CN102971388B - The antifouling paint composition of excellent in te pins of durability - Google Patents
The antifouling paint composition of excellent in te pins of durability Download PDFInfo
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- CN102971388B CN102971388B CN201180032375.0A CN201180032375A CN102971388B CN 102971388 B CN102971388 B CN 102971388B CN 201180032375 A CN201180032375 A CN 201180032375A CN 102971388 B CN102971388 B CN 102971388B
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- 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
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- 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
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- 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
Abstract
The object of the invention is to, the antifouling paint composition that can be formed and can keep the film of resistance to soiling and erosion resistance well in the environment such as rainwater is provided, especially provide the top being suitable for the metal sheet forming coating to be coated with the antifouling paint composition of film, this antifouling paint composition is specially adapted to the film by the following gloss of light in the formation such as matting agent.For reaching above-mentioned purpose, the invention provides the coating composition containing specific organosilicate and/or its condenses composition in the resin glue of the melamine resin composition of the polyester resin component at the vibrin containing special fatty acid modification and the melamine resin containing butyl etherificate.
Description
Technical field
The present invention relates to formed mainly to rainwater etc. through time the antifouling paint composition of film of hold facility excellence of resistance to soiling, the top that is particularly applicable to the metal sheet forming coating be coated with film antifouling paint composition, use this antifouling paint composition form the method for the film of resistance to rainwater pollution excellence and utilize this antifouling paint composition to form the metal sheet of the coating of cured coating film.
Background technology
In the past, on the base material (such as buildings, mark, guardrail, utensil, machine etc.) of outdoor, to decorate or to apply the outdoor use coating had excellent weather resistance for the purpose of protecting.As the coating that outdoor application uses, urethane resin system coating, fluorine resin system coating, the coating containing silicone resin, the coating containing acrylic resin, coating etc. containing polyester can be listed.But because these applicator are exposed to outdoor, because applicator surface is easily polluted in the impact of sand and dust, iron powder, rain (acid rain), solar ray etc., there is the shortcoming that appearance of film deterioration is such.
The applicant is in order to solve this problem, propose the top coating composition of resistance to soiling excellence, it is characterized in that, be to the fluoro-resin containing hydroxyl and amino resin crosslinking agent as react solidify form organic resin containing in the coating composition (1) of organic solvent, or to the fluoro-resin containing hydroxyl and/or hydroxyl acrylic resin and (blocked) polyisocyanate compounds linking agent as react solidify form organic resin contain in the coating composition (2) of organic solvent, coordinate tetraalkyl silicate and/or its condenses and the coating composition that obtains, film coated surface after acid treatment is less than 70 degree (with reference to patent documentation 1 International Publication WO94/06870 publications) to the contact angle of water.
But, the top coating composition of patent documentation 1, when outdoor application, insufficient to the hold facility of the resistance to soiling of rainwater etc., such as, easily there is rainprint pollution etc., and, in the initial stage of outdoor application, also insufficient to the resistance to soiling of rainwater etc.
In addition, as the pre-coated steel plate coating composition of the resistance to soiling polluted rainprint, processibility, appearance of film excellence, propose the hot curing resin composition (with reference to patent documentation 2) be made up of the polyol resin of (A) hydroxyl value 5 ~ 300, number-average molecular weight 500 ~ 20000, (B) aminoresin, (C) alkoxysilane compound containing trialkylsilyl group in molecular structure, (D) curing catalysts.But, the film obtained by this hot curing resin composition is if the film of high gloss, when to stand rainprint for a long time and pollute, its resistance to soiling is good, but, if the film by adding the following gloss of middle light (60 ° of gloss are less than or equal to about 50) that matting agent etc. is formed, when to stand rainprint for a long time and pollute, just resistance to soiling and erosion resistance can not be kept well.
Prior art document
Patent documentation
Patent documentation 1: International Publication WO94/06870 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-67945 publication
Summary of the invention
The invention provides the antifouling paint composition of the film that can be formed the resistance to soiling of rainwater etc. and the hold facility excellence of erosion resistance, be particularly applicable to being formed in the top of metal sheet of coating of the following gloss of light be coated with the antifouling paint composition of film.
In order to solve the problems referred to above in the past, the present inventor conducts in-depth research repeatedly, found that, in the resin glue of melamine resin composition comprising the polyester resin component of the vibrin containing special fatty acid modification and the melamine resin containing butyl etherificate, coating composition containing specific organosilicate and/or its condenses composition, the film of the hold facility excellence of the resistance to soiling to rainwater etc. can be formed, be particularly useful for the film of the gloss (60 ° of gloss are less than or equal to about 50) of below light, thus complete the present invention.
That is, the present invention comprises following invention:
Item 1. antifouling paint compositions, it comprises:
(A) vibrin, this vibrin contains the fatty acid modified vibrin (A1) that solids content is 50 to 100 % by weight, the number-average molecular weight of described fatty acid modified vibrin (A1) is 5,000 to 30,000, hydroxyl value is 5 to 100mgKOH/g and oil length is 3 to 30%, and
Described fatty acid modified vibrin (A1) is obtained by the reaction of following material, that is,
(a1): the polyprotonic acid containing alicyclic polyprotonic acid (a1-1),
(a2): the alcohol containing polyvalent alcohol (a2-1) more than ternary, and
(a3): lipid acid;
In described reaction, based on the total content of described polyprotonic acid (a1), in described polyprotonic acid (a1), the content of described alicyclic polyprotonic acid (a1-1) is 50 to 100mol%; Based on the total content of described alcohol (a2), in described alcohol (a2), the content of polyvalent alcohol (a2-1) more than described ternary is 10 to 70mol%;
(B) melamine resin, this melamine resin comprises the melamine resin (B1) that solids content is the butyl etherificate of 50 to 100 % by weight; And
(C) organosilicate expressed by the following formula and/or its condenses:
General formula: (R
1)
n-Si-(OR
2)
4-n
Wherein R
1represent the alkyl or phenyl with 1 to 18 carbon atom, each group can be replaced by epoxy group(ing) or sulfydryl, R
2represent the alkyl with 1 to 6 carbon atom, and n represents 0 or 1,
Further, based on the total solids level of described component (A) and described component (B), the solids content of described component (C) is 0.1 to 50 % by weight.
The antifouling paint composition of item 2. according to item 1, wherein in the reaction obtaining described fatty acid modified vibrin (A1), based on the total content of described polyacid component (a1), in described polyacid component (a1), the total content of described alicyclic polyprotonic acid (a1-1) is 85 to 100mol%.
The antifouling paint composition of item 3. according to item 1 or 2, wherein based on the total solids level of described polyester resin component (A) and described melamine resin component (B), described composition comprise solids content be 50 to 90 % by weight described polyester resin component (A) and solids content be 10 to 50 % by weight described melamine resin component (B).
The antifouling paint composition of item 4. according to any one of item 1 ~ 3, wherein said alicyclic polyprotonic acid (a1-1) comprises and is selected from alicyclic multivalent carboxylic acid, at least one in the acid anhydrides of described alicyclic multivalent carboxylic acid and the low alkyl group carboxylate of described alicyclic multivalent carboxylic acid, described alicyclic multivalent carboxylic acid comprises 1, 2-cyclohexane dicarboxylic acid, 1, 3-cyclohexane dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, 4-tetrahydrobenzene-1, 2-dicarboxylic acid, 3-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 4-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 1, 2, 4-cyclohexanetricarboxylic acid and 1, 3, 5-cyclohexanetricarboxylic acid.
The antifouling paint composition of item 5. according to any one of item 1 ~ 4, polyvalent alcohol (a2-1) more than wherein said ternary comprise be selected from more than ternary polyvalent alcohol, by least one in poly-lactone polyol compound and three (hydroxyalkyl) isocyanuric acid ester that polyvalent alcohol addition more than lactone compound and described ternary is obtained, polyvalent alcohol more than described ternary comprises glycerine, trimethylolethane, TriMethylolPropane(TMP), two glycerine, triglycerin, 1,2,6-hexanetriol, tetramethylolmethane, Dipentaerythritol, sorbyl alcohol and N.F,USP MANNITOL.
