CN103906577A - Method for forming multilayer coating film - Google Patents
Method for forming multilayer coating film Download PDFInfo
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- CN103906577A CN103906577A CN201280050091.9A CN201280050091A CN103906577A CN 103906577 A CN103906577 A CN 103906577A CN 201280050091 A CN201280050091 A CN 201280050091A CN 103906577 A CN103906577 A CN 103906577A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/542—No clear coat specified the two layers being cured or baked together
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2504/00—Epoxy polymers
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Abstract
Provided is a method whereby an object to be coated can be suitably furnished with a multilayer coating film excellent both in corrosion resistance and weathering resistance. The method for forming the multilayer coating film includes: a base coating film formation step in which a base coating composition is applied onto the object to be coated, forming an undried base coating film; a top coating film formation step in which a top coating composition is applied in a wet-on-wet process over the resulting undried base coating film, forming an undried top coating film; and a drying step in which the resulting undried base coating film and the undried top coating film are simultaneously dried, forming a multilayer coating film; wherein the method for forming the multilayer coating film imposes a limit as to the difference in surface tension between the base coating film and the top coating film.
Description
Technical field
The present invention relates to a kind of method that forms duplex coating, described method can be by wet-wet mode (wet-on-wet) coating bottom coating composition and topcoat compositions.
Background of invention
Industrial machine and construction machine have following characteristic: they are generally extensive and by construction substrate (steel substrate) thick composition, very thick compared with its thickness and car body etc., to bear heavy load.Therefore, when such industrial machine and construction machine are during as base material to be coated, they have thermal capacitance high and in heated oven the insufficient problem that is delivered to them of heat.According to above-mentioned reason, the thermosetting types of coatings composition that is generally used for being coated with car body is not suitable for industrial machine and construction machine.They are for example conventionally used in and are coated with lower than the coating composition that can form solidified coating at the temperature of 100 ℃.
JP 2003-226839 A [PTL 1] discloses a kind of coating composition, described composition comprises: the resin that (A) contains hydroxyl as base resin, (B) polyisocyanate compounds is as curing agent and (C) organo-tin compound is as carbamate curing catalysts, wherein phosphate group is present in (claim 1 of PTL 1 etc.) in the component being included in described composition.It is good at dry property and finishing properties that it has described this coating composition, and pot life extends.Generally speaking, at the coating composition for industrial machine and construction machine, for example, the cured with isocyanates types of coatings composition of describing in JP 2003-226839 A [PTL 1] is through repeatedly (2 times) of coating, to improve anticorrosion character etc.But in the time using coating composition, said composition does not provide the film of the coating with enough anticorrosion character and weatherability, even coating operation is carried out twice.
Meet the two the method for coating of anticorrosion character and weatherability as formation, can consider following methods: wherein anticorrosive property good coating composition of fine quality, as bottom coating composition, uses the topcoat compositions that weatherability is good subsequently.For example, JP 2010-188239 A [PTL 2] discloses a kind of method that forms thick film type erosion shield, wherein the epoxy resin of Weak solvent type high solid modification paint (A) contains binder resin component, described binder resin component comprises: (a) (wherein epoxide equivalent weight is 400-2000 g/eq to the epoxy resin of modification, based on the gross mass of binder resin component), (b) polyimide resin and (c) reactive diluent, and Weak solvent type high solid polyurethane resin paint (B) contains binder resin component, described binder resin component comprises: the polyol resin that (d) hydroxyl value is 10-100mgKOH/g and (e) polyisocyanate resin, by the epoxy resin of high solid modification (A) primary coat cloth, subsequently by high solid polyurethane resin paint (B) top coating (claim 1).In PTL 2, also describe and can obtain anticorrosion ability by the method for corresponding one deck priming coat and one deck top coat and be equal to by the anticorrosion character that obtains of conventional duplex coating more than once coating.But the method for describing in JP 2010-188239 A should be coated with top coat (paragraph [0005] etc.) after dry 24 hours after formation priming coat under typical temperature.Therefore, the method has the inefficient problem of application step, because need to be coated with for a long time.
That existence is called is wet-coating process of wet mode, the method can shorten application step, way is first to apply bottom coating composition to form priming coat, apply subsequently topcoat compositions to form top coat moist priming coat, then dry two coatings simultaneously.But in the time that bottom coating composition and topcoat compositions are coated with by wet-wet mode, it has, and two wet coating layers mix and the problem of the appearance degradation of coating.In wet-wet mode is coated with, may produce once in a while coating problem, for example, shrink, this causes being included in the delay evaporation of the volatile component in priming coat, this priming coat is present in below top coat, because top coat contacts with unlimited air and more Zao drier than priming coat.Therefore, not the coating composition of thermoset coating composition in the case of using, also do not set up up to now by wet-wet method and be successfully coated with dissimilar bottom coating composition and the method for topcoat compositions.
[reference listing]
[patent documentation]
[PTL?1]?JP?2003-226839?A
[PTL?2]?JP?2010-188239?A
Summary of the invention
An object of the present invention is to solve the problem of above-mentioned prior art and application.Particularly, the object of this invention is to provide a kind of method that is coated with formation anticorrosion character and the two good duplex coating of weatherability by the mode that wets-wet, after painting bottom coating composition, there is no a lot of interval times, and can greatly shorten application step.
The invention provides a kind of method that forms duplex coating, described method comprises:
Form the step of priming coat, wherein painting bottom coating composition on base material to be coated, to form wet priming coat,
Form the step of top coat, wherein on obtained wet priming coat, be coated with topcoat compositions by wet-wet mode, to form wet top coat, and
Dry step, wherein by simultaneously dry to obtained wet priming coat and wet top coat, to form duplex coating,
Wherein said bottom coating composition comprises:
Film-forming resin, comprises acrylic resin (A-1) and epoxy resin (C),
Curing agent, comprise isocyanate compound (D-1) and
Surface conditioner (E-1),
The solid content ratio of acrylic resin (A-1), epoxy resin (C), isocyanate compound (D-1) and surface conditioner (E-1) is: the acrylic resin (A-1) of 25-70% quality, the epoxy resin (C) of 5-30% quality, the isocyanate compound (D-1) of 20-60% quality and the surface conditioner (E-1) of 0.01-5% quality
Described topcoat compositions comprises:
Film-forming resin, comprises acrylic resin (A-2),
Curing agent, comprise isocyanate compound (D-2) and
Surface conditioner (E-2),
The solid content ratio of acrylic resin (A-2), isocyanate compound (D-2) and surface conditioner (E-2) is: the surface conditioner (E-2) of the acrylic resin (A-2) of 30-70% quality, the isocyanate compound (D-2) of 20-60% quality and 0.01-5% quality, and
Value △ γ (γ
1-γ
2) be 2-8 mN/m, this value representation is from the capillary value (γ of described bottom coating composition
1) in deduct the capillary value (γ of described topcoat compositions
2).
In the present invention, the two solid content hydroxy value of acrylic resin (A-1) and acrylic resin (A-2) can be preferably 50-250 mgKOH/g, and the epoxide equivalent of epoxy resin (C) can be preferably 100-1000 g/eq.
The described film-forming resin being included in described bottom coating composition can preferably also comprise mylar (B-1),
The solid content ratio of acrylic resin (A-1), mylar (B-1), epoxy resin (C), isocyanate compound (D-1) and surface conditioner (E-1) can be preferably: epoxy resin (C), the isocyanate compound (D-1) of 20-50% quality and the surface conditioner (E-1) of 0.01-5% quality of the acrylic resin (A-1) of 25-50% quality, the mylar (B-1) of 5-30% quality, 5-25% quality
The described film-forming resin being included in described topcoat compositions can preferably also comprise mylar (B-2), and
The solid content ratio of acrylic resin (A-2), mylar (B-2), isocyanate compound (D-2) and surface conditioner (E-2) can be preferably the acrylic resin (A-2) of 30-60% quality, mylar (B-2), the isocyanate compound (D-2) of 20-50% quality and the surface conditioner (E-2) of 0.01-5% quality of 5-35% quality.
In addition, the two solid content hydroxy value of mylar (B-1) and mylar (B-2) can be preferably 80-350 mgKOH/g.
In addition, the hexane tolerance of surface conditioner (E-1) is not less than 150 ml, and the hexane of surface conditioner (E-2) tolerates in 50-150 ml scope.
In addition, described surface conditioner (E-1) can preferably comprise acrylic acid surface conditioner and silicone surface conditioning agent one of at least, and surface conditioner (E-2) can preferably comprise silicone surface conditioning agent and fluorinated surface conditioning agent one of at least.
Especially, can be preferably 0-60 minute the interval time between the operation of the coating in the step that forms described priming coat and the operation of the coating in the step that forms described top coat.
In addition, described base material to be coated can be preferably construction machine or industrial machine.
