CN103906577B - Form the method for multilayer coating film - Google Patents
Form the method for multilayer coating film Download PDFInfo
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- CN103906577B CN103906577B CN201280050091.9A CN201280050091A CN103906577B CN 103906577 B CN103906577 B CN 103906577B CN 201280050091 A CN201280050091 A CN 201280050091A CN 103906577 B CN103906577 B CN 103906577B
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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
Abstract
Provide a kind of method, object to be coated can be suitably thus the multilayer coating film that both anticorrosive property and weatherability are all excellent is provided.Method for the formation of multilayer coating film comprises: primary coat tunic forming step, wherein applies bottom coating composition on object to be coated, forms undried primary coat tunic; Top coat film forming step, wherein in wet-wet process, applies topcoat compositions, forms undried top coat film on obtained undried primary coat tunic; And drying steps, wherein by obtained undried primary coat tunic and the drying simultaneously of undried top coat film, form multilayer coating film; Method wherein for the formation of multilayer coating film applies to limit to difference capillary between primary coat tunic and top coat film.
Description
Technical field
The present invention relates to a kind of method forming duplex coating, described method applies bottom coating composition and topcoat compositions by wet-wet mode (wet-on-wet).
Background of invention
Industrial machine and construction machine have following characteristic: they are generally extensive and form by construction substrate (steel substrate) is thick, and its thickness is very thick compared with car body etc., to bear heavy load.Therefore, when such industrial machine and construction machine are used as base material to be coated, they have thermal capacitance high and in heated oven the insufficient problem being delivered to them of heat.According to above-mentioned reason, the thermosetting type coating composition being generally used for being coated with car body is not suitable for industrial machine and construction machine.They are usually used in and are such as coated with lower than the coating composition that can form solidified coating at the temperature of 100 DEG C.
JP2003-226839A [PTL1] discloses a kind of coating composition, described composition comprises: (A), containing resin based on the resin of hydroxyl, (B) polyisocyanate compounds as curing agent and (C) organo-tin compound as carbamate curing catalysts, wherein phosphate group is present in (claim 1 of PTL1 etc.) in the component comprised in the composition.Which depict this coating composition excellent with finishing properties at dry property, and pot life extends.Such as, generally speaking, in the coating composition for industrial machine and construction machine, at the middle cured with isocyanates types of coatings composition described of JP2003-226839A [PTL1] through coating repeatedly (2 times), to improve anticorrosion character etc.But when using coating composition, said composition does not provide the film of the coating with enough anticorrosion character and weatherability, even if carried out twice by painting work.
As forming the method meeting the coating of both anticorrosion character and weatherability, following methods can be considered: wherein the coating composition of anticorrosion good properties is used as bottom coating composition, uses the topcoat compositions that weatherability is excellent subsequently.Such as, JP2010-188239A [PTL2] discloses a kind of method forming thick film type erosion shield, wherein epoxy resin paint (A) of Weak solvent type high solid modification is containing binder resin component, described binder resin component comprises: (wherein epoxy equivalent weights is 400-2000g/eq to the epoxy resin of (a) modification, gross mass based on binder resin component), (b) polyimide resin and (c) reactive diluent, and Weak solvent type high solid polyurethane resin paint (B) is containing binder resin component, described binder resin component comprises: (d) hydroxyl value is polyol resin and (e) polyisocyanate resin of 10-100mgKOH/g, by epoxy resin (A) the primary coat cloth of high solid modification, subsequently by high solid polyurethane resin paint (B) top coating (claim 1).Also describe in PTL2 and can obtain anticorrosion ability by the method for corresponding one deck priming coat and one deck top coat and be equal to anticorrosion character by obtaining more than the typical bilayer coating be once coated with.But the method described in JP2010-188239A 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.
There is the coating process being called wet-wet mode, the method can shorten application step, and way first applies bottom coating composition to form priming coat, applies topcoat compositions subsequently to form top coat and moist priming coat, drying two coatings while of then.But when bottom coating composition and topcoat compositions are coated with by wet-wet mode, it has two wet coating layer mixing and the problem of the appearance degradation of coating.In wet-wet mode is coated with, may produce coating problem once in a while, such as, shrink, this causes the delay of the volatile component be included in priming coat to be evaporated, this priming coat is present in below top coat, because top coat contacts with the air opened wide and drying more Zao than priming coat.Therefore, when use is not the coating composition of thermoset coating composition, does not also set up up to now and be successfully coated with dissimilar bottom coating composition and the method for topcoat compositions by wet-wet method.
[reference listing]
[patent document]
[PTL1]JP2003-226839A
[PTL2]JP2010-188239A
Summary of the invention
An object of the present invention is the problem solving above-mentioned prior art and application.Particularly, the object of this invention is to provide a kind of method being coated with the excellent duplex coating of both formation anticorrosion character and weatherability by wet-wet mode, after painting bottom coating composition, there is no a lot of interval times, and greatly can shorten application step.
The invention provides a kind of method forming 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 obtained wet priming coat and the drying simultaneously of 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 2-8mN/m, this value represents the capillary value (γ from 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 50-250mgKOH/g, and the epoxide equivalent of epoxy resin (C) can be preferably 100-1000g/eq.
The described film-forming resin be included in described bottom coating composition preferably can 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: the surface conditioner (E-1) of the acrylic resin (A-1) of 25-50% quality, the mylar (B-1) of 5-30% quality, the epoxy resin (C) of 5-25% quality, the isocyanate compound (D-1) of 20-50% quality and 0.01-5% quality
The described film-forming resin be included in described topcoat compositions preferably can 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 surface conditioner (E-2) of the acrylic resin (A-2) of 30-60% quality, the mylar (B-2) of 5-35% quality, the isocyanate compound (D-2) of 20-50% quality and 0.01-5% quality.