The antifouling paint composition of item 6. according to any one of item 1 ~ 5, wherein said lipid acid (a3) comprises at least one in the monocarboxylic acid being selected from following straight chain hydrocarbon, the monocarboxylic acid of described straight chain hydrocarbon comprises coco-nut oil fatty acid, cottonseed oil fatty acid, hempseed oil lipid acid, rice bran oil fatty acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, linseed oil lipid acid, tung oil fatty acid, rapeseed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, safflower oil fatty acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linoleic acid plus linolenic acid.
The antifouling paint composition of item 7. according to any one of item 1 ~ 6, it is also containing matting agent (D).
The antifouling paint composition of item 8. according to item 7, based on the total solids level of described vibrin (A) and described melamine resin (B), described composition comprises the described matting agent (D) that solids content is 0.1 to 30 % by weight.
Item 9. forms the method for films, and it comprises: use Chrome-free base paint to form bottom coating on the single or double of metal sheet; And use antifouling paint composition according to any one of item 1 ~ 8 formed described bottom coating at least one on form top and be coated with film.
The method of the metal sheet of item 10. preparation coating, it comprises: use Chrome-free base paint to form bottom coating on the single or double of metal sheet; And use antifouling paint composition according to any one of item 1 ~ 8 formed described bottom coating at least one on form top and be coated with film.
The metal sheets of item 11. coating, are obtained by the method described in item 9 or 10.
invention effect
Antifouling paint composition of the present invention is, in the resin glue of melamine resin composition comprising the polyester resin component of the vibrin containing special fatty acid modification and the melamine resin containing butyl etherificate, the coating composition containing specific organosilicate and/or its condenses composition.This coating composition can form the film that can keep resistance to soiling in the environment such as rainwater well, is particularly useful for the film of the gloss (60 ° of gloss are for being less than or equal to about 50) of below middle light.
In addition; in vibrin as the special fatty acid modification of required composition, in polyacid constituent, more than 50mol% is alicyclic polyprotonic acid, and weathering resistance, hydrolytic resistance are good; in addition, fatty acid modified part can participate in the absorption to the pigment composition used in this antifouling paint composition usually.
Why the film obtained by antifouling paint composition of the present invention, particularly during the film of the following gloss of light, can form the film that can keep resistance to soiling in the environment such as rainwater well, be thought of as following content though indefinite in making.
As antifouling paint composition of the present invention matrix resin, polyacid constituent, weathering resistance, the hydrolytic resistance of the fatty acid modified vibrin of the alicyclic polyprotonic acid of frequent use are good, and have and the absorbed portion of pigment composition (fatty acid modified part), therefore think the composition being conducive to suppressing pigment composition deterioration.
The film of the following gloss of middle light utilizing matting agent etc. to be formed, compared with the film with high gloss, surface shape is concavo-convex, and the wettability of water is good.Under this film is often placed in the easily impaired harsh and unforgiving environments of hydrolytic resistance.Therefore, if adopt polyester coating in the past, coated surface will speed up deterioration (efflorescence etc.), thus easily damages the aesthetics of coated surface outward appearance.
The hydrolytic resistance of the film utilizing antifouling paint composition of the present invention to obtain is excellent, and the deterioration of pigment composition is also suppressed, therefore, compares with polyester coating in the past, can realize excellent outward appearance and can keep resistance to soiling well.
Embodiment
Antifouling paint composition
Antifouling paint composition of the present invention is the coating composition containing following polyester resin component (A), melamine resin composition (B) and organosilicate and/or its condenses composition (C).
(A) polyester resin component
In coating composition of the present invention, relative to the total solids level of polyester resin component (A), polyester resin component (A) is the following fatty acid modified vibrin (A1) of 50 ~ 100 quality % containing solids content.
(A1) fatty acid modified vibrin
Fatty acid modified vibrin (A1) as the required composition of polyester resin component (A) is obtained by the reaction of following polyacid constituent (a1), alcohol composition (a2) and lipid acid (a3).
(a1) polyacid constituent
In the reaction obtaining above-mentioned fatty acid modified vibrin (A1), polyacid constituent (a1) is containing alicyclic polyprotonic acid (a1-1).Based on the total amount of polyacid constituent (a1), the total content of the alicyclic polyprotonic acid (a1-1) in polyacid constituent (a1) is 50 ~ 100mol%.The total content of alicyclic polyprotonic acid (a1-1) is preferably 70 ~ 100mol%, is more preferably 85 ~ 100mol%.
Above-mentioned alicyclic polyprotonic acid (a1-1), generally, refer to, in 1 molecule, there is the ester ring type structure (such as 4 ~ 6 rings) of more than 1 and compound, the acid anhydrides of this compound, the carboxylate of this compound of more than 2 carboxyls, such as 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 4-tetrahydrobenzene-1,2-dicarboxylic acid, 3-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 4-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 1,2, the alicyclic polycarboxylic acid of 4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid etc.; The acid anhydrides of this alicyclic polycarboxylic acid; The low alkyl group carboxylate (herein, so-called low alkyl group such as refers to the alkyl of carbon number about 1 ~ 5) etc. of this alicyclic polycarboxylic acid.Wherein, 1,2-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid acid anhydride, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 4-tetrahydrobenzene-1,2-dicarboxylic acid, 4-tetrahydrobenzene-1,2-dicarboxylic anhydride can preferably be used.
In above-mentioned, from the view point of hydrolytic resistance, particularly preferably 1,2-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid acid anhydride.
Above-mentioned alicyclic polyprotonic acid (a1-1) may be used singly or in combination of two or more.
In the reaction obtaining above-mentioned fatty acid modified vibrin (A1), as polyacid constituent, except alicyclic polyprotonic acid (a1-1), aromatic polyvalent acid (a1-2) and aliphatic polybasic acids (a1-3) can also be contained.
Above-mentioned aromatic polyvalent acid (a1-2), generally, refer to aromatics, the acid anhydrides of this aromatics, the carboxylate of this aromatics of the carboxyl in 1 molecule with more than 2, such as phthalic acid, m-phthalic acid, terephthalic acid, naphthalene dicarboxylic acids, 4, the aromatic polycarboxylic acid of 4 '-diphenyl dicarboxylic acid, trimellitic acid, pyromellitic acid etc.; The acid anhydrides of this aromatic polycarboxylic acid; The low alkyl group carboxylate (herein, so-called low alkyl group such as refers to the alkyl of carbon number about 1 ~ 5) etc. of this aromatic polycarboxylic acid.Above-mentioned aromatic polyvalent acid (a1-2) may be used singly or in combination of two or more.
Above-mentioned aliphatic polybasic acids (a1-3), generally, refers to fatty compounds, the acid anhydrides of this fatty compounds, the carboxylate of this fatty compounds in 1 molecule with more than 2 carboxyls.Specifically, can the aliphatic polycarboxylic acid of such as succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, octadecane diacid, citric acid etc.; The acid anhydrides of this aliphatic polycarboxylic acid; The low alkyl group carboxylate (herein, so-called low alkyl group such as refers to the alkyl of carbon number about 1 ~ 5) etc. of this aliphatic polycarboxylic acid.Above-mentioned aliphatic polybasic acids may be used singly or in combination of two or more.
As above-mentioned aliphatic polybasic acids (a1-3), preferably use the dicarboxylic acid with the alkyl chain of carbon number 4 ~ 18.As the dicarboxylic acid of alkyl chain with above-mentioned carbon number 4 ~ 18, such as hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, octadecane diacid etc. can be enumerated, wherein preferably hexanodioic acid can be used.
(a2) alcohol composition
In the reaction obtaining above-mentioned fatty acid modified vibrin (A1), alcohol composition (a2) is containing polyvalent alcohol (a2-1) more than ternary.Based on the total amount of alcohol composition (a2), polyvalent alcohol (a2-1) the total content more than ternary in alcohol composition (a2) is 10 ~ 70mol%.The total content of polyvalent alcohol (a2-1) more than ternary is preferably 20 ~ 65mol%, is more preferably 30 ~ 60mol%.
