CN104471004B - Coating composition - Google Patents
Coating composition Download PDFInfo
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- CN104471004B CN104471004B CN201480001869.6A CN201480001869A CN104471004B CN 104471004 B CN104471004 B CN 104471004B CN 201480001869 A CN201480001869 A CN 201480001869A CN 104471004 B CN104471004 B CN 104471004B
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/027—Dispersing agents
Abstract
Provided is a coating composition that has good storage stability, that makes it possible to maintain stain resistance during outdoor exposure, and that makes it possible to form a coating film having good coating film hardness and workability. The present invention includes a coating composition that: comprises a hydroxyl group-containing resin (a), a cross-linking agent (b), an anionic surfactant (c) that includes a sulfonic acid group or a sulfonic acid base, and a cationic surfactant (d); and that contains 1-20 parts by mass of the anionic surfactant (c) that includes a sulfonic acid group or a sulfonic acid base and 0.1-20 parts by mass of the cationic surfactant (d) with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the cross-linking agent (b).
Description
Technical field
Cross-Reference to Related Applications
This application claims the priority of the 2013-116583 Japan Patent submitted on June 3rd, 2013, it is whole
Content is incorporated herein by.
The present invention relates to storage stability is excellent and coating composition that can form following films, described film is when long
Between outdoor exposure when can keep stain resistance and there is excellent hardness of film and processability.
Background technology
For decoration or protection purpose, generally to outdoor substrates (for example, building, display screen, guardrail, utensil and machinery)
The outdoor coating composition that application has excellent weather resistance.Example for the coating composition of outdoor application includes polyurethane resin
Coating composition, coat composition of fluorine, silicon resin coating compositionss, Acrylic resin paint composition and polyester coating
Compositionss.However, the shortcoming of these compositionss is when being exposed to open air with the product of such composition application, its surface is easy
In dirty, and its stain resistance is reduced due to the impact of coal smoke, sand and dust, iron powder, rain (acid rain), sunray etc..
Patent document 1 discloses that the coating composition for pre-coated steel plate, it comprises (A) polyol resin, (B) amino tree
Fat, (C) alkoxysilane compound containing trialkylsilyl group in molecular structure and (D) curing catalysts, and there is excellent stain resistance and excellent adding to rainwater
Work.
Patent document 2 discloses that coating composition, the resin and the ammonia that form film of its hydroxyl based on 100 mass parts
Base resin cross-linking agent comprises organosilicate and/or its condensation substance, boronic acid compounds, untreated silica dioxide granule and coloring
Pigment, and the film to rainwater etc. with excellent stain resistance can be formed.
However, by the anti-pollution being coated with the film that the coating composition disclosed in patent documentation 1 or patent documentation 2 obtains
The persistence of property is unsatisfactory, and when half optical coating of its delustering agent of comprising such as silicon dioxide exposes out of doors especially
Show significantly reduced stain resistance.
Reference listing
Patent documentation
Patent documentation 1：JPH10-067945A
Patent documentation 2：JP2008-081719A
Content of the invention
Technical problem
The present invention relates to storage stability is excellent and coating composition that can form following films, described film is when long
Between outdoor exposure when can keep stain resistance and there is excellent hardness of film and processability.
The solution of problem
Present inventor has performed numerous studies, discovery can be by comprising the resin of (a) hydroxyl, (b) cross-linking agent, (c)
Anion surfactant containing sulfonic acid group or sulfonate groups and the coating composition of (d) cationic surfactant
To realize this purpose, the resin (a) based on the described hydroxyl of 100 mass parts for the described compositionss is total with described cross-linking agent (b)
The anion surface active of sulfonic acid group or sulfonate groups is contained described in the amount that solid constituent comprises 1 mass parts to 20 mass parts
The described cationic surfactant (d) of the amount of agent (c) and 0.1 mass parts to 20 mass parts.
Specifically, the present invention provides herein below：
Item 1. coating compositions, it comprises：The resin of (a) hydroxyl, (b) cross-linking agent, (c) contains sulfonic acid group or sulfonate
The anion surfactant of group, and (d) cationic surfactant,
Described compositionss are become with the total solid of described cross-linking agent (b) based on the resin (a) of the described hydroxyl of 100 mass parts
Anion surfactant (c) containing sulfonic acid group or sulfonate groups described in the amount containing 1 mass parts to 20 mass parts for the subpackage
Described cationic surfactant (d) with the amount of 0.1 mass parts to 20 mass parts.
Item 2. coating compositions as described in item 1, the resin (a) of the described hydroxyl based on 100 mass parts and described friendship
The total solid content of connection agent (b), it comprises the resin (a) of the described hydroxyl of the amount of 60 mass parts to 95 mass parts and 5 mass
Part to 40 mass parts amount described cross-linking agent (b).
Item 3. coating compositions as described in item 1 or 2, the wherein said anion table containing sulfonic acid group or sulfonate groups
Face activating agent (c) is alkyl sulfosuccinic anion surfactant.
Item 4. coating compositions as any one of item 1 to 3, wherein said cationic surfactant (d) is alkane
Base amine salt cationic surfactant or quaternary cationicses.
Item 5. coating compositions as any one of item 1 to 4, the resin of the described hydroxyl based on 100 mass parts
A the total solid content of () and described cross-linking agent (b), it comprises urea resin granule (e) of the amount to 50 mass parts for 1 mass parts.
Item 6. is used for the methods forming film, and it includes forming priming paint painting on a surface or two surfaces of metallic plate
Film, and the painting of the coating composition any one of item 1 to 5 is formed at least one surface of described primer coating film
Film.
The metallic plate of item 7. applications, the method that it passes through described in item 6 obtains.
Beneficial effect
The invention provides the excellent coating composition of storage stability.The painting being formed by using described coating composition
Film can keep stain resistance and have excellent hardness of film and processability in long-time outdoor exposure.
Specific embodiment
The coating composition of the present invention
The coating composition of the present invention comprises the resin of (a) hydroxyl, (b) cross-linking agent, (c) containing sulfonic acid group or sulfonate
The anion surfactant of group and (d) cationic surfactant, and optionally also comprise (e) urea resin
Grain.This coating composition is described in detail below.
The resin (a) of hydroxyl
Resin (a) per molecule of hydroxyl contains two or more hydroxyls, and optionally also contains one or more
Carboxyl.The example of the resin (a) of hydroxyl includes acrylic resin, polyester resin, epoxy resin and polyurethane resin.From increasing
From the viewpoint of strong stain resistance, hardness of film and processability, the acrylic resin of hydroxyl, polyester resin of hydroxyl etc. are
Preferably, and the polyester resin of hydroxyl is particularly preferred.
The acrylic resin of hydroxyl be by make the acrylic monomerss of hydroxyl and one or more with hydroxyl third
The copolymer resin that the different monomer of acrylic monomer carries out copolyreaction and obtains.
The example of the monomer of hydroxyl includes C2-20Glycol and (methyl) acrylic acid monoesters, such as (methyl) acrylic acid hydroxyl
Ethyl ester, (methyl) Hydroxypropyl acrylate, (methyl) hy-droxybutyl and (methyl) dihydroxypropyl eicosane base ester.
