CN100381517C - Coating composition and coating article - Google Patents
Coating composition and coating article Download PDFInfo
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- CN100381517C CN100381517C CNB2004100324257A CN200410032425A CN100381517C CN 100381517 C CN100381517 C CN 100381517C CN B2004100324257 A CNB2004100324257 A CN B2004100324257A CN 200410032425 A CN200410032425 A CN 200410032425A CN 100381517 C CN100381517 C CN 100381517C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D15/00—Printed matter of special format or style not otherwise provided for
- B42D15/02—Postcards; Greeting, menu, business or like cards; Letter cards or letter-sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D15/00—Printed matter of special format or style not otherwise provided for
- B42D15/0073—Printed matter of special format or style not otherwise provided for characterised by shape or material of the sheets
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Abstract
To obtain a coating material composition excellent in weather resistance, not generating rain trace stain and not damaging an existing coated film when applied to the surface of the existing coated film. The coating material composition comprises (a) a fluoroolefin-based polymer having a reaction curable part and >=5 mass% fluorine content, (b) a polyisocyanate-based curing agent containing average >=1.5 isocyanate groups in the molecule, (c) a medium containing a paraffin-based solvent and/or naphthene-based solvent in an amount of >=30 mass% based on total solvent and (d) a multimer of tetrafunctional hydrolyzable silane compound.
Description
Technical field
The present invention relates to coating composition and coated article.
Background technology
Coating is good with the weathering resistance of fluorine resin, but life-time service is good to the defencive function of building civil structure; maintenance service such as can reduce that obviously cleaning is whitewashed again; help the raising of living environment, can keep new bright colour for a long time, can carry out Color Scheme freely.As this coating composition, the 2 liquid type coating compositions (for example, opening clear 62-022862 communique with reference to the Japanese Patent spy) that formed by polymkeric substance that contains isocyanate group and fluoroalkyl and the fluoropolymer that contains hydroxyl have been proposed.
The 2 liquid type coating compositions that contain solidifying agent that this motion is such are usually a large amount of and with strong solvents such as ester based compound such as aromatics such as toluene and butylacetates.
But,, then can occur the existing problems such as causing damage of filming if be coated with this coating composition that uses strong solvent in existing film coated surface for existing filming repaired.
In order to eliminate this problem, the coating composition that has proposed to comprise fluorine resin adopt the more weak so-called Weak solvent of solvency powers such as paraffinic hydrocarbons series solvent or naphthenic hydrocarbon series solvent as solvent, do not contain the 1 liquid type coating composition (for example, opening clear 63-199770 communique) of solidifying agent with reference to the Japanese Patent spy.
But, even can not form three-dimensional eyed structure, so there is the relatively poor shortcoming of no solvent resistance, stain resistance and resistance of filming after the film forming because this 1 liquid type coating composition solidifies.
Therefore, developed the coating composition (for example, with reference to Japanese patent laid-open 8-302281 communique) that the 2 liquid types that can be dissolved in or be scattered in the such Weak solvent of paraffinic hydrocarbons series solvent or naphthenic hydrocarbon series solvent and contain solidifying agent comprise fluorine resin.
But, use formed the filming of the coating composition that comprises fluorine resin of Japanese patent laid-open 8-302281 communique record, identical to the didirtresistance that is attached to its surperficial dirt with other synthetic resin coating, when using, require its didirtresistance is improved as the high-performance commodity.
The present invention finishes in order to address the above problem, and is applied to existing surface of filming and also can produce the coating composition of damage to existing filming even provide weathering resistance well, can not produce rainwater stain.
Summary of the invention
The feature of coating composition of the present invention is, contain (a) and have reaction solidified nature position, and the fluoroolefin based polymer of fluorine content more than 5 quality %, (b) polymeric polyisocyanate that on average contains the isocyanate group more than 1.5 in the molecule is a solidifying agent, (c) contain the above paraffinic hydrocarbons series solvent of 30 quality % of full solvent and/or the medium of naphthenic hydrocarbon series solvent, (d) polymkeric substance of the water-disintegrable silane compound of four senses, aforementioned (a) composition and (b) composition dissolve in and maybe can be scattered in (c) composition, (b) components in proportions is 1～100 mass parts corresponding to (a) composition of 100 mass parts, and (d) components in proportions is 0.1～100 mass parts corresponding to (a) composition of 100 mass parts.
The feature of coated article of the present invention is that aforementioned coating composition is coated on article.
Embodiment
(a) composition:
(a) composition is the medium that dissolves in or be scattered in above paraffinic hydrocarbons series solvent of the 30 quality % that contain full solvent and/or naphthenic hydrocarbon series solvent, has reaction solidified nature position and fluorine content corresponding to the fluoroolefin based polymer (hereinafter referred to as fluorine resin) of polyalcohol integral more than 5 quality %.Among the present invention, polymkeric substance is meant single polymers and/or multipolymer.This has reaction solidified nature position and the fluoroolefin based polymer of fluorine content more than 5 quality %, and to be to use fluoroolefin be monomer polymerization and the polymkeric substance that obtains as the fluorine of polymer raw.This fluoroolefin comprises the fluoroolefin of carbonatomss 2～3 such as tetrafluoroethylene, trifluorochloroethylene, R 1216, vinylidene fluoride, vinyl fluoride, and good especially is tetrafluoroethylene and trifluorochloroethylene.These fluoroolefin can use a kind also can more than 2 kinds and use.