The beneficial effect of the invention
According to the present invention, having the two duplex coating of good weatherability and anticorrosion character can be coated with and be formed by wet-wet mode.The duplex coating forming by the present invention also has such characteristic: after painting bottom coating composition, can be coated with topcoat compositions, there is no thermal cure step and there is no a lot of interval times.Therefore, it has the following advantages: do not need the firing equipment for heating priming coat, the investment of coating apparatus can reduce, and application step can shorten greatly.The method of formation duplex coating of the present invention is especially applicable to coating scale greatly and has the base material to be coated of large thermal capacitance, for example industrial machine and construction machine.
DESCRIPTION OF THE PREFERRED
The method that is used to form duplex coating of the present invention comprises the following steps: form the step of priming coat, wherein painting bottom coating composition, to form wet priming coat; Form the step of top coat, be wherein coated with topcoat compositions by wet-wet mode, to form wet top coat; With dry step, wherein by simultaneously dry to obtained wet priming coat and wet top coat.
Bottom coating composition comprises film-forming resin (comprising acrylic resin (A-1) and epoxy resin (C)), surface conditioner (E-1) and the isocyanate compound (D-1) as curing agent, and it also can comprise mylar (B-1).
Topcoat compositions comprises film-forming resin (comprising acrylic resin (A-2)), surface conditioner (E-2) and the isocyanate compound (D-2) as curing agent, and it also can comprise mylar (B-2).
Common above-mentioned mylar (B-1) and above-mentioned mylar (B-2) are not prepared on earth coating composition and topcoat compositions in the two, or are formulated in the two.Rare, they are only included among any of bottom coating composition and topcoat compositions.In the description of the component of corresponding coating composition, main explanation comprises mylar (B-1) as the film-forming resin of bottom coating composition and comprises the film-forming resin of mylar (B-2) as topcoat compositions, with simplified characterization.
In the method that is used to form duplex coating of the present invention, there is such advantage: even be coated with bottom coating composition and the topcoat compositions with different coating compositions by wet-wet mode, the duplex coating weatherability and the anticorrosive property that obtain are of fine quality good, the coating problem of not following, for example appearance of coat deteriorated (for example, the layer of mixing) and contraction.
bottom coating composition
Bottom coating composition of the present invention comprises: film-forming resin, comprises acrylic resin (A-1), mylar (B-1) and epoxy resin (C); Curing agent, comprises isocyanate compound (D-1); And surface conditioner (E-1).Corresponding component is below described.As mentioned above, the situation that does not comprise mylar (B-1) is also in the scope of bottom coating composition, and this bottom coating composition is for the method for formation duplex coating of the present invention.
acrylic resin (A-1)
Bottom coating composition of the present invention comprises acrylic resin (A-1) as film-forming resin.By comprising acrylic resin (A-1), for priming coat provides good coating performance, for example cohesive and water proofing property.The acrylic resin (A-1) being included in bottom coating composition can be prepared with another kind of monomer (b) copolymerization by the monomer (a) that contains hydroxyl.
The monomer (a) that contains hydroxyl comprises, for example, 2-hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, 2, the esterification products of product, multivalence alcohol (such as polyethyleneglycol (methyl) acrylate) and the acrylic or methacrylic acid of 3-dihydroxy butyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, epsilon-caprolactams and these (methyl) acrylate that contain hydroxyl etc.The product that in addition, also can use the ring-opening polymerisation of the mono-esterification product by epsilon-caprolactams and above-mentioned multivalence alcohol and acrylic or methacrylic acid to obtain.A kind of in these monomers (a) that contain hydroxyl can be used alone or can use two or more in these.In this manual, " (methyl) acrylate " refers to " acrylate or methacrylate ".
Other monomer (b) comprises, for example:
The monomer that contains carboxyl, for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and fumaric acid; And dicarboxylic acid monoesters, for example ethyl maleate, maleic acid butyl ester, itaconic acid ethyl ester and itaconic acid n-butyl;
(methyl) acrylic acid Arrcostab, for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate or (methyl) tert-butyl acrylate, (methyl) 2-EHA and (methyl) acrylic acid Lauryl Ester;
The monomer that contains alicyclic group, for example (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid three encircle ester and (methyl) acrylic acid adamantane esters in the last of the ten Heavenly stems;
Aminoalkyl (methyl) acrylate, for example (methyl) acrylic-amino ethyl ester, (methyl) acrylic acid dimethylamino ethyl ester and (methyl) acrylic acid butyl amino ethyl ester;
Aminoalkyl (methyl) acrylamide, for example amino-ethyl (methyl) acrylamide, dimethylaminomethyl (methyl) acrylamide and methylamino propyl group (methyl) acrylamide;
The monomer that contains another amide group, for example acrylamide, Methacrylamide, N hydroxymethyl acrylamide, methoxyl group butyl acrylamide and DAAM;
Vinyl cyanide, for example (methyl) acrylonitrile and α-chloro-acrylonitrile;
The vinyl ester monomers of saturated aliphatic carboxylic acid, for example vinyl acetate and propionate;
Styrene monomer, such as styrene, AMS and vinyltoluene etc.Other monomer (b) but can be used alone or two or more are used in combination.
In above-mentioned other monomer (b), can preferably use acrylic acid, methacrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid Lauryl Ester, (methyl) cyclohexyl acrylate etc.
The monomer (a) that the normally used method of those skilled in the art can be used as containing hydroxyl and the polymerization of other monomer (b).Polymerization comprises, for example, two steps of bulk polymerization, solution polymerization process and body-suspension polymerization are wherein used radical polymerization initiator to carry out suspension polymerisation after bulk polymerization.In these methods, can preferably use solution polymerization process.Solution polymerization process comprises, for example, under radical polymerization initiator exists, heats above-mentioned monomer mixture, the method simultaneously stirring at the temperature of 80-200 ℃ for example.
Above-mentioned acrylic resin (A-1) can preferred number average molecular weight be 1,000-15,000.When number-average molecular weight was lower than 1,000 o'clock, the coating performance of the duplex coating obtaining may be inferior.On the other hand, when number-average molecular weight exceedes at 15,000 o'clock, the viscosity of resin Composition improves, and can need a lot of solvents preparing in coating composition.In this manual, number-average molecular weight is the number-average molecular weight of calculating according to polystyrene, and it is measured by gel-permeation chromatography (GPC).Acrylic resin (A-1) can preferred number average molecular weight be 1,000-8,000, more preferably 1, and 000-5,000.
Above-mentioned acrylic resin (A-1) preferably solid content hydroxy value is 50-250 mgKOH/g.When solid content hydroxy value is during lower than 50 mgKOH/g, can reduce and the reactivity of isocyanate compound (D-1), the coating performance of the duplex coating obtaining can be deteriorated, and the cohesive of coating can be deteriorated.On the other hand, in the time that solid content hydroxy value exceedes 250 mgKOH/g, the water proofing property of the duplex coating obtaining can be deteriorated.More preferably 60-200 mgKOH/g of the solid content hydroxy value of acrylic resin (A-1), most preferably 80-180 mgKOH/g.
Above-mentioned acrylic resin (A-1) preferably solid content acid number is 2-50 mgKOH/g.When solid content acid number is during lower than 2 mgKOH/g, the coating performance of the duplex coating obtaining can be deteriorated.On the other hand, in the time that solid content acid number exceedes 50 mgKOH/g, the water proofing property of the duplicature obtaining can be deteriorated.More preferably 5-20 mgKOH/g of the solid content acid number of acrylic resin (A-1).
Can use commercially available acrylic resin as acrylic resin (A-1).Acrylic resin comprises that the trade name " ACRYDIC " of being manufactured by DIC company is serial (for example, ACRYDIC A-837, ACRYDIC A-871, ACRYDIC A-1370 etc.), trade name " HARIACRON " series of being manufactured by Harima Chemicals (for example, HARIACRON D-1703, HARIACRON N-2043-60MEX etc.), by MITSUBISHI RAYON CO., LTD. trade name " Dianal " series of manufacturing, by Hitachi Chemical Co., Ltd. trade name " HITALOID " series of manufacturing, trade name " OLESTER " series of being manufactured by Mitsubishi Chemicals Corporation etc.
mylar (B-1)
Bottom coating composition of the present invention can comprise mylar (B-1) as film-forming resin.By comprise mylar (B-1) in bottom coating composition, there is the machinability of improving coating and the advantage of improving the outward appearance of the coating obtaining.Mylar (B-1) is included in the mylar in a molecule with two or more hydroxyls, and it is commonly referred to PEPA, and it can preferably use.Mylar can be prepared by multivalence alcohol and polyacid or its acid anhydrides polycondensation (esterification).