The example of the monomer different from the monomer of hydroxyl includes (methyl) acrylic acid C1-22Arrcostab, (methyl) propylene
The C of acid2-18Alkoxy alkyl, containing the monomer of epoxy radicals, carboxylic monomer, there are isocyanate groups in same molecule
With the monomer of polymerizable unsaturated group, styrene, α-methyl styrene, vinyltoluene, acrylonitrile, vinyl acetate
Ester, vinyl chloride etc..
(methyl) acrylic acid C1-22The example of Arrcostab include (methyl) acrylic acid methyl ester., (methyl) acrylic acid second
Ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 1-Octyl acrylate, (methyl)
Dodecylacrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate, the different ice of (methyl) acrylic acid
Piece ester etc..(methyl) acrylic acid C2-18The example of alkoxy alkyl include (methyl) methoxyethyl butyl ester, (first
Base) methoxyethyl acrylate etc..The example of the monomer containing epoxy radicals includes glycidyl acrylate, Glycidyl methacrylate
Glyceride etc..The example of carboxylic monomer include acryllic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid and
Mesaconic acid；Their anhydride or half-esterification product；Deng.The such monomer different from the monomer of hydroxyl can be used alone, or
Person is applied in combination two or more.
The number that the acrylic resin of hydroxyl preferably has about 1,000 to 50,000, more preferably from about 2,000 to 20,000 is equal
Molecular weight.The acrylic resin of hydroxyl preferably has about 20mg KOH/g to 200mg KOH/g, more preferably from about 50mg KOH/g
Hydroxyl value to 150mg KOH/g.
The polyester resin of hydroxyl typically can be by the esterification of polyacid component (a1) and alkoxide component (a2) or ester exchange
React and to prepare.The compound of the polyacid component being typically used as in polyester resin preparation can serve as described polyacid component
(a1).The example of polyacid component (a1) includes alicyclic polyprotic acid, aliphatic polybasic acids, aromatic polyvalent acid etc..
Generally, alicyclic polyprotic acid includes per molecule and has one or more alicyclic structures (mainly 4 to 6 yuan of rings) and two
The compound of individual or more carboxyls；The anhydride of described compound；Ester with described compound.The example bag of alicyclic polyprotic acid
Include alicyclic polycarboxylic acid, such as 1,2- cyclohexane cyclohexanedimethanodibasic, 1,3- cyclohexane cyclohexanedimethanodibasic, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 4- ring
Hexene -1,2- dioctyl phthalate, 3- methyl isophthalic acid, 2- cyclohexane cyclohexanedimethanodibasic, 4- methyl isophthalic acid, 2- cyclohexane cyclohexanedimethanodibasic, 1,2,4- hexamethylene
Tricarboxylic acid and 1,3,5- hexamethylene tricarboxylic acid；The anhydride of these alicyclic polycarboxylic acid；These alicyclic polycarboxylic acid's is rudimentary
Arrcostab；Deng.Such alicyclic polyprotic acid can be used alone, or two or more are applied in combination.
The example of particularly preferred alicyclic polyprotic acid include 1,2- cyclohexane cyclohexanedimethanodibasic, 1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride,
1,3- cyclohexane cyclohexanedimethanodibasic, 1,4 cyclohexanedicarboxylic acid, 4- cyclohexene -1,2- dioctyl phthalate and 4- cyclohexene -1,2- dicarboxylic acid anhydride.
Wherein, particularly preferably using 1,2- cyclohexane cyclohexanedimethanodibasic and 1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride from the viewpoint of hydrolytic resistance.
Generally, aliphatic polybasic acids include the aliphatic compound that per molecule has two or more carboxyls；This lipoid
The anhydride of fat compounds of group；And the ester of such aliphatic compound.The example of aliphatic polybasic acids includes aliphatic polybasic carboxylic
Acid, such as succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, heneicosanedioic acid, dodecane two
Acid, tridecandioic acid, octadecane diacid and citric acid；The anhydride of such aliphatic polycarboxylic acid；Such aliphatic polycarboxylic acid
Lower alkyl esters；Deng.Such aliphatic polybasic acids can be used alone, or two or more combination types use.
Aliphatic polybasic acids preferably have C4-18The dicarboxylic acids of alkyl chain.There is C4-18The example of the dicarboxylic acids of alkyl chain
Including adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, 18
Docosandioic acid etc..Wherein it is possible to preferably use adipic acid.
Generally, aromatic polyvalent acid includes the aromatic compound that per molecule has two or more carboxyls；Such virtue
The anhydride of fragrant compounds of group；And the ester of this quasi-aromatic compound.The example of aromatic polyvalent acid includes aromatic polyvalent carboxylic
Acid, such as phthalic acid, M-phthalic acid, p-phthalic acid, naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid, trimellitic acid and
Pyromellitic Acid；The anhydride of such aromatic polycarboxylic acid；And the lower alkyl esters of such aromatic polycarboxylic acid.Such virtue
Fragrant race polyprotic acid can be used alone, or two or more are applied in combination.
The polyhydric alcohol that per molecule has two or more hydroxyls can preferably act as described alkoxide component (a2).Such many
The example of first alcohol includes alicyclic diol, aliphatic diol, aromatic diol etc..
Alicyclic diol is usually per molecule and has one or more alicyclic structures (mainly 4 to 6 yuan of rings) and two hydroxyls
The compound of base.The example of alicyclic diol includes such as 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, hydrogenated bisphenol A
And the dihydroxylic alcohols of A Hydrogenated Bisphenol A F；Obtained by the lactone compound of such as 6-caprolactone is added to these dihydroxylic alcohols is poly-
Interior esterdiol；Deng.Such compound can be used alone, or two or more are applied in combination.
Aliphatic diol is usually the aliphatic compound that per molecule has two hydroxyls.The example of described aliphatic diol
Including ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tetraethylene glycol (TEG), 2,2'-ethylenedioxybis(ethanol)., dipropylene glycol, 1,4- butanediol, 1,3- fourth
Glycol, 2,3- butanediol, 1,2- butanediol, 3- methyl isophthalic acid, 2- butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2- penta
Glycol, 1,5- pentanediol, 1,4- pentanediol, 2,4-PD, 2,3- dimethyl dipropylene glycol, tetramethylene glycol, 3- methyl isophthalic acid,
5- pentanediol, 2,2,4- trimethyl -1,3- pentanediol, 1,6-HD, 1,5- hexanediol, 1,4- hexanediol, 2,5-HD,
1,9- nonanediol, 1,10- decanediol, 1,12- dodecanediol, neopentyl glycol etc..Such aliphatic diol can be used alone,
Or two or more are applied in combination.
Aromatic diol typically refers to the aromatic compound that per molecule has two hydroxyls.The example bag of aromatic diol
Include the esterdiol compound of such as double (ethoxy) terephthalate；The alkylene oxide adduct of bisphenol-A；Deng.Such compound
Can be used alone, or two or more are applied in combination.