The fluoroolefin based polymer is a fluorine when being the multipolymer of the comonomer beyond monomer and the fluorine system, and this comonomer is preferably vinyl monomer.This vinyl monomer comprises vinyl ether, allyl ethers, vinyl carboxylates, allyl carboxylate, alkene etc., and good especially is vinyl ether and vinyl carboxylates etc.
Vinyl ether comprises alkyl vinyl ethers such as cycloalkyl group vinyl ether, nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, n-butyl vinyl ether, tert-Butyl vinyl ether such as cyclohexyl vinyl ether.
In order can be dissolved in or to be scattered in in the medium that has comprised paraffinic hydrocarbons series solvent and/or naphthenic hydrocarbon series solvent at high proportion, best is has the vinyl ether of straight or branched of the alkyl of carbonatoms 1～18.
Allyl ethers comprises alkyl allyl etherss such as ethyl allyl ether, hexyl allyl ethers.
Vinyl carboxylates, allyl carboxylate comprise the vinyl of carboxylic acids such as acetate, butyric acid, trimethylacetic acid, Ba Dousuan, phenylformic acid, toxilic acid or allyl ester etc.In addition, prop up the catenate vinyl acetate and also can use commercially available ベ オ バ-9, ベ オ バ-10 (all by shell chemical company system, trade(brand)name) etc.
Olefines comprises ethene and iso-butylene etc.
Above-mentioned comonomer can a kind uses separately, also can be used in combination more than 2 kinds.
(a) the reaction solidified nature position in the composition is so long as form crosslinked position with solidifying agent reaction and get final product.This reaction solidified nature position be by carrying out appropriate selection with the combination of solidifying agent, for example hydroxyl, carboxyl, water-disintegrable silyl, glycidyl, epoxy group(ing), amino etc.The group of active hydrogen is preferably contained at reaction solidified nature position, because this group and solidifying agent is reactive good.This group that contains active hydrogen is preferably hydroxyl, carboxyl, amino.
As the method that will react solidified nature position importing polymkeric substance, comprise the method that makes monomer copolymerization, or import the method at reaction solidified nature position after the polymerization with reaction solidified nature position.
The monomer that among the former this has reaction solidified nature position can exemplify the hydroxyethyl vinyl ether, the 4-hydroxy butyl vinyl ether, hydroxyalkyl vinyl ether such as cyclohexanediol one vinyl ether, hydroxyalkyl allyl etherss such as 2-hydroxyethyl allyl ether, hydroxyalkyl Vinyl crotonate etc. contains the monomer that the vinyl carboxylates of hydroxyl or allyl ester etc. have hydroxyl, Vinyl crotonates etc. have the monomer of carboxyl, three epoxy group(ing) vinyl silanes etc. have the monomer of water-disintegrable silyl, the Racemic glycidol vinyl ether, the Racemic glycidol allyl ethers, Beta-methyl glycidyl ether etc. has the monomer of epoxy group(ing), and aminopropyl vinyl ether etc. has amino monomer etc.
The latter's method comprises that the saponification of the polymkeric substance that obtains by the co-poly carboxylic acid vinyl acetate imports the method for hydroxyl, make polymkeric substance with hydroxyl and polycarboxylic acid or its anhydride reaction and import the method for carboxyl, make isocyanic ester organoalkoxysilane reaction and import the method for water-disintegrable silyl, make polynary silyl isocyanate compound reaction and import the method etc. of isocyanate group.
Reaction solidified nature number positional in the above-mentioned fluoroolefin based polymer, admittedly form the chemical reaction equivalent that branch is converted into potassium hydroxide corresponding to resin, preferably 1～150mg/g dissolves in paraffinic hydrocarbons series solvent and/or naphthenic hydrocarbon series solvent, and that good especially is 10～70mg/g.
The fluorine content of the fluoroolefin based polymer that the present invention is used is 5～100 quality % corresponding to all fluoroolefin based polymers, 10～70 quality % more preferably, and good especially is 20～35 quality %.The fluoroolefin based polymer can a kind uses separately, also can be used in combination more than 2 kinds.
Except (a) composition, also can contain other resin in the coating composition of the present invention.But other resin exemplified by acrylic resin, vibrin, acrylic polyol resin, polyester polyol resin, urethane resin or (a) fluorine resin beyond the composition.Other resin also can have reaction solidified nature position.(a) fluorine resin beyond the composition can exemplify カ イ Na-500, カ イ Na-SL, カ イ Na-ADS are (above by ア ト Off
イNa Co., Ltd. system, trade(brand)name), Off ロ-レ Application (Japan Synthetic Rubber Co. Ltd's system, trade(brand)name) etc.This other resin can a kind uses separately, also can be used in combination more than 2 kinds.The proportional quantity of other resin can carry out appropriate selection in the scope that does not influence effect of the present invention, (a) composition corresponding to 100 mass parts is 1～200 mass parts usually.