Multivalence alcohol comprises ethylene glycol, diglycol, polyethylene glycol, propane diols, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1, 2-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexylene glycol, hydrogenated bisphenol A, hydroxy alkylated bisphenol-A, 1, 4-cyclohexanedimethanol, 2, 2-dimethyl-3-hydroxypropyl-2, 2-dimethyl-3-hydroxy propionate, 2, 2, 4-trimethyl-1, 3-pentanediol, N, N-pair-(2-hydroxyethyl) dimethyl hydantoin, polytetramethylene ether diol, polycaprolactone polyol, glycerine, D-sorbite, trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, hexanetriol, pentaerythrite, dipentaerythritol, three-(ethoxy) isocyanates etc.A kind of multivalence alcohol and can use two or more combination can be used alone.
Polyacid or its acid anhydrides comprise phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrabydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyl tetrahydrophthalic acid, methyl tetrahydrophthalic anhydride, hymic acid anhydrides, trimellitic acid, trimellitic anhydride, pyromellitic acid, PMA, M-phthalic acid, terephthalic acid (TPA), maleic acid, maleic anhydride, fumaric acid, itaconic acid, adipic acid, azelaic acid, decanedioic acid, butanedioic acid, succinyl oxide, lactic acid, dodecenyl succinic butanedioic acid, dodecenyl succinic anhydride, cyclohexane-1, 4-dicarboxylic acids, carbic anhydride etc.These polyacids or their acid anhydrides one type and two types of uses capable of being combined or more kinds of can be used alone.
Also can use the mylar of modification as mylar (B-1), the mylar of modification is by using lactone, fat or aliphatic acid, melmac, carbamate resins etc., and modification obtains according to the above mylar of describing preparation.For example, by fatty or fatty acid modified mylar, by using fat or being obtained by these fat extracted fatty acid modified mylar, described fat is castor oil, dehydrated castor oil, cocounut oil, corn oil, cottonseed oil, Linseed oil, perilla herb oil, poppy seed oil, safflower oil, soybean oil and wood oil for example.In producing by fat or fatty acid modified mylar, can be preferably the above-mentioned fat of approximately 30 mass parts and/or aliphatic acid be altogether joined to the mylar of 100 mass parts.
Above-mentioned mylar (B-1) can preferred number average molecular weight be 500-6,000, calculate by gpc measurement according to polystyrene.When number-average molecular weight is lower than 500 time, the cohesive of the coating obtaining can be deteriorated.On the other hand, in the time that number-average molecular weight exceedes 6000, in the time of coating, the wettability of base material to be coated can be deteriorated.The number-average molecular weight of mylar (B-1) can be more preferably 1,000-4,000.
Above-mentioned mylar (B-1) the preferably hydroxyl value of solid content is 80-350 mgKOH/g.When the hydroxyl value of solid content is during lower than 80 mgKOH/g, can reduce with the reactivity of isocyanate compound (D-1), the coating performance of the duplex coating obtaining can be deteriorated, and the cohesive of coating can be deteriorated.On the other hand, in the time that the hydroxyl value of solid content exceedes 350 mgKOH/g, the water proofing property of the duplex coating obtaining can be deteriorated.More preferably 80-300 mgKOH/g of the solid content hydroxy value of mylar (B-1), most preferably 150-250 mgKOH/g.
epoxy resin (C)
Bottom coating composition of the present invention comprises epoxy resin (C) as film-forming resin.By comprise epoxy resin (C) in bottom coating composition, there is the advantage of the anticorrosion character of improving the duplex coating obtaining.Can preferably include in bisphenol-A type of epoxy resin or linear phenol-aldehyde resin type of epoxy resin at least any as epoxy resin (C).
In the present invention, except above-mentioned bisphenol-A type of epoxy resin and/or linear phenol-aldehyde resin type of epoxy resin, epoxy resin (C) also can comprise another kind of epoxy resin.Other epoxy resin comprises, for example, epoxy resin of Bisphenol F type of epoxy resin, bisphenol-A D type of epoxy resin, bisphenol S type of epoxy resin, biphenyl type of epoxy resin, naphthalene type of epoxy resin, glycidyl esters type of epoxy resin, glycidyl group amine type of epoxy resin, modified rubber etc.
For the total amount of epoxy resin (C), the amount of bisphenol-A type of epoxy resin and/or linear phenol-aldehyde resin type of epoxy resin can be preferably 10-100% quality, more preferably 20-100% quality.When the amount of bisphenol-A type of epoxy resin and/or linear phenol-aldehyde resin type of epoxy resin during lower than 10% quality, can not obtain the cohesive enough with base material to be coated for the total amount of epoxy resin (C).
The epoxide equivalent of epoxy resin (C) can be preferably 100-1,000 g/eq, more preferably 150-1,000 g/eq.In the time that epoxide equivalent exceedes 1,000 g/eq, in some cases, cohesive is tended to reduce, and the toughness of the coating obtaining sometimes may be deteriorated.When it is during lower than 100 g/eq, this is not preferred, because viscosity improves and machinability may reduce.In addition,, in the time that epoxy resin (C) is the mixture of resin of two kinds of quantity, the epoxide equivalent of all epoxy resin that preferably include is in above-mentioned scope.
The number-average molecular weight of epoxy resin (C) can be preferably 20-2, and 000, by gpc measurement, calculate according to polystyrene.In the time that number-average molecular weight is in above-mentioned scope, there is the advantage that obtains good coating performance and good coating machinability.
The instantiation that can be used as the commercially available product of epoxy resin (C) comprises " EPICOAT #828 ", it is commercially available product (the bisphenol-A types of liquid epoxy resin of bisphenol-A type of epoxy resin, epoxide equivalent is 184-194 g/eq, number-average molecular weight is approximately 380, and is manufactured by Mitsubishi Chemical Corporation); " EPICOAT #834-90X " (bisphenol-A type solid epoxy resin, epoxide equivalent is 230-270 g/eq, number-average molecular weight is approximately 470, and is manufactured by Mitsubishi Chemical Corporation); " EPICOAT #872-X-75 " (bisphenol-A solid type of epoxy resin, epoxide equivalent is 600-700 g/eq, and is manufactured by Mitsubishi Chemical Corporation); " EPICOAT #1001 " (bisphenol-A type solid epoxy resin, epoxide equivalent is 450-500 g/eq, number-average molecular weight is approximately 900, and is manufactured by Mitsubishi Chemical Corporation); " EPICOAT #1004 " (bisphenol-A type solid epoxy resin, epoxide equivalent is 875-975 g/eq, number-average molecular weight is approximately 1600, and is manufactured by Mitsubishi Chemical Corporation) etc.;
" EPICLON 5250-801X ", it is commercially available product (the phenol linear phenol-aldehyde resin type of epoxy resin of linear phenol-aldehyde resin type of epoxy resin, epoxide equivalent is 230-250 g/eq, number-average molecular weight is approximately 470, and by Dainippon Ink and Chemicals, Incorporated (DIC Corporation) manufactures); " EPICLON 5270-801X " (phenol linear phenol-aldehyde resin type of epoxy resin, epoxide equivalent is 245-270 g/eq, number-average molecular weight is approximately 540, and by Dainippon Ink and Chemicals, Incorporated (DIC Corporation) manufactures); " EPICOAT #154 " (phenol linear phenol-aldehyde resin type of epoxy resin, epoxide equivalent is 176-180 g/eq, number-average molecular weight is 540, and is manufactured by Mitsubishi Chemical Corporation) etc.;
" EPICOAT #807 ", it is commercially available product (the Bisphenol F types of liquid epoxy resin of other epoxy resin, epoxide equivalent is 160-175 g/eq, and number-average molecular weight is approximately 330, and is manufactured by Mitsubishi Chemical Corporation); " YR-450 " (epoxy resin of modified rubber, epoxide equivalent is 400-500 g/eq, number-average molecular weight is about 800-1000, and by Tohto Kasei Co., Ltd. manufactures) etc.The epoxy resin (C) using is in the present invention not limited to above epoxy resin, and can use other commercially available epoxy resin.
isocyanate compound (D-1)
Bottom coating composition of the present invention comprises isocyanate compound (D-1) as curing agent.Isocyanate compound (D-1) comprises polyfunctional isocyanate compound, the for example trimer of the dimer of aliphatic series, the aliphatic series that contains aliphatic series, alicyclic and aromatic group or aromatic diisocyanates, vulcabond, vulcabond (preferably, isocyanurate type isocyanates (so-called isocyanuric acid ester)).Such isocyanate compound can be so-called asymmetric type.
Vulcabond comprises, for example, comprises 5-24 carbon atom, preferably the vulcabond of 6-18 carbon atom.Vulcabond comprises, for example, and trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl cyclohexane vulcabond, hendecane vulcabond (1,11), lysine ester vulcabond, cyclohexane-1,3-vulcabond and cyclohexane-Isosorbide-5-Nitrae-vulcabond, 1-isocyano-3-isocyano methyl-3,5,5-trimethyl-cyclohexane (IPDI: IPDI), 4,4 '-bis-isocyanos two encircle methane, ω, ω '-dipropyl ether vulcabond, sulfo-dipropyl vulcabond, cyclohexyl-Isosorbide-5-Nitrae-vulcabond, dicyclohexyl methyl hydride-4,4 '-vulcabond, 1,5-dimethyl-2, two (isocyano methyl) benzene of 4-, 1,5-trimethyl-2, two (ω-isocyano ethyl) benzene of 4-, 1,3,5-trimethyl-2, two (isocyano methyl) benzene of 4-, 1,3,5-triethyl group-2, two (isocyano methyl) benzene of 4-, dicyclohexyl dimethylmethane-4,4 '-vulcabond etc.In addition, also can use aromatic diisocyanates, for example 2,4-bis-isocyano toluene and/or 2,6-, bis-isocyano toluene, 4,4 '-bis-isocyano diphenyl methanes and Isosorbide-5-Nitrae-bis-isocyano cumene.