From the example of above-mentioned alicyclic diol, aliphatic diol and the different polyhydric alcohol of aromatic diol include all
PTMEG compound as Polyethylene Glycol, polypropylene glycol and polytetramethylene glycol；Such as glycerol, trimethylolethane, trihydroxy methyl
Propane, diglycerol, triglycerin, 1,2,6- hexanetriol, tetramethylolmethane, dipentaerythritol, three (2- ethoxy) chlorinated isocyanurates, mountain
The alcohol of the ternary of pears sugar alcohol and mannitol or more polynary；By by the lactone compound of such as 6-caprolactone be added to these three
First or more polynary alcohol and the poly-lactone polyol compound that obtains；Deng.
Wherein, from increasing molecular weight and improve the viewpoint with the reactivity of the modified-reaction of fatty acid when using fatty acid
From the point of view of, preferably use the alcohol of ternary or more polynary.The example of the alcohol of ternary or more polynary include glycerol, trimethylolethane, three
Hydroxymethyl-propane, diglycerol, triglycerin, 1,2,6- hexanetriol, tetramethylolmethane, dipentaerythritol, Sorbitol and mannitol；
The poly-lactone polyol being obtained by the lactone compound of such as 6-caprolactone being added to the alcohol of these ternarys or more polynary
Compound；And such as three (2- ethoxy) chlorinated isocyanurates, three (2- hydroxypropyl) chlorinated isocyanurates and three (2- hydroxyl butyl) are different
Three (hydroxy alkyl) chlorinated isocyanurates of cyanurate.Wherein, trimethylolpropane is particularly preferred.
If necessary, as the alkoxide component (a2) different from above mentioned polyhydric alcohol, can also use for example, such as first
Alcohol, ethanol, propanol, the monohydric alcohol of butanol, stearyl alcohol and 2- phenyl phenol；By making acid react with mono-epoxy compound
The alcoholic compound obtaining, described mono-epoxy compound is, for example, the highly branched of expoxy propane, epoxy butane and synthesis
The ethylene oxidic ester (trade name " Cardura E10 " is produced by Hexion Specialty Chemicals) of satisfied fatty acid；
Deng.
Method for preparing the polyester resin of hydroxyl is not particularly limited, and it can be conventional method.For example, institute
The polyester resin stating hydroxyl can be prepared by the following method, i.e. will include above mentioned polyacid component as necessity
The acid constituents of composition and alkoxide component react 5 to 10 hours at 150 DEG C to 250 DEG C in nitrogen stream, with carry out esterification or
Ester exchange reaction.
In described esterification or ester exchange reaction, described acid constituents and described alkoxide component can together with add, or with separately
Partial form is added.A part of carboxyl after synthesizing described carboxylic polyester resin, in carboxylic polyester resin
Can be esterified with alkoxide component.Or, synthesize the polyester resin of hydroxyl first, then make it with anhydride reaction so that hydroxyl
Polyester resin is half-esterification.
Described esterification or ester exchange reaction in, it is possible to use catalyst come to promote react.Known catalysis can be used
Agent, such as Dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, butyl titanate and
Tetraisopropyl titanate.
In described resin-made for period or after esterification or ester exchange reaction, the polyester resin of described hydroxyl is permissible
With modifications such as fatty acid, oil, mono-epoxy compound, polyisocyanate compounds.With the modified hydroxyl of fatty acid or oil
Polyester resin is referred to as alkyd resin.
The example of described fatty acid includes such as palm oil fatty acid, cottonseed oil fatty acid, hemp-seed oil fatty acid, Testa oryzae
Fatty acid oil, fish oil fatty acid, ready denier oil acid, soya fatty acid, Semen Lini oil fatty acid, tung oil fatty acid, Semen Allii Tuberosi
Fatty acid oil, Castor Oil Fatty Acid, the fatty acid of dehydrated castor oil fatty acid Flos Carthami fatty acid oil；Lauric acid, myristic acid,
Palmic acid, stearic acid, Oleic acid, linoleic acid, linolenic acid etc..Oil example include Petiolus Trachycarpi oil, Oleum Gossypii semen, hemp-seed oil, Testa oryzae oil,
Fish oil, tall oil, soybean oil, Semen Lini oil, Oleum Verniciae fordii, Oleum Brassicae campestriss, Oleum Ricini, dehydrogenated castor oil, safflower oil etc..
Used in modification, the example of polyisocyanate compounds includes：Aliphatic diisocyanate compound,
Such as lysinediisocyanate, hexamethylene diisocyanate and trimethylhexane diisocyanate；Alicyclic two Carbimide .s
Ester compounds, such as hydrogenation eylylene diisocyanate, isophorone diisocyanate, hexahydrotoluene -2,4- bis- is different
Cyanate, hexahydrotoluene -2,6- diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and 1,3- (isocyano
Close methyl) hexamethylene；Aromatic diisocyanate compounds, such as toluylene diisocya-nate, xylylene two are different
Cyanate and methyl diphenylene diisocyanate；Organic polyisocyanates, the such as polyisocyanate of ternary or more Gao Yuan are as relied
Propylhomoserin triisocyanate, and the adduction of these organic polyisocyanates and polyhydric alcohol, low molecular weight polyester resin or water etc.
Thing thing；The biuret form adduct of above mentioned organic diisocyanate and cyclopolymer (for example, isocyanuric acid ester)；
Deng.These can be used alone, or two or more are applied in combination.
From the viewpoint of the hardness of film of the film being obtained, processability and finishability, the polyester resin of hydroxyl
Preferably there is 2,000 to 30,000, particularly 3,000 to 25,000 number-average molecular weight.
Number-average molecular weight used herein and weight average molecular weight are the molecular weight based on polystyrene standards, by conversion
The number-average molecular weight being measured using gel permeation chromatography (GPC) and weight average molecular weight are measured.More specifically, the equal molecule of number
Amount and weight average molecular weight can use " HLC-8120GPC " chromatograph of gel permeation, and (trade name, by Tosoh Corporation
Produce) and four posts：" TSKgel G-4000HXL ", " TSKgel G-3000HXL ", " TSKgel G-2500HXL " and
" TSKgel G-2000HXL " (trade name is produced by Tosoh Corporation) measures together under the following conditions：Flowing
Phase：Oxolane；Measurement temperature：40℃；Flow velocity：1mL/min；And detector：RI.
From the viewpoint of the curable of the film being obtained, the polyester resin of hydroxyl preferably has 5mg KOH/g extremely
250mg KOH/g, the hydroxyl value of particularly preferred 10mg KOH/g to 200mg KOH/g.Come from the viewpoint of processability and resistance to water etc.
See, the polyester resin of hydroxyl preferably has below 30mg KOH/g, more preferably 20mg KOH/g acid number less than.
Cross-linking agent (b)
The cross-linking agent (b) comprising in the coating composition of the present invention is not particularly limited, as long as this crosslinking in heating
Agent with the hydroxyl reaction of the resin (a) of hydroxyl and can make resin (a) solidify.Its instantiation includes tripolycyanamide tree
Fat, benzoguanamine resin, urea resin, end-sealed type polyisocyanate etc..
The example of melmac is included by with C1-18Monohydric alcohol is (as methanol, ethanol, normal propyl alcohol, isopropanol, positive fourth
Alcohol, isobutanol, 2-ethyl butanol or 2-Ethylhexyl Alcohol) make some or all of methylol etherificate in methylolated melamine
And partial ethers or etherificate completely the melmacs prepared.