As (a) composition, can use also that only to extract Le ミ Off ロ Application LF200, Le ミ Off ロ Application LF400, Le ミ Off ロ Application LF500, Le ミ Off ロ Application LF544 etc. (above by Asahi Glass Co., Ltd's system, trade(brand)name), Off Le オ ネ-ト (Dainippon Ink. ﹠ Chemicals Inc's system, trade(brand)name), セ Off ラ Le コ-ト (セ Application ト ラ Le nitre Co., Ltd. system, trade(brand)name), ザ Off ロ Application 200, ザ Off ロ Application 300 (East Asia synthetic chemistry Co., Ltd. system, trade(brand)name), ゼ
StarThe resinous principle of Off Le GK510 commercially available products such as (Daikin Ind Ltd's system, trade(brand)names) is dissolved or dispersed in the medium of the paraffinic hydrocarbons series solvent that contains more than the 30 quality % and/or naphthenic hydrocarbon series solvent with it and the composition that forms.
In addition, (a) polymkeric substance of composition is by the polymerization in paraffinic hydrocarbons series solvent and/or naphthenic hydrocarbon series solvent, perhaps part or all of solvent or dispersion medium is replaced into paraffinic hydrocarbons series solvent and/or naphthenic hydrocarbon series solvent after the polymerization, can form Weak solvent type resin.
(b) composition:
(b) composition is that to dissolve in or be scattered in the polymeric polyisocyanate that on average contains the isocyanate group more than 1.5 in the medium that contains above paraffinic hydrocarbons series solvent of 30 quality % and/or naphthenic hydrocarbon series solvent, the molecule be solidifying agent.The upper limit to isocyanate group contained in the molecule is not particularly limited, but preferably on average below 3.
(b) composition can exemplify two isocyanic acid ethyls, two isocyanic acid Aden esters, the inferior own ester of two isocyanic acids, two isocyanic acids ester in the inferior last of the ten Heavenly stems, 2,4 or 2,6-tolylene diisocyanate, 4,4-methylene radical-two (phenyl isocyanate), 4,4-diethyl Xylene Diisocyanate, 4, polymeric polyisocyanate classes such as 4-methylene radical-two (cyclohexyl isocyanate), triphenylmethane triisocyanate etc.In addition, the polymeric polyisocyanate that also comprises polyol reactions such as these isocyanic ester and water or ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane and obtain, polymeric polyisocyanate with biuret structure, polymeric polyisocyanate with allophanic acid ester structure has the polymeric polyisocyanate of isocyanurate structure etc.In addition, in order to improve the dilution of polymeric polyisocyanate, also can exemplify with alcohols, thio-alcohol and react and the composition of importing hydrocarbon chain.
(b) composition also can be that isocyanate group is with blocks such as hexanolactam, isophorone, beta-diketons and the composition that obtains.
(b) but also several are used in combination composition.(b) proportioning of composition in composition is 1～100 mass parts corresponding to 100 mass parts (a) composition, more preferably 1～50 mass parts.If this ratio is more than 1 mass parts, then solvent resistance and hardness are enough, if below 100 mass parts, then processibility and shock-resistance are good, so very desirable.
(a) composition in the composition of the present invention is when containing the fluorine resin of hydroxyl, and (b) components in proportions is corresponding to the hydroxyl in 1 mole of fluorine resin that contains hydroxyl, in isocyanate group more than 0.8 mole.If isocyanate group is more than 0.8 mole, then the curing of coating composition is abundant, and solvent resistance etc. are functional, so very desirable.Good especially is if more than 1.1 moles, then can increase the effect that prevents that rainwater stain from producing.Though the upper limit to the content of isocyanate group is not particularly limited, but in order photostabilization and other performance not to be produced detrimentally affect, the remaining unreacted isocyanate group of filming better is below 2.0 moles, more preferably 1.2～1.6 moles of the ratios of isocyanate group.
(c) composition:
(c) composition is to contain the above paraffinic hydrocarbons series solvent of 30 quality % and/or the medium of naphthenic hydrocarbon series solvent.
The paraffinic hydrocarbons series solvent comprises Skellysolve A, iso-pentane, normal hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, normal heptane, 2-methyl hexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, octane, 2-methylheptane, positive nonane, 2-methyloctane, 2,3,4-trimethylpentane, n-decane, 2-methylnonane, 2-methyl decane etc.
The naphthenic hydrocarbon series solvent comprises pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, suberane, methyl suberane, cyclooctane, methyl cyclooctane, cyclononane, cyclodecane etc.
Paraffinic hydrocarbons series solvent, naphthenic hydrocarbon series solvent can use separately, also can more than 2 kinds and use.
Paraffinic hydrocarbons series solvent, naphthenic hydrocarbon series solvent are preferably mineral turpentine, mineral turpentine etc.
(c) composition has multiple commercially available product, for example, the system mineral turpentine A of Shin Nihon Oil Co., Ltd, A solvent, Ha イ ア ロ system 2S, shell KCC system LAWS, HAWS, ペ ガ ソ-Le 3040, the AN45 of エ Network ソ Application モ-PVC Le Co., Ltd. system, coating, the general what is called of using " coating thinner " of field of coating etc.
(c) composition comprises that toluene, dimethylbenzene etc. are aromatic hydrocarbon based, ketones such as ethyl methyl ketone, hexone, ester classes such as ethyl acetate, butylacetate, alcohols such as propyl carbinol, isopropylcarbinol etc.
(c) proportional quantity of paraffinic hydrocarbons series solvent in the composition and/or naphthenic hydrocarbon series solvent is more preferably more than 50 quality % more than 30 quality %, and good especially is more than 70 quality %.(c) aniline point of composition is preferably 10～55 ℃.This aniline point is one of solvent yardstick of weighing Weak solvent, and the low more solvency power of expression temperature is high more.This aniline point is the minimum temperature that waits the aniline of capacity and Weak solvent can uniform solution to exist, and tries to achieve according to JIS-K2256, ASTM D611.
(c) components in proportions in the coating composition of the present invention is not particularly limited, can do suitably decision according to the viscosity of coating composition, corresponding to (a) composition of 100 mass parts and (b) the total amount of composition, be preferably 80～600 mass parts, good especially is 100～250 mass parts.
(d) composition:
(d) composition is the polymkeric substance of the water-disintegrable silane compound of four senses.The water-disintegrable silane compound of four senses is the compound that 4 hydrolization groups directly are incorporated into Siliciumatom, and (d) composition is this compound generation condensation and the polymkeric substance that forms.
Hydrolization group is alkoxyl group, alkoxyalkyl, acyloxy, aryloxy, hydroxy amino, amide group, ketoxime base, isocyanate group, halogen atom etc.Be preferably alkoxyl group, alkoxyalkyl etc. and removed the group of hydrogen atom from the hydroxyl of monohydroxy-alcohol.Wherein, good especially is alkoxyl group, and the carbonatoms of this alkoxyl group better is below 4, and good especially is 1 or 2.
About the polymerization degree of the polymkeric substance of the water-disintegrable silane compound of four senses, as long as composition does not generate the gel resultant, the polymerization degree is meant the condensation molecule number of the water-disintegrable silane compound of four senses.
(d) composition is preferably the polymkeric substance of tetraalkoxysilane.The tetraalkoxysilane of linear chain structure is preferably the compound with following formula 1 expression.
RO (Si (OR)
2O)
nR ... formula 1
In the formula 1, n represents the polymerization degree of polymkeric substance, and R represents the alkyl of carbonatoms 1～4, and the R of the n in the polymkeric substance can be the same or different.
Usually easily the polymkeric substance that obtains is the mixture of polymers that n has nothing in common with each other, and its polymerization degree is with average n value representation.
R in the formula 1 can be methyl, ethyl, propyl group, butyl, is preferably methyl and ethyl.(d) composition is more preferably the polymkeric substance of tetramethoxy-silicane, the polymkeric substance of tetraethoxysilane, and best is the polymkeric substance of tetraethoxysilane.
The polymerization degree of the water-disintegrable silane compound of four senses such as tetraalkoxysilane or its polymkeric substance also available " silica composition " expression." silica composition " is meant the silicon-dioxide (SiO that is generated by this compound
2) mass ratio.Obtain by measuring the silica volume that the hydrolysis stably of this compound, calcining generate.In addition, " silica composition " also represents the ratio of the silicon-dioxide that generates corresponding to this compound of 1 molecule, for calculate by following formula value.
Silica composition (the mass parts)=polymerization degree * SiO
2The molecular weight of molecular weight/this compound
Be under the situation of polymkeric substance of tetraalkoxysilane at the water-disintegrable silane compound of four senses, by making silica composition more than 40 mass parts, perhaps under the situation of the polymkeric substance of the compound beyond the water-disintegrable silane compound of four senses is tetraalkoxysilane, by making silica composition more than 35 mass parts, make the coating composition that contains this polymkeric substance can prevent the generation of rainwater stain for a long time.
(d) composition also can use commercially available product, for example, the system MKC of Mitsubishi chemical Co., Ltd silicate MS51, MS56, コ Le コ-ト Co., Ltd. system methyl silicate 51 (polymkeric substance of tetramethoxy-silicane), ethyl silicate 40,40T, 48 (all being the polymkeric substance of tetraethoxysilane), the オ Le ガ チ of this friendship of pine company
StarNetwork ス SI series, KCC's system ethyl silicate 40,45 (all being the polymkeric substance of tetraethoxysilane) etc. rubs more.Wherein, be preferably the product of silica composition more than 45 quality % of tetraethoxysilane, good especially is ethyl silicate 48 and ethyl silicate 45.