Above-mentioned isocyanurate type isocyanates can comprise the trimer of above-mentioned vulcabond.
Isocyanate compound can be used alone, and can use the mixture of two or more isocyanates.
It is the compound of isocyanurate type isocyanate compound that isocyanate compound (D-1) is preferably wherein at least a portion isocyanate compound.In addition, in the present invention, above-mentioned isocyanurate type isocyanate compound also can be used as with the mixture of the aliphatic series that contains other aliphatic series, alicyclic and aromatic group or aromatics polyfunctional isocyanate compound (preferably vulcabond) combination and uses.In this case, in the total amount of isocyanate compound (D-1), the content ratio of preferred above-mentioned isocyanurate type isocyanate compound is 60% quality or more.
With respect to the sum 1 that is included in the hydroxyl in above-mentioned film-forming resin, the content of isocyanate compound in above-mentioned film-forming resin (D-1) is preferably the isocyanate groups of 0.5-1.5 in isocyanate compound (D-1).When the sum 1 with respect to being included in the hydroxyl in above-mentioned film-forming resin, the quantity that the content of isocyanate compound (D-1) is isocyanate groups during lower than 0.5 amount, is solidified not enough.In the time that the quantity of isocyanate groups exceedes 1.5, the pliability of coating reduces and coating is easily peeled off by impacting.
In addition,, in the time not comprising mylar (B-1), film-forming resin is the combination of acrylic resin (A-1) and epoxy resin (C).
surface conditioner (E-1)
Except film-forming resin and curing agent, bottom coating composition of the present invention also comprises surface conditioner (E-1).Add surface conditioner (E-1) for controlling and the affinity of top coat.By making the capillary difference of bottom coating composition and topcoat compositions in preset range mentioned below, make to wet-mode of wetting is coated with effectively.
Surface conditioner (E-1) can be two types or more kinds of, and one of can comprise in acrylic acid surface conditioner and silicone surface conditioning agent at least.Acrylic acid surface conditioner comprises acrylic copolymer, for example BYK352, BYK392, BYK358N (they are manufactured by BYK Japan K.K.), DISPERLON LC-900 and DISPERLON LC-951 (being manufactured by Kusumoto Chemicals Ltd.), as commercially available product.Silicone surface conditioning agent comprises the poly-methyl alkyl siloxane of polyether-modified siloxanes, polyester modification, polyether-modified dimethyl silicone polymer, the polyether-modified dimethyl silicone polymer that contains acrylic acid groups etc., the commercially available product that obtains of for example BYK331, BYK306, BYK323 and BYK325 (they are manufactured by BYK Japan K.K.).By using surface conditioner, the capillary value of coating composition can be adjusted to preferred scope.Capillary value (the γ of preferred undercoat composition
1) within the scope of 25-30 mN/m.
In this manual, the surface tension of coating composition can utilize the ring method of platinum loop to measure by use.Surface tension can be by being used for example DYNOMETER (Germany, BYK Gardner Inc.) to measure.
Surface conditioner (E-1) preferably hexane tolerance is not less than 150 ml.Measure the hexane tolerance of surface conditioner according to following methods: the 0.5 g surface conditioner of weighing, and be placed in glass beaker, add wherein subsequently acetone, to dissolve surface conditioner.Then, titration hexane, and measure by limiting the point that solution becomes white opacity.The hexane tolerance of surface conditioner (E-1) can more preferably be not less than 200 ml.When hexane tolerance is during lower than 150ml, owing to lacking wetting to material, appearance of coat can be deteriorated.
With 0.01-10% quality, and preferably the amount of 0.1-3% quality comprises surface conditioner (E-1), based on the solid content of film-forming resin in bottom coating composition.When it is during lower than 0.01% quality, the wetting property on base material to be coated is deteriorated, and degraded appearance.On the other hand, in the time that it is greater than 10% quality, can not preventing layer mix, and appearance degradation.
In addition,, in the time not comprising mylar (B-1), film-forming resin is acrylic resin (A-1) and epoxy resin (C).
For the solid content ratio that is included in acrylic resin (A-1), mylar (B-1), epoxy resin (C), isocyanate compound (D-1) and surface conditioner (E-1) in bottom coating composition, setting total amount is 100% quality, in view of water proofing property, anticorrosion character and the finishing character of coating, preferably can preferably contain the acrylic resin (A-1) of 25-50% quality.In view of the durability of coating machinability and coating, preferably contain the mylar (B-1) of the amount of 5-30% quality.In view of anticorrosion character, crack produce and with the cohesive of base material to be coated, also preferably contain the epoxy resin (C) of the amount of 5-25% quality.In addition,, in view of curing properties and scratching resistent property, preferably contain the isocyanate compound (D-1) of the amount of 20-50% quality.In view of wettability and the inhibition of the base material to be coated (are oozed out by oozing out on coating surface; Components dissolved and arrive the phenomenon outside top coat) open defect that causes, preferably contain the surface conditioner (E-1) of the amount of 0.01-5% quality.
In the time not comprising mylar (B-1), setting is included in the acrylic resin (A-1) in bottom coating composition, epoxy resin (C), the total solid content ratio of isocyanate compound (D-1) and surface conditioner (E-1) is 100% quality, in view of above-mentioned reason, preferably contain the acrylic resin (A-1) of the amount of 25-70% quality, the epoxy resin (C) of the amount that contains 5-30% quality, the isocyanate compound (D-1) of the amount that contains 20-60% quality, and the surface conditioner of the amount that contains 0.01-5% quality (E-1).
pigment (F-1)
Bottom coating composition of the present invention preferably comprises pigment (F-1).Pigment can be those that are generally used for coatings art, and comprise, for example, filler pigments, for example talcum, clay, calcium carbonate, magnesium carbonate, barium sulfate, silicic acid, silicate, hydrated alumina, calcium sulfate, gypsum, micaceous iron oxide (MIO), glass flake, suzorite mica and clarite mica; Colored pigment, for example titanium dioxide, carbon black, zinc white, blacklead, zinc sulphide, zinc oxide (zinc flower), chromium oxide, yellow NiTi, yellow chromium titanium, yellow ferric oxide, red ferric oxide, Black Rouge, phthalocyanine blue, phthalocyanine green, ultramarine blue, quinacridone, azo red pigment and azophosphine pigment; Corrosion-inhibiting pigment, such as zinc molybdate, molybdic acid aluminium, zinc powder (Zn), trbasic zinc phosphate and aluminium powder (A1) etc.About filler pigments, colored pigment and corrosion-inhibiting pigment, corresponding one can be used alone and use capable of being combined two or more.
Preferably, in bottom coating composition, comprise one or more corrosion-inhibiting pigments and one or more filler pigments.Existence comprises that these pigment are to improve the advantage of coating performance, and the anticorrosion of the duplex coating that for example obtained and weatherability and coating are covered character, and obtain the excellent appearance of coating.
In the situation that bottom coating composition contains pigment (F-1), be included in the pigment volume concentration (PVC) (PVC of the pigment (F-1) in coating composition
1) can be preferably in 10-40% scope.As (PVC
1) while being greater than 40%, the viscosity of coating composition can improve, and coating machinability can reduce.
In this manual, PVC " pigment volume concentration (PVC) " refers to the percent by volume (%) of pigment in the total amount that is contained in all resin Compositions in coating composition and all pigment.
In this manual, for the proportion of pigment that calculates pigment volume concentration based at " material of paint handbook (Handbook of Painting Materials) ", sixth version, the explanation of describing in Japan paint Manufactures Association.The proportion of resin is temporarily set as 1.
If needed, bottom coating composition of the present invention can comprise the various additives beyond above-mentioned additive.About various additives, can relate to organic solvent, sinking inhibitor, sedimentation inhibitor, curing catalysts (organo-metallic catalyst), anti-look dispersant, dispersant, defoamer, viscosity modifier (thickener), levelling agent, play creme, ultra-violet absorber, antioxidant, plasticizer, film forming agent etc.
About organic solvent, can comprise those that are usually used in type of solvent coating.Solvent comprises, for example, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, Solvesso 100, Solvesso 150 and Solvesso 200 (by ExxonMobil Chemical Co., Ltd. manufactures), toluene, dimethylbenzene, methoxyl group butylacetic acid ester, cellosolve acetate, butylacetic acid cellosolve, methyl acetate, ethyl acetate, butyl acetate, benzinum, naphtha etc.