As polyvalent alcohol (a2-1) more than above-mentioned ternary, such as can enumerate glycerine, trimethylolethane, TriMethylolPropane(TMP), two glycerine, triglycerin, 1, the polyvalent alcohol more than ternarys such as 2,6-hexanetriol, tetramethylolmethane, Dipentaerythritol, sorbyl alcohol, N.F,USP MANNITOL; The lactone compound addition of polyvalent alcohols more than these ternarys and 6-caprolactone etc. and the poly-lactone polyol compound obtained; Three ((hydroxyalkyl)) isocyanuric acid ester etc. of three ((2-hydroxyethyl)) isocyanuric acid ester, three ((2-hydroxypropyl)) isocyanuric acid ester, three ((2-hydroxyl butyl)) isocyanuric acid ester etc.
Wherein, quantize from the view point of the polymer of fatty acid modified vibrin (A1) and increase the modified-reaction between lipid acid (a3), particularly preferably TriMethylolPropane(TMP).
In the reaction obtaining above-mentioned fatty acid modified vibrin (A1), as alcohol (a2) composition, except polyvalent alcohol (a2-1) more than ternary, dibasic alcohol (a2-2) and monohydroxy-alcohol (a2-3) can also be used.
As dibasic alcohol (a2-2), such as ethylene glycol can be enumerated, propylene glycol, Diethylene Glycol, triglycol, TEG, triethylene glycol, dipropylene glycol, 1, 4-butyleneglycol, 1, 3-butyleneglycol, 2, 3-butyleneglycol, 1, 2-butyleneglycol, 3-methyl isophthalic acid, 2-butyleneglycol, 2-butyl-2-ethyl-1, 3-propane diol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 4-pentanediol, 2, 4-pentanediol, 2, 3-dimethyl triglycol, butyleneglycol, 3-methyl-4, 3-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2, 2, 4-trimethylammonium-1, 3-pentanediol, 1, 6-hexylene glycol, 1, 5-hexylene glycol, 1, 4-hexylene glycol, 2, 5-hexylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol, three ring dimethanols in the last of the ten Heavenly stems, Hydrogenated Bisphenol A, the dibasic alcohol of A Hydrogenated Bisphenol A F etc., the lactone compound addition of these dibasic alcohol and 6-caprolactones etc. and the polylactone diol obtained, the esterdiol compound of two ((hydroxyethyl)) terephthalate etc., the polyether glycol compound etc. of the oxirane affixture, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. of dihydroxyphenyl propane.
As monohydroxy-alcohol (a2-3), such as, can enumerate the monohydroxy-alcohol of methyl alcohol, ethanol, propyl alcohol, butanols, stearyl alcohol, 2-phenoxyethyl alcohol etc.; Make propylene oxide, butylene oxide ring, the mono-epoxy compounds of glycidyl ester (trade(brand)name " CARDURAE-10 ", Hexion Specialty Chemicals Inc.) etc. of synthesis height chain saturated fatty acid and acid-respons and the alkylol cpd etc. that obtains.
(a3) lipid acid
In the reaction obtaining above-mentioned fatty acid modified vibrin (A1), lipid acid (a3) is the monocarboxylic acid of straight chain hydrocarbon, such as, can enumerate the lipid acid of coco-nut oil fatty acid, cottonseed oil fatty acid, hempseed oil lipid acid, rice bran oil fatty acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, linseed oil lipid acid, tung oil fatty acid, rapeseed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, safflower oil fatty acid etc.; Lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid etc.Above-mentioned lipid acid may be used singly or in combination of two or more.
Wherein, from the view point of weathering resistance, the material that preferred degree of unsaturation is lower, specifically, iodine number is less than 20, particularly preferably less than 10.Iodine number is the numerical value of the degree of unsaturation index representing compound, represents the grams of the iodine that sample 100g absorbs.Can measure according to the standard of JISK5421.
From the view point of above-mentioned degree of unsaturation, as lipid acid (a3), can preferably use coco-nut oil fatty acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, particularly coco-nut oil fatty acid.
The preparation of fatty acid modified vibrin (A1) is not particularly limited, and can carry out according to usual method.Such as, by described polyacid constituent (a1), alcohol composition (a2) and lipid acid (a3) in nitrogen gas stream, react 5 ~ 10 hours at 150 ~ 250 DEG C, the method for esterification or transesterification reaction can be carried out thus.
Utilize the modification of lipid acid (a3) can carry out with the esterification of described polyacid constituent (a1) and alcohol composition (a2) or transesterification reaction simultaneously, or, carry out after esterification, or, carry out after transesterification reaction.
Above-mentioned polyacid constituent (a1), alcohol composition (a2) and lipid acid (a3) can once add, and also can add several times.In addition, first can synthesize the fatty acid modified vibrin containing carboxyl, then, use above-mentioned alcohol composition (a2), make this contain the fatty acid modified vibrin esterification of carboxyl.And then, first can synthesize the fatty acid modified vibrin containing hydroxyl, then, make anhydride reaction, make the fatty acid modified vibrin containing hydroxyl half-esterification.
When described esterification or transesterification reaction, in order to promote reaction, catalyzer can be used.As described catalyzer, the catalyzer that Dibutyltin oxide, weisspiessglanz, zinc acetate, manganese acetate, Cobaltous diacetate, calcium acetate, plumbic acetate, four titanium butoxide, titanium isopropylate etc. are known can be used.
In addition, fatty acid modified vibrin (A1) can also use mono-epoxy compound modification in the modulation of this resin or after modulation.As mono-epoxy compound, such as, preferably can use the glycidyl ester (trade(brand)name " CARDURAE-10 ", Hexion Specialty Chemicals Inc.) of the high chain saturated fatty acid of synthesis.
From the view point of processibility, the smoothness of film obtained, the number-average molecular weight of fatty acid modified vibrin (A1) is 5000 ~ 30000, preferably 7000 ~ 25000, more preferably 10000 ~ 20000.
In addition, from the view point of the solidified nature of the film obtained, generally, the hydroxyl value scope of fatty acid modified vibrin (A1) is 5 ~ 100mgKOH/g, preferably 10 ~ 90mgKOH/g, more preferably 40 ~ 80mgKOH/g.
In addition, from the view point of the weathering resistance of film obtained, the oil length of fatty acid modified vibrin (A1) is 3 ~ 30%, preferably 5 ~ 20%.Herein, so-called oil length refers to the quality % of fatty acid component (a3) relative to the total amount as the polyacid constituent (a1) of constituent, alcohol composition (a2) and fatty acid component (a3).
In addition, from the viewpoint such as hardness, processibility of the film obtained, the glass transition temp of fatty acid modified vibrin (A1) is 0 ~ 50 DEG C, preferably 10 ~ 40 DEG C.
Number-average molecular weight and the hydroxyl value of fatty acid modified vibrin (A1) such as can be adjusted by following method, that is: by adjusting the method for the equivalence ratio (COOH/OH) of the carboxyl in described polyacid constituent (a1) and fatty acid component (a3) and the hydroxyl in described alcohol composition (a2); The method in reaction times is adjusted in described esterification or transesterification reaction.
In addition, as the equivalence ratio (COOH/OH) of the hydroxyl in the carboxyl in above-mentioned polyacid constituent (a1) and alcohol composition (a2), be generally 0.5 ~ 0.98, preferably 0.6 ~ 0.95.
It should be noted that, number-average molecular weight in this specification sheets and weight-average molecular weight are with the value of the molecular weight of polystyrene standard for obtaining after basis conversion by the number-average molecular weight that records with gel permeation chromatography (TOSOH Co., Ltd's system, " HLC8120GPC ") and weight-average molecular weight.In this mensuration, use chromatographic column is " TSK-gelG4000H
xL", " TSK-gelG3000H
xL", " TSK-gelG2500H
xL", " TSK-gelG2000H
xL" (being trade(brand)name, TOSOH Co., Ltd's system) 4, condition determination: moving phase is tetrahydrofuran (THF), mensuration temperature is 40 DEG C, flow velocity is 1mL/min, detector is RI.
In addition, in this manual, glass transition temp (Tg) is the temperature utilizing dsc (DSC) to obtain.