In addition, the two solid content hydroxy value of mylar (B-1) and mylar (B-2) can be preferably 80-350mgKOH/g.
In addition, the hexane tolerance of surface conditioner (E-1) is not less than 150ml, and the tolerance of the hexane of surface conditioner (E-2) is in 50-150ml scope.
In addition, described surface conditioner (E-1) preferably can comprise acrylic surface conditioning agent and silicone surface conditioning agent one of at least, and surface conditioner (E-2) preferably can comprise silicone surface conditioning agent and fluorinated surface conditioning agent one of at least.
Especially, the painting work in the step forming described priming coat and the interval time between the painting work in the step forming described top coat can be preferably 0-60 minute.
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, there is excellent weatherability and the duplex coating both anticorrosion character and be coated with by wet-wet mode and formed.The duplex coating formed by the present invention also has such characteristic: after painting bottom coating composition, can be coated with topcoat compositions, does not have thermal cure step and does not have a lot of interval times.Therefore, it has the following advantages: there is no need for the firing equipment heating priming coat, the investment of coating apparatus can reduce, and application step can shorten greatly.It is large and have the base material to be coated of large thermal capacitance, such as industrial machine and construction machine that the method for formation duplex coating of the present invention is especially applicable to coating scale.
DESCRIPTION OF THE PREFERRED
Method for the formation of duplex coating of the present invention comprises the following steps: the step forming priming coat, and wherein painting bottom coating composition, to form wet priming coat; Form the step of top coat, be wherein coated with topcoat compositions, to form wet top coat by wet-wet mode; With the step of drying, wherein by obtained wet priming coat and the drying simultaneously of 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).
Usual above-mentioned mylar (B-1) and above-mentioned mylar (B-2) are not prepared on earth in both coating composition and topcoat compositions, or are formulated in the two.Rare, they be only included in bottom coating composition and topcoat compositions any one among.In the description of the component of corresponding coating composition, main explanation comprise mylar (B-1) as bottom coating composition film-forming resin and comprise the film-forming resin of mylar (B-2) as topcoat compositions, with simplified characterization.
Of the present invention for the formation of in the method for duplex coating, there is such advantage: even if be coated with the bottom coating composition and topcoat compositions with different coating compositions by wet-wet mode, the duplex coating weatherability obtained and anticorrosion good properties, there is no adjoint coating problem, such as appearance of coat deterioration (such as, 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); With surface conditioner (E-1).Corresponding component is below described.As mentioned above, do not comprise the situation of mylar (B-1) also in the scope of bottom coating composition, this bottom coating composition is used 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, such as cohesive and water proofing property.The acrylic resin (A-1) be included in bottom coating composition is prepared by the monomer (a) containing hydroxyl and another kind of monomer (b) copolymerization.
Monomer (a) containing hydroxyl comprises, such as, 2-hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, 2,3-dihydroxy butyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, epsilon-caprolactams and these contain the esterification products etc. of the product of (methyl) acrylate of hydroxyl, multivalence alcohol (such as polyethyleneglycol (methyl) acrylate) and acrylic or methacrylic acid.In addition, the product obtained by the ring-opening polymerisation of the mono-esterification product of epsilon-caprolactams and above-mentioned multivalence alcohol and acrylic or methacrylic acid can also be used.Can be used alone containing a kind of in these monomers (a) of hydroxyl or two or more in these can be used.In this manual, " (methyl) acrylate " refers to " acrylate or methacrylate ".
Other monomer (b) comprises, such as:
Monomer containing carboxyl, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and fumaric acid; And dicarboxylic acid monoesters, such as ethyl maleate, butyl maleate, itaconic acid ethyl ester and itaconic acid n-butyl;
(methyl) acrylic acid Arrcostab, such as (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) lauryl acrylate;
Monomer containing alicyclic group, such as (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring ester in the last of the ten Heavenly stems and (methyl) acrylic acid adamantane esters;
Aminoalkyl (methyl) acrylate, such as (methyl) acrylate, (methyl) acrylate and (methyl) acrylic acid butylaminoethyl;
Aminoalkyl (methyl) acrylamide, such as amino-ethyl (methyl) acrylamide, dimethylaminomethyl (methyl) acrylamide and dimethylaminopropyl (methyl) acrylamide;
Monomer containing another amide group, such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, methoxybutyl acrylamide and DAAM;
Vinyl cyanide, such as (methyl) acrylonitrile and α-chloro-acrylonitrile;
The vinyl ester monomers of saturated aliphatic carboxylic acid, such as vinyl acetate and propionate;
Styrene monomer, such as styrene, AMS and vinyltoluene etc.But other monomer (b) can be used alone or two or more combinationally use.
In other monomer (b) above-mentioned, preferably can use acrylic acid, methacrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate etc.
The normally used method of those skilled in the art can be used as the polymerization of monomer (a) containing hydroxyl and other monomer (b).Polymerization comprises, and such as, two steps of bulk polymerization, solution polymerization process and bulk-suspension polymerization method, wherein use radical polymerization initiator to carry out suspension polymerisation after bulk polymerization.In these methods, preferably solution polymerization process can be used.Solution polymerization process comprises, and such as, under radical polymerization initiator exists, heats above-mentioned monomer mixture, the method simultaneously stirred at the temperature of such as 80-200 DEG C.
Above-mentioned acrylic resin (A-1) can preferred number average molecular weight be 1,000-15,000.When number-average molecular weight is lower than 1, when 000, the coating performance of the duplex coating obtained may be inferior.On the other hand, when number-average molecular weight is more than 15, when 000, the viscosity of resin Composition improves, and can need a lot of solvent preparing in coating composition.In this manual, number-average molecular weight is the number-average molecular weight calculated 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 1,000-5,000.
Above-mentioned acrylic resin (A-1) can solid content hydroxy value be preferably 50-250mgKOH/g.When solid content hydroxy value is lower than 50mgKOH/g, can reduce the reactivity with isocyanate compound (D-1), the coating performance of the duplex coating obtained can be deteriorated, and the cohesive of coating can deterioration.On the other hand, when solid content hydroxy value is more than 250mgKOH/g, the water proofing property of the duplex coating obtained can deterioration.The solid content hydroxy value of acrylic resin (A-1) can be more preferably 60-200mgKOH/g, most preferably 80-180mgKOH/g.
Above-mentioned acrylic resin (A-1) can solid content acid number be preferably 2-50mgKOH/g.When solid content acid number is lower than 2mgKOH/g, the coating performance of the duplex coating obtained can deterioration.On the other hand, when solid content acid number is more than 50mgKOH/g, the water proofing property of the duplicature obtained can deterioration.The solid content acid number of acrylic resin (A-1) can be more preferably 5-20mgKOH/g.
Commercially available acrylic resin can be used as acrylic resin (A-1).It is serial (such as that acrylic resin comprises the trade name " ACRYDIC " manufactured by DIC company, ACRYDICA-837, ACRYDICA-871, ACRYDICA-1370 etc.), trade name " HARIACRON " series manufactured by HarimaChemicals (such as, HARIACROND-1703, HARIACRONN-2043-60MEX etc.), by MITSUBISHIRAYONCO., LTD. trade name " Dianal " series manufactured, by HitachiChemicalCo., Ltd. trade name " HITALOID " series manufactured, trade name " OLESTER " series etc. manufactured by MitsubishiChemicalsCorporation.
mylar (B-1)
Bottom coating composition of the present invention can comprise mylar (B-1) as film-forming resin.By comprising mylar (B-1) in bottom coating composition, there is the advantage of the machinability improving coating and the outward appearance improving the coating obtained.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 is 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.Can be used alone a kind of multivalence alcohol and can use two or more combination.
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 acid, dodecenyl succinic anhydride, cyclohexane-1, 4-dicarboxylic acids, carbic anhydride etc.Can be used alone a type of these polyacids or their acid anhydrides, and use two type capable of being combined or more is planted.
The mylar of modification also can be used 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 mylar of above description preparation.Such as, passed through use fat or obtained by these fat extracted fatty acid modified mylar by fat or 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 such as.Producing by fat or fatty acid modified mylar, can preferably by the above-mentioned fat of about 30 mass parts and/or aliphatic acid join the mylar of 100 mass parts altogether.
Above-mentioned mylar (B-1) can preferred number average molecular weight be 500-6,000, calculated by gpc measurement according to polystyrene.When number-average molecular weight lower than 500 time, the cohesive of the coating obtained can deterioration.On the other hand, when number-average molecular weight is more than 6000, when being coated with, the wettability of base material to be coated can deterioration.The number-average molecular weight of mylar (B-1) can be more preferably 1,000-4,000.
Above-mentioned mylar (B-1) can the hydroxyl value of preferred solid content be 80-350mgKOH/g.When the hydroxyl value of solid content is lower than 80mgKOH/g, can reduce with the reactivity of isocyanate compound (D-1), the coating performance of the duplex coating obtained can be deteriorated, and the cohesive of coating can deterioration.On the other hand, when the hydroxyl value of solid content is more than 350mgKOH/g, the water proofing property of the duplex coating obtained can deterioration.The solid content hydroxy value of mylar (B-1) can be more preferably 80-300mgKOH/g, most preferably 150-250mgKOH/g.
epoxy resin (C)
Bottom coating composition of the present invention comprises epoxy resin (C) as film-forming resin.By comprising epoxy resin (C) in bottom coating composition, there is the advantage of the anticorrosion character improving the duplex coating obtained.Can preferably include in bisphenol A-type epoxy resin or linear phenol-aldehyde resin type of epoxy resin at least any one as epoxy resin (C).
In the present invention, except above-mentioned bisphenol A-type 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, such as, the epoxy resin etc. of bisphenol F type epoxy resin, bisphenol-A D type of epoxy resin, bisphenol S type of epoxy resin, biphenyl type epoxy resin, naphthalene type of epoxy resin, glycidyl esters type of epoxy resin, glycidyl group amine type of epoxy resin, modified rubber.
For the total amount of epoxy resin (C), the amount of bisphenol A-type 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 epoxy resin and/or linear phenol-aldehyde resin type of epoxy resin for the total amount of epoxy resin (C) lower than 10% quality time, the cohesive enough with base material to be coated can not be obtained.
The epoxide equivalent of epoxy resin (C) can be preferably 100-1,000g/eq, more preferably 150-1,000g/eq.When epoxide equivalent more than 1,000g/eq time, in some cases, cohesive tend to reduce, and the toughness of the coating obtained sometimes may deterioration.When it is lower than 100g/eq, this is preferred, because viscosity improves and machinability may reduce.In addition, when epoxy resin (C) is the mixture of the resin of two kinds of quantity, the epoxide equivalent of all epoxy resin preferably included is in above-mentioned scope.
The number-average molecular weight of epoxy resin (C) can be preferably 20-2,000, by gpc measurement, calculates according to polystyrene.When number-average molecular weight is in above-mentioned scope, there is the advantage obtaining good coating performance and good coating workability.
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-type liquid epoxies of bisphenol A-type epoxy resin, epoxide equivalent is 184-194g/eq, number-average molecular weight is about 380, and is manufactured by MitsubishiChemicalCorporation); " EPICOAT#834-90X " (bisphenol A-type solid epoxy, epoxide equivalent is 230-270g/eq, and number-average molecular weight is about 470, and is manufactured by MitsubishiChemicalCorporation); " EPICOAT#872-X-75 " (bisphenol-A solids versions epoxy resin, epoxide equivalent is 600-700g/eq, and is manufactured by MitsubishiChemicalCorporation); " EPICOAT#1001 " (bisphenol A-type solid epoxy, epoxide equivalent is 450-500g/eq, and number-average molecular weight is about 900, and is manufactured by MitsubishiChemicalCorporation); " EPICOAT#1004 " (bisphenol A-type solid epoxy, epoxide equivalent is 875-975g/eq, and number-average molecular weight is about 1600, and is manufactured by MitsubishiChemicalCorporation) etc.;
" EPICLON5250-801X ", it is commercially available product (the phenol novolaks type of epoxy resin of linear phenol-aldehyde resin type of epoxy resin, epoxide equivalent is 230-250g/eq, number-average molecular weight is about 470, and manufactured by DainipponInkandChemicals, Incorporated (DICCorporation)); " EPICLON5270-801X " (phenol novolaks type of epoxy resin, epoxide equivalent is 245-270g/eq, number-average molecular weight is about 540, and is manufactured by DainipponInkandChemicals, Incorporated (DICCorporation)); " EPICOAT#154 " (phenol novolaks type of epoxy resin, epoxide equivalent is 176-180g/eq, and number-average molecular weight is 540, and is manufactured by MitsubishiChemicalCorporation) etc.;
" EPICOAT#807 ", it is commercially available product (the bisphenol F type liquid epoxies of other epoxy resin, epoxide equivalent is 160-175g/eq, and number-average molecular weight is about 330, and is manufactured by MitsubishiChemicalCorporation); " YR-450 " (epoxy resin of modified rubber, epoxide equivalent is 400-500g/eq, and number-average molecular weight is about 800-1000, and is manufactured by TohtoKaseiCo., Ltd.) etc.The epoxy resin (C) used in the present invention is 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, such as aliphatic series, aliphatic series containing aliphatic, alicyclic and aromatic group or aromatic diisocyanates, the dimer of vulcabond, the trimer (preferred, isocyanurate type isocyanates (so-called isocyanuric acid ester)) of vulcabond.Such isocyanate compound can be so-called asymmetric type.
Vulcabond comprises, and such as, comprises 5-24 carbon atom, the vulcabond of a preferred 6-18 carbon atom.Vulcabond comprises, such as, and trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate, hendecane vulcabond (1,11), lysine ester vulcabond, cyclohexane-1,3-vulcabond and cyclohexane-Isosorbide-5-Nitrae-vulcabond, 1-isocyano-3-iso-cyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI: IPDI), 4,4 '-two isocyano two ring methane, ω, ω '-dipropyl ether vulcabond, thiodipropyl diisocyanate, cyclohexyl-Isosorbide-5-Nitrae-vulcabond, dicyclohexyl methyl hydride-4,4 '-vulcabond, two (iso-cyanatomethyl) benzene of 1,5-dimethyl-2,4-, two (ω-isocyano ethyl) benzene of 1,5-trimethyl-2,4-, two (iso-cyanatomethyl) benzene of 1,3,5-trimethyl-2,4-, two (iso-cyanatomethyl) benzene of 1,3,5-triethyl group-2,4-, dicyclohexyl dimethylmethane-4,4 '-vulcabond etc.In addition, also aromatic diisocyanates can be used, such as 2,4-bis-isocyano toluene and/or 2,6-bis-isocyano toluene, 4,4 '-two isocyano diphenyl methane and Isosorbide-5-Nitrae-two 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 isocyanate compound at least partially.In addition, in the present invention, above-mentioned isocyanurate type isocyanate compound also can be used as the mixture combined with the aliphatic series containing other aliphatic, alicyclic and aromatic group or aromatics polyfunctional isocyanate compound (preferred vulcabond) 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.
Relative to the sum 1 of the hydroxyl be included in above-mentioned film-forming resin, in above-mentioned film-forming resin, the content of isocyanate compound (D-1) is preferably the isocyanate groups of 0.5-1.5 in isocyanate compound (D-1).When the sum 1 relative to the hydroxyl be included in above-mentioned film-forming resin, when the content of isocyanate compound (D-1) is amount lower than 0.5 of the quantity of isocyanate groups, solidify not enough.When the quantity of isocyanate groups is more than 1.5, the pliability of coating reduces and coating is easily peeled off by impacting.
In addition, when 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 the affinity with 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 and plants, and can to comprise in acrylic surface conditioning agent and silicone surface conditioning agent one of at least.Acrylic surface conditioning agent comprises acrylic copolymer, such as BYK352, BYK392, BYK358N (they are manufactured by BYKJapanK.K.), DISPERLONLC-900 and DISPERLONLC-951 (being manufactured by KusumotoChemicalsLtd.), as commercially available product.Silicone surface conditioning agent comprises polyether-modified siloxanes, the poly-methyl alkyl siloxane of polyester modification, polyether-modified dimethyl silicone polymer, polyether-modified dimethyl silicone polymer etc. containing acrylic acid groups, such as BYK331, BYK306, BYK323 and BYK325 (they are manufactured by BYKJapanK.K.) commercially product.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 25-30mN/m.
In this manual, the surface tension of coating composition utilizes the ring method of platinum loop to measure by using.Surface tension is measured by using such as DYNOMETER (Germany, BYKGardnerInc.).
Surface conditioner (E-1) preferably hexane tolerance can be not less than 150ml.Measure the hexane tolerance of surface conditioner according to following methods: 0.5g surface conditioner of weighing, and be placed in glass beaker, subsequently to wherein adding acetone, to dissolve surface conditioner.Then, titration hexane, and become the point of white opacity by restriction solution and measure.The hexane tolerance of surface conditioner (E-1) more preferably can be not less than 200ml.When hexane tolerance is lower than 150ml, owing to lacking soaking material, appearance of coat can deterioration.
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 lower than 0.01% quality, the wetting property deterioration on base material to be coated, and degraded appearance.On the other hand, when it is greater than 10% quality, can not preventing layer mix, and appearance degradation.
In addition, when not comprising mylar (B-1), film-forming resin is acrylic resin (A-1) and epoxy resin (C).
For the solid content ratio of the acrylic resin be included in bottom coating composition (A-1), mylar (B-1), epoxy resin (C), isocyanate compound (D-1) and surface conditioner (E-1), setting total amount is 100% quality, in view of the water proofing property of coating, anticorrosion character and finishing character, preferably can acrylic resin (A-1) preferably containing 25-50% quality.In view of the durability of coating workability and coating, the mylar (B-1) of the amount preferably containing 5-30% quality.In view of anticorrosion character, crack generation and the cohesive with base material to be coated, the epoxy resin (C) of the amount also preferably containing 5-25% quality.In addition, in view of curing properties and scratching resistent property, the isocyanate compound (D-1) of the amount preferably containing 20-50% quality.(ooze out by coating surface oozes out with suppressing in view of to the wettability of base material to be coated; Components dissolved and the phenomenon arrived outside top coat) open defect that causes, the surface conditioner (E-1) of the amount preferably containing 0.01-5% quality.
When not comprising mylar (B-1), set the acrylic resin (A-1) be included 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, the acrylic resin (A-1) of the amount preferably containing 25-70% quality, the epoxy resin (C) of the amount containing 5-30% quality, the isocyanate compound (D-1) of the amount containing 20-60% quality, and the surface conditioner of the amount containing 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 be generally used for coatings art, and comprise, such as, filler pigments, such as 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, such as 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 may be combined with and uses two or more.
Preferably in bottom coating composition, comprise one or more corrosion-inhibiting pigments and one or more filler pigments.Exist and comprise these pigment to improve the advantage of coating performance, the anticorrosion of such as obtained duplex coating and weatherability and coating cover character, and obtain the excellent appearance of coating.
When 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 preferably in 10-40% scope.As (PVC
1) when being greater than 40%, the viscosity of coating composition can improve, and coating workability can reduce.
In this manual, PVC " pigment volume concentration (PVC) " refers to the percent by volume (%) of pigment in the total amount of all resin Compositions be contained in coating composition and all pigment.
In this manual, for the proportion that calculates the pigment of pigment volume concentration based at " material of paint handbook (HandbookofPaintingMaterials) ", sixth version, the explanation described in JapanpaintManufacturesAssociation.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 additive, organic solvent, sinking inhibitor, sedimentation inhibitors, curing catalysts (organo-metallic catalyst), anti-look dispersant, dispersant, defoamer, viscosity modifier (thickener), levelling agent can be related to, play creme, ultra-violet absorber, antioxidant, plasticizer, film forming agent etc.
About organic solvent, those that be usually used in type of solvent coating can be comprised.Solvent comprises, such as, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, Solvesso100, Solvesso150 and Solvesso200 (being manufactured by ExxonMobilChemicalCo., Ltd.), toluene, dimethylbenzene, methoxybutyl acetic acid esters, 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 the amount of environmental protection in recent years and environmental load uses.
Sinking inhibitor and sedimentation inhibitors preferably include, such as, and " DISPERLON6700 " (trade name; Aliphatic series bisamide thixotropic agent, is manufactured by KusumotoChemicalsLtd.).About above-mentioned anti-look dispersant, can preferably use such as, " DISPERLON2100 " (trade name; Aliphatic polyvalent carboxylic acids, wherein adds silicone, is manufactured by KusumotoChemicalsLtd.).About above-mentioned defoamer, can preferably use such as, " DISPERLON1950 " (trade name; Specific polyvinyl, is manufactured by KusumotoChemicalsLtd.).
topcoat compositions
Topcoat compositions of the present invention comprises containing acrylic resin (A-2) and the film-forming resin of mylar (B-2), the curing agent containing isocyanate compound (D-2) and surface conditioner (E-2).
Acrylic resin (A-2) can be included in the acrylic resin (A-1) described in above-mentioned bottom coating composition, and mylar (B-2) also can be included in the mylar (B-1) described in above-mentioned bottom coating composition.Isocyanate compound (D-2) can be included in the isocyanate compound (D-1) described in above-mentioned bottom coating composition.Being included in bottom coating composition and the above-mentioned film-forming resin in topcoat compositions and curing agent can be identical and can be different.In addition, as mentioned above, do not comprise the situation of mylar (B-2) also in the scope of topcoat compositions, this topcoat compositions is used for the method for formation duplex coating of the present invention.
Surface conditioner (E-2) needs controlled surface tension, mentions as following.Therefore, surface conditioner (E-2) is not identical with surface conditioner (E-1).But surface conditioner (E-1) can be identical with the component type of (E-2).Surface conditioner (E-2) can comprise two or more surface conditioners.Surface conditioner (E-2) containing in silicone surface conditioning agent and fluorinated surface conditioning agent one of at least.Silicone surface conditioning agent can be identical with surface conditioner (E-1).Fluorinated surface conditioning agent comprises, such as, the oligomer containing perfluoroalkyl, such as, commercially available component, such as BYK340 (being manufactured by BYKJapanK.K.), MegafacF-443 and F-470 (being manufactured by DICCorporation) etc.By using surface conditioner, can 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 20-25mN/m.
By compatibly using above-mentioned surface conditioner etc., can at the capillary value of preferred range regulation topcoat compositions (γ 2).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 2-8mN/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 2-8mN/m scope, namely, γ
1be greater than γ
2, and be worth △ γ (γ
1-γ
2) in 2-8mN/m scope.When △ γ on duty is lower than 2mN/m, when wet-wet mode painting bottom coating composition and topcoat compositions, generating layer can mixes, and priming coat and top coat reversing can be produced.In addition, upset can be produced on the surface of the coating.On the other hand, when △ γ on duty is more than 8mN/m, the superficial layer of the duplex coating obtained in wet-wet mode painting bottom coating composition and topcoat compositions can produces and ooze out.Can more preferably △ γ (γ
1-γ
2) be 3-6mN/m.
Surface conditioner (E-2) can hexane tolerance be preferably 50-150ml, more preferably 70-120ml.When hexane tolerance is lower than 50ml, owing to oozing out on superficial layer, appearance degradation can be produced.When hexane tolerance is greater than 150ml, owing to lacking the control of interstratification, appearance degradation can be produced.
Preferably can contain 0.01-10% quality, the surface conditioner (E-2) of the amount of preferred 0.1-3% quality, based on the solid content of film-forming resin in topcoat compositions.When it is lower than 0.01% quality, can not mix by key-course, and degraded appearance.On the other hand, when it is greater than 10% quality, by oozing out on superficial layer, appearance degradation.
When not comprising mylar (B-2), film-forming resin can be preferably acrylic resin (A-2).
Relative to the sum 1 of the hydroxyl be included in above-mentioned film-forming resin, for the isocyanate groups of isocyanate compound (D-2) preferably containing 0.5-1.5 in isocyanate compound (D-2) of above-mentioned film-forming resin.When the sum 1 relative to the hydroxyl be included in above-mentioned film-forming resin, when the content of isocyanate compound (D-2) is amount lower than 0.5 of the quantity of isocyanate groups, mustn't go to enough solidifications.When the quantity of isocyanate groups is more than 1.5, the pliability of coating reduces, and coating is easily peeled off by impacting.When not comprising mylar (B-1), film-forming resin can be preferably acrylic resin (A-2).
About the solid content ratio of the acrylic resin be included in topcoat compositions (A-2), mylar (B-2), isocyanate compound (D-2) and surface conditioner (E-2), setting total amount is 100% quality, in view of the weatherability of coating, coating workability and curing properties, the acrylic resin (A-2) of the amount preferably preferably containing 30-60% quality, the more preferably amount of 35-55% quality.In view of the intensity of coating workability, weatherability and coating, the mylar (B-2) of the amount preferably containing 5-35% quality, more preferably 5-30% quality.In view of curing properties and scratching resistent property, the isocyanate compound (D-2) of the amount preferably containing 20-50% quality, more preferably 25-45% quality.In view of the wettability on priming coat and suppression are by coating surface oozing out the open defect caused, the surface conditioner (E-2) of the amount preferably containing 0.01-5% quality.
When not comprising mylar (B-2), the total solid content ratio of acrylic resin component (A-2), isocyanate compound (D-2) and surface conditioner (E-2) that setting is included in topcoat compositions is 100% quality, the acrylic resin (A-2) of the amount preferably containing 30-70% quality, the isocyanate compound (D-2) of the amount containing 20-60% quality, and the surface conditioner (E-2) containing the amount of 0.01-5% quality.
In addition, topcoat compositions can comprise the various additives (such as, organic solvent, curing catalysts, sinking inhibitor and sedimentation inhibitors, viscosity modifier, ultra-violet absorber etc.) that can be included in bottom coating composition.
Topcoat compositions of the present invention preferably can contain pigment (F-2).The instantiation of pigment (F-2) also can be included in the pigment (F-1) described in above-mentioned bottom coating composition.
When 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 preferably in 10-35% scope.
As (PVC
2) when being greater than 35%, the viscosity of coating composition can improve, and coating workability can reduce.
In the present invention, △ PVC (PVC is worth
1-PVC
2) be preferably-2 to 8%, wherein from the pigment volume concentration (PVC) (PVC of the pigment be included in described bottom coating composition (F-1)
1) deduct the pigment volume concentration (PVC) (PVC of the pigment (F-2) be 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 may be provided in the decline of internal stress difference that produces when forming duplex coating and can provide the good membranes outward appearance of available duplex coating.△ PVC (PVC on duty
1-PVC
2) when being greater than 8%, film appearance degradation, such as, can produce wrinkling in wet-wet mode painting bottom coating composition and topcoat compositions.Value △ PVC (PVC
1-PVC
2) can more preferably in-1 to 5% scope.
Term " wrinkling " refers to holiday wrinkling in a part of duplex coating surface.This defect seem by distortion and priming coat and top coat rate of drying difference and produce.
the method of duplex coating
Duplex coating of the present invention is formed by following methods: described method comprises the step forming wet priming coat, by being 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, to form wet top coat by wet-wet mode; And drying steps, wherein by obtained wet priming coat and the drying simultaneously of 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, such as, and metal base, such as iron, zinc, tin, copper, titanium, sheet metal and galvanized iron.Base material can use the plating such as zinc, copper, chromium, and its usable surface inorganic agent (such as 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 metal base to the insufficient heat transfer of base material.Base material to be coated comprises, such as, the machine of construction machine (such as, bull-dozer, scraper, hydraulic crawler excavator, excavator), carrying machine (truck (track), trailer etc.), crane and load and non-load, for the machine (diesel engine hammer, fluid operated hammer etc.) of foundation construction, the machine (ball winder, roller etc.) for tunnel construction; Photoelectricity alleged by general industry and heavy electrical apparatus, farming machine, steel systeming equipment, machine tools and industrial machine such as heavy vehicles and hardly by heating by the base material etc. with high heat capacity heated.The method of formation duplex coating of the present invention can be preferred for being coated with there is high heat capacity and hardly by heating by the construction machine that heats 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: such as, dipping, brush, roller, roll coater, aerial spraying, airless spraying, curtain stream coating machine, roll-in curtain coater, die applicator, electrostatic applications etc.Wherein, preferred aerial spraying, airless spraying and curtain stream coating machine.These compatibly can be selected according to the purposes of base material to be coated and shape.
Bottom coating composition is preferably coated with the amount of dry coating thickness within the scope of 10-100 μm, and preferred with the amount coating of dry coating thickness within the scope of 15-70 μm further.After forming wet priming coat like this, (wet-wet mode is coated with) topcoat compositions can be coated with.In view of operating efficiency, under room temperature (5-35 DEG C), until the coating interval of coating topcoat compositions is preferably 0-60 minute, more preferably 1-30 minute after forming wet priming coat, preferred 1-15 minute further.When using the method for formation duplex coating of the present invention, the duplex coating that appearance of coat is excellent can be obtained, even if be coated with top coat under the dry hardly state of priming coat.In addition, can by priming coat about 1-10 minute of drying in advance at the temperature (such as, 40-100 DEG C, more preferably 40-80 DEG C) exceeding usual room temperature, and topcoat compositions also can be coated with under the state that priming coat is half-dried.
Topcoat compositions can preferably be coated with the amount that wherein build is 10-200 μm, can more preferably be coated with the amount that wherein build is 20-100 μm, most preferably 20-50 μm.Keep 1-10 days by making them under room temperature (5-35 DEG C) or pass through exceeding the temperature of usual room temperature (such as, 50-100 DEG C, more preferably 60-80 DEG C) under force drying 15-60 minute, by the wet priming coat that obtains like this and wet top coat dry, can duplex coating be obtained.
The method of formation duplex coating of the present invention has such advantage: even if be coated with the bottom coating composition and topcoat compositions with different coating compositions by wet-wet mode, also the duplex coating with good appearance can be formed, and can not with coating problem, such as layer mixing and wrinkling.In addition, by having the priming coat of the function providing good anticorrosion character and having the top coat of the function providing weatherability, the duplex coating obtained by the method obtains excellent 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, topcoat compositions can be coated with on the bottom coating composition of coating, 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 the firing equipment being provided for cured base coating, and 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 the base material extensive to be coated that coating has large thermal capacitance, such as industrial machine or construction machine.
[embodiment]
Further illustrate the present invention according to following examples, but the present invention is not limited to these embodiments.Unless otherwise indicated, otherwise in an embodiment " part " and " % " is based on quality.
production example 1 produces acrylic resin 1
Be equipped with nitrogen induction pipe, agitator, temperature adjuster device, dropping funel and provide decanter cooling tube 1 liter of reaction vessel in loading 25 parts of dimethylbenzene and 10 parts of butyl acetates, and be heated to 120 DEG C of temperature.Subsequently, 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 are loaded as acrylic monomers, to prepare monomer solution in dropping funel.When making reaction vessel remain on 120 DEG C, dropwise added monomer solution through 3 hours.After dropping, at 120 DEG C, keep 1 hour again.The number-average molecular weight of the acrylic resin 1 obtained is 2,500 (by gpc measurement, calculating according to polystyrene), and solid content hydroxy value is 180mgKOH/g, and solid content acid number is 7mgKOH/g, and solid content solids level concentration is 75%.
production example 2 produces 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 obtained is 5,500 (by gpc measurements, the value changed by polystyrene), and solid content hydroxy value is 55mgKOH/g, and solid content acid number is 7mgKOH/g, and solids level concentration is 75%.
production example 3 produces mylar 1
In the 2 liters of reaction vessels being equipped with agitator, temperature adjuster device and cooling tube, load 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, the DOPCP of 6.1 parts of hydroxy new pentane acids, 7.9 parts of CarduraE (manufactured by RoyalDutchShellPLC., have the glycidyl esters of the alkanecarboxylic acid (versaticacid) of side chain) and 15.4 parts of 6-caprolactones, heat subsequently.By evaporating with xylenes, remove the water produced by reaction.Be heated to 190 DEG C subsequently, from starting backflow through about 2 hours.Continue to stir and dehydration, until be 8 corresponding to the acid number equivalent of carboxylic acid, and cessation reaction.Then, 16 parts of dimethylbenzene are added wherein.The number-average molecular weight of the mylar 1 obtained is 1,500 (by gpc measurements, the value changed by polystyrene), and solid content hydroxy value is 230mgKOH/g, and solid content acid number is 8mgKOH/g, and solids level concentration is 80%.
production example 4 produces mylar 2
Mylar 2 is prepared as summary description in production example 1, and difference is that monomer becomes 45.6 parts of M-phthalic acids, 16.0 parts of neopentyl glycols, 5.2 parts of trimethylolpropanes, 12.0 part of 1,6-hexylene glycol and 21.2 parts of 6-caprolactones.The number-average molecular weight of the mylar 2 obtained is 4,200 (by gpc measurement, calculating according to polystyrene), and solid content hydroxy value is 54mgKOH/g, and solid content acid number is 7mgKOH/g, and solids level concentration is 80%.
production example 5 produces the dispersion paste 1 containing acrylic resin and pigment
Mixture 215 parts of ACRYDICA-859B (acrylic resins in dispersion cup, by DainipponInkandChemicals, Incorporated (DICCorporation) manufactures, solids level concentration is 75% quality, solid content hydroxy value is 130mgKOH/g, and number-average molecular weight is 2, 100), 15 parts of amine dispersant B YK161 (are manufactured by BYKJapanK.K., solids level concentration is 30% quality), 9 parts of dispersant B YK110 (are manufactured by BYKJapanK.K, solids level concentration is 52% quality), 164 parts of titanium oxide pigments Ti-PureR-706 are (by DuPontCo., Ltd. manufacture), 1 part of carbon black MitsubishiCarbonBlackMA-100 (being manufactured by MitsubishiChemicalCorporation), 111 parts of powdered whitings are (by MARUOCALCIUMCO., LTD. manufacture), 160 parts of trbasic zinc phosphate corrosion-inhibiting pigment LFBOUSEIZP-DL (being manufactured by KIKUCHICOLOR & CHEMICALsCORPORATION), 64 parts of Solvesso100 (registration marks, by ExxonMobilCo., Ltd. manufacture) and 60 parts of methoxy butyl acetates.Subsequently, load bead, and disperse, until particle diameter becomes 10 μm or less, to obtain disperseing paste 1.
production example 6-10 produces dispersion paste 2-6
Dispersion paste 2-5 is prepared as summary description in production example 5, and difference is that the quantitative change of respective components is the amount shown in the following table 1 mentioned." organic yellow uitramarine " in table 1 is HostapermYellowH3G (ClariantJapanK.K.).
[table 1]
production example 11 produces bottom coating composition 1
87 parts of mylar obtained in production example 3,1,96 parts of EPICOAT#872 (bisphenol A-type epoxy resin are added in 799 parts of dispersion pastes obtained in production example 5, manufactured by MitsubishiChemicalCorporation, solids level concentration is 75% quality, epoxide equivalent is 650g/eq) (manufactured by BYKJapanK.K. as epoxy resin and 8 parts of acrylic surfaces conditioning agent BYK392, solids level concentration is 52% quality), and mix.Load 204 parts of CORONATEHXLV (isocyanurate type isocyanate resins subsequently, solids level concentration is 100% quality, by NipponPolyurethaneIndustryCo., Ltd. manufacture, the isocyanurate type (trimer) of HDI) xylene solution (solids level concentration is 75%), make to be included in the sum of hydroxyl in acrylic resin and mylar (for film-forming resin) and the ratio of isocyanate groups 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%, calculated by the proportion of pigment and other component used.
In addition, when use DYNOMETER (BYKGardnerInc., Germany), when being measured by platinum loop method, the surface tension (γ of bottom coating composition 1
1) be 27.2mN/m.
Weighing surface conditioning agent (0.5g), and be placed in glass beaker, subsequently to wherein adding acetone, to dissolve surface conditioner, then, titration hexane, becomes the point of white opacity by restriction solution and measures.The hexane tolerance of BYK392 is 250ml.
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 the amount shown in the following table 2 mentioned.As measured the surface tension (r of the bottom coating composition obtained in production example 11 with mentioning
1) and lamella length, result is shown in table 2.
The epoxy resin 2 being shown in the following table 2 mentioned is EPICOAT#828 (bisphenol A-type epoxy resin, is manufactured by MitsubishiChemicalCorporation., and solids level concentration is 75% quality, and epoxide equivalent is 185g/eq).
The identical mode described in production example 11 is adopted to measure the hexane tolerance of BYK3441, LC-900 and LC-951.BYK3441 is 120ml, LC-900 is 300ml, and LC-951 is 330ml.
[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 the amount shown in the following table 3 mentioned.Pigment volume concentration (PVC) (the PVC of topcoat compositions 1-10 is calculated as summary description in production example 11
2).Surface tension (the γ of topcoat compositions 1-10 is measured as summary description in production example 11
2).Result is shown in table 3.Mode identical is as mentioned above adopted to measure the hexane tolerance of BYK322, BYK306, BYK331 and BYK333.BYK322 is 120ml, BYK306 be 90ml, BYK331 is 85ml, and BYK333 is 100ml.The topcoat compositions 2 of production example 22 does not have hexane to tolerate data, because topcoat compositions does not comprise surface conditioner.
[table 3]
embodiment 1 forms duplex coating
The cold-rolled steel sheet JISG3141 (SPCC-SB) being of a size of 0.8 × 70 × 150mm uses dimethylbenzene degreasing.Subsequently, use airless spraying to be coated on the bottom coating composition 1 obtained in production example 11, make build be 30 μm-40 μm, to form wet priming coat.Subsequently, at room temperature behind 3 minutes intervals, when priming coat is hygrometric state, