butyl mixed etherified melamine resin), and the like. It is done.
  • Examples of the melamine resin etherified with methyl alcohol include Sumimar M-100, Sumimar M-40S, Sumimar M-55 (all trade names, manufactured by Sumitomo Chemical Co., Ltd.), Cymel 300, Cymel 303, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 730, Cymel 736, Cymel 738 (all are trade names manufactured by Nippon Cytec Industries, Inc.), Mellan 522, Mellan 523 (all are Hitachi Chemical Industries, Ltd.) Co., Ltd., trade name), Nicarak MS17, Nicarak MS15, Nicarak MS001, Nicarak MX430, Nicarak MX650 (all are Sanwa Chemical Co., Ltd., trade name), Resimin 740, Resimin 741, Resimin 747 (all above, all Monsan Company Ltd., methyl etherified melamine resins trade name).
  • Examples of melamine resins etherified with methyl alcohol and butyl alcohol include Cymel 232, Cymel 235, Cymel 202, Cymel 238, Cymel 254, v266, Cymel 272, Cymel 1130, Cymel XV-514, Cymel XV805 (all in Japan) Cytec Industries Co., Ltd., trade name), Sumimar M66B (Sumitomo Chemical Co., trade name), Resimin 753, Resimin 755 (all of which are made by Monsanto, trade name), etc. Mention may be made of etherified melamine resins.
  • the solid content of the butyl etherified melamine resin (B1) is based on the total solid content of the melamine resin component (B), from the viewpoint of the workability of the resulting coating film and the stain resistance retention, It is within the range of 30 to 100% by mass. It is preferably in the range of 50 to 100% by mass, more preferably 70 to 100% by mass.
  • the butyl etherified melamine resin (B1) has a lower polarity than the methyl etherified melamine resin, methyl / butyl mixed etherified melamine resin and the like, and has good compatibility with the polyester resin (A) as the base resin. Therefore, the coating film obtained from the antifouling paint composition containing the butyl etherified melamine resin (B1) has excellent uniformity of crosslinking.
  • the butyl etherified melamine resin (B1) is less likely to be localized on the surface layer in the coating film than the methyl etherified melamine resin and the methyl / butyl mixed etherified melamine resin. Therefore, the coating film obtained from the stain-resistant coating composition containing the butyl etherified melamine resin (B1) has excellent weather resistance.
  • a curing catalyst can be used as necessary.
  • a sulfonic acid compound or a neutralized product of a sulfonic acid compound can be generally used.
  • Examples of the sulfonic acid compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like.
  • Examples of the neutralizing agent in the neutralized product of the sulfonic acid compound include basic compounds such as primary amine, secondary amine, tertiary amine, ammonia, caustic soda, and caustic potash.
  • the ratio of the polyester resin component (A) and the melamine resin component (B) is based on the total amount of the polyester resin component (A) and the melamine resin component (B).
  • the component (A) is 50 to 90% by mass, particularly 60 to 80% by mass
  • the melamine resin component (B) is 10 to 50% by mass, particularly 20 to 40% by mass
  • the resulting coating film is cured. From the viewpoint of resistance, contamination resistance, mechanical strength, workability, solvent resistance, corrosion resistance, weather resistance, and the like.
  • (C) Organosilicate and / or its condensate component (C) component of the present invention, General formula: (R 1 ) n —Si— (OR 2 ) 4-n [Wherein, R 1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group which may be substituted with an epoxy group or a mercapto group, R 2 is an alkyl group having 1 to 6 carbon atoms, and n is 0 or 1. ] It is the organosilicate represented by these, and / or its condensate.
  • the component (C) used in the coating composition of the present invention is blended in order to efficiently exhibit a hydrophilic effect on the substrate surface after coating. From the viewpoint of this effect, the condensation of the above-described organosilicate. More preferred.
  • R 1 in the above general formula examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, Examples include tetradecyl, hexadecyl, octadecyl, glycidyl, methylglycidyl (2-methylglycidyl), mercaptomethyl, 2-mercaptoethyl, 2-mercaptopropyl, 3-mercaptopropyl, 4-mercaptobutyl, phenyl, p-mercaptophenyl groups, etc. be able to.
  • organosilicate of component (C) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane; methyltrimethoxysilane, methyl Triethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltriisobutoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, phenyltri n-butoxysilane, phenyltriisobutoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane,
  • the organosilicate condensate can be produced by a conventional method.
  • examples of commercially available products include MKC silicate MS51, MS56, MS57, MS56S, MS56SB5, MS58B15, MS58B30, ES40, EMS31, BTS (all of which are Mitsubishi Chemical Co., Ltd., trade name), Methyl silicate 51, Ethyl silicate 40, Ethyl silicate 40T, Ethyl silicate 48 (all are trade names, produced by Colcoat Co., Ltd.), KR500, KR9218, X-41-1805, X-41-1810, X-41-1818, X-41-1053, X-41-1056 (all are trade names manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • organosilicate condensates can be obtained by single hydrolysis or by partial hydrolysis condensation using a combination of two or more.
  • the organosilicate condensate is a branched or linear condensate, and the degree of condensation is preferably 2 to 100, preferably 2 to 20.
  • the (C) component organosilicate or organosilicate condensate may be used alone or in combination of two or more.
  • the organosilicate represented by the above general formula and / or its condensate it has a methoxy group and an alkoxy group having 2 to 6 carbon atoms as an OR 2 group, and a methoxy group / an alkoxy group having 2 to 6 carbon atoms; It is preferable that the ratio of the number is in the range of 95/5 to 30/70 from the viewpoint of pot life after the preparation of the paint.
  • the solid content of the component (C) is 1 to 20% by mass, preferably 1 to 10%, based on the total solid content of the components (A) and (B). % By mass, more preferably 3 to 7% by mass.
  • the component (D) of the coating composition of the present invention is a fluorine atom-containing non-aqueous dispersion (NAD) resin.
  • the fluorine atom-containing non-aqueous dispersion resin can also be referred to as a fluorine atom-containing non-aqueous dispersion.