As polyester resin component (A), except fatty acid modified vibrin (A1), the common oil-free polyester resin (A2) of usual unreacted fatty acid modification can also be comprised.
Oil-free polyester resin (A2) utilizes well-established law by the esterification of polyacid constituent (a1) and alcohol composition (a2) or transesterification reaction and the vibrin obtained, use by the illustrative material of above-mentioned fatty acid modified vibrin (A1) as polyacid constituent (a1) and alcohol composition (a2), can manufacture by the method identical with by the illustrative method of above-mentioned fatty acid modified vibrin (A1).
In the present invention, relative to the total solids level of polyester resin component (A), the solids content of fatty acid modified vibrin (A1) is 50 ~ 100 quality %.Especially, from the maintenance weathering resistance of film obtained and the ability of erosion resistance, preferably 60 ~ 100 quality %, more preferably 70 ~ 100 quality %.
(B) melamine resin composition
In coating composition of the present invention, relative to the total solids level of melamine resin composition (B), melamine resin composition (B) is the melamine resin (B1) of the following butyl etherificate of 50 ~ 100 quality % containing solids content.
(B1) melamine resin of butyl etherificate
The melamine resin of butyl etherificate is using the methylol propyl carbinol of part or all in the methylolated melamine resin of the addition reaction product of the aldehyde composition as trimeric cyanamide and formaldehyde, paraformaldehyde etc. (can be any one in monomer and polymer) or isopropylcarbinol etherificate and the melamine resin obtained.Herein, the melamine resin of butyl etherificate comprises: the melamine resin methylol propyl carbinol etherificate of part or all in methylolated melamine resin obtained, the melamine resin obtained by isopropylcarbinol etherificate, the melamine resin obtained with propyl carbinol and isopropylcarbinol etherificate.From the angle of the processibility of film obtained and resistance to soiling etc., the number-average molecular weight of the melamine resin of this butyl etherificate is 800 ~ 8000, particularly preferably in 1000 ~ 5000.The melamine resin (B1) of butyl etherificate, can use one, also can use with two or more mixtures.
As the commercially available product of the melamine resin (B1) of butyl etherificate, such as UVAN20SE, UVAN225 (being Mitsui Chemicals, Inc's system above), SUPERBECKAMINEJ820-60, SUPERBECKAMINEL-117-60, SUPERBECKAMINEL-109-65, SUPERBECKAMINE47-508-60, SUPERBECKAMINEL-118-60, SUPERBECKAMINEG821-60 (above by Dainippon Ink Chemicals's system) etc. can be enumerated.
As melamine resin composition (B), the melamine resin (melamine resin (B2) beyond the melamine resin (B1) that can also comprise above-mentioned butyl etherificate.
Specifically, can enumerate such as: the methylol propyl carbinol of part or all in the methylolated melamine resin of the addition reaction product of the aldehyde composition as trimeric cyanamide and formaldehyde, paraformaldehyde etc. (can be any one in monomer and polymer) and the one kind or two or more alcohol beyond isopropylcarbinol are carried out etherificate and the melamine resin obtained; Etherificate is carried out and the melamine resin obtained with the one kind or two or more alcohol beyond propyl carbinol and/or isopropylcarbinol and propyl carbinol and isopropylcarbinol.As the example of the alcohol beyond the propyl carbinol used during etherificate and isopropylcarbinol, the monohydroxy-alcohol of methyl alcohol, ethanol, n-propyl alcohol, Virahol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc. can be enumerated.As the concrete example of melamine resin (B2), can enumerate and utilize methanol etherification and the melamine resin (methyl etherified melamine resin) obtained, utilize methyl alcohol and butanol etherification and the melamine resin (methyl/butyl complex etherified melamine resin) etc. obtained.
The melamine resin obtained as utilizing methanol etherification, such as SumimalM-100 can be enumerated, SumimalM-40S, SumimalM-55 is (by Sumitomo Chemical Co's system, trade(brand)name), CYMEL300, CYMEL303, CYMEL325, CYMEL327, CYMEL350, CYMEL370, CYMEL730, CYMEL736, CYMEL738 is (above by Japanese cyanogen secret service industry Inc., trade(brand)name), MELAN522, MELAN523 is (above by Hitachi Chemical Co., Ltd.'s system, trade(brand)name), NIKALACMS17, NIKALACMS15, NIKALACMS001, NIKALACMX430, NIKALACMX650 is (by Sanwa Co., Ltd.'s chemistry system, trade(brand)name), Resin740, Resin741, Resin747 is (above by Monsanto Company's system, trade(brand)name) etc. methyl etherified melamine resin.
As the melamine resin obtained by methyl alcohol and butanol etherification, such as can enumerate CYMEL232, CYMEL235, CYMEL202, CYMEL238, CYMEL254, CYMEL266, CYMEL272, CYMEL1130, CYMELXV-514, CYMELXV805 (by Japanese cyanogen secret service industry Inc., trade(brand)name), SumimalM66B (Sumitomo Chemical Co's system, trade(brand)name), Resin753, Resin755 (above by Monsanto Company's system) etc. methyl/butyl complex etherified melamine resin.
In the present invention, relative to the total solids level of melamine resin composition (B), the solids content of the melamine resin (B1) of butyl etherificate is 50 ~ 100 quality %.Especially, from the view point of the processibility of the film obtained and the ability of maintenance resistance to soiling, preferably 70 ~ 100 quality %, more preferably at 80 ~ 100 quality %.
Compared with methyl etherified melamine resin, methyl/butyl complex etherified melamine resin etc., melamine resin (B1) polarity of butyl etherificate is low, good with the intermiscibility of the vibrin (A) as matrix resin.Therefore, from the film that the antifouling paint composition of the melamine resin (B1) containing butyl etherificate obtains, its crosslinked excellent in uniformity.
In addition, with methyl etherified melamine resin, methyl/butyl complex etherified melamine resin-phase ratio, not easily there is the Localization Phenomenon on the top layer of film in the melamine resin (B1) of butyl etherificate.Therefore, from the film that the antifouling paint composition of the melamine resin (B1) containing butyl etherificate obtains, weathering resistance is also excellent.
In addition, in order to promote the curing reaction of polyester resin component (A) and melamine resin composition (B), curing catalysts can be used as required.As the curing catalysts for promoting this curing reaction, generally, the corrective of sulfoacid compound or sulfoacid compound can be used.
As sulfoacid compound, tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid etc. can be enumerated.As the neutralizing agent in the corrective of sulfoacid compound, the basic cpd of primary amine, secondary amine, tertiary amine, ammonia, sodium hydroxide, potassium hydroxide etc. can be enumerated.
In antifouling paint composition of the present invention, the solids content ratio of above-mentioned polyester resin component (A) and melamine resin composition (B) is: based on the total solids level of polyester resin component (A) and melamine resin composition (B), polyester resin component (A) is 50 ~ 90 quality %, and melamine resin composition (B) is 10 ~ 50 quality %.Especially, from the view point of the solidified nature, resistance to soiling, physical strength, processibility, solvent resistance, erosion resistance, weathering resistance etc. of the film obtained, the solids content ratio of above-mentioned polyester resin component (A) and melamine resin composition (B) is preferably: polyester resin component (A) is 60 ~ 80 quality %, and melamine resin composition (B) is 20 ~ 40 quality %.
(C) organosilicate and/or its condenses composition
(C) of the present invention composition is the organosilicate and/or its condenses that are represented by following general formula,
(R
1)
n-Si-(OR
2)
4-n
In formula, R
1the alkyl or phenyl of the carbon number 1 ~ 18 that can be replaced by epoxy group(ing) or sulfydryl, R
2be the alkyl of carbon number 1 ~ 6, n is 0 or 1.
(C) composition contained by coating composition of the present invention is the composition used to make film play hydrophilic effect at substrate surface efficiently after coating, from the view point of this effect, and the more preferably condenses of above-mentioned organosilicate.
As the R in above-mentioned general formula
1concrete example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl, heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, glycidyl, methylglycidyl (2-methylglycidyl), mercapto methyl, 2-mercaptoethyl, 2-mercaptopropyi, 3-mercaptopropyi, 4-mercaptobutyl, phenyl, to mercaptophenyl etc.