The content of organic solvent without particular limitation of, but preferably to consider that environmental protection in recent years and the amount of environmental load are used.
Sinking inhibitor and sedimentation inhibitor preferably include, for example, and " DISPERLON 6700 " (trade name; Aliphatic series bisamide thixotropic agent, is manufactured by Kusumoto Chemicals Ltd.).About above-mentioned anti-look dispersant, can for example preferably use " DISPERLON 2100 " (trade name; Aliphatic series polyvalent carboxylic acid, wherein adds silicone, is manufactured by Kusumoto Chemicals Ltd.).About above-mentioned defoamer, can for example preferably use " DISPERLON 1950 " (trade name; Specific polyvinyl, is manufactured by Kusumoto Chemicals Ltd.).
topcoat compositions
Topcoat compositions of the present invention comprises the film-forming resin that contains acrylic resin (A-2) and mylar (B-2), the curing agent that contains isocyanate compound (D-2) and surface conditioner (E-2).
Acrylic resin (A-2) can be included in the acrylic resin (A-1) of describing in above-mentioned bottom coating composition, and mylar (B-2) also can be included in the mylar (B-1) of describing in above-mentioned bottom coating composition.Isocyanate compound (D-2) can be included in the isocyanate compound (D-1) of describing in above-mentioned bottom coating composition.Being included in above-mentioned film-forming resin in bottom coating composition and topcoat compositions and curing agent can be identical and can be different.In addition, as mentioned above, the situation that does not comprise mylar (B-2) is also in the scope of topcoat compositions, and this topcoat compositions is for the method for formation duplex coating of the present invention.
Surface conditioner (E-2) needs controlled surface tension, as mentioned below.Therefore, surface conditioner (E-2) is not identical with surface conditioner (E-1).But surface conditioner (E-1) and component type (E-2) can be identical.Surface conditioner (E-2) can comprise two or more surface conditioners.Surface conditioner (E-2) one of contains in silicone surface conditioning agent and fluorinated surface conditioning agent at least.Silicone surface conditioning agent can be identical with surface conditioner (E-1).Fluorinated surface conditioning agent comprises, for example, the oligomer that contains perfluoroalkyl, for example, commercially available component, such as BYK 340 (being manufactured by BYK Japan K.K.), Megafac F-443 and F-470 (being manufactured by DIC Corporation) etc.By using surface conditioner, can be in the surface tension of preferred range regulation coating composition.The capillary value (γ 2) of preferred top coat composition is within the scope of 20-25 mN/m.
By compatibly using above-mentioned surface conditioner etc., can be in the capillary value (γ 2) of preferred range regulation topcoat compositions.The various additives that can be used for bottom coating composition also can be used for topcoat compositions.
In the present invention, preferred value △ γ (γ
1-γ
2) be 2-8 mN/m, wherein from the capillary value (γ of bottom coating composition
1) in deduct the capillary value (γ of topcoat compositions
2).In the present invention, preferred value △ γ (γ
1-γ
2) in 2-8 mN/m scope, namely, γ
1be greater than γ
2, and value △ γ (γ
1-γ
2) in 2-8 mN/m scope.△ γ on duty during lower than 2 mN/m, in the time of wet-wet mode painting bottom coating composition and topcoat compositions, can produce layer and mix, and can produce priming coat and top coat reversing.In addition, on the surface of coating, can produce upset.On the other hand, when △ γ on duty exceedes 8 mN/m, on the superficial layer of the duplex coating obtaining in wet-wet mode painting bottom coating composition and topcoat compositions, can produce and ooze out.More preferably △ γ (γ
1-γ
2) be 3-6 mN/m.
Surface conditioner (E-2) preferably hexane tolerance is 50-150 ml, more preferably 70-120 ml.In the time that hexane tolerates lower than 50ml, owing to oozing out, can produce appearance degradation on superficial layer.In the time that hexane tolerance is greater than 150 ml, owing to lacking the control of interstratification, can produce appearance degradation.
Can preferably contain 0.01-10% quality, the preferably surface conditioner (E-2) of the amount of 0.1-3% quality, based on the solid content of film-forming resin in topcoat compositions.When it is during lower than 0.01% quality, can not mix by key-course, and degraded appearance.On the other hand, in the time that it is greater than 10% quality, by oozing out on superficial layer, appearance degradation.
In the time not comprising mylar (B-2), film-forming resin can be preferably acrylic resin (A-2).
With respect to the sum 1 that is included in the hydroxyl in above-mentioned film-forming resin, preferably contain the isocyanate groups of 0.5-1.5 at isocyanate compound (D-2) for the isocyanate compound (D-2) of above-mentioned film-forming resin.When the sum 1 with respect to being included in the hydroxyl in above-mentioned film-forming resin, the quantity that the content of isocyanate compound (D-2) is isocyanate groups during lower than 0.5 amount, be mustn't go to enough solidifying.In the time that the quantity of isocyanate groups exceedes 1.5, the pliability of coating reduces, and coating is easily peeled off by impacting.In the time not comprising mylar (B-1), film-forming resin can be preferably acrylic resin (A-2).
About the solid content ratio that is included in acrylic resin (A-2), mylar (B-2), isocyanate compound (D-2) and surface conditioner (E-2) in topcoat compositions, setting total amount is 100% quality, in view of weatherability, coating machinability and the curing properties of coating, preferably preferably contain the acrylic resin (A-2) of the amount of 30-60% quality, the more preferably amount of 35-55% quality.In view of the intensity of coating machinability, weatherability and coating, preferably contain the mylar (B-2) of the amount of 5-35% quality, more preferably 5-30% quality.In view of curing properties and scratching resistent property, preferably contain the isocyanate compound (D-2) of the amount of 20-50% quality, more preferably 25-45% quality.In view of the wettability on priming coat and suppress by oozing out the open defect causing on coating surface, preferably contain the surface conditioner (E-2) of the amount of 0.01-5% quality.
In the time not comprising mylar (B-2), the total solid content ratio that setting is included in acrylic resin component (A-2), isocyanate compound (D-2) and surface conditioner (E-2) in topcoat compositions is 100% quality, preferably contain the acrylic resin (A-2) of the amount of 30-70% quality, the isocyanate compound (D-2) of the amount that contains 20-60% quality, and the surface conditioner of the amount that contains 0.01-5% quality (E-2).
In addition, topcoat compositions can comprise the various additives (for example, organic solvent, curing catalysts, sinking inhibitor and sedimentation inhibitor, viscosity modifier, ultra-violet absorber etc.) that can be included in bottom coating composition.
Topcoat compositions of the present invention can preferably contain pigment (F-2).The instantiation of pigment (F-2) also can be included in the pigment (F-1) of describing in above-mentioned bottom coating composition.
In the situation that topcoat compositions contains pigment (F-2), be included in the pigment volume concentration (PVC) (PVC of the pigment (F-2) in coating composition
2) can be preferably in 10-35% scope.
As (PVC
2) while being greater than 35%, the viscosity of coating composition can improve, and coating machinability can reduce.
In the present invention, value △ PVC (PVC
1-PVC
2) be preferably-2 to 8 %, wherein from being included in the pigment volume concentration (PVC) (PVC of the pigment (F-1) described bottom coating composition
1) deduct the pigment volume concentration (PVC) (PVC of the pigment (F-2) being included in topcoat compositions
2).In the present invention, the value △ PVC (PVC in-2 to 8% scopes
1-PVC
2) PVC is provided
1and PVC
2approximation, this can provide in the good membranes outward appearance that forms the decline of the internal stress difference producing when duplex coating and available duplex coating can be provided.△ PVC (PVC on duty
1-PVC
2) while being greater than 8%, film appearance degradation, for example, can produce wrinkling in wet-wet mode painting bottom coating composition and topcoat compositions.Value △ PVC (PVC
1-PVC
2) can be more preferably in-1 to 5% scope.
Term " wrinkling " refers to wrinkling holiday in a part of duplex coating surface.This defect seems to produce by the rate of drying difference of distortion and priming coat and top coat.
the method of duplex coating
Duplex coating of the present invention can form by the following method: described method comprises the step that forms wet priming coat, by be coated with above-mentioned bottom coating composition on base material to be coated; Form the step of top coat, wherein on obtained wet priming coat, be coated with above-mentioned topcoat compositions by wet-wet mode, to form wet top coat; And drying steps, wherein by simultaneously dry to obtained wet priming coat and wet top coat.
base material to be coated
In the formation method of duplex coating of the present invention, base material to be coated comprises, for example, and metal base, for example iron, zinc, tin, copper, titanium, sheet metal and galvanized iron.Base material can be used the plating such as zinc, copper, chromium, and its usable surface inorganic agent (for example chromic acid, trbasic zinc phosphate or zirconates) surface treatment.The method of formation duplex coating of the present invention can be preferred for having large thermal capacitance and the metal base to the insufficient heat transfer of base material.Base material to be coated comprises, for example, the machine of construction machine (for example, bull-dozer, scraper, hydraulic crawler excavator, excavator), carrying machine (truck (track), trailer etc.), crane and load and not load, for the machine (diesel engine hammer, fluid operated hammer etc.) of foundation construction, for the machine (ball winder, roller etc.) of tunnel construction; The photoelectricity that general industry is alleged and such as heavy vehicles of heavy electrical apparatus, farming machine, steel systeming equipment, machine tools and industrial machine and almost can not be by heating heated base material with high heat capacity etc.The method of formation duplex coating of the present invention can be preferred for coating to be had high heat capacity and almost can not pass through heating and heated construction machine and industrial machine.