  • a non-aqueous dispersion resin (D1) in which polymer particles are dispersed in an organic solvent liquid containing a fluorine atom-containing dispersion stabilizer and an organic solvent containing a dispersion stabilizer
  • a non-aqueous dispersion type resin (D2) in which polymer particles containing a fluoroalkyl group-containing (meth) acrylate as a constituent component are dispersed in the liquid.
  • (meth) acrylate refers to acrylate or methacrylate.
  • non-aqueous dispersion type resin a polymerizable unsaturated monomer is copolymerized in a mixed solution of a fluorine atom-containing dispersion stabilizer (D1a) and an organic solvent (D1b) to be insoluble in the mixed solution.
  • Non-water-dispersed resin that can be prepared by forming polymer particles (D1c) is exemplified.
  • the non-aqueous dispersion resin (D1) is a non-aqueous dispersion resin containing a dispersion medium, polymer particles (dispersion particles) and a dispersion stabilizer, and the dispersion stabilizer is a dispersion stabilizer containing a fluorine atom.
  • the non-aqueous dispersion resin (D1) is a non-aqueous dispersion in which polymer particles are dispersed in an organic solvent liquid containing a fluorine atom-containing dispersion stabilizer, and the fluorine atom-containing dispersion stabilizer (D1a)
  • D1a fluorine atom-containing dispersion stabilizer
  • a non-aqueous dispersion in which polymer particles (D1c) insoluble in the organic solvent (D1b) contained therein are dispersed may be used.
  • the dispersion stabilizer (D1a) contains a fluorine atom and is a dispersion stabilizer for stably dispersing the polymer particles (D1c) in the organic solvent (D1b).
  • the dispersion stabilizer (D1a) is preferably one that is mutually soluble with the organic solvent (D1b) and is not compatible with the polymer particles (D1c).
  • the polymer can contain one or more functional groups selected from a hydroxyl group, a carboxyl group, an epoxy group, a silanol group, an alkoxysilyl group and the like per molecule.
  • fluoroalkyl group-containing (meth) acrylate examples include, for example, General formula CH 2 ⁇ C (R) —COO— (CH 2 ) n —Rf [R is a hydrogen atom or a methyl group, n is an integer of 1 to 10, and Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms]
  • Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms
  • the compound shown by can be mention
  • the “fluoroalkyl group” is a group in which part or all of hydrogen of a linear or branched hydrocarbon group having 1 to 21 carbon atoms is substituted with a fluorine atom.
  • F-acrylates include perfluoromethyl methyl acrylate, perfluoromethyl methyl methacrylate, perfluorobutyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluoroisononyl ethyl acrylate, perfluoroisononyl ethyl methacrylate, perfluorooctyl ethyl.
  • fluoroolefin examples include tetrafluoroethylene, hexafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, and trifluoroethylene.
  • the polymerizable unsaturated monomer for obtaining the dispersion stabilizer (D1a) one or more selected from the group consisting of the F-acrylate and the fluoroolefin can be used.
  • the dispersion stabilizer (D1a) is a polymer of one or more selected from the group consisting of F-acrylates and fluoroolefins, or one or more selected from the group consisting of F-acrylates and fluoroolefins And other polymerizable unsaturated monomers can be polymerized.
  • Other polymerizable unsaturated monomers are not particularly limited as long as they are radical polymerizable unsaturated monomers. For example, the following polymerizable unsaturated monomers can be mentioned.
  • Acrylic acid or methacrylic acid ester (i): methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate C 1-20 alkyl ester of acrylic acid or methacrylic acid such as isobornyl acrylate, isobornyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate; , C 3 ⁇ 20 cycloalkyl esters of acrylic acid or methacrylic acid cyclohexyl methacrylate; allyl acrylate, acrylic acid and allyl methacrylate or meta C 2 ⁇ 8 alkenyl esters of
  • Glycidyl group-containing unsaturated monomer (ii) glycidyl acrylate, glycidyl methacrylate and the like.
  • hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether
  • hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate C 2 ⁇ 8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate: hydroxyl group-containing unsaturated monomer (iii) Alcohol, methallyl alcohol; etc.
  • Unsaturated monomer (vii) having two or more polymerizable unsaturated bonds ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and the like.
  • the dispersion stabilizer (D1a) both in the system obtained by copolymerizing F-acrylate and / or fluoroolefin and other polymerizable unsaturated monomer (F-acrylate and / or fluoro).
  • the ratio of the olefin and the other two components of the polymerizable unsaturated monomer can be arbitrarily selected. From the viewpoint of stain resistance, it is preferable that the F-acrylate and / or fluoroolefin is 100 to 1% by mass, particularly 30 to 5% by mass, based on the total solid content of the two components.
  • the other polymerizable unsaturated monomer is preferably in the range of 0 to 99% by mass, particularly 70 to 95% by mass as a solid content.
  • the polymerization reaction of one or more selected from F-acrylate and fluoroolefin, or the copolymerization reaction of these with other polymerizable unsaturated monomers is preferably performed in the presence of a radical polymerization initiator.
  • a radical polymerization initiator include azo compounds such as 2,2-azoisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, tert-butyl peroxide.
  • peroxides such as octoate.
  • initiators are used in an amount of 0.2 to 10 as solids with respect to the total solids of F-acrylate and / or fluoroolefin and other polymerizable unsaturated monomers used as necessary. It is preferable to be in the range of mass%, particularly 0.5 to 5 mass%.
  • dispersion stabilizer (D1a) in the polymerization reaction for preparing the dispersion stabilizer (D1a), as other polymerizable unsaturated monomer, (ii) glycidyl group-containing unsaturated monomer, (iii) hydroxyl group-containing unsaturated monomer, (iv) alkoxysilyl group-containing Dispersion stability having functional groups such as glycidyl group, hydroxyl group, alkoxysilyl group, carboxyl group, isocyanate group by using unsaturated monomer, (v) unsaturated carboxylic acid, (vi) isocyanate group-containing unsaturated monomer, etc.
  • An agent can be obtained.