As the concrete example of the organosilicate of (C) composition, four functional silanes of tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, tetraisobutoxy-silicane alkane etc. can be enumerated, methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three isobutoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl tripropoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, phenyl three isobutoxy silane, hexyl Trimethoxy silane, hexyl triethoxyl silane, dodecyltrimethoxysilane, dodecyl triethoxysilane, mercapto methyl Trimethoxy silane, mercaptoethyl Trimethoxy silane, mercapto methyl triethoxyl silane, mercaptoethyl triethoxyl silane, mercaptopropyi Trimethoxy silane, the trifunctional silane of Mercaptopropyltriethoxysilane etc.As the condenses of above-mentioned organosilicate, the condenses etc. of their four functional silanes or the one kind or two or more combination of trifunctional silane can be enumerated.
The condenses of organosilicate can be manufactured by well-established law, such as MKCSilicateMS51 can be enumerated as commercially available product, MS56, MS57, MS56S, MS56SB5, MS58B15, MS58B30, ES40, EMS31, BTS is (above by Mitsubishi chemical Co., Ltd's system, trade(brand)name), MethylSilicate51, EthylSilicate40, EthylSilicate40T, EthylSilicate48 is (above by Japanese COLCOAT Co., Ltd. system, trade(brand)name), KR500, KR9218, X-41-1805, X-41-1810, X-41-1818, X-41-1053, X-41-1056 is (above by Shin-Etsu Chemial Co., Ltd's system, trade(brand)name) etc.In addition, the condenses of these organosilicates also can carry out partial hydrolysis condensation with monomer or combination of more than two kinds and obtain.The condenses of organosilicate is the condenses of branched or straight-chain, and condensation degree is 2 ~ 100, preferably 2 ~ 20.In coating composition of the present invention, the organosilicate of (C) composition, the condenses of organosilicate can be used alone, and also can combine two or more and use.
In the organosilicate represented by described general formula and/or its condenses, as OR
2base, has the alkoxyl group of methoxyl group and carbonatoms 2 ~ 6.Serviceable time (working life) after making from the view point of coating, the ratio of the number of the alkoxyl group of methoxyl group/carbonatoms 2 ~ 6 is comparatively suitable in the scope of 95/5 ~ 30/70.
In coating composition of the present invention, based on the total solids level of (A) composition and (B) composition, the solids content of (C) composition is 0.1 ~ 50 quality %, preferably 0.5 ~ 30 quality %, more preferably 1 ~ 20 quality %.
By making (C) component amount in above-mentioned scope, the effect of contained (C) composition can be played better, from the initial stage resistance to soiling of gained film and the physical strength of the hold facility of resistance to soiling and the film of gained and the angle of weather resistance, be also comparatively suitable for.
In coating composition of the present invention, except above-mentioned (A), (B) and (C) composition, the well known materials that the paint additive, solvent etc. that also can comprise the pigment extender, organic resin powder, mineral aggregate, pigment dispersing agent, UV light absorber, ultra-violet stabilizer, defoamer, surface conditioner etc. of the hydrolytic accelerating agent, tinting pigment, silicon dioxide microparticle etc. of display acid tensio-active agent, boric acid based compound etc. use all the time in coating.
The tensio-active agent of above-mentioned display acidity, boric acid based compound, have the effect of the hydrolysis promoting above-mentioned organosilicate and/or its condenses composition (C).The hydrolytic accelerating agent of tensio-active agent, boric acid based compound etc. that display is acid, if share, shortens the working life of coating composition of the present invention, but from the view point of raising resistance to soiling, can use.
As the tensio-active agent that display is acid, such as, can enumerate the phosphate ester salt of polyoxyethylene kind phosphate ester, alkyl phosphate salt etc.; The alkyl of such as sodium laurylsulfonate (sodiumlaurylSulfonic), Sodium dodecylbenzene sulfonate etc. or the sulfonate such as sulfonated alkyl naphathalene, alkyl diphenyl ether sulfonate of alkylbenzene sulfonate, isopropyl naphthalene sulfonate etc.; The sulfuric acid of such as alkyl or alkyl sulfate, alkyl phenyl (gathering) oxygen Vinyl Ether series vitriol etc.; The tensio-active agent of the carboxylate salt of such as salts of alkyl sulfosuccinates salt etc. etc.As boric acid based compound, such as, can enumerate the trialkyl borates such as trimethyl borate, triethyl borate, tributyl borate; Boric acid etc.Relative to the total solids level of described (A) composition and (B) composition, the solids content of these hydrolytic accelerating agents is below 30 quality %, particularly preferably 0.5 ~ 20 quality %, particularly preferred 1 ~ 10 quality %.
As above-mentioned pigment extender, silicon dioxide microparticle, talcum, mica powder, barium oxide etc. can be enumerated.Relative to the total solids level of described (A) composition and (B) composition, the solids content of pigment extender is 0.1 ~ 20 quality %, particularly preferably 0.5 ~ 15 quality %, particularly preferred 1 ~ 10 quality %.
In addition, in coating composition of the present invention, matting agent (D) can be contained with the gloss making the film of acquisition make the finished appearance of delustring, middle light etc.Matting agent (D) uses to make the gloss of gained film decline, and can be any one in organic system matting agent and inorganic flatting agent.In addition, these materials can be used alone, or combine two or more use.
In the film of the finished appearance that the gloss that antifouling paint composition of the present invention is applicable to delustring, middle light etc. declines, the film of hold facility excellence of resistance to soiling, erosion resistance can be formed especially.
As organic system matting agent, such as can for the organic resin particulate do not melted completely because toasting when forming film.From the view point of appearance of film, coating workability etc., the median size of this organic resin particulate be generally 3 ~ 80 μm, preferably comparatively suitable in the scope of 5 ~ 60 μm.As organic system matting agent, such as, can enumerate the polymeric amide etc. of the fluorine resin such as polyvinylidene difluoride (PVDF), tetrafluoroethylene, polymeric amide, acrylic resin, urethane, resol, containing silicone resin, polypropylene and nylon 11, nylon 12 etc.
As inorganic system matting agent, silicon-dioxide, mica, aluminum oxide, talcum, clay, calcium carbonate, barium sulfate etc. can be enumerated.
Above-mentioned matting agent (D) can be used alone, or combines two or more use.Relative to the total solids level of described (A) composition and (B) composition, the solids content of matting agent (D) is preferably 0.1 ~ 30 quality %, particularly preferably 0.5 ~ 20 quality %.
Antifouling paint composition of the present invention, can manufacture by mixing mentioned component (A) ~ (C) equably, and, can also become to assign to manufacture by above-mentioned other of further Homogeneous phase mixing as required.Preferably, by pigment composition in advance with the part of resinous principle (A) and/or pigment dispersing agent mixes, disperse and make pigment thickener, this pigment thickener can be mixed with remaining composition and manufactures thus.
Coating composition of the present invention, can make single-liquid type coating, in addition, also can make two-pack type coating, that is, as the organosilicate of (C) composition and/or its condenses in advance and other component separating, and mixes before use.From the viewpoint etc. of Storage, preferably make two-pack type coating.
As the method using antifouling paint composition of the present invention to form film, such as, following method etc. can be enumerated, that is: add after organic solvent etc. adjusts to required viscosity as required in the coating composition, the coating machine, bristle, bar coater, application member etc. of use aerial spraying, static air spraying, roller coating machine, flow coating machine, dip-coating form carry out applying and make dried film thickness be generally 0.5 ~ 300 μm, preferably 5 ~ 50 μm, then, at the temperature of 80 ~ 300 DEG C, usually heating 5 seconds ~ 1 hours makes it solidify.It should be noted that, as coating method, in the above-mentioned methods, the coating of spray application, roller coating machine is comparatively suitable.
form the method for film
The method of formation film of the present invention, it is characterized in that, single or double on a metal plate utilizes do not form bottom coating containing the Chrome-free base paint being feature containing the antirust composition of chromium, in at least one side of bottom coating, utilize the antifouling paint composition of the invention described above to form top and be coated with film and obtain.