(d) composition is under the situation of polymkeric substance of the polymkeric substance of tetramethoxy-silicane or tetraethoxysilane, and it contains proportional (a) composition corresponding to 100 mass parts in composition, be preferably 5～50 mass parts.If contain proportionally more than 5 mass parts, then can increase the effect that prevents that rainwater stain from producing.If below 50 mass parts, then can obtain not have bad good the filming of curing of coating.
The proportioning of (d) composition in the composition is more preferably the non-a little above amount that mixes corresponding to (a) composition.This is non-mix a little be meant with (a) composition and (d) composition be dissolved in (c) composition and the solution coat that forms can have or not the index that the gonorrhoea phenomenon confirms [corresponding to (d) composition quality of the minimum that gonorrhoea do not occur of the quality of (a) composition] according to filming in glass pane surface, when making it dry for 20 ℃.
(d) if composition with the non-a little above proportioning that mixes, then can more effectively prevent the generation of rain mark shape dirt.Its principle is also indeterminate, supposition is to cause (a) composition and (d) being separated of composition after the application, (d) composition can more effectively prevent the cause of the generation of rain mark shape dirt in the near surface hydrolysis of filming of the composition that is formed at outdoor article surface by the wetting ability on surface.Kind, the polymerization degree of this non-kind because of (a) composition that mixes, (d) composition have different values.
The generation that can prevent rainwater stain with filming of forming of coating composition of the present invention is because the surperficial possess hydrophilic property of filming and scold oiliness to infer.
Film coated surface is if hydrophobic, and then the oily dirt in the rainwater adheres to along the flow direction of rainwater in film coated surface, the residual rain mark shape dirt in dry back.On the other hand, be wetting ability and scold butyrous that then film coated surface does not have the oily dirt diffusion if film, the contact area of film coated surface and oily dirt reduces.Therefore, oily dirt is low to the tack of film coated surface, flows down together along with rainwater flows easily.
Hydrophobicity-hydrophilic the degree on surface can be known by the octane contact angle of measuring in the water.The wetting ability on the big more surface of octane contact angle in the water is strong more, scolds oiliness good more.In order fully to prevent the generation of rainwater stain, the octane contact angle in the water is preferably in more than 102 °.
Octane contact angle in the water of filming that coating composition of the present invention forms is more than 102 °.
In addition, there is dependency between the complexity of the advance tension force and the rainwater stain generation of discovery film coated surface.
The tension force that advances on surface is when instigating the sample with film to immerse in the distilled water, the tension force of the unit perimeter during corresponding to the sample contact water surface.The tension force of the unit perimeter when sample leaves the water surface when sample is carried from distilled water is called as stretching resistance to show difference.
This tension force that advances can record with the dynamic contact angle determinator.In addition, owing to be difficult to aforementioned tension force is directly measured, so make on one side in the distilled water of sample with 25 ℃ of certain speed immersions, the quality change of measuring sample on one side is certain until quality change amount (dyn), the straight line of this variable quantity is inserted to that sample contacts the water surface outward, quality change amount when trying to achieve the sample contact water surface can be tried to achieve this tension force that advances with this variable quantity divided by the unit perimeter (cm) of sample.This tensile that advances is surveyed periodic impregnating speed can adopt 20mm/min.
That is, the surface advances tension force when 0dyn/cm (0N/m) is above, the very difficult generation of rainwater stain.
Though also very not clear and definite to its mechanism of action, under the situation of tension force of advancing of film coated surface, rainwater accumulative tendency when flowing down, rainwater is arranged, because rainwater stream becomes the water mark, so may flow through the dirt that the back produces water mark shape at rainwater less than 0dyn/cm.On the other hand, if film surface advance tension force more than 0dyn/cm, the tendency of rain water-harvesting weakened when then rainwater flowed down, so be difficult to produce rain mark shape dirt.
Therefore, for the outdoor article surface that prevents to be coated produces rainwater stain, the tension force that advances of film coated surface is preferably in more than the 0dyn/cm.
Also can containing as required in the coating composition of the present invention films makes composition solidified curing catalysts when forming.Particularly use under the situation of tetraethoxysilane, in order to promote to solidify preferably and use curing catalysts at (d) composition.
This curing catalysts can adopt the used curing catalysts of general coating, for example dibutyl tin dilaurate etc.If use (e) zirconium compounds as curing catalysts, then useful life equates with dibutyl tin dilaurate, but the drying of filming is fast during than the use dibutyl tin dilaurate, and can shorten fingering print or thumb print time of drying of filming, so better.
Should can exemplify zirconium chelate etc. by (e) zirconium compounds.In addition, as the commercially available product of zirconium compounds, can use K-KAT XC-4205 (nanmu originally changes into Co., Ltd.'s system, trade(brand)name) etc.
(e) ratio of zirconium compounds in composition is preferably 0.000001～10 mass parts, more preferably 0.001～1 mass parts corresponding to (a) composition of 100 mass parts.
Form if coating composition of the present invention is applied to the surface of outdoor article and to film, become branch near film coated surface, to cause hydrolysis owing to consider (d), so also can contain the catalyzer that promotes hydrolysis in the said composition.This catalyzer comprises metal compound as catalyst such as metallo-chelate, metal ester, metal alkoxide.This metal comprises aluminium, titanium, silicon, tin, zinc etc.Metal compound as catalyst can exemplify aluminium-mono-acetylacetonate bis (methyl aceto acetate), aluminium tris(acetylacetonate) etc.The ratio of this catalyzer in composition is preferably 0.1～20 mass parts, more preferably 1～10 mass parts corresponding to (d) composition of 100 mass parts.
Also can admix tinting pigment or dyestuff in the coating composition of the present invention, can improve the silane coupling agent of ADHESION OF PAINTS etc.
Tinting pigment comprises mineral dyes such as carbon black that weathering resistance is good and titanium dioxide, and phthalocyanine blue, phthalocyanine green, quinacridine are red, pyranthrone orange, isoindoline-1-ketone are pigment dyestuffs such as Huang etc.
Also can suitably add photostabilizer, UV light absorber and matting agent etc. as required in the coating composition of the present invention.In addition, when solidifying agent is aminoresin, can and with an acidic catalysts such as tosic acid.Photostabilizer is a hindered amine light stabilizer etc., for example, MARX LA62, MARX LA67 (above), チ ヌ PVC Application 292, チ ヌ PVC Application 141, チ ヌ PVC Application-123, チ ヌ PVC Application 440 (above チ バ ス ペ シ by ア デ カ ア-ガ ス KCC system, trade(brand)name
ヤLe テ
イKCC's system, trade(brand)name) etc.
As UV light absorber, can exemplify benzophenone based compound, benzotriazole based compound, triazine based compound, cyanoacrylate based compound etc.This compound can exemplify Viosorb130, Viosorb582, Viosorb583 (above by common Pharmaceutical Co., Ltd system, trade(brand)name), チ ヌ PVC Application 320, チ ヌ PVC Application 982, チ ヌ PVC Application 1130, チ ヌ PVC Application 400 (more than, チ バ ス ペ シ
ヤLe テ
イKCC's system, trade(brand)name) etc.
Matting agent can exemplify super-fine powder synthetic silica etc.Use under the situation of matting agent, can form good the filming of inferior gloss, extinction effect with gracefulness.
Can admix tensio-active agent in the coating composition of the present invention.Tensio-active agent is effective when for control surface tension force surface concn being adjusted into special component.This tensio-active agent comprises any in non-ionic type, cationic, the anionic, can exemplify レ オ レ
StarNetwork ス ASE (first Industrial Co., Ltd's system, trade(brand)name), fluorochemical surfactant " サ-Off ロ Application " (Asahi Glass Co., Ltd's system, trade(brand)name), " モ ダ Off ロ-" (モ Application サ Application ト Co., Ltd. system, trade(brand)name) of acrylic acid series, " レ オ Off
The ア Starト " series (Kao Corp's system, trade(brand)name) etc.
The manufacturing of coating composition of the present invention is undertaken by mixing the above-mentioned various additives of must composition, adding as required.Order by merging, interpolation are not particularly limited in proper order.
The method of using coating composition of the present invention to carry out application comprises any methods such as spraying method, hairbrush coating method, pickling process, roller painting, flow coat method.
The material that is coated article is not particularly limited, can exemplifies inorganicss such as concrete, natural stone, glass, metals such as iron, stainless steel, aluminium, copper, brass, titanium, organism such as plastics, rubber, jointing material, timber.In addition, can also be FRP, resin reinforcing concrete, fiber strengthening concrete etc. as organic/inorganic composite material.
Coating composition of the present invention is applicable to the application on the surface of filming that has formed.
The article that are coated can exemplify transportation means such as automobile, electric car, aircraft, bridge parts, building parts such as iron tower, Industrial materials such as water-proof material sheet, groove, pipe, building elements such as skin, door, door and window parts, monument, pillar, road circuit units such as light-passing board such as the central partition of road, guardrail, sound-proof wall, polycarbonate and vinylformic acid, the communication apparatus and electrical and electronic parts etc.
Below, the present invention will be described in more detail based on embodiment, but the present invention is not limited to this.
The coating that following each embodiment (example 1～3), comparative example (example 4～6) are obtained carries out following assessment, and it the results are shown in table 1.
(rainwater stain)
Visual observation is assessed according to following assessment benchmark in the film coated surface of outdoor exposure after 1 year in Prefectura de Kanagawa Kawasaki city.
Zero: rainwater stain does not appear in film coated surface,
*: film coated surface is observed rainwater stain.
(weathering resistance)
(gloss is measured meter: Japanese electric look Industrial Co., Ltd system) measure the gloss before and after day light climate determinator irradiation 3000 hours, assess according to following evaluation criteria with PG-1M.
Zero: gloss retention is more than 80%,
*: gloss retention is less than 80%.
(stickiness feeling)
Sensation when slipping over the film coated surface of application after 8 hours according to following criterion evaluation finger.