The example of the commercial products of melmac include " Cymel 202 ", " Cymel 232 ", " Cymel 235 ",
“Cymel 238”、“Cymel 254”、“Cymel 266”、“Cymel 267”、“Cymel 272”、“Cymel 285”、
“Cymel 301”、“Cymel 303”、“Cymel 325”、“Cymel 327”、“Cymel 350”、“Cymel 370”、
" Cymel 701 ", " Cymel 703 ", " Cymel 1141 " (all by Nihon Cytec Industries Inc. produce) and
" U-VAN 20SE60 " (by Mitsui Cytec, Ltd. produces).
The example of benzoguanamine resin includes the methylolation benzoguanamine obtaining by making benzoguanamine and aldehyde reaction
Resin.The example of aldehyde includes formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde etc..Benzoguanamine resin is also included by with a kind of or many
Plant the compound that alcohol makes such methylolation benzoguanamine resin etherificate and obtains.Can be used for be etherified alcohol example include all
Monohydric alcohol as methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, 2-ethyl butanol and 2-Ethylhexyl Alcohol.Wherein,
Preferably it is etherified with least a portion methylol that the monohydric alcohol of 1 to 4 carbon atom makes methylolation benzoguanamine resin and obtain
Benzoguanamine resin.
The instantiation of above benzoguanamine resin includes methyl-etherified benzoguanamine resin, such as Mycoat 102,
Mycoat 105, Mycoat 106 (all being produced by Mitsui Cytec Ltd.), Nikalac SB-201, Nikalac SB-
203rd, Nikalac SB-301, Nikalac SB-303 and Nikalac SB-401 (all by Sanwa Chemical Co.,
Ltd. produce)；The methyl of mixing-and ethyl-etherificate benzoguanamine resin, for example Cymel 1133 is (by Mitsui Cytec
Ltd. produce)；The methyl of mixing-and butyl-etherificate benzoguanamine resin, for example Mycoat 136 is (by Mitsui Cytec
Ltd. produce), Nikalac SB-255, Nikalac SB-355, Nikalac BX-37 and Nikalac BX-4000 (all by
Sanwa Chemical Co., Ltd. produce)；And butyl-etherificate benzoguanamine resin, such as Mycoat 1128 (Mitsui
The product of Cytec Ltd.).
The condensation reaction that urea resin passes through between carbamide and formaldehyde obtains, and can be dissolved or dispersed in solvent or water
In.
Polyisocyanate compounds are the compounds in per molecule with two or more isocyanate groups.Poly- isocyanide
The example of ester compound includes such as toluylene diisocya-nate, methyl diphenylene diisocyanate, xylylene
Diisocyanate and the aromatic diisocyanate of naphthalene diisocyanate；Such as tetramethylene diisocyanate, hexa-methylene two
The aliphatic diisocyanate of isocyanates, dimer acid diisocyanate and lysinediisocyanate；Such as di-2-ethylhexylphosphine oxide (ring
Hexyl isocyanates), isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexane diisocyanate and ring penta
The alicyclic diisocyanate of alkane diisocyanate；The biuret form adduct of these polyisocyanate or chlorinated isocyanurates ring add
Compound；And by making these polyisocyanate and low-molecular-weight or high molecular weight polyols compound (for example, acrylic acid multielement
Alcohol, PEPA and polyether polyol) under conditions of isocyanate groups excess reaction and obtain containing free Carbimide.
The prepolymer of ester.Can also be using by end-capping reagent (for example, phenolic compound, oxime compound, activity methene compound, interior
Amide compound, alcoholic compound, mercaptan compound, amide compound, imide compound, amines, imidazolium compoundss, urea
Compound, carbamic acid compound and group with imine moiety) come to block these polyisocyanate free isocyanate groups roll into a ball and obtain
The blocked polyisocyanate obtaining.
From the viewpoint of the adhesiveness and curable with base material, the resin (a) of hydroxyl and the mixing of cross-linking agent (b)
Ratio is preferably：The total solid content of these components based on 100 mass parts, by 60 mass parts to 95 mass parts, more preferably 70 matter
Measure the friendship of the hydroxy-containing resin (a) to 90 mass parts for the part and 5 mass parts to 40 mass parts, more preferably 10 mass parts to 30 mass parts
Connection agent (b) mixing.
Additionally, the total solid content of the coating composition based on the present invention, the resin (a) of hydroxyl and cross-linking agent (b)
Total solid content is usually 20 mass % to 95 mass %, more preferably 35 mass % to 85 mass %.
Anion surfactant (c) containing sulfonic acid group or sulfonate groups
The coating composition of the present invention contains the anion surfactant (c) containing sulfonic acid group or sulfonate groups.Contain
Presence in the film of the coating composition of the present invention for the anion surfactant (c) of sulfonic acid group or sulfonate groups can
To improve the washability of the pollutant sticking to coating surface.
Example containing sulfonic acid group or the anion surfactant (c) of sulfonate groups includes such as monoalkyl sulfo group amber
Amber acid esters salt, dialkylsulfosuccinic, sulfosuccinic dialkylaminobenzoic acid disalt, polyxyethylated 2-Sulfosuccinic acid disalt,
Alkyl amine oxide double tridecyl sodium sulfosuccinate, dioctyl sodium sulphosuccinate, dihexyl sodium sulfosuccinate, two hexamethylenes
Base sodium sulfosuccinate, diamyl sodium sulfosuccinate, diisobutyl sodium sulfosuccinate, isodecyl disodium sulfosuccinate,
N- octadecyl sulfosuccinic amide disodium and the sulfo group of N- (1,2- bis- carboxyethyl)-N- octadecyl sulfosuccinic amide four sodium
Succinic acid anion surfactant；The alkyl benzene sulphonate anion surfactant of such as dodecylbenzene sodium sulfonate；Such as
The alkyl diphenyl base ether disulfonic acid anion surfactant of dodecyl diphenyl ether sodium disulfonate；Such as polyxyethylated
The sulfur containing polyoxy alkylidene of ether ammonium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate and the multi-ring phenyl ether ammonium sulfate of polyoxyethylene
Acid esters ammonium salt anion surfactant；And single- or double- disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, diisopropyl sodium naphthalene sulfonate,
LOMAR PWA EINECS 246-676-2-formaldehyde condensation products sodium salt, alkyl sulfoacetate and alpha-alkene sulfonate.
Anion surfactant (c) containing sulfonic acid group or sulfonate groups can be used alone, or two kinds or more
Multiple combination uses.
In the aforementioned anion surfactant (c) containing sulfonic acid group or sulfonate groups, sulfosuccinic acid anion
Surfactant, the particularly following dialkyl sodium sulfosuccinate shown in structural formula being represented by formula (1), for enhancing resistant
It is particularly preferred for metachromia.
[chemical formula 1]
(wherein R1And R2Identical or different, and represent C respectively1-15Alkyl).