In other words, the method for formation film of the present invention, is characterized in that, comprising:
Single or double on a metal plate utilizes Chrome-free base paint formed bottom coating operation and
In at least one side of the bottom coating of above-mentioned formation, the antifouling paint composition of the invention described above is utilized to form the operation that top is coated with film.
In addition, the metal sheet of the coating that the manufacture method comprising the manufacture method of the metal sheet of the coating of each operation of the method for above-mentioned formation film and the method for above-mentioned formation film or metallic sheet obtains also provides by the present invention.
The method of formation film of the present invention not only can use in precoating coating, also can use in rear painting coating.As preferred example, the coating etc. carried out to aforesaid substrate outdoors (such as buildings, indicator, guardrail, utensil, machine etc.) can be enumerated.
As the metal sheet of the coated article in the method for formation film of the present invention, cold-rolled steel sheet, hot-dip galvanizing sheet steel, electrogalvanizing steel plate, alloy steel plate galvanized (the alloy steel plate galvanizeds of iron-zinc, aluminium-zinc, nickel-zinc etc.), aluminium sheet, stainless-steel sheet, copper coin, Copper Plated Steel, tin plate etc. can be enumerated.
When metal species applies, if as the metallic surface of coated material not by wet goods contaminants, then directly carry out primary coat also harmless, in order to improve tack between film, erosion resistance and preferably impose known metal finishing.As these known surface treatment methods, phosphate-based surface treatment, chromate surface treatment, the surface treatment of zirconium system etc. can be enumerated.
In the present invention, as the priming paint forming bottom coating on a metal plate, from the view point of environment protection, use not contain the Chrome-free base paint that the antirust composition of chromium is feature.If above-mentioned priming paint Chrome-free base paint, then can be useful in the known priming paint used in painted color steel sheet coating field, industrial machine coating field, metal parts coating field etc.
Chrome-free base paint suitably can be selected according to the kind of the kind of coated material, metal finishing.Particularly epoxy, Polyester base paint and their modification base paint are comparatively suitable, and when there being special requirement to processibility, Polyester base paint is comparatively suitable.
As the concrete means forming bottom coating, coating base paint can be illustrated, carry out as required afterwards heating the means making it solidify.In this case, utilize the known coating method such as roll coating, spray application to carry out coating base paint, make primary coat thickness be 1 ~ 30 μm, preferably 2 ~ 20 μm, at the temperature of atmosphere temperature 80 ~ 300 DEG C, usually heat 5 seconds ~ 1 hours make it solidify.When carrying out precoating coating, preferably under material arrival top temperature is the condition of 140 ~ 250 DEG C, heating makes it solidify in 15 seconds ~ 120 seconds.
The layer structure of bottom coating is not particularly limited, and can be such as one deck, also can be on the 1st bottom coating, define the 2nd bottom coating (middle painting film) two layers.When bottom coating being made two layers, two layers of bottom coating can be made to have different functions, such as, the 1st bottom coating has corrosion proof function, and the 2nd bottom coating (middle painting film) has processibility, chipping resistance energy etc.
Then, in the method for formation film of the present invention, at least one side of the bottom coating that the single or double on above-mentioned metal sheet is formed, utilize antifouling paint composition of the present invention to form top and be coated with film.That is, painting film in top is formed overlappingly at least one side of the bottom coating formed.Herein, so-called " at least one side of bottom coating ", when one side on a metal plate defines bottom coating, refers on bottom coating that this one side is formed; When on a metal plate two-sided defines bottom coating, refer on bottom coating that the one side on the metal sheet in the bottom coating of this two-sided upper formation is formed or on the bottom coating of this two-sided upper formation.
As the concrete method forming top painting film, coating antifouling paint composition of the present invention can be illustrated, then carry out as required heating the method making it solidify.As coating method, showering curtain type coating, roller coating machine coating, immersion coating, spray coating etc.About thickness, usually reach 5 ~ 50 μm with dried painting thickness, preferably apply in the scope of 8 ~ 25 μm.
When precoating applies coating composition of the present invention, this coating method is not limited, but from the economy that pre-coated steel plate applies, preferred showering curtain type coating, roller coating machine coating.When applicable roller coating machine coating, from the view point of practicality, preferably utilize the bottom feed mode of bigeminy roller (so-called coating (naturalreversepainting) counterclockwise, clockwise coating (naturalpainting)).Or, become the best from the view point of the homogeneity in the painting face of making, also can carry out the top feeding or the bottom feed mode that utilize three rollers.
Utilize the top of coating composition of the present invention to be coated with the condition of cure of film, normally at material arrives top temperature 120 ~ 260 DEG C, carry out 15 seconds ~ about 30 minutes.In the precoating coating field utilizing coil coat (coilcoating) to carry out applying, usually toast 15 ~ 90 seconds at material arrives top temperature 160 ~ 260 DEG C.
[embodiment]
Below, the present invention is further illustrated by Production Example, embodiment.The invention is not restricted to following embodiment.It should be noted that, below, " part " and " % " all obtained by quality criteria.
The preparation of vibrin
Preparation example 1
Following material is added in the flask of equipment thermometer, stirrer, heating unit and rectifying tower:
1,2-cyclohexane dicarboxylic acid acid anhydride 150.9 parts (0.98 mole)
Neopentyl glycol 38.9 parts (0.37 mole)
Butyl ethyl propane diol 9.6 parts (0.06 mole)
TriMethylolPropane(TMP) 77.8 parts (0.57 mole)
Coco-nut oil fatty acid 44.1 parts (0.21 mole)
Dibutyltin oxide (catalyzer) 0.03 part.
Next, limit is stirred content limit and is warming up to 160 DEG C, slowly heat up from 160 DEG C to 230 DEG C with 3 hours, at 230 DEG C, sustained reaction is after 30 minutes, rectifying tower water separator is replaced, in order to promote the removing of by product condensation water, add relative to feeding quantity 5% dimethylbenzene, react further at 230 DEG C, heating is stopped when acid number reaches 4mgKOH/g, add SWASOL1500 (hydrocarbon system solvent) dilution, obtain vibrin (A1-1) solution of solids content 65%.
The resin obtained, its number-average molecular weight 15000, the hydroxyl value milligram number of potassium hydroxide needed for 1g resin (in and) 75mgKOH/g, oil length 14.7%, iodine number are greater than 5.
Preparation example 2 ~ 13
With the proportioning shown in following table 1, in the same manner as preparation example 1, obtain the solution of each vibrin (A1-2) ~ (A1-13) of solids content 65%.In table 1, the ratio of components of each composition is mol ratio.
The number-average molecular weight of each resin, hydroxyl value, oil length and iodine number are shown in table 1 in the lump.It should be noted that, vibrin (A1-7) ~ (A1-13) of preparation example 7 ~ 13 is resins of comparative example.
[table 1]
The preparation and property test of antifouling paint composition
Embodiment 1 ~ 18 and comparative example 1 ~ 10
Carry out coating according to the composition shown in aftermentioned table 2 and table 3, obtain each antifouling paint composition No.1 ~ 28.Antifouling paint composition No.19 ~ 28 are coating compositions of comparative example.
The heat 55% imposing the thickness 0.35mm changing into process aluminize-front and back of zinc steel plate (Al-Zn coated steel) applies KPCOLOR8620 priming paint (Kansai Paint Co., Ltd's system, pre-coated steel plate Polyester priming paint) respectively and makes dry film thickness be 5 μm, it is 220 DEG C that heating makes material arrive top temperature, toast 40 seconds, obtain the steel plate that primary coat is covered.It is about 15 μm that each antifouling paint composition bar coater obtained in the above described manner is applied into dry film thickness by the front of the steel plate covered in this primary coat, and carrying out heating, to make material arrive top temperature be 230 DEG C, and baking obtains the steel plate of each coating for 50 seconds.Following performance test is carried out to the steel plate of each coating of gained.
Test-results is shown in table 2 and table 3 in the lump.It should be noted that, the amount of each composition in table 2 and table 3 is solid masses.It should be noted that, when the coating of antifouling paint composition, carry out the dispersion as the titanium dioxide of white pigment.In addition, the mixed solvent of pimelinketone/SWASOL1500 (Wan Shan oil Co., Ltd. system, aromatic base crude oil system high boiling solvent)=60/40 (mass ratio) is viscosity for adjusting coating composition etc. and uses.When applying, with Ford cup #4, coating composition viscosity is adjusted to about 100 seconds (25 DEG C).
[table 2]
[table 3]
It should be noted that, (note 1) ~ (note 11) of table 2 and table 3 is as follows.
(note 1) UVAN20SE-60: Mitsui Chemicals, Inc's system, the melamine resin of butyl etherificate, weight-average molecular weight are about 4000.
(note 2) SUPERBECKAMINEJ820-60: trade(brand)name " SUPERBECKAMINEJ-820-60 ", the melamine resin solution of Dainippon Ink Chemicals's system, normal-butyl etherificate.
(note 3) SUPERBECKAMINEL-118-60: trade(brand)name " SUPERBECKAMINEL-118-60 ", Dainippon Ink Chemicals's system, the melamine resin solution of normal-butyl etherificate.
(note 4) CYMEL303: Japanese cyanogen secret service industry Inc., lower molecular weight methyl etherified melamine resin.The content of hexamethylolmelamine pregnancy ether (hexakis (methoxymethyl) melamine) is more than 60 % by weight.
(note 5) SUMIJULEBL3175:SumikaBayerUrethane Co., Ltd. system, the methyl ethyl ketone oxime block compound of TriMethylolPropane(TMP) add-on type hexamethylene diisocyanate.
(note 6) MS56S: Mitsubishi chemical Co., Ltd's system, trade(brand)name " MKCSilicateMS56S ", as the methyl silicate of tetramethoxy-silicane condenses.
(note 7) MS58B30: Mitsubishi chemical Co., Ltd's system, is 70/30 as the methyl/butyl mixed ester SiClx hydrochlorate of tetraalkoxysilane condenses, the ratio of methyl/butyl number at trade(brand)name " MKCSilicateMS58B30 ".
(note 8) X-41-1805: Shin-Etsu Chemial Co., Ltd's system, trade(brand)name, the condenses of trialkoxy silane containing mercaptoalkyl, the carbon number of mercaptoalkyl are less than 18, the carbon number of alkoxyl group is less than 6.
(note 9) SYLOID161W:GRACEGMBH society system, trade(brand)name, through fine silica powder, the oil number 170ml/100g of organic process.
The aqueous isopropanol of the secondary amine corrective of (note 10) Nacure5225:KINGINDUSTRIES system, Witco 1298 Soft Acid.The degree of neutralization of Witco 1298 Soft Acid/amine is about 1.1 (mol ratios).Effective constituent is about 33 % by weight, and wherein Witco 1298 Soft Acid/amine (mass ratio) is about 8/25.Numerical value in table 2 is solid masses part of Witco 1298 Soft Acid.
(note 11) " Off ォ-メ-ト TK-1 ": trade name, Takede Chemical Industries Ltd's system, as the curing catalysts of organotin solution, the dissociation catalyst of blocked polyisocyanate compounds.
Performance test in table 2 and table 3 is carried out according to following method and judgement criteria.
60 ° of gloss:
According to 60 degree of mirror surface lusters of regulation in JISK-54007.6 (1990), measure 60 degree of specular reflectances.
Processibility:
The indoor of 20 DEG C, make painting face be outside, folding test plate 180 degree, display dogleg section does not produce the T number of crackle.So-called T number, refer to and do not press from both sides any object in the inner side of dogleg section and the situation of bending 180 degree is denoted as 0T, clip one with the plate of test board same thickness and the situation of bending is denoted as 1T, the situation of 2 is denoted as 2T, the situation of 3 is denoted as 3T, the situation of 4 is denoted as 4T, the situation of 5 is denoted as 5T, the situation of 6 is denoted as 6T.Result is judged by following:
A: in 4T bending machining, almost do not see crackle.
B: in 4T bending machining, sees obvious crackle, in 6T bending machining, does not almost see crackle.
C: in 6T bending machining, sees obvious crackle.
Outdoor exposure test:
By outdoor exposure test test film (100 × 300mm) in the mode of coated surface to north side, be arranged in the modeled setting table in eaves front end, the Kansai Paint Co., Ltd roof of the rugged raised path between farm fields of Ni Qi city god carries out exposure test, resistance to soiling and resistance to rainprint contaminative (stain of rainprint shape) are evaluated according to following standard.About resistance to soiling, based on JISZ8370, measure the aberration (Δ E) before and after exposing to the open air with the multiple light courcess spectrophotometric colorimeter MSC-5N of SUGA trier Co., Ltd..Resistance to rainprint contaminative is judged by visual.
Resistance to soiling:
The Δ E before and after outdoor exposure test is utilized to be evaluated by following standard:
S: Δ E is less than 2.
A: Δ E is more than 2 and is less than 3.
B: Δ E is more than 3 and is less than 5.
C: Δ E is more than 5.
Resistance to rainprint contaminative:
Rainprint mark after atmospheric exposure test is evaluated by following standard:
S: have no rainprint mark,
A: see some rainprint marks,
B: see a lot of rainprint mark,
C: residual very many rainprint marks.
Accelerate weathering resistance:
A situation arises in the efflorescence of the coated board after utilizing hydrogen peroxide xenon 7 cycle (161 hours) to test, and evaluated by following standard:
S: the generation having no efflorescence.
A: slightly turning white of efflorescence generation slight as seen or as seen film.
B: turn white as seen, there is efflorescence in lackluster sense slightly.
C: visible significantly efflorescence occurs.
Comprehensive evaluation:
For antifouling paint composition, the processibility of coated article, the resistance to soiling of gained film, resistance to rainprint contaminative and the equal height of acceleration weathering resistance are very important.Thus, comprehensive evaluation is carried out according to following standard.
S: processibility, resistance to soiling, resistance to rainprint are polluted and the evaluation of acceleration weathering resistance is all S or A, and at least one is S.
A: processibility, resistance to soiling, resistance to rainprint are polluted and the evaluation of acceleration weathering resistance is all A.
B: processibility, resistance to soiling, resistance to rainprint are polluted and the evaluation of acceleration weathering resistance is all S, A or B, and at least one is B.
C: at least one in the evaluation of scuff resistance, initial stage tack and weathering resistance is C.
Claims (11)
1. antifouling paint composition, it comprises:
(A) vibrin, this vibrin contains the fatty acid modified vibrin (A1) that solids content is 50 ~ 100 % by weight, the number-average molecular weight of described fatty acid modified vibrin (A1) is 5,000 ~ 30,000, hydroxyl value is 5 ~ 100mgKOH/g and oil length is 3 ~ 30%, and
Described fatty acid modified vibrin (A1) is obtained by the reaction of following material, that is,
(a1): the polyprotonic acid containing alicyclic polyprotonic acid (a1-1),
(a2): the alcohol containing polyvalent alcohol (a2-1) more than ternary, and
(a3): lipid acid;
In described reaction, based on the total content of described polyprotonic acid (a1), in described polyprotonic acid (a1), the content of described alicyclic polyprotonic acid (a1-1) is 50 ~ 100mol%; Based on the total content of described alcohol (a2), in described alcohol (a2), the content of polyvalent alcohol (a2-1) more than described ternary is 10 ~ 70mol%;
(B) melamine resin, this melamine resin comprises the melamine resin (B1) that solids content is the butyl etherificate of 50 ~ 100 % by weight; And
(C) organosilicate expressed by the following formula and/or its condenses:
General formula: (R
1)
n-Si-(OR
2)
4-n
Wherein R
1represent the alkyl or phenyl with 1 to 18 carbon atom, each group can be replaced by epoxy group(ing) or sulfydryl, R
2represent the alkyl with 1 to 6 carbon atom, and n represents 0 or 1,
Further, based on the total solids level of described component (A) and described component (B), the solids content of described component (C) is 0.1 ~ 50 % by weight.
2. antifouling paint composition as claimed in claim 1, wherein in the reaction obtaining described fatty acid modified vibrin (A1), based on the total content of described polyacid component (a1), in described polyacid component (a1), the total content of described alicyclic polyprotonic acid (a1-1) is 85 ~ 100mol%.
3. antifouling paint composition as claimed in claim 1, based on the total solids level of described polyester resin component (A) and described melamine resin component (B), described composition comprise solids content be 50 ~ 90 % by weight described polyester resin component (A) and solids content be 10 ~ 50 % by weight described melamine resin component (B).
4. antifouling paint composition as claimed in claim 1, wherein said alicyclic polyprotonic acid (a1-1) comprises and is selected from alicyclic multivalent carboxylic acid, at least one in the acid anhydrides of described alicyclic multivalent carboxylic acid and the low alkyl group carboxylate of described alicyclic multivalent carboxylic acid, described alicyclic multivalent carboxylic acid comprises 1, 2-cyclohexane dicarboxylic acid, 1, 3-cyclohexane dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, 4-tetrahydrobenzene-1, 2-dicarboxylic acid, 3-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 4-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 1, 2, 4-cyclohexanetricarboxylic acid and 1, 3, 5-cyclohexanetricarboxylic acid.
5. antifouling paint composition as claimed in claim 1, polyvalent alcohol (a2-1) more than wherein said ternary comprise be selected from more than ternary polyvalent alcohol, by least one in poly-lactone polyol compound and three (hydroxyalkyl) isocyanuric acid ester that polyvalent alcohol addition more than lactone compound and described ternary is obtained, polyvalent alcohol more than described ternary is selected from glycerine, trimethylolethane, TriMethylolPropane(TMP), two glycerine, triglycerin, 1,2,6-hexanetriol, tetramethylolmethane, Dipentaerythritol, sorbyl alcohol and N.F,USP MANNITOL.
6. antifouling paint composition as claimed in claim 1, wherein said lipid acid (a3) comprises at least one in the monocarboxylic acid being selected from following straight chain hydrocarbon, the monocarboxylic acid of described straight chain hydrocarbon comprises coco-nut oil fatty acid, cottonseed oil fatty acid, hempseed oil lipid acid, rice bran oil fatty acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, linseed oil lipid acid, tung oil fatty acid, rapeseed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, safflower oil fatty acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linoleic acid plus linolenic acid.
7. antifouling paint composition as claimed in claim 1, it also comprises matting agent (D).
8. antifouling paint composition as claimed in claim 7, based on the total solids level of described vibrin (A) and described melamine resin (B), described composition comprises the described matting agent (D) that solids content is 0.1 ~ 30 % by weight.
9. form the method for film, it comprises:
Chrome-free base paint is used to form bottom coating on the single or double of metal sheet; And
Use antifouling paint composition described in claim 1 formed described bottom coating at least one on form top and be coated with film.
10. the method for the metal sheet of preparation coating, it comprises
Chrome-free base paint is used to form bottom coating on the single or double of metal sheet; And
Use antifouling paint composition described in claim 1 formed described bottom coating at least one on form top and be coated with film.
The metal sheet of 11. coatings, it is obtained by the method as described in claim 9 or 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-146689 | 2010-06-28 | ||
| JP2010146689 | 2010-06-28 | ||
| PCT/JP2011/062626 WO2012002095A1 (en) | 2010-06-28 | 2011-06-01 | Contamination resistant coating composition with excellent durability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102971388A CN102971388A (en) | 2013-03-13 |
| CN102971388B true CN102971388B (en) | 2016-01-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180032375.0A Expired - Fee Related CN102971388B (en) | 2010-06-28 | 2011-06-01 | The antifouling paint composition of excellent in te pins of durability |
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| Country | Link |
|---|---|
| JP (1) | JP5705220B2 (en) |
| CN (1) | CN102971388B (en) |
| TW (1) | TWI518152B (en) |
| WO (1) | WO2012002095A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013159622A (en) * | 2012-02-01 | 2013-08-19 | Dainippon Toryo Co Ltd | Two-pack type urethane coating composition, and metal coated body |
| JP2014009288A (en) * | 2012-06-29 | 2014-01-20 | Kansai Paint Co Ltd | Metallic coating composition |
| CN104002518A (en) * | 2014-05-15 | 2014-08-27 | 合肥禾盛新型材料有限公司 | Pollution-proof special effect panel and making method thereof |
| CN104277680A (en) * | 2014-10-29 | 2015-01-14 | 安徽朗凯奇建材有限公司 | Germicidal negative-radical waterproof coating and preparation method thereof |
| CN104693975A (en) * | 2015-02-11 | 2015-06-10 | 常州常松金属复合材料有限公司 | Anti-fouling metal plate |
| CN107667146B (en) | 2015-04-17 | 2021-01-01 | 欧尼克斯荷兰有限公司 | Process for producing crosslinkable compositions |
| CN107683312B (en) | 2015-04-17 | 2020-12-08 | 欧尼克斯荷兰有限公司 | Improved epoxy primers for improved adhesion of RMA crosslinkable coating compositions |
| WO2016166361A1 (en) | 2015-04-17 | 2016-10-20 | Nuplex Resins B.V. | Floor coating compositions |
| CA2982874C (en) | 2015-04-17 | 2022-10-11 | Allnex Netherlands B.V. | Rma crosslinkable compositions and rma crosslinkable resins for easy to clean coatings |
| WO2017050511A1 (en) * | 2015-09-25 | 2017-03-30 | Akzo Nobel Coatings International B.V. | Thermosetting composition, paint finishing method, and method for producing painted articles |
| CN106764823A (en) * | 2016-12-09 | 2017-05-31 | 重庆新派新智能科技有限公司 | Road lamp for garden |
| CN107603444A (en) * | 2017-09-21 | 2018-01-19 | 河北晨阳工贸集团有限公司 | Sealing wax suit and its preparation method and application |
| JP6733835B1 (en) * | 2018-08-28 | 2020-08-05 | Dic株式会社 | Reactive adhesive, laminate, and package |
| CN116102958B (en) * | 2021-11-09 | 2024-03-22 | 广东华润涂料有限公司 | Solvent-based acid-curable coating compositions and articles coated therewith |
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| CN1250460A (en) * | 1997-03-17 | 2000-04-12 | 协和油化株式会社 | Polyester resin composition, cured resin, and coating material |
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| CN101583679A (en) * | 2007-01-23 | 2009-11-18 | 大金工业株式会社 | Coating composition |
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| JPH1067945A (en) * | 1996-08-28 | 1998-03-10 | Nippon Paint Co Ltd | Thermosetting resin composition |
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| JP5074055B2 (en) * | 2006-08-17 | 2012-11-14 | 関西ペイント株式会社 | Top coating composition |
| JP5074056B2 (en) * | 2006-08-30 | 2012-11-14 | 関西ペイント株式会社 | Top coating composition |
| JP5081608B2 (en) * | 2006-12-28 | 2012-11-28 | 関西ペイント株式会社 | Multi-layer coating formation method |
-
2011
- 2011-06-01 CN CN201180032375.0A patent/CN102971388B/en not_active Expired - Fee Related
- 2011-06-01 WO PCT/JP2011/062626 patent/WO2012002095A1/en active Application Filing
- 2011-06-01 JP JP2012522531A patent/JP5705220B2/en active Active
- 2011-06-13 TW TW100120531A patent/TWI518152B/en not_active IP Right Cessation
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|---|---|---|---|---|
| CN1250460A (en) * | 1997-03-17 | 2000-04-12 | 协和油化株式会社 | Polyester resin composition, cured resin, and coating material |
| CN101089104A (en) * | 2006-06-16 | 2007-12-19 | 关西涂料株式会社 | Two surface coating steel plate for tank |
| CN101583679A (en) * | 2007-01-23 | 2009-11-18 | 大金工业株式会社 | Coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012002095A1 (en) | 2012-01-05 |
| JPWO2012002095A1 (en) | 2013-08-22 |
| TWI518152B (en) | 2016-01-21 |
| JP5705220B2 (en) | 2015-04-22 |
| TW201209113A (en) | 2012-03-01 |
| CN102971388A (en) | 2013-03-13 |
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