The method of painting bottom coating composition and topcoat compositions without particular limitation of, and can relate to and be generally used for following coating process: for example, dipping, brush, roller, roll coater, aerial spraying, airless spraying, curtain stream coating machine, roll-in curtain coater, die head coating machine, electrostatic applications etc.Wherein, preferred aerial spraying, airless spraying and curtain stream coating machine.These can compatibly be selected according to the purposes of base material to be coated and shape.
The preferably coating of the amount within the scope of 10-100 μ m with dry coating thickness of bottom coating composition, and the further preferably coating of the amount within the scope of 15-70 μ m with dry coating thickness.Forming like this after wet priming coat, can be coated with (wet-wet mode is coated with) topcoat compositions.In view of operating efficiency, under room temperature (5-35 ℃), after the wet priming coat of formation, be preferably 0-60 minute until be coated with the coating interval of topcoat compositions, more preferably 1-30 minute, further preferred 1-15 minute.In the time using the method for formation duplex coating of the present invention, can obtain the good duplex coating of appearance of coat, even be coated with top coat under the state being dried hardly at priming coat.In addition, priming coat for example can exceeded, at the temperature of common room temperature (, 40-100 ℃, more preferably 40-80 ℃) to dry about 1-10 minute in advance, and topcoat compositions also can be coated with under the half-dried state of priming coat.
Topcoat compositions can be preferably take build wherein as the amount coating of 10-200 μ m, can be more preferably take build wherein as the amount coating of 20-100 μ m, most preferably 20-50 μ m.For example, by making their keep under room temperature (5-35 ℃) 1-10 days or by the temperature exceeding common room temperature (, 50-100 ℃, more preferably 60-80 ℃) lower force drying 15-60 minute, by dry to the wet priming coat obtaining like this and wet top coat, can obtain duplex coating.
The method of formation duplex coating of the present invention has advantages of such: even be coated with bottom coating composition and the topcoat compositions with different coating compositions by wet-wet mode, also can form the duplex coating with good appearance, and can not follow coating problem, for example layer mixes and is wrinkling.In addition,, by having the priming coat of the function that good anticorrosion character is provided and the top coat of function of the weatherability of providing being provided, the duplex coating being obtained by the method obtains good anticorrosion character, weatherability and coating physical property.The method of formation duplex coating of the present invention also has such characteristic: by wet-wet mode, can on the bottom coating composition of coating, be coated with topcoat compositions, and without heating and curing schedule and cooling step, and almost do not set interval time.Therefore, it has the following advantages: do not need to be provided for the firing equipment of cured base coating, the investment of coating apparatus can reduce, and application step can shorten.The method of formation duplex coating of the present invention is especially applicable to being coated with the base material extensive to be coated with large thermal capacitance, for example industrial machine or construction machine.
[embodiment]
Be described more specifically the present invention according to following examples, but the present invention is not limited to these embodiment.Unless otherwise indicated, otherwise in an embodiment " part " and " % " is based on quality.
production example 1 is produced acrylic resin 1
In being equipped with nitrogen induction pipe, agitator, temperature adjuster device, dropping funel and providing 1 liter of reaction vessel of cooling tube of decanter, pack 25 parts of dimethylbenzene and 10 parts of butyl acetates into, and be heated to 120 ℃ of temperature.Subsequently, in dropping funel, pack 16.0 parts of styrene, 1.0 parts of methacrylic acids, 23.0 parts of 2-Ethylhexyl Methacrylates, 25.0 parts of 2-EHAs, 35.0 parts of 2-hydroxyethyl methacrylates and 4 parts of t-butyl peroxy-2 ethyl hexanoic acid esters into as acrylic monomers, to prepare monomer solution.In the time making reaction vessel remain on 120 ℃, dropwise added monomer solution through 3 hours.After dropping, at 120 ℃, keep again 1 hour.The number-average molecular weight of the acrylic resin 1 obtaining is 2,500 (by gpc measurement, calculating according to polystyrene), and solid content hydroxy value is 180 mgKOH/g, and solid content acid number is 7 mgKOH/g, and solid content solid content concentration is 75%.
production example 2 is produced acrylic resin 2
Acrylic resin 2 is prepared as summary description in production example 1, and difference is that monomer becomes 52.3 parts of styrene, 1.3 parts of methacrylic acids, 36.1 parts of ethyl acrylates and 10.4 parts of 2-hydroxyethyl methacrylates.The number-average molecular weight of the acrylic resin 2 obtaining is 5,500 (by gpc measurements, the value of being changed by polystyrene), and solid content hydroxy value is 55 mgKOH/g, and solid content acid number is 7 mgKOH/g, and solid content concentration is 75%.
production example 3 is produced mylar 1
Be equipped with in 2 liters of reaction vessels of agitator, temperature adjuster device and cooling tube pack the DOPCP of 15.6 parts of M-phthalic acids, 21.8 parts of hexahydrophthalic acid anhydrides, 15.2 parts of neopentyl glycols, 18.0 parts of trimethylolpropanes, 6.1 parts of hydroxy new pentane acids into, 7.9 parts of Cardura E (are manufactured by Royal Dutch Shell PLC., have the glycidyl esters of the alkanecarboxylic acid (versatic acid) of side chain) and 15.4 parts of 6-caprolactones, subsequently heating.By with dimethylbenzene azeotropic vaporization, remove the water producing by reaction.Be heated to subsequently 190 ℃, from start reflux through approximately 2 hours.Continue to stir and dehydration, until be 8 corresponding to the acid number equivalent of carboxylic acid, and cessation reaction.Then, add wherein 16 parts of dimethylbenzene.The number-average molecular weight of the mylar 1 obtaining is 1,500 (by gpc measurement, the value of being changed by polystyrene), and solid content hydroxy value is 230 mgKOH/g, and solid content acid number is 8 mgKOH/g, and solid content concentration is 80%.
production example 4 is produced mylar 2
Mylar 2 is prepared as summary description in production example 1, difference be monomer become 45.6 parts of M-phthalic acids, 16.0 parts of neopentyl glycols, 5.2 parts of trimethylolpropanes, 12.0 part 1,6-hexylene glycol and 21.2 parts of 6-caprolactones.The number-average molecular weight of the mylar 2 obtaining is 4,200 (by gpc measurement, calculating according to polystyrene), and solid content hydroxy value is 54 mgKOH/g, and solid content acid number is 7 mgKOH/g, and solid content concentration is 80%.
production example 5 is produced the dispersion paste 1 that contains acrylic resin and pigment
215 parts of ACRYDIC A-859B (acrylic resins of mixture in dispersion cup, by Dainippon Ink and Chemicals, Incorporated (DIC Corporation) manufactures, solid content concentration is 75% quality, solid content hydroxy value is 130 mgKOH/g, and number-average molecular weight is 2, 100), 15 parts of amine dispersant B YK161 (are manufactured by BYK Japan K.K., solid content concentration is 30% quality), 9 parts of dispersant B YK110 (are manufactured by BYK Japan K.K, solid content concentration is 52% quality), 164 parts of titanium oxide pigments Ti-Pure R-706 are (by Du Pont Co., Ltd. manufacture), 1 part of carbon black Mitsubishi Carbon Black MA-100 (being manufactured by Mitsubishi Chemical Corporation), 111 parts of powdered whitings are (by MARUO CALCIUM CO., LTD. manufacture), 160 parts of trbasic zinc phosphate corrosion-inhibiting pigment LF BOUSEI ZP-DL (being manufactured by KIKUCHI COLOR & CHEMICALs CORPORATION), 64 parts of Solvesso 100 (registration marks, by ExxonMobil Co., Ltd. manufacture) and 60 parts of methoxy butyl acetates.Subsequently, pack bead into, and disperse, until particle diameter becomes 10 μ m or less, to obtain disperseing paste 1.
production example 6-10 produces and disperses paste 2-6
Disperse paste 2-5 to prepare as summary description in production example 5, difference is that the quantitative change of respective components is in the amount shown in the table 1 of mentioning below." organic yellow uitramarine " in table 1 is Hostaperm Yellow H3G (Clariant Japan K.K.).