Zero: finger tip slips over without barrier,
△: finger tip has the sensation that comes into the picture,
*: finger tip has the sensation of adhesion.
(solvent resistance)
With the gauze wiping maintenance that contains dimethylbenzene filming 20 times of 1 week, according to following benchmark to this moment the membrane stage that is coated with assess.
Zero: the not dissolving of filming,
*: filming dissolving occurs.
(application property)
The completion status of filming of visual assessment application after 1 day.
Zero: no problem,
*: some problems are arranged.
(example 1)
Multipolymer (the hydroxyl value: 40mg/g of the trifluorochloroethylene/ethyl vinyl ether/hydroxy butyl vinyl ether/cyclohexyl vinyl ether=50/2/8/40 mole % of uniform mixing 100 mass parts, 22 quality %) and mineral turpentine A (Shin Nihon Oil Co., Ltd's system of 135.7 mass parts fluorine content:, the content of aromatic hydrocarbons: 30 quality %, aniline point: 43 ℃), obtain resin solution.
In the gained resin solution of 82.5 mass parts, be mixed into D-918 (the Sakai KCC system of 17.5 mass parts, titanium oxide), 4.68 the ケ ネ of mass parts-ト D-178N (Mitsui Takeda Chemical Co., Ltd's system, polyisocyanate composition, NCO content 18.9%), 0.01 (nanmu originally changes into Co., Ltd.'s system to the K-KAT XC4205 of mass parts, zirconium compounds is a curing catalysts), 3.5 the ethyl silicate 48 of mass parts (コ Le コ-ト Co., Ltd. system, the polymkeric substance of tetraethoxysilane) and Ha イ ア ロ system 2S (Shin Nihon Oil Co., Ltd's system of 6 mass parts, the content of aromatic hydrocarbons: 50 quality %, aniline point: 44 ℃), make coating composition (A).
Resulting composition (A) has been coated on the vinyl chloride paint spraying on the iron member in 10 years, and has carried out above-mentioned assessment.
(example 2)
Except use the multipolymer (hydroxyl value: 40mg/g of trifluorochloroethylene/2-ethylhexyl vinyl ether/hydroxy butyl vinyl ether/cyclohexyl vinyl ether=50/20/10/20 mole % as multipolymer, fluorine content: 22 quality %), other is identical with example 1, makes coating composition (B).Carry out application equally with example 1, and assess.
(example 3)
Except admixing as curing catalysts the dibutyl tin dilaurate of 0.00025 mass parts, other is identical with example 1, makes coating composition (C).Carry out application equally with example 1, and assess.
(example 4)
Except not admixing ethyl silicate 48 and Ha イ ア ロ system 2S, other is identical with example 1, makes coating composition (D).Carry out application equally with example 1, and assess.
(example 5)
Except the dimethylbenzene that uses 135.7 mass parts replaces the mineral turpentine A, other is identical with example 1, makes coating composition (E).Carry out application equally with example 1, and assess.
(example 6)
Except not admixing ケ ネ-ト D-178N and K-KAT XC4205, other is identical with example 1, makes coating composition (F).Carry out application equally with example 1, and assess.
Table 1
| Rainwater stain | Weathering resistance | Stickiness feeling | Solvent resistance | Application property | |
| Example 1 | ○ | ○ | ○ | ○ | ○ |
| Example 2 | ○ | ○ | ○ | ○ | ○ |
| Example 3 | ○ | ○ | △ | ○ | ○ |
| Example 4 | × | ○ | ○ | ○ | ○ |
| Example 5 | ○ | ○ | ○ | ○ | * substrate is floated |
| Example 6 | × | ○ | × | × | ○ |
Can find out that from table 1 the anti-rainwater stain of coating composition (D) of example 4 that does not contain (d) composition is insufficient.The coating composition (E) of example 5 that substitutes the paraffinic hydrocarbons series solvent of (c) composition and/or naphthenic hydrocarbon series solvent with dimethylbenzene is influential to base coating, floats for substrate in the application property assessment.Coating composition (F) stickiness feeling of example 6 that does not contain (b) composition is not good, and solvent resistance is also not enough.Coating composition of the present invention (A)～(C) possesses the distinctive weathering resistance of fluorine resin, and rainwater stain can not occur, films attractive in appearancely so can not destroy, and solvent resistance and application property are good, and stickiness feeling is also very good.Using under the situation of zirconium compound as curing catalysts, stickiness feeling is good especially.
The feature of coating composition of the present invention is that weathering resistance is good, can not produce rainwater stain, even coat existing film coated surface, also can not cause damage to existing filming.
Claims (5)
1. coating composition, it is characterized in that, contain (a) and have reaction solidified nature position, and the fluoroolefin based polymer of fluorine content more than 5 quality %, (b) polymeric polyisocyanate that on average contains the isocyanate group more than 1.5 in the molecule is a solidifying agent, (c) contain the above paraffinic hydrocarbons series solvent of 30 quality % of full solvent and/or the medium of naphthenic hydrocarbon series solvent, (d) polymkeric substance of the water-disintegrable silane compound of four senses, aforementioned (a) composition and (b) composition dissolve in and maybe can be scattered in (c) composition, (b) components in proportions is 1～100 mass parts corresponding to (a) composition of 100 mass parts, (d) components in proportions is 0.1～100 mass parts corresponding to (a) composition of 100 mass parts, (c) components in proportions corresponding to (a) composition of 100 mass parts and (b) the total amount of composition be 80～600 mass parts.
2. coating composition as claimed in claim 1, its feature are that also previous reaction solidified nature position is at least a kind of group that is selected from hydroxyl, carboxyl, amino.
3. coating composition as claimed in claim 1 or 2, its feature are that also (d) polymkeric substance of the water-disintegrable silane compound of four senses is the polymkeric substance of tetraalkoxysilane.
4. coating composition as claimed in claim 1, its feature also are, also contain (e) zirconium compounds, and (e) components in proportions is 0.000001～10 mass parts corresponding to (a) composition of 100 mass parts.
5. a coated article is characterized in that, each described coating composition in the claim 1～4 is coated on article and makes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003096409 | 2003-03-31 | ||
| JP2003096409A JP2004300319A (en) | 2003-03-31 | 2003-03-31 | Coating material composition and coated article |
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| Publication Number | Publication Date |
|---|---|
| CN1536038A CN1536038A (en) | 2004-10-13 |
| CN100381517C true CN100381517C (en) | 2008-04-16 |
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| CNB2004100324257A Expired - Fee Related CN100381517C (en) | 2003-03-31 | 2004-03-31 | Coating composition and coating article |
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| Country | Link |
|---|---|
| JP (1) | JP2004300319A (en) |
| KR (1) | KR101101736B1 (en) |
| CN (1) | CN100381517C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5188008B2 (en) * | 2005-01-07 | 2013-04-24 | ダイキン工業株式会社 | Curable fluorine-containing paint composition |
| JP5127123B2 (en) | 2005-07-22 | 2013-01-23 | ダイキン工業株式会社 | Solar cell backsheet |
| US8507029B2 (en) | 2007-02-16 | 2013-08-13 | Madico, Inc. | Backing sheet for photovoltaic modules |
| US9735298B2 (en) | 2007-02-16 | 2017-08-15 | Madico, Inc. | Backing sheet for photovoltaic modules |
| JP2012082270A (en) * | 2010-10-07 | 2012-04-26 | Agc Coat-Tech Co Ltd | Coating composition and kit for the coating composition |
| JP2013006898A (en) * | 2011-06-22 | 2013-01-10 | Agc Coat-Tech Co Ltd | Heat ray highly reflective paint composition, kit for preparing heat ray highly reflective paint composition, heat ray highly reflective coated article, and production method of heat ray highly reflective coated article |
| JP2013006897A (en) * | 2011-06-22 | 2013-01-10 | Agc Coat-Tech Co Ltd | Heat ray highly reflective paint composition, kit for preparing heat ray highly reflective paint composition, heat ray highly reflective coated article, and coating method of heat ray highly reflective coated article |
| CN103224742B (en) * | 2013-04-24 | 2015-10-28 | 同济大学 | A kind of Penetration type transparent concrete protection paint and preparation method thereof |
| KR102050921B1 (en) * | 2018-08-02 | 2019-12-03 | 에스케이이노베이션 주식회사 | Organic solvent composition and paint composition comprising the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525422A (en) * | 1991-07-19 | 1993-02-02 | Asahi Glass Co Ltd | Preparation of coating composition |
| JPH0812921A (en) * | 1993-07-14 | 1996-01-16 | Asahi Glass Co Ltd | Coating resin composition |
| JPH10298486A (en) * | 1997-04-24 | 1998-11-10 | Asahi Glass Co Ltd | Coated article and repair coating method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08302281A (en) * | 1995-05-10 | 1996-11-19 | Toupe:Kk | Coating composition for coating material |
| JPH111659A (en) * | 1997-04-14 | 1999-01-06 | Daikin Ind Ltd | Weather-resistant coating composition |
-
2003
- 2003-03-31 JP JP2003096409A patent/JP2004300319A/en active Pending
-
2004
- 2004-03-31 KR KR1020040022224A patent/KR101101736B1/en not_active IP Right Cessation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525422A (en) * | 1991-07-19 | 1993-02-02 | Asahi Glass Co Ltd | Preparation of coating composition |
| JPH0812921A (en) * | 1993-07-14 | 1996-01-16 | Asahi Glass Co Ltd | Coating resin composition |
| JPH10298486A (en) * | 1997-04-24 | 1998-11-10 | Asahi Glass Co Ltd | Coated article and repair coating method |
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| Publication number | Publication date |
|---|---|
| KR101101736B1 (en) | 2012-01-05 |
| JP2004300319A (en) | 2004-10-28 |
| KR20040085080A (en) | 2004-10-07 |
| CN1536038A (en) | 2004-10-13 |
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