The commercial products of 2-Sulfosuccinic acid anion surfactant include " Pelex OT-P ", " Pelex TR ",
" Pelex CS " and " Pelex TA ", is all produced by Kao Corporation；“Newcol 290-A”、“Newcol 290-
M ", " Newcol 291-M ", " Newcol 291-PG ", " Newcol 291-GL ", " Newcol 292-PG " and " Newcol
293 ", all produced by Nippon Nyukazai Co., Ltd.；And " Neocol SW-C ", " Neocol YSK ",
" Neocol P ", is all produced by Dai-ichi Kogyo Seiyaku Co., Ltd..
Come from the viewpoint obtaining the film with excellent stain resistance, excellent hardness of film and excellent processability
See, the resin (a) of the hydroxyl based on 100 mass parts for the compositionss and the total solid content of cross-linking agent (b) preferably comprise 1 mass
Part to 20 mass parts, the amount of more preferably 2 mass parts to 10 mass parts the anionic surface containing sulfonic acid group or sulfonate groups
Activating agent (c).
Cationic surfactant (d)
When comprising cationic surfactant (d) in the coating composition of the present invention, it is provided in the film obtaining
Retain the effect of anion surfactant (c), and make anion surfactant (c) avoid soaking from film because of rainwater etc.
Go out, so that it is guaranteed that the holding of stain resistance.
Cationic surfactant (d) is not particularly limited it is possible to suitably be selected according to intended use.In fact
Example includes alkylamine cationic surfactant, quaternary cationicses etc..
The instantiation of cationic surfactant (d) includes the alkyl of such as coconut amine acetass and stearylamine acetass
Amine cation surfactant；And such as Dodecyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl three
Ammonio methacrylate, the season of stearyl trimethyl ammonium chloride, VARISOFT TA100 and alkyl benzyl dimethyl ammonium chloride
Ammonium salt cationic surfactant.
The commercial products of cationic surfactant (d) include Acetamin 24, Acetamin 86 (all by Kao
Corporation produce, alkylamine cationic surfactant), Disper BYK-108, Disper BYK-109, Disper
BYK-116, Disper BYK-161 (is all produced by BYK Japan KK；Alkylamine cationic surfactant),
Quartamin 24P、Quartamin 86P CONC、Quartamin 60W、Quartamin 86W、Quartamin D86P、
Sanisol C, Sanisol B-50 (are all produced by Kao Corporation；Quaternary cationicses),
Catiogen TML、Catiogen TMP、Catiogen TMS、Catiogen ES-O、Catiogen ES-L、Catiogen
ES-P, Catiogen DDM-PG, Catiogen S, Catiogen BC-50, Catiogen D2 and Catiogen TBB is (complete
Portion is produced by Dai-Ichi Kogyo Seiyaku Co., Ltd.；Quaternary cationicses).
From the viewpoint of obtaining the film with excellent stain resistance, hardness of film and processability, compositionss base
Preferably comprise 0.1 mass parts in the resin (a) of hydroxyl of 100 mass parts and the total solid content of cross-linking agent (b) to 20 mass
Part, more preferably 2 mass parts to 16 mass parts, the cationic surfactant (d) even more preferably from 3 mass parts to 10 mass parts.
Urea resin granule (e)
The coating composition of the present invention, when comprising urea resin granule (e), can reduce the glossiness of film, and can
Be 1 to 65 to form such as 60 degree mirror surface lusters, preferably 5 to 55 dumb light film.
The form of described urea resin granule (e) is by pulverizing the resin being obtained by the condensation reaction of carbamide and aldehyde component
And the powder obtaining.Mean diameter is 1 μm to 10 μm, preferably 2 μm to 8 μm of granule is preferred.Mean diameter is use
Microtrack Size Distribution Analyzer (trade name " MT3300 ", produced by Nikkiso Co., Ltd. ") pass through laser diffraction
Median size (d50) value of the volume reference particle diameter distribution of scattering method.
The example of aldehyde component includes formaldehyde, acetaldehyde, crotonic aldehyde, benzaldehyde etc..Especially, be conducive to condensation anti-using formaldehyde
The progress answered, is therefore favourable.
The example of the commercial products of urea resin granule (e) includes Pergopak M3, Pergopak M4, Pergopak
M5 (all being produced by Lonza Japan Ltd., trade name), Soofine JJ Powder are (by J Color Chemicals
Corp., Ltd. produces, trade name) etc..
It is optionally incorporated into urea resin granule (e) in coating composition of the present invention when forming dumb light film, according to institute
Desired dumb light degree is being incorporated to.From the viewpoint of the stability obtaining coating composition and dumb light film, compositionss are based on
The resin (a) of the hydroxyl of 100 mass parts and the total solid content of cross-linking agent (b) usually contain 1 mass parts to 50 mass parts, excellent
Select 2 mass parts to 30 mass parts, urea resin granule (e) of the amount to 15 mass parts for more preferably 3 mass parts.
The coating composition of the present invention can optionally comprise lubricity imparting agent, pigment such as coloring pigment and extender,
Coating additive for example curing catalysts, pigment dispersing agent, ultraviolet absorber, UV stabilizer, defoamer, surface control agent and
Above-mentioned anion surfactant (c) and the different surfactant of above-mentioned cationic surfactant (d), other delustering agents are such as
Fine silica powder, organic solvent, other resins, general known coating material etc..
Lubricity imparting agent can be known any lubricant in coating composition field, as long as described lubricant is not
Damage the outward appearance of film and lubricity can be given to coating surface.The instantiation of such lubricity imparting agent includes：
The polyolefin-wax of such as Tissuemat E；Such as polyether modified silicon oil, high-grade aliphatic ester modified silicon oil, higher alkoxy modified silicon
The modified silicon oil of oil；The hard paraffin of such as microcrystalline wax；Such as montanin wax, lanolin wax, Brazil wax, Cera Flava and spermaceti
Fatty acid ester wax；And the fluorine wax of such as tetrafluoroethene.
The instantiation of pigment includes：The Chinese white of such as titanium white and the flowers of zinc；Such as phthalocyanine blue and indanthrene blue
Blue pigment；The viridine green of such as phthalocyanine green and Aerugo；Such as azo red and quinacridone red organic red
Pigment；The red pigment of such as iron oxide red；Such as benzimidazolone yellow pigment, iso-indoles yellow pigment, isoindoline yellow pigment
Organic yellow uitramarine with quinophthalone yellow pigment；The yellow uitramarine of such as titan yellow, chrome yellow and iron oxide yellow；Such as white carbon black, graphite
Black pigment with the Masson Pine burnt；The extender of such as clay, Talcum, barite and Calcium Carbonate；Such as aluminium triphosphate, molybdenum
Sour zinc and the rust resisting pigment of vanadic anhydride；Deng.The resin (a) of the hydroxyl based on 100 mass parts for the described pigment and cross-linking agent
B the total solid content of () is usually 10 mass parts to 300 mass parts, the amount of preferably 20 mass parts to 150 mass parts (based on coating
Compositionss total solid content, usually 3 mass % to 70 mass %, preferably 8 mass % are to 50 mass %).
For example, it is incorporated to curing catalysts as needed anti-between the resin (a) of hydroxyl and cross-linking agent (b) to promote
Should.When cross-linking agent (b) is amino resins, preferably use the amine neutralized reaction product of sulfoacid compound or sulfoacid compound.