[table 1]
production example 11 is produced bottom coating composition 1
In 799 parts of dispersion pastes that obtain, add 1,96 parts of EPICOAT #872 (bisphenol-A type of epoxy resin of 87 parts of mylar that obtain in production example 3 in production example 5, manufactured by Mitsubishi Chemical Corporation, solid content concentration is 75% quality, epoxide equivalent is 650g/eq) (manufactured by BYK Japan K.K. as epoxy resin and 8 parts of acrylic compounds surface conditioner BYK392, solid content concentration is 52% quality), and mix.Pack subsequently 204 parts of CORONATE HXLV (isocyanurate type isocyanate resins into, solid content concentration is 100% quality, by Nippon Polyurethane Industry Co., Ltd. manufacture, the isocyanurate type (trimer) of HDI) xylene solution (solid content concentration is 75%), making the sum of hydroxyl and the ratio of isocyanate groups that are included in acrylic resin and mylar (for film-forming resin) is 1:1, and stir, to obtain bottom coating composition 1.
Pigment volume concentration (PVC) (the PVC of bottom coating composition 1
1) be 25%, calculate by the proportion of pigment and other component used.
In addition, when using DYNOMETER (BYK Gardner Inc., Germany), while measurement by platinum loop method, the surface tension (γ of bottom coating composition 1
1) be 27.2 mN/m.
Weigh surface conditioner (0.5 g), and is placed in glass beaker, adds wherein subsequently acetone, to dissolve surface conditioner, then, titration hexane, the point that becomes white opacity by limiting solution is measured.The hexane tolerance of BYK 392 is 250 ml.
production example 12-20 produces bottom coating composition 2-10
Bottom coating composition 2-10 is prepared as summary description in production example 11, and difference is that the quantitative change of respective components is in the amount shown in the table 2 of mentioning below.As mentioned the surface tension (r of the bottom coating composition measuring in production example 11
1) and lamella length, the results are shown in table 2.
The epoxy resin 2 that is shown in the following table 2 of mentioning is EPICOAT #828 (bisphenol-A type of epoxy resin, is manufactured by Mitsubishi Chemical Corporation., and solid content concentration is 75% quality, and epoxide equivalent is 185g/eq).
Adopt the identical mode of describing in production example 11 to measure the hexane tolerance of BYK 3441, LC-900 and LC-951.BYK 3441 is 120 ml, and LC-900 is 300 ml, and LC-951 is 330 ml.
[table 2]
production example 21-30 production topcoat compositions 1-10
Topcoat compositions 1-10 is prepared as summary description in production example 11, and difference is that the quantitative change of respective components is in the amount shown in the table 3 of mentioning below.As summary description in production example 11, calculate the pigment volume concentration (PVC) (PVC of topcoat compositions 1-10
2).As summary description in production example 11, measure the surface tension (γ of topcoat compositions 1-10
2).The results are shown in table 3.Adopt the hexane tolerance that identical mode is measured BYK 322, BYK 306, BYK 331 and BYK 333 as mentioned above.BYK 322 is 120 ml, and BYK 306 is 90 ml, and BYK 331 is 85 ml, and BYK 333 is 100 ml.The topcoat compositions 2 of production example 22 does not have hexane tolerance data, because topcoat compositions does not comprise surface conditioner.
[table 3]
embodiment 1 forms duplex coating
The cold-rolled steel sheet JIS G 3141 (SPCC-SB) that is of a size of 0.8 × 70 × 150 mm uses dimethylbenzene degreasing.Subsequently, use airless spraying to be coated on the bottom coating composition 1 obtaining in production example 11, making build is 30 μ m-40 μ m, to form wet priming coat.Subsequently, at room temperature behind 3 minutes intervals, in the time that priming coat is hygrometric state, use airless spraying, be coated with by wet-wet mode, be coated on the topcoat compositions 1 obtaining in production example 21, making build is 30 μ m-40 μ m, to obtain wet top coat.Be allowed to condition under room temperature and keep after 10 minutes, by its at 80 ℃ dry 30 minutes (force drying), to obtain having the duplex coating of fixing build.Obtaining build is the film of two types of 60-80 μ m.
embodiment 2
As summary description in embodiment 1, obtain duplex coating, difference is, behind at room temperature 3 minutes intervals, obtained wet priming coat is dried to 2 minutes in advance at 80 ℃, is coated with subsequently topcoat compositions 1.
embodiment 3-14 and comparative example 1-4
As summary description in embodiment 1, obtain duplex coating, difference is, change the kind of bottom coating composition and topcoat compositions and after painting bottom coating composition, exist and do not exist dry in advance, as shown in table 4 and 5.
As summary description in embodiment 1, carry out comparative example 2, difference is, coating topcoat compositions 1 rather than bottom coating composition 1, and again apply topcoat compositions 1.
Above-mentioned embodiment and comparative example's duplex coating is carried out to the following evaluation of mentioning.Result is also shown in table 4 and 5.
the weatherability of accelerating
The weatherability test of accelerating, according to the xenon lamp method of describing in JIS K 5600-7-7, is waited meter SX2-75 (by Suga Test Instruments Co., Ltd. manufactures) by super xenon and is carried out.Measure the gloss number of coating after 500 hour testing time by multi-angle glossmeter GS-4K (by Suga Test Instruments Co., Ltd. manufactures), and before test, usage rate (gloss retention rate) is evaluated gloss number.When 60 ° of gloss numbers are 80% or when more gloss retention rate, be evaluated as and pass through.
anticorrosion character
Use cutter cross-cut duplex coating to reach the surface of base material, to form the cross-cut cut of length as 10 cm.According to the sprinkling method of testing for neutral brine patience of describing in JIS K 5600-7-1 (JIS Z 2371), spray test machine ST-11L (by Suga Test Instruments Co. by salt solution, Ltd. manufacture), salt solution is sprayed to test and carry out 240 hours.Subsequently, based on basis described below, visual valuation is apart from the generation of rust and the bubble of cross-cut part.
A: the rust of generation or the Breadth Maximum of bubble are less than 2 mm apart from cross-cut part.
B: the rust of generation or the Breadth Maximum of bubble are 2 mm or more and be less than 4 mm apart from cross-cut part.
C: the rust of generation or the Breadth Maximum of bubble are 4 mm or more apart from cross-cut part.
secondary bonding
Along the cross-cut for anticorrosion character, on the plate of coating, adhere to a slice glassine paper adhesive tape, peeled off subsequently, and measuring distance cross-cut peel off width.When peeling off width in 1 mm time, be evaluated as and pass through.
water proofing property
According to JIS K 5600-6-2, by sample submergence 96 hours in the water of 23 ℃, based on the basis of mentioning below, visual valuation.
A: there is no defect.
B: Partial Observation is to crack and peeling off.
C: major part is observed crack and peeled off.
layer mixed nature
Based on the basis of mentioning below, visual valuation is just being coated with after topcoat compositions, the outward appearance of wet duplex coating.
A: there is no defect.
B: observe part reversion and observe priming coat.
C: observe most of reversion and observe priming coat.
the outward appearance (wrinkling) of coating
Based on the basis of mentioning below, visual valuation is just being coated with after topcoat compositions, the outward appearance of wet duplex coating.
A: there is no defect.
B: observe a part wrinkling.
C: observe most of wrinkling.
the outward appearance (gloss) of coating
By multi-angle glossmeter GS-4K (by Suga Test Instruments Co., Ltd. manufactures), measure the gloss number (60 ° of gloss numbers) of the duplex coating obtaining.In the time that 60 ° of gloss numbers are 80 or more, be evaluated as and pass through, 85 or more be evaluated as good.
dust compatibility
Based on the basis of mentioning below, the state of the rough surface that visual valuation is caused by dust in the time of coating.
A: do not find rough surface.
B: extremely slightly find rough surface.
C: slightly find rough surface.
D: significantly find rough surface.
coating efficiency
Based on the basis of mentioning below, evaluate at the coating efficiency forming in duplex coating.
A: after coating bottom coating composition, there is no heating process, the process of for example preheating or heat cure, coating topcoat compositions.
B: after coating bottom coating composition preheating, coating topcoat compositions, condition is the process that this process does not comprise heat cure.
C: after the process of coating bottom coating composition and heat cure, coating topcoat compositions.
[table 4]
RT stands for room temperature
[table 5]
RT stands for room temperature
Each embodiment can form weatherability and secondary bonding, anticorrosion character and the good duplex coating of water proofing property.In addition, at priming coat and top coat, the score of the two embodiment 1-6 that comprises mylar in dust compatibility is A, and they are very good.
Comparative example 1 for wherein not comprising the experiment of acrylic resin in topcoat compositions.In this case, the outward appearance of coating (gloss) and weatherability are deteriorated.
Comparative example 2 be wherein topcoat compositions 1 as the experiment of bottom coating composition.In this case, because the △ γ (mN/m) between priming coat and top coat is zero, anticorrosion character is excessively deteriorated.
Comparative example 3 does not comprise the experiment of surface conditioner for topcoat compositions wherein.In this case, the △ γ (mN/m) between priming coat and top coat reduces (0.2), and layer mixed nature and dust compatibility are deteriorated.
Comparative example 4 is that the hexane tolerance of wherein bottom coating composition reduces the experiment of (120ml).In this case, layer mixed nature is deteriorated.
According to the present invention, be coated with by wet-wet mode, can form there is good appearance, good weatherability and the duplex coating of anticorrosion character.The duplex coating forming in the present invention also has the characteristic that can form without thermal cure step.Therefore, it has following industrial advantage: do not need to provide firing equipment, can reduce and application step can shorten for the investment of coating apparatus.The method that forms duplex coating is particularly suitable for being coated with the base material with extensive and large thermal capacitance, for example industrial machine and construction machine.
Claims (8)
1. form a method for duplex coating, described method comprises:
Form the step of priming coat, wherein painting bottom coating composition on base material to be coated, to form wet priming coat,
Form the step of top coat, wherein on obtained wet priming coat, be coated with topcoat compositions by wet-wet mode, to form wet top coat, and
Dry step, wherein by simultaneously dry to obtained wet priming coat and wet top coat, to form duplex coating,
Wherein said bottom coating composition comprises:
Film-forming resin, comprises acrylic resin (A-1) and epoxy resin (C),
Curing agent, comprise isocyanate compound (D-1) and
Surface conditioner (E-1),
The solid content ratio of acrylic resin (A-1), epoxy resin (C), isocyanate compound (D-1) and surface conditioner (E-1) is: the acrylic resin (A-1) of 25-70% quality, the epoxy resin (C) of 5-30% quality, the isocyanate compound (D-1) of 20-60% quality and the surface conditioner (E-1) of 0.01-5% quality
Described topcoat compositions comprises:
Film-forming resin, comprises acrylic resin (A-2),
Curing agent, comprise isocyanate compound (D-2) and
Surface conditioner (E-2),
The solid content ratio of acrylic resin (A-2), isocyanate compound (D-2) and surface conditioner (E-2) is: the surface conditioner (E-2) of the acrylic resin (A-2) of 30-70% quality, the isocyanate compound (D-2) of 20-60% quality and 0.01-5% quality, and
Value △ γ (γ
1-γ
2) be 2-8 mN/m, this value representation is from the capillary value (γ of described bottom coating composition
1) in deduct the capillary value (γ of described topcoat compositions
2).
2. the method for the formation duplex coating of claim 1, wherein the two solid content hydroxy value of acrylic resin (A-1) and acrylic resin (A-2) is 50-250 mgKOH/g, and the epoxide equivalent of epoxy resin (C) is 100-1000 g/eq.
3. the method for the formation duplex coating of claim 1 or 2, the described film-forming resin being wherein included in described bottom coating composition also comprises mylar (B-1),
The solid content ratio of acrylic resin (A-1), mylar (B-1), epoxy resin (C), isocyanate compound (D-1) and surface conditioner (E-1) is: epoxy resin (C), the isocyanate compound (D-1) of 20-50% quality and the surface conditioner (E-1) of 0.01-5% quality of the acrylic resin (A-1) of 25-50% quality, the mylar (B-1) of 5-30% quality, 5-25% quality
The described film-forming resin being included in described topcoat compositions also comprises mylar (B-2), and
The solid content ratio of acrylic resin (A-2), mylar (B-2), isocyanate compound (D-2) and surface conditioner (E-2) is the acrylic resin (A-2) of 30-60% quality, mylar (B-2), the isocyanate compound (D-2) of 20-50% quality and the surface conditioner (E-2) of 0.01-5% quality of 5-35% quality.
4. the method for the formation duplex coating of claim 3, wherein the two solid content hydroxy value of mylar (B-1) and mylar (B-2) is 80-350 mgKOH/g.
5. the method for the formation duplex coating of any one in claim 1-4, wherein the tolerance of the hexane of surface conditioner (E-1) is not less than 150 ml, and the hexane of surface conditioner (E-2) tolerates in 50-150 ml scope.
6. the method for the formation duplex coating of any one in claim 1-5, wherein said surface conditioner (E-1) comprises acrylic acid surface conditioner and silicone surface conditioning agent one of at least, and surface conditioner (E-2) comprises silicone surface conditioning agent and fluorinated surface conditioning agent one of at least.
7. the method for the formation duplex coating of any one in claim 1-6, be wherein 0-60 minute the interval time between the operation of the coating in the step that forms described priming coat and the operation of the coating in the step that forms described top coat.
8. the method for the formation duplex coating of any one in claim 1-7, wherein said base material to be coated is construction machine or industrial machine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011176649 | 2011-08-12 | ||
| JP2011-176649 | 2011-08-12 | ||
| PCT/JP2012/070350 WO2013024784A1 (en) | 2011-08-12 | 2012-08-09 | Method for forming multilayer coating film |
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| CN103906577A true CN103906577A (en) | 2014-07-02 |
| CN103906577B CN103906577B (en) | 2015-11-25 |
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| JP (1) | JP5221822B1 (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980804A (en) * | 2013-02-07 | 2014-08-13 | 日本油漆株式会社 | Method for forming dual-layer coating |
| CN107817539A (en) * | 2016-09-13 | 2018-03-20 | 迎辉科技股份有限公司 | Quantum dot thin film and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI626999B (en) * | 2014-09-25 | 2018-06-21 | Fujifilm Corp | Method of manufacturing pattern forming body |
| JP6125125B1 (en) * | 2016-07-08 | 2017-05-10 | 関西ペイント株式会社 | Multi-layer coating formation method |
| JP6138323B1 (en) | 2016-07-13 | 2017-05-31 | 関西ペイント株式会社 | Multi-layer coating formation method |
| JP7433853B2 (en) * | 2019-11-19 | 2024-02-20 | トヨタ自動車東日本株式会社 | Formation method of multi-layer coating and multi-layer coating |
| JP7101715B2 (en) * | 2020-03-31 | 2022-07-15 | 大日本塗料株式会社 | Laminated coating and its manufacturing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62258782A (en) * | 1986-04-30 | 1987-11-11 | Nippon Paint Co Ltd | Formation of composite layered film |
| JPH0657177A (en) * | 1992-08-05 | 1994-03-01 | Nippon Paint Co Ltd | Transparent anticorrosive thick-coating composition, and method for forming transparent coating film |
| JPH06190335A (en) * | 1992-12-24 | 1994-07-12 | Nippon Steel Corp | Preparation of coated metal sheet with high vividness |
| JPH09299873A (en) * | 1996-05-15 | 1997-11-25 | Toyota Motor Corp | Patterned coating film formation |
| JP2002241674A (en) * | 2001-02-20 | 2002-08-28 | Nippon Paint Co Ltd | Rust-proofing primer coating composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6031858A (en) * | 1983-07-29 | 1985-02-18 | Nippon Oil & Fats Co Ltd | Formation of paint film from aqueous paint |
| JPS63310673A (en) * | 1987-06-10 | 1988-12-19 | Kansai Paint Co Ltd | Formation of paint film |
| JPH06262131A (en) * | 1993-03-09 | 1994-09-20 | Sumitomo Metal Ind Ltd | Coating method |
-
2012
- 2012-08-09 WO PCT/JP2012/070350 patent/WO2013024784A1/en active Application Filing
- 2012-08-09 CN CN201280050091.9A patent/CN103906577B/en active Active
- 2012-08-09 JP JP2012550648A patent/JP5221822B1/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62258782A (en) * | 1986-04-30 | 1987-11-11 | Nippon Paint Co Ltd | Formation of composite layered film |
| JPH0657177A (en) * | 1992-08-05 | 1994-03-01 | Nippon Paint Co Ltd | Transparent anticorrosive thick-coating composition, and method for forming transparent coating film |
| JPH06190335A (en) * | 1992-12-24 | 1994-07-12 | Nippon Steel Corp | Preparation of coated metal sheet with high vividness |
| JPH09299873A (en) * | 1996-05-15 | 1997-11-25 | Toyota Motor Corp | Patterned coating film formation |
| JP2002241674A (en) * | 2001-02-20 | 2002-08-28 | Nippon Paint Co Ltd | Rust-proofing primer coating composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980804A (en) * | 2013-02-07 | 2014-08-13 | 日本油漆株式会社 | Method for forming dual-layer coating |
| CN103980804B (en) * | 2013-02-07 | 2016-08-24 | 日涂工业涂料有限公司 | The method forming duplex coating |
| CN107817539A (en) * | 2016-09-13 | 2018-03-20 | 迎辉科技股份有限公司 | Quantum dot thin film and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5221822B1 (en) | 2013-06-26 |
| CN103906577B (en) | 2015-11-25 |
| WO2013024784A1 (en) | 2013-02-21 |
| JPWO2013024784A1 (en) | 2015-03-05 |
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