  • the dispersion stabilizer having a hydroxyl group reacts with the polymer particles (D1c) having a hydroxyl group and reacts with the melamine resin component (B) and the organosilicate and / or the condensate component (C) thereof to form a tertiary.
  • An originally crosslinked cured coating film can be formed.
  • the dispersion stabilizer (D1a) one having an average of 0.1 or more polymerizable unsaturated bonds in one molecule can be suitably used. If the dispersion stabilizer (D1a) has a polymerizable unsaturated bond, a covalent bond can be formed with the polymer particles (D1c), so that the storage stability of the non-aqueous dispersion resin can be improved. This is preferable because the mechanical stability and stain resistance are improved.
  • a polymerizable unsaturated monomer containing another functional group that reacts with the functional group is added to the functional group present in the dispersion stabilizer.
  • the method of making it react can be mentioned.
  • a dispersion stabilizer (D1a) containing a carboxyl group with a glycidyl group-containing polymerizable unsaturated monomer (for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc.)
  • the dispersion stabilizer is polymerizable unsaturated. Bonds can be introduced.
  • the dispersion stabilizer (D1a) containing a glycidyl group may be reacted with a carboxyl group-containing polymerizable monomer (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.).
  • a polymerizable monomer for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
  • a polymerizable unsaturated bond can be introduced into the stabilizer.
  • examples of such a combination of functional groups include an acid anhydride group and a hydroxyl group, an acid anhydride group and a mercaptan group, and an isocyanate group and a hydroxyl group.
  • a fluorine atom-containing resin fluorine resin, for example, a resin obtained by copolymerizing F-acrylate and / or fluoroolefin and other polymerizable unsaturated monomer
  • a dispersion stabilizer having a polymerizable unsaturated bond introduced into a fluororesin can be preferably used.
  • fluororesin include commercially available fluororesins such as Lumiflon LF800 (Asahi Glass Co., Ltd.).
  • the molecular weight of the dispersion stabilizer (D1a) is not particularly limited, but the number average molecular weight is preferably in the range of 1000 to 60000, particularly 2000 to 30000.
  • organic solvent (D1b) a fluoroalkyl group-containing (meth) acrylate and / or fluoroolefin used for preparing the dispersion stabilizer (D1a) and the polymer particles (D1c), and other polymerizable unsaturation
  • a polymerizable unsaturated monomer such as a monomer can be dissolved, but those that do not substantially dissolve the polymer particles (D1c) obtained from the polymerizable unsaturated monomer can be used.
  • the dispersion stabilizer (D1a) and polymer particles (D1c) to be used are arbitrarily selected depending on the composition, molecular weight and other characteristic values.
  • aliphatic hydrocarbons such as hexane, heptane and octane
  • benzene Aromatic hydrocarbons such as xylene, toluene, cyclohexane
  • ester compounds such as methyl acetate, ethyl acetate, isobutyl acetate, acyl acetate, ethylene glycol monomethyl ether, 2-ethylhexyl acetate, diethylene glycol monomethyl ether
  • cellosolve butyl cellosolve, isopropyl ether Ether compounds such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether
  • ethyl alcohol isopropyl alcohol, n-butyl alcohol, i-butyl alcohol, octyl Alcohol
  • an organic solvent mainly composed of an aliphatic hydrocarbon organic solvent and an organic solvent such as an aromatic hydrocarbon, alcohol, ether compound, ester compound or ketone compound examples include mineral spirits obtained by fractional distillation of crude oil (for example, those specified in JIS K 22014).
  • the non-aqueous dispersion type resin (D1) is, for example, insoluble in the mixed solution by copolymerizing a polymerizable unsaturated monomer in a mixed solution of the fluorine atom-containing dispersion stabilizer (D1a) and the organic solvent (D1b). It can be prepared by forming polymer particles (D1c).
  • the polymerizable unsaturated monomer for obtaining the polymer particles (D1c) is not particularly limited as long as it is a radical polymerizable unsaturated monomer. Specifically, acrylic acid or methacrylic acid ester (i), glycidyl group-containing unsaturated monomer (ii), hydroxyl group exemplified as “other polymerizable unsaturated monomer” in the fluorine atom-containing dispersion stabilizer (D1a).
  • the polymerization reaction of the polymerizable unsaturated monomer for obtaining the polymer particles (D1c) is preferably performed in the presence of a radical polymerization initiator.
  • a radical polymerization initiator examples include azo compounds such as 2,2-azoisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, tert- Examples thereof include peroxides such as butyl peroctoate, and the amount of these initiators used is 0.2 to 10% by mass, particularly 0.5 to 5% by mass, based on the total amount of polymerizable unsaturated monomers. It is preferable to be within the range.
  • the polymer particles (D1c) include, as polymerizable unsaturated monomers, the aforementioned glycidyl group-containing unsaturated monomer (ii), hydroxyl group-containing unsaturated monomer (iii), alkoxysilyl group-containing unsaturated monomer (iv), unsaturated carboxylic acid.
  • polymerizable unsaturated monomers the aforementioned glycidyl group-containing unsaturated monomer (ii), hydroxyl group-containing unsaturated monomer (iii), alkoxysilyl group-containing unsaturated monomer (iv), unsaturated carboxylic acid.
  • the polymer particles having a hydroxyl group react with the melamine resin component (B) and the organosilicate and / or its condensate component (C) together with the dispersion stabilizer (D1a) having a hydroxyl group in three dimensions.
  • a crosslinked cured coating film can be formed.
  • the number average molecular weight of the polymer particles (D1c) is preferably 10,000 or more, particularly preferably 20,000 or more from the viewpoint of stain resistance.
  • polymer particles (D1c) polymer particles crosslinked in the particles can be suitably used from the viewpoint of improving the stain resistance.
  • a carboxyl group-containing polymerizable unsaturated monomer for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
  • a glycidyl group-containing polymerizable unsaturated monomer for example, glycidyl acrylate, glycidyl methacrylate, Allyl glycidyl ether, etc.
  • the polymer particles crosslinked in the particle are prepared by addition reaction of the carboxyl group and glycidyl group of each polymerizable unsaturated monomer. be able to.
  • Examples of such combinations of functional groups include combinations of an acid anhydride group and a hydroxyl group, an acid anhydride group and a mercaptan group, an isocyanate group and a hydroxyl group, in addition to a carboxyl group and a glycidyl group.
  • the ratio of the dispersion stabilizer (D1a) and the polymer particles (D1c) can be arbitrarily selected.
  • the storage stability and stain resistance of the non-aqueous dispersion type resin (D1) can be selected.
  • the dispersion stabilizer (D1a) is 3 to 70% by mass, particularly 5 to 60% by mass
  • the polymer particles (D1c) are 97 to 30% by mass, particularly 95 to 95%, based on the total amount of the two components. It is preferably within the range of 40% by mass.
  • the total concentration of the dispersion stabilizer (D1a) and the polymer particles (D1c) is 30 to 70 based on the total amount of the dispersion stabilizer (D1a), the organic solvent (D1b), and the polymer particles (D1c). It is preferably in the range of 40% by mass, especially 40-60% by mass.
  • the polymerization reaction of the polymerizable unsaturated monomer for obtaining the polymer particles (D1c) in the organic solvent (D1b) containing the dispersion stabilizer (D1a) is generally about 1 to 15 at a temperature of about 60 to 160 ° C. Can be done in time.
  • the non-aqueous dispersion resin (D1) thus obtained is extremely excellent in dispersion stability, particularly in terms of the polymer particles (D1c).
  • the average particle size of the non-aqueous dispersion resin (D1) is preferably in the range of 20 to 500 nm, particularly 50 to 400 nm, and more particularly 100 to 300 nm from the viewpoint of stain resistance.
  • the average particle size is a value obtained by diluting a sample with xylene using a submicron particle size distribution measuring apparatus “COULTER N4 type” (manufactured by Beckman Coulter, Inc.) and measuring at 20 ° C. .
  • the non-aqueous dispersion resin (D2) is a non-aqueous dispersion resin in which polymer particles containing a fluoroalkyl group-containing (meth) acrylate as a constituent component are dispersed in an organic solvent liquid containing a dispersion stabilizer.
  • Specific examples of the non-aqueous dispersion type resin (D2) include a fluoroalkyl group-containing (meth) acrylate and other polymerizable unsaturated monomers in a mixed solution of the dispersion stabilizer (D2a) and the organic solvent (D2b).
  • a non-aqueous dispersion type resin that can be prepared by forming polymer particles (D2c) insoluble in the mixed solution are examples of the non-aqueous dispersion type resin (D2) include a fluoroalkyl group-containing (meth) acrylate and other polymerizable unsaturated monomers in a mixed solution of the dispersion stabilizer (D2a) and the organic solvent (D
  • the non-aqueous dispersion resin (D2) is a non-aqueous dispersion in which polymer particles (D2c) insoluble in the dispersion stabilizer and the organic solvent are dispersed in the organic solvent (D2b) containing the dispersion stabilizer (D2a).
  • the resin particles may be a non-aqueous dispersion resin in which the polymer particles (D2c) are made of a copolymer of a fluoroalkyl group-containing (meth) acrylate and another polymerizable unsaturated monomer.
  • the dispersion stabilizer (D2a) is for stably dispersing the polymer particles (D2c) in the organic solvent (D2b).
  • the dispersion stabilizer (D2a) is mutually dissolved in the organic solvent (D2b), and the polymer particles (D2c) Those incompatible with each other are preferred.
  • acrylic resin vinyl resin, polyester resin, alkyd resin, urethane resin, fluorine-containing resin and the like can be mentioned.
  • these resins can contain one or more functional groups selected from a hydroxyl group, a carboxyl group, an epoxy group, a silanol group, an alkoxysilane group and the like per molecule.
  • dispersion stabilizer (D2a) those having an average of 0.1 or more polymerizable unsaturated bonds per molecule can be suitably used.
  • a method for introducing a polymerizable unsaturated bond for example, a glycidyl group-containing polymerizable unsaturated monomer (for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether) is added to a dispersion stabilizer containing a carboxyl group.
  • a carboxyl group-containing polymerizable unsaturated monomer for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
  • a carboxyl group-containing polymerizable unsaturated monomer for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
  • the method of making it react can be mentioned.
  • combinations of such functional groups may include acid anhydride groups and hydroxyl groups, acid anhydride groups and mercaptan groups, and combinations of isocyanate groups and hydroxyl groups.
  • a polymerizable unsaturated bond is introduced into the dispersion stabilizer (D2a)
  • a covalent bond can be formed with the polymer particles (D2c). It is preferable because the mechanical stability, stain resistance and the like can be improved.
  • the molecular weight of the dispersion stabilizer (D2a) is not particularly limited, but the number average molecular weight is preferably in the range of 1000 to 60000, particularly 2000 to 30000.
  • Organic solvent (D2b) dissolves polymerizable unsaturated monomers such as fluoroalkyl group-containing (meth) acrylate and other polymerizable unsaturated monomers for preparing dispersion stabilizer (D2a) and polymer particles (D2c). However, those which do not substantially dissolve the polymer particles (D2c) obtained from the polymerizable unsaturated monomer can be used.
  • the dispersion stabilizer (D2a) and polymer particles (D2c) to be used are arbitrarily selected according to the characteristic values such as the composition and molecular weight, and the organic solvent (D2b) is exemplified as the organic solvent (D1b).
  • the organic solvent (D2b) is exemplified as the organic solvent (D1b).
  • an organic solvent mainly composed of an aliphatic hydrocarbon organic solvent and an organic solvent such as an aromatic hydrocarbon, alcohol, ether compound, ester compound or ketone compound examples include mineral spirits obtained by fractional distillation of crude oil (for example, those specified in JIS K 2201-4).
  • the non-aqueous dispersion resin (D2) is a mixture of a fluoroalkyl group-containing (meth) acrylate and another polymerizable unsaturated monomer in a mixed solution of a dispersion stabilizer (D2a) and an organic solvent (D2b). It can adjust by making it polymerize and forming a polymer particle (D2c) insoluble in this liquid mixture.
  • Examples of the fluoroalkyl group-containing (meth) acrylate (F-acrylate) for obtaining the polymer particles (D2c) include: General formula CH 2 ⁇ C (R) —COO— (CH 2 ) n —Rf [R is a hydrogen atom or a methyl group, n is an integer of 1 to 10, and Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms]
  • the compound shown by can be mention
  • those exemplified for the dispersion stabilizer (D1a) can be used in the same manner.
  • any radically polymerizable unsaturated monomer other than the F-acrylate can be used without any particular limitation.
  • Other polymerizable unsaturated monomers (iv) other than vinyl aromatic compounds (viii) and (i) to (viii) can be used in the same manner.
  • the ratio of F-acrylate to other polymerizable unsaturated monomers can be arbitrarily selected. From the viewpoint of stain resistance, the ratio of the F-acrylate and the other polymerizable unsaturated monomers can be selected based on the total amount of the two components. It is preferable that the acrylate is 90 to 1% by mass, particularly 30 to 5% by mass, and the other polymerizable unsaturated monomer is 10 to 99% by mass, particularly 70 to 95% by mass.
  • the copolymerization reaction of F-acrylate and other polymerizable unsaturated monomer is preferably performed in the presence of a radical polymerization initiator.
  • a radical polymerization initiator examples include azo compounds such as 2,2-azoisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, tert-butyl peroxide. These initiators are used in amounts of 0.2 to 10% by weight, particularly 0.5%, based on the total amount of F-acrylate and other polymerizable unsaturated monomers. It is preferably in the range of ⁇ 5% by weight.
  • the polymer particles (D2c) include, as polymerizable unsaturated monomers, the glycidyl group-containing unsaturated monomer (ii), the hydroxyl group-containing unsaturated monomer (iii), the alkoxysilyl group-containing unsaturated monomer (iv), and the unsaturated carboxylic acid.
  • an acid (v) an isocyanate group-containing unsaturated monomer (vi), or the like, polymer particles having these functional groups can be obtained.
  • the polymer particles having a hydroxyl group react with the melamine resin component (B) and the organosilicate and / or its condensate component (C) together with the dispersion stabilizer (D2a) having a hydroxyl group in three dimensions.
  • a crosslinked cured coating film can be formed.
  • the number average molecular weight of the polymer particles (D2c) is preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of contamination resistance.
  • polymer particles (D2c) polymer particles crosslinked in the particles can be preferably used from the viewpoint of improving the stain resistance.
  • intraparticle crosslinked polymer particles for example, a method in which a combination of polymerizable unsaturated monomers having functional groups that react with each other is used as a component of the polymerizable unsaturated monomer, the polymerizable unsaturated bond is changed.
  • the method etc. which use the unsaturated monomer (vii) which has 2 or more as a structural component of a polymerizable unsaturated monomer can be mention
  • a carboxyl group-containing polymerizable unsaturated monomer for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
  • a glycidyl group-containing polymerizable unsaturated monomer for example, glycidyl acrylate, glycidyl methacrylate, Allyl glycidyl ether, etc.
  • the polymer particles crosslinked in the particle are prepared by addition reaction of the carboxyl group and glycidyl group of each polymerizable unsaturated monomer. be able to.
  • Examples of such combinations of functional groups include combinations of an acid anhydride group and a hydroxyl group, an acid anhydride group and a mercaptan group, an isocyanate group and a hydroxyl group, in addition to a carboxyl group and a glycidyl group.
  • the ratio of the dispersion stabilizer (D2a) and the polymer particles (D2c) can be arbitrarily selected.
  • the storage stability and stain resistance of the non-aqueous dispersion type resin (D2) can be selected.
  • the dispersion stabilizer (D2a) is 3 to 70% by mass, particularly 5 to 60% by mass
  • the polymer particles (D2c) are 97 to 30% by mass, particularly 95 to 95%. It is preferably within the range of 40% by mass.
  • the total concentration of the dispersion stabilizer (D2a) and the polymer particles (D2c) is 30 to 70 based on the total amount of the dispersion stabilizer (D2a), the organic solvent (D2b), and the polymer particles (D2c). It is preferably in the range of 40% by mass, especially 40-60% by mass.
  • the polymerization reaction of F-acrylate and other polymerizable unsaturated monomers for obtaining polymer particles (D2c) in an organic solvent (D2b) containing a dispersion stabilizer (D2a) is generally about 60 to 160 ° C. For about 1 to 20 hours.
  • the non-aqueous dispersion resin (D2) obtained in this way is extremely excellent in dispersion stability.
  • the average particle diameter of the non-aqueous dispersion resin (D2) is preferably in the range of 20 to 500 nm, particularly 50 to 400 nm, and more particularly 100 to 300 nm from the viewpoint of stain resistance.
  • fluorine atom-containing non-aqueous dispersion resin component (D) instead of or together with the non-aqueous dispersion resin (D1) in which polymer particles are dispersed in an organic solvent liquid containing a fluorine atom-containing dispersion stabilizer
  • a non-aqueous dispersion resin (D2) in which polymer particles containing a fluoroalkyl group-containing (meth) acrylate as a constituent component are dispersed in an organic solvent liquid containing a stabilizer can be used.
  • the amount of the component (D) is 5 to 30% by mass, preferably 10 to 30% by mass, based on the total amount of the components (A) and (B). More preferably, it is in the range of 15 to 25% by mass.
  • component (D) When the amount of component is in the above range, the effect of component (D) is exhibited, and the initial stain resistance of the coating film, retention of stain resistance, mechanical strength of the coating film, and durability Is also preferable.
  • a surfactant and boric acid exhibiting acidity within a range not inhibiting the effects of the present invention.
  • paints such as hydrolysis accelerators such as contained compounds, extender pigments such as colored pigments, silica fine particles, organic resin powders, inorganic aggregates, pigment dispersants, UV absorbers, UV stabilizers, antifoaming agents and surface conditioners
  • Known materials conventionally used for paints such as agents and solvents can also be used.
  • the solvent is preferably a solvent having good solubility in each of the component (C) and the component (D).
  • a solvent having good solubility in each of the component (C) and the component (D) By using such a solvent, each of the component (C) and the component (D) is dispersed without coarsening, and a coating film particularly excellent in stain resistance can be formed.
  • the acidic surfactant or boric acid-containing compound has an action of promoting hydrolysis of the organosilicate and / or its condensate component (C).
  • Hydrolysis accelerators such as acidic surfactants and boric acid-containing compounds, when used in combination, can shorten the pot life of the coating composition of the present invention, but can be used from the viewpoint of improving stain resistance.
  • the surfactant exhibiting acidity examples include phosphate ester salts such as polyoxyethylene phosphate ester and alkyl phosphate ester salt; for example, alkyl or alkylbenzene sulfonate salts such as sodium lauryl sulfonate and sodium dodecylbenzene sulfonate, Alkyl naphthalene sulfonates such as sodium isopropyl naphthalene sulfonate, sulfonates such as alkyl diphenyl ether sulfonate; sulfate esters such as alkyl or alkyl benzene sulfate, (poly) oxyethylene alkyl phenyl ether sulfate; eg alkyl sulfosuccinic acid
  • the surfactant include carboxylate salts such as salts.
  • boric acid-containing compound examples include trialkyl borate such as trimethyl borate, triethyl borate, and tributyl borate; boric acid and the like.
  • the blending amount of these hydrolysis accelerators is 30% by mass or less, particularly 0.5 to 20% by mass, more particularly 1 to 10% by mass, based on the total amount of the component (A) and the component (B). Preferably there is.
  • the extender pigment examples include silica fine particles, talc, mica powder, and barita.
  • the amount of the extender is 0.1 to 20% by mass, particularly 0.5 to 15% by mass, more particularly 1 to 10% by mass, based on the total amount of the component (A) and the component (B). preferable.
  • the matting agent (E) can be used in the coating composition of the present invention for the purpose of adjusting the gloss so that the obtained coating film has a finished appearance such as matte or semi-gloss.
  • the matting agent (E) is used for lowering the gloss of the resulting coating film, and may be either an organic matting agent or an inorganic matting agent. Or two or more types can be used in combination.
  • the stain resistant paint composition of the present invention can form a paint film having excellent finish of stain resistance and corrosion resistance, in particular, in a paint film having a finished appearance with reduced gloss such as matte and semi-gloss. .
  • Examples of the organic matting agent include organic resin fine particles that are not completely melted by baking at the time of forming the coating film.
  • the organic resin fine particles usually have an average particle diameter in the range of 3 to 80 ⁇ m, preferably 5 to 60 ⁇ m, from the viewpoint of coating film appearance, coating workability, and the like.
  • Examples of organic matting agents include fluorine resins such as polyvinylidene fluoride and polytetrafluoroethylene, polyamides, acrylic resins, polyurethanes, phenol resins, silicone resins, polypropylene, and polyamides such as nylon 11 and nylon 12. be able to.
  • inorganic matting agents examples include silica, mica, alumina, talc, clay, calcium carbonate, barium sulfate and the like.
  • the matting agent (E) can be used alone or in combination of two or more.
  • the blending amount of the matting agent (E) is preferably from 0.1 to 30% by mass, particularly preferably from 0.5 to 20% by mass, based on the total amount of the component (A) and the component (B).
  • the antifouling coating composition of the present invention can be produced by uniformly mixing the above components (A) to (D) and, if necessary, the above other components.
  • the pigment component is prepared by previously mixing and dispersing a part of the resin component (A) and / or a pigment dispersant to prepare a pigment paste, and mixing the pigment paste with the remaining components. it can.
  • the coating composition of the present invention may be a one-pack type paint, but the two-component mixture is prepared immediately before use by separating the organosilicate and / or its condensate as component (C) from other components. It can also be a mold paint. From the viewpoint of storability and the like, a two-component paint is preferred.
  • the paint composition is adjusted to a desired viscosity by adding an organic solvent or the like as necessary, and then air spray, electrostatic air spray, roll coater, Using a flow coater, dipping type coating machine, brush, bar coater, applicator, etc., the coating film thickness after drying is usually 0.5 to 300 ⁇ m, preferably 5 to 50 ⁇ m, and usually 80 to Examples include a method of curing by heating at a temperature of 300 ° C. for about 5 seconds to 1 hour. As the coating method, spray coating or roll coater coating is preferable among the above methods.
  • the coating film forming method of the present invention comprises forming a primer coating film with a chromium-free primer coating which does not contain a chromium-containing rust-preventing component on one or both surfaces of a metal plate. It is a coating film forming method characterized by forming a top coating film with the antifouling paint composition of the present invention on at least one surface of a film.
  • the method for forming a coating film according to the present invention includes a step of forming a primer coating film on one or both surfaces of a metal plate with a primer coating using a chromium-free primer coating, and at least one of the formed primer coating films. Furthermore, it is a coating film forming method characterized by including the process of forming a top coat film with the said contamination
  • the present invention also provides a method for producing a coated metal plate including the steps of the method for forming a coating film and a coated metal plate obtained by the method for forming a coating film or the method for producing a coated metal plate.
  • the coating film forming method of the present invention can be used for both pre-coating and post-coating.
  • Preferable examples of use include coating on the above-mentioned outdoor base materials (for example, buildings, display objects, guard fences, appliances, machines, etc.).
  • Examples of the metal plate to be coated in the coating film forming method of the present invention include cold rolled steel plate, hot dip galvanized steel plate, electrogalvanized steel plate, alloy galvanized steel plate (iron-zinc, aluminum-zinc, nickel-zinc, etc. Alloy galvanized steel plate), aluminum plate, stainless steel plate, copper plate, copper plated steel plate, tin plated steel plate and the like.
  • the primer When painting on metals, the primer can be applied as it is if the metal surface, which is the material to be coated, is not contaminated with oil or other contaminants, but in order to improve the adhesion and corrosion resistance with the coating film. It is desirable to apply a known metal surface treatment. These known surface treatment methods include phosphate surface treatment, chromate surface treatment, zirconium surface treatment and the like.
  • a chromium-free primer coating characterized by not containing a chromium-containing rust preventive component is used from the viewpoint of environmental protection. If the said primer is a chromium free primer coating, the well-known primer used in the coloring color steel plate coating field
  • the chrome-free primer coating is appropriately selected depending on the type of material to be coated and the type of metal surface treatment. Epoxy-based and polyester-based primer coatings and their modified primer coatings are particularly suitable, and workability is particularly required. In this case, a polyester primer paint is suitable.
  • a specific means for forming the primer coating film there is exemplified a means for applying a primer coating and then heating and curing as necessary.
  • the primer coating is applied by a known coating method such as roll coating or spray coating so that the primer coating thickness is 1 to 30 ⁇ m, preferably 2 to 20 ⁇ m.
  • the atmospheric temperature is 80 to 300 ° C. For 5 seconds to 1 hour to cure. In the case of pre-coating, it is preferable to cure by heating for 15 seconds to 120 seconds under the condition that the maximum material reaching temperature is 140 to 250 ° C.
  • the layer structure of the primer coating is not particularly limited.
  • the primer coating may be a single layer or a second primer coating (intermediate coating) formed on the first primer coating. It may be a layer.
  • the primer film has two layers, the first primer film has an anticorrosion function, and the second primer film (intermediate film) has processability and chipping resistance.
  • the primer coating can also have different functions.
  • a top coating film is formed from at least one of the primer coating films formed on one side or both sides of the metal plate by the stain resistant coating composition of the present invention.
  • the top coat film is formed so as to overlap on at least one side of the formed primer coat film.
  • “on at least one of the primer coatings” refers to the top of the primer coating formed on one side when the primer coating is formed on one side of the metal plate, When a primer coating is formed on both sides of the upper surface, it is formed on or on the primer coating formed on one side of the metal plate among the primer coatings formed on both sides. It points on the applied primer coating.
  • a means for coating the antifouling paint composition of the present invention and then heating and curing as necessary is exemplified.
  • the coating method include curtain coating, roll coater coating, dip coating, and spray coating.
  • the film thickness is usually applied so that the coating thickness after drying is in the range of 5 to 50 ⁇ m, preferably 8 to 25 ⁇ m.
  • the coating method is not limited, but curtain coating and roll coater coating are preferred from the economical viewpoint of pre-coated steel sheet coating.
  • a bottom feed method (so-called natural reverse coating or natural coating) using two rolls is preferable from the viewpoint of practicality.
  • a top feed or bottom feed method using three rolls can be performed from the viewpoint of achieving the best uniformity of the coating surface.
  • the curing condition of the top coating film by the coating composition of the present invention is usually about 15 seconds to 30 minutes at the maximum material reaching temperature of 120 to 260 ° C. In the field of pre-coating, which is applied by coil coating or the like, it is usually performed at a material reaching maximum temperature of 160 to 260 ° C. for a baking time of 15 to 90 seconds.
  • the obtained resin had a number average molecular weight of 15000, a hydroxyl value of 75 mgKOH / g, an oil length of 14.7%, and an iodine value of 5>.
  • Production Examples 2-3 Solutions of each of the hydroxyl group-containing polyester resins (A1-2) to (A1-3) having a solid content of 65% were obtained in the same manner as in Production Example 1 with the formulation shown in Table 1 below.
  • the composition ratio of each component in Table 1 is a molar ratio.
  • Production Example 5 A four-necked flask equipped with a stirrer, thermometer, condenser, and oxygen gas inlet was charged with 45.4 parts of mineral spirit, heated to 120 ° C. under a nitrogen atmosphere, and 2-perfluorooctylethyl methacrylate 15 Parts, isobornyl acrylate 30 parts, 2-ethylhexyl acrylate 10 parts, 2-ethylhexyl methacrylate 37 parts, 2-hydroxyethyl methacrylate 5 parts, acrylic acid 3 parts and 2,2'-azobisisobutyronitrile (polymerization started) Agent) A mixture of 7 parts was added dropwise over 3 hours.
  • Dispersion Stabilizer (D2a) A four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen / oxygen gas inlet is charged with 45.4 parts of mineral spirit, heated to 120 ° C. in a nitrogen atmosphere, and 30 parts of isobornyl acrylate. A mixture of 10 parts of 2-ethylhexyl acrylate, 52 parts of 2-ethylhexyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, 3 parts of acrylic acid and 7 parts of 2,2′-azobisisobutyronitrile (polymerization initiator) The solution was added dropwise over 3 hours.
  • the temperature was raised to 100 ° C., 125 parts of dispersion stabilizer (D1a-1), 40 parts of methyl methacrylate, 29 parts of methyl acrylate, 25 parts of 2-hydroxyethyl acrylate, 5 parts of glycidyl methacrylate, 1 part of methacrylic acid and 2,2 ′
  • a mixture of 1 part azobisisobutyronitrile was added dropwise over 3 hours.
  • the mixture was aged for 30 minutes while bubbling nitrogen gas at 100 ° C., and then a mixture of 30 parts of mineral spirit and 0.5 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour. Thereafter, the mixture was further aged for 1 hour to obtain a non-aqueous dispersion resin (D1-1) (mass solid content concentration 50%).
  • the special values of the obtained non-aqueous dispersion resin (D1-1) are also shown in Table 2.
  • Non-aqueous dispersion resins (D1-2) to (D1-10) and (D2-1) were obtained in the same manner as in Production Example 7 with the formulation shown in Table 2 below.
  • the special values of the obtained non-aqueous dispersion resins (D1-2) to (D1-10) and (D2-1) are shown together in Table 2.
  • Antifouling paint composition No. 23 to 28 are coating compositions for comparative examples.
  • KP color 8620 primer manufactured by Kansai Paint Co., Ltd., polyester-based primer for precoated steel sheet
  • a molten 55% aluminum-galvanized steel sheet galvalume steel sheet having a thickness of 0.35 mm subjected to chemical conversion treatment
  • the dry film thickness was 5 ⁇ m
  • heated so that the maximum material arrival temperature was 220 ° C. was baked for 40 seconds to obtain a primer-coated steel sheet.
  • each of the anti-stain coating compositions obtained as described above is applied with a bar coater so that the dry film thickness is about 15 ⁇ m, so that the maximum material temperature reaches 230 ° C.
  • Each coated steel sheet was obtained by heating and baking for 50 seconds. The following performance test was done about each obtained coated steel plate.
  • test results are also shown in Table 3 and Table 4.
  • the quantity of each component in Table 3 and Table 4 is solid content mass.
  • the white pigment, titanium dioxide was dispersed.
  • a mixed solvent of cyclohexanone / swazol 1500 manufactured by Maruzen Petroleum Co., Ltd., aromatic high-boiling solvent
  • 60/40 mass ratio
  • Hydroxyl-containing polyester resin Arachid 7018, trade name, manufactured by Arakawa Chemical Industries, Ltd., number average molecular weight 18000, hydroxyl value 6-12 mgKOH / g, acid value 5 mgKOH / g>, glass transition temperature 50 ° C. (DSC ), A hydroxyl group-containing oil-free polyester resin whose acid components are three components of terephthalic acid, isophthalic acid and sebacic acid.
  • Super Becamine J820-60 Trade name “Super Becamine J-820-60”, manufactured by DIC Corporation, n-butyl etherified melamine resin solution.
  • Cymel 303 Low molecular weight methylated melamine resin manufactured by Nippon Cytec Industries Co., Ltd. The content of hexakis (methoxymethyl) melamine is 60% by weight or more.
  • Sumidur BL3175 a methyl ethyl ketone oxime block compound of trimethylolpropane adduct type hexamethylene diisocyanate manufactured by Sumika Bayer Urethane Co., Ltd.
  • MS56S Trade name “MKC silicate MS56S” manufactured by Mitsubishi Chemical Corporation, methyl esterified silicate which is a condensate of tetramethoxysilane.
  • MS58B30 manufactured by Mitsubishi Chemical Corporation, trade name “MKC silicate MS58B30”, methyl / butyl mixed esterified silicate which is a condensate of tetraalkoxysilane, and the ratio of methyl / butyl number is 70/30.
  • Lumiflon LF800 manufactured by Asahi Glass Co., Ltd., trade name, fluororesin (fluoroethylene / vinyl ether alternating copolymer), hydroxyl value 38 mgKOH / g, acid value 2 mgKOH / g, number average molecular weight 8100, resin mass solid content 60%.
  • Thyroid 161W manufactured by GRACE GMBH, trade name, organically treated silica fine powder, oil absorption 170 ml / 100 g.
  • Nacure 5225 Isopropanol solution of neutralized secondary amine of dodecylbenzenesulfonic acid, manufactured by King Industries, USA.
  • the degree of neutralization of dodecylbenzenesulfonic acid / amine is about 1.1 (molar ratio).
  • the active ingredient is about 33% by weight, of which dodecylbenzenesulfonic acid / amine (mass ratio) is about 8/25.
  • the numerical values in Table 2 are parts by mass of solid content of dodecylbenzenesulfonic acid.
  • 60 ° gloss according to the 60 ° specular gloss specified in JIS K-5400 ⁇ 7.6 (1990), the 60 ° specular reflectance was measured.
  • Outdoor exposure test An outdoor exposure test specimen (100 x 300 mm) is mounted on the installation stand that models the eaves so that the coating film faces the north side, and exposed on the roof of Kansai Paint Co., Ltd. in Kanzaki-cho, Amagasaki City. The test was conducted, and the stain resistance and rain-stain stain resistance (rain-stained stains) were evaluated according to the following criteria. Contamination resistance was measured by using a multi-light source spectrocolorimeter MSC-5N manufactured by Suga Test Instruments Co., Ltd. based on JIS Z8370. Rain resistance stain resistance was judged visually.
  • Contamination resistance evaluated according to the following criteria by ⁇ E before and after the outdoor exposure test: S: ⁇ E is less than 2, A: ⁇ E is 2 or more and less than 3, B: ⁇ E is 3 or more and less than 5 C: ⁇ E is 5 or more.
  • Rain-stain stain resistance Rain-strip traces after outdoor exposure tests were evaluated according to the following criteria: S: Rain traces are not seen, A: A slight trace of rain streak is observed, but it can be easily wiped off with gauze soaked with water. B: There are considerable traces of rain streaks, and it cannot be wiped off completely with gauze soaked with water. C: Rain traces remain dark and can hardly be wiped off with gauze soaked with water

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Abstract

La présente invention s'attaque au problème de la mise à disposition d'une composition de revêtement résistante à la contamination qui peut former une couche de revêtement ayant une excellente rétention de résistance à la corrosion et de résistance à la contamination par l'eau de pluie et similaire, en particulier, d'une composition de revêtement résistante à la contamination qui est appropriée pour la formation d'un film de couche de finition sur une feuille de métal revêtue ayant un brillant qui n'est pas supérieur à un brillant moyen. La composition de revêtement comprend un organosilicate spécifique et/ou un composant de condensat de celui-ci et un composant de résine de dispersion non aqueuse à teneur en atome de fluor dans un liant de résine contenant : un composant de résine polyester qui contient une résine polyester à teneur en groupe hydroxyle ; et un composant de résine mélamine qui contient une résine de butyl éther mélamine.
PCT/JP2011/070932 2010-09-16 2011-09-14 Composition de revêtement résistante à la contamination ayant une excellente durabilité Ceased WO2012036183A1 (fr)

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JP2016509093A (ja) * 2013-01-04 2016-03-24 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ ポリエステルシリケート
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WO2020095774A1 (fr) * 2018-11-08 2020-05-14 昭和電工株式会社 Copolymère, et composition de résine contenant ce copolymère
JPWO2021024604A1 (fr) * 2019-08-02 2021-02-11
CN116041666A (zh) * 2023-01-18 2023-05-02 安徽恒泰新材料科技股份有限公司 高流平低温快速固化粉末涂料用环氧树脂及其制备方法
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JP2016509093A (ja) * 2013-01-04 2016-03-24 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ ポリエステルシリケート
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