The representative example of sulfoacid compound includes p-methyl benzenesulfonic acid, DBSA, dinonylnaphthalene sulfonic acid, two nonyls
Base naphthalenedisulfonic acid etc..Sulfoacid compound can be any primary amine, secondary amine and tertiary amine with the amine in the neutralized reaction product of amine.Wherein, from
From the viewpoint of applying the physical property of membrane stability, reaction facilitation and the film being obtained, to benzene methanesulfonic acid and amine
Neutralized reaction product and/or DBSA are preferred with the neutralized reaction product of amine.
When cross-linking agent (b) is blocked polyisocyanate compound, the example of curing catalysts include such as tin octoate, two
(2 ethyl hexanoic acid) dibutyl tin, two (2 ethyl hexanoic acid) dioctyl tin, dioctyl tin diacetate, dibutyl tin laurate,
Dibutyltin oxide, the organo-metallic compound of three sad Monobutyltins, 2 ethyl hexanoic acid lead and zinc octoate.Such solidification catalysis
The resin (a) of the hydroxyl based on 100 mass parts for the amount of agent and the total solid content of cross-linking agent (b) are preferably 0.1 mass
Part is to 5.0 mass parts, more preferably 0.2 mass parts to 1.5 mass parts.
The coating composition of the present invention can by equably the mixing resin (a) of hydroxyl, cross-linking agent (b), contain sulfonic acid
The anion surfactant (c) of group or sulfonate groups, cationic surfactant (d), optional urea resin granule
E () and above mentioned other components are obtaining.
The method forming the film of the present invention
When coating the coating composition of the present invention, preferably granule density is adjusted to 20 mass % to 60 mass %
Scope, to realize the viscosity (at 20 DEG C) of 10 to 100 seconds in No. 4 Ford cups.
It is characterised by, methods described is included in metallic plate using the method that the coating composition of the present invention forms film
Primer coating film, and the painting forming the present invention at least one surface of primer coating film are formed on one surface or two surfaces
The top surface film of feed composition.
More specifically, the example of metallic plate to be coated includes cold-rolled steel sheet, hot-dip galvanized steel sheet, plated steel sheet, electricity
Galvanized alloy steel plate (with the steel plate of the such as Zinc alloy electroplating of ferrum-zinc, aluminum-zinc and nickel-zinc), aluminium sheet, corrosion resistant plate, copper coin,
Copper plated steel, tin plate etc..
If metal surface to be coated, can be in the situation of no any process not by the contaminants of such as oil
Lower this metallic plate of coating.However, in order to improve the adhesiveness between metallic plate and film and improve corrosion resistance, preferably making metal
Surface carries out known Treatment of Metal Surface.The example of such known surface treatment method includes Bonderisation, chromium
Hydrochlorate surface treatment, zirconium surface treatment etc..
As the priming paint forming primer coating film on a metal plate, it is possible to use color steel coating, industrial machinery apply coated with
And the known priming paint used in metal parts coating field.From the viewpoint of environmental conservation, without the antirust component of chromium
Non-chrome primer coating composition is preferred.
Non-chrome primer coating composition can be fitted according to the type of the type of material to be coated and Treatment of Metal Surface
Preferably select.Especially, epoxy primer coating composition, polyester primer coating compositions and its modified primer coating composition are
Preferably.When having special requirement to processability, polyester primer coating compositions are suitable.By such as roller coat and spraying
Known painting method primer coating coating composition is so that primer coating film thickness is 1 μm to 30 μm, preferably 2 μm to 20 μm.80
DEG C carry out to 300 DEG C of ambient temperature rolling coating (coil coating) about 5 seconds to 1 little constantly, film preferably passes through
Heat 15 to 120 seconds under conditions of the maximum temperature of substrate is for 140 DEG C to 250 DEG C and solidify.
Primer coating film can be monolayer or the second primer coating film by the first primer coating film and on the first primer coating film
The two-layer that (the second film) is formed.When primer coating film is made up of two-layer, different functions can be given to each layer.For example, may be used
To give anticorrosive function to the first primer coating film, and processability can be given to the second primer coating film (second film) and open with anti-
Fragility.
In the method for the formation film according to the present invention, the coating composition of the present invention is applied to above mentioned bottom
At least one surface of paint film.Available painting method includes curtain coating, roll coater coating, dip-coating, spraying etc..Generally will
It is 5 μm to 50 μm and preferably 8 μm to 25 μm that coating composition is applied to build.
The method being coated the coating composition to be coated with the present invention by rolling is not particularly limited；However, from rolling
It is recommended that curtain coating and roll coater coat from the viewpoint of the economy of coating.When being coated using roll coater, using inclusion two
The conventional bottom feed system (so-called inverse painting or coating naturally) of individual roller is preferred for practicality.In order to optimize warp
The uniformity on the surface of coating, can also be using its top feed or the bottom feed system including three rollers.
The method of the formation film according to the present invention can include making the coating group of the present invention of acquisition in above-mentioned steps
The curing of coating of compound.Generally carry out about 15 seconds to 30 points by using the film that the coating composition of the present invention is formed in heating
The maximum temperature of clock and substrate solidifies under conditions of being about 120 DEG C to 260 DEG C.Wherein by rolling coating be coated pre-
Coating etc. is in field, and solidification is generally 15 seconds to 90 seconds in baking time and the maximum temperature of substrate is about 160 DEG C to 260 DEG C
Under the conditions of carry out.
Contain the anionic surface containing sulfonic acid group or sulfonate groups by the film that the coating composition of the present invention is formed
Activating agent (c) and cationic surfactant (d).Which enhance hydrophilic, therefore enhance the pollutant adhering to film
Cleaning action, creates following effect simultaneously, i.e. cationic surfactant (d) is by containing sulfonic acid group or sulfonate groups
Anion surfactant (c) is retained in film, so that the anion surface active containing sulfonic acid group or sulfonate groups
Agent (c) avoids being leached from film by rainwater etc., therefore ensures that the holding of stain resistance.Additionally, by using comprising the present invention
Compositionss and the coating composition of urea resin granule (f) and the dumb light film that formed has more resistance to the adhesion of pollutant.
And hence it is also possible to give enhanced stain resistance to dumb light film.
Embodiment
With reference to embodiment and comparative example, the present invention is described more particularly below.The present invention is not limited by following examples.
Hereinafter, " part " and " % " is all based on quality.
The preparation of the polyester resin (a) of hydroxyl
Preparation example 1：The preparation (component a1) of polyester resin solution
1079 parts of M-phthalic acids, 407 parts of adipic acids, 466 parts of neopentyl glycols and 802 parts of trimethylolpropanes are positioned over
It is equipped with the reaction unit of thermometer, agitator, heater and distillation column, and be heated to 160 DEG C.Described temperature is little through 3
When gradually rise to 230 DEG C from 160 DEG C.
Subsequently, reaction is made to carry out 30 minutes afterwards at 230 DEG C, distillation column to be replaced by water separator.By 124 parts of dimethylbenzene
It is added in mixture, and dimethylbenzene is also added in water separator so that water and xylenes, and remove condensed water.Make
The mixture reaction obtaining, until reaching the acid number of 10mg KOH/g.After the mixture was cooled, add 855 parts of Ketohexamethylene with
The polyester resin solution that solid constituent is 55% is provided.The resin being obtained have the hydroxyl value of 184mg KOH and 3,400 number equal
Molecular weight.
Preparation example 2：The preparation (component a2) of acrylic resin soln
480 parts of butyl acetates are placed into and are equipped with thermometer, thermostat, agitator, reflux condenser and Dropping funnel
Reaction pot in.While nitrogen blowing, heat the mixture to 130 DEG C.Then, while keeping temperature, in 3 hours
From Dropping funnel dropwise 200 parts of styrene of Deca, 290 parts of methyl methacrylates, 250 parts of cyclohexyl methacrylates, 260
Part methacrylic acid -2- hydroxy methacrylate and the mixed solution of 50 parts of 2,2 '-azos double (2- methylbutyronitrile).
After being added dropwise over, make reactant mixture in 130 DEG C of ripenings 1 hour, and adjust solid constituent using Ketohexamethylene
With the acrylic resin soln providing resin solid content to be 55%.The resin being obtained have 107mg KOH/g hydroxyl value and
8,000 number-average molecular weight.
Embodiment 1：The preparation of No. 1 coating composition
Polyester resin solution that 80 parts (solid constituent) obtains in preparation example 1,20 parts of (solid constituent) Cymel 303
(note 2), 5 parts of Newcol 291-GL (note 4), 5 parts of (solid constituent) Catiogen ES-L (note 7), 120 parts of Tipaque CR-
The mixture of 95 (notes 12) and 0.5 part of DBSA passes through to add organic solvent (Ketohexamethylene/Swasol 1500=40/
The mixed solvent of 60 (based on quality)) and dilute, to prepare viscosity for No. 1 Coating material composition of 80 seconds (No. 4 Ford cups, 25 DEG C)
Thing.
Embodiment 2 to 21：No. 2 preparations to No. 21 coating compositions
Except using the formula shown in table 1 below and 2, preparing No. 2 to No. 21 Coating material compositions in the way of similarly to Example 1
Thing.
Comparative example 1：The preparation of No. 22 coating compositions
Polyester resin solution that 80 parts (solid constituent) obtains in preparation example 1,20 parts of (solid constituent) Cymel 303
The mixture of (note 2), 120 parts of Tipaque CR-95 (note 13) and 0.5 part of DBSA passes through to add organic solvent
(mixed solvent of Ketohexamethylene/Swasol 1500=40/60) and dilute, to prepare viscosity for 80 seconds (No. 4 Ford cups, 25 DEG C)
No. 22 coating compositions.
Comparative example 2 to 8：No. 23 preparations to No. 29 coating compositions
Except using formula shown in table 3, preparing the coating composition of No. 23 to No. 29 in the way of same with comparative example 1.
The preparation of test board
Preparation have the primer coating film being formed on 3 μm of builds Zn-Al alloy-coating steel plate (GL material,
Plate thickness：0.35mm).No. 1 to No. 29 coating group that will be obtained in embodiment described above and comparative example using roll-coater
Compound is coated on the steel plate of described Zn-Al alloy-coating, makes build be 18 μm.It is 200 DEG C in the maximum temperature of substrate
Under conditions of by film toast 40 seconds.Each test board is tested under the test condition of described below.Table 1 below illustrates to survey to 3
Test result.
(note 1) Byran KS-1430V：Produced by Toyobo Co., Ltd., polyester resin, number-average molecular weight：12000,
Hydroxyl value：11mg KOH/g, glass transition point：1℃.
(note 2) Cymel 303：Produced by Nihon Cytec Industries Inc., trade name, methyl-etherified trimerization
Melamine resin.
(note 3) blocked polyisocyanate compound A：The oxime end-cap product of hexamethylene diisocyanate trimer, solid
Composition：37 mass %, NCO content：3.6%.
(note 4) Newcol 291-GL：Trade name, is produced by Nippon Nyukazai Co., Ltd., by formula illustrated above
(1) the dialkyl sodium sulfosuccinate salt of the structural formula representing.
(note 5) Newcol 292-PG：Trade name, is produced by Nippon Nyukazai Co., Ltd., by formula illustrated above
(1) the dialkyl sodium sulfosuccinate salt of the structural formula representing.
(note 6) Newcol 293：Trade name, is produced by Nippon Nyukazai Co., Ltd., by formula shown below (2)
The monoalkyl disodium sulfosuccinate salt of the structural formula representing.
[chemical formula 2]
(wherein R3For C1-15Alkyl).
(note 7) Catiogen ES-L：Produced by Dai-Ichi Kogyo Seiyaku Co., Ltd., trade name, quaternary ammonium
Cationic surfactants.
(note 8) Acetamin 86：Produced by Kao Corporation, trade name, alkylamine cationic surfactant.
(note 9) Sanisol C：Produced by Kao Corporation, trade name, quaternary cationicses.
(note 10) Disper BYK-161：Produced by BYK Japan KK, alkylamine cationic surfactant.
(note 11) Soofine JJ Powder：By J Color Chemicals Corp., Ltd. produces, trade name, urine
Plain resin particle, mean diameter：2.5μm.
(note 12) Sylysia 445：By Fuji Silysia Chemical, Ltd. produces, trade name, and silicon dioxide is micro-
Powder, delustering agent.
(note 13) Tipaque CR-95：By Ishihara Sangyo Kaisha, Ltd. produces, trade name, titanium white.
Implement table 1 under the following conditions to the test shown in table 3.
(note 14) storage stability：
Each coating composition fully seals, and stores in 40 DEG C of thermostatic chamber.Each coating group is evaluated according to following standard
Compound is in 90 days states afterwards of storage.
S：Coating composition is quickly returned to the state before storing after agitation, and problem does not occur.
A：Sedimentary is formed by the precipitation of coating composition；However, in the stirring less than 10 minutes, (500rpm uses
The stirring vane of a diameter of 3cm) after, coating composition returns to the state before storage, does not have aggregation.
B：Sedimentary is formed by the precipitation of coating composition；However, in stirring, (500rpm, using straight within 10 to 60 minutes
Footpath is the stirring vane of 3cm) after, coating composition returns to the state before storage, does not have aggregation.
C：Sedimentary is formed by the precipitation of coating composition；Even in stirring 60 minutes or more (500rpm, using straight long
Footpath is the stirring vane of 3cm) after, still remain aggregation.
The outward appearance on the coated surface of (note 15) incipient stage
A：The abnormal conditions such as shunk, be recessed and be atomized are not observed on coated surface.
B：The abnormal conditions such as shunk, be recessed are not observed on coated surface, but on coated surface
On observe atomization.
C：The abnormal conditions such as shunk and be recessed are observed on coated surface.
(note 16) pencil hardness：
Pencil scratch test is carried out to the film on each test board according to JIS K 5600-5-4 (1999), and evaluates film
Damaged.Higher hardness is preferred.
(note 17) outdoor exposure is tested：
Outdoor exposure is tested in Tokyo land for growing field crops area Kansai Paint Co., on the roof of Ltd, by surveying outdoor exposure
Test plate (panel) (100 × 300mm) is fixed to and imitates the articles holding table of eaves and make the film of test board to be in 4 degree of angle with vertical direction
To carry out towards northwardly mode.Each film " after exposing 2 months " and " after the exposing 12 months " aberration (Δ E) with the incipient stage
According to JIS Z 8370 using the MSC-5N multiple light courcess spectrophotometer being manufactured by Suga Test Instruments, Co., Ltd
To measure.Result is according to following standard evaluation：
S：Δ E is less than 1.
A：Δ E is more than or equal to 1, and is less than 2.
B：Δ E is more than or equal to 2, and is less than 5.
C：Δ E is more than or equal to 5.
(note 18) processability：
At 20 DEG C within doors, using vice, each test plate (panel) is bent to 180 degree in the way of coated surfaces facing outward.Illustrate
There is not the T number ftractureing in sweep.T number is defined as follows.
0T：Carry out 180 degree bending in the case of any object not being inserted sweep.
1T：Carry out the bending of 180 degree using one block of plate and insert with the test board same thickness in sweep.
2T to 6T is similarly defined and carries out 180 degree bending for being utilized respectively 2 to 6 blocks of plates.
Result is evaluated according to following standard.
S：2T bending is not ftractureed.
A：2T bending is ftractureed, but cracking is not observed in 4T bending.
B：4T bending is ftractureed, but cracking is not observed in 6T bending.
C：6T bending is ftractureed.
(note 19) 60 degree of mirror surface lusters：
The measuring method of 60 degree of specular reflectivitys, 60 degree of mirror surface lusters according to defined in JIS Z 8741 (1997) Lai
Measurement.
Overall merit
In the field of the invention, that is, it is desirable to coating composition has good storage characteristics in coating composition field,
And following film can be formed, this film exposes out of doors and lower can keep stain resistance and have high hardness of film and good
Processability.Therefore, overall merit is carried out according to following standard.
A：Storage stability, outdoor exposure test (2 months after exposure starts), outdoor exposure test (start in exposure
12 months afterwards) and processability be all S or A, and pencil hardness is more than or equal to 3H.
B：Storage stability, outdoor exposure test (2 months after exposure starts), outdoor exposure test (start in exposure
12 months afterwards) and processability all be S, A or B；At least one in four is B；And pencil hardness is more than or equal to 3H.
C：Storage stability, outdoor exposure test (2 months after exposure starts), outdoor exposure test (start in exposure
12 months afterwards) and processability all be S, A, B or C；At least one in four is C；And pencil hardness is less than or equal to 2H.
Industrial applicibility
The present invention can provide storage stability excellent and can form the coating composition of following film, and described film is at family
Stain resistance can be kept and there is excellent hardness of film and processability during outer exposure.
Claims (7)
1. coating composition, it comprises：The resin of (a) hydroxyl, (b) cross-linking agent, (c) contains sulfonic acid group or sulfonate groups
Anion surfactant, and (d) cationic surfactant,
The resin (a) based on the described hydroxyl of 100 mass parts for the described compositionss and the total solid content bag of described cross-linking agent (b)
The anion surfactant (c) and 0.1 of sulfonic acid group or sulfonate groups is contained described in amount containing 1 mass parts to 20 mass parts
Mass parts to the amount of 20 mass parts described cationic surfactant (d),
The wherein said anion surfactant (c) containing sulfonic acid group or sulfonate groups is 2-Sulfosuccinic acid anionic surface
Activating agent.
2. coating composition as claimed in claim 1, the resin (a) of the described hydroxyl based on 100 mass parts and described friendship
The total solid content of connection agent (b), it comprises the resin (a) of the described hydroxyl of the amount of 60 mass parts to 95 mass parts and 5 mass
Part to 40 mass parts amount described cross-linking agent (b).
3. coating composition as claimed in claim 1 or 2, the wherein said anion table containing sulfonic acid group or sulfonate groups
Face activating agent (c) is dialkyl sodium sulfosuccinate salt.
4. coating composition as claimed in claim 1, wherein said cationic surfactant (d) is alkylamine cation form
Face activating agent or quaternary cationicses.
5. coating composition as claimed in claim 1, the resin (a) of the described hydroxyl based on 100 mass parts and described friendship
The total solid content of connection agent (b), it comprises urea resin granule (e) of the amount to 50 mass parts for 1 mass parts.
6. the method being used for forming film, it includes being formed primer coating film on a surface or two surfaces of metallic plate, with
And the painting of the coating composition any one of claim 1 to 5 is formed at least one surface of described primer coating film
Film.
7. the metallic plate of application, the method that it passes through described in claim 6 obtains.
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| CN108756889B (en) * | 2018-06-08 | 2019-08-30 | 北京中煤矿山工程有限公司 | Anti- well drilling machine reaming construction broken formation gib method |
| JP2021143312A (en) * | 2020-03-13 | 2021-09-24 | 株式会社Lixil | Hydrophilic treatment coating composition |
| CN111575414A (en) * | 2020-06-16 | 2020-08-25 | 遂昌润德皮饰有限公司 | Tensile leather surface layer water treatment process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114334A (en) * | 1994-06-08 | 1996-01-03 | 日本涂料株式会社 | Coating resin composition |
| CN101316908A (en) * | 2005-11-25 | 2008-12-03 | 巴斯福涂料股份有限公司 | Paint compositions, method of paint finishing and painted objects |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0636259A (en) * | 1992-07-16 | 1994-02-10 | Konica Corp | Magnetic recording medium |
| JPH1069024A (en) * | 1996-08-28 | 1998-03-10 | Fuji Photo Film Co Ltd | Photographic coating liquid composition and silver halide photographic sensitive material using the same |
| JPH1069025A (en) * | 1996-08-29 | 1998-03-10 | Fuji Photo Film Co Ltd | Photographic coating liquid composition and support using the same and silver halide photographic sensitive material |
| JP2003128985A (en) * | 2001-10-30 | 2003-05-08 | Dainippon Ink & Chem Inc | One-pack type coating composition for metal material and coated metal material |
| JP2005298686A (en) * | 2004-04-13 | 2005-10-27 | Nissan Motor Co Ltd | Flat coating composition and matte coated article |
| JP2006095372A (en) * | 2004-09-28 | 2006-04-13 | Fuji Photo Film Co Ltd | Coating method and coating solution |
| WO2010131690A1 (en) * | 2009-05-13 | 2010-11-18 | 関西ペイント株式会社 | Coating composition, method for formation of coating film, and article having the coating film |
| JP5586799B2 (en) * | 2012-02-10 | 2014-09-10 | 関西ペイント株式会社 | Paint composition |
-
2014
- 2014-01-21 CN CN201480001869.6A patent/CN104471004B/en active Active
- 2014-01-21 JP JP2014534845A patent/JP5675005B1/en active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114334A (en) * | 1994-06-08 | 1996-01-03 | 日本涂料株式会社 | Coating resin composition |
| CN101316908A (en) * | 2005-11-25 | 2008-12-03 | 巴斯福涂料股份有限公司 | Paint compositions, method of paint finishing and painted objects |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5675005B1 (en) | 2015-02-25 |
| WO2014196217A1 (en) | 2014-12-11 |
| CN104471004A (en) | 2015-03-25 |
| JPWO2014196217A1 (en) | 2017-02-23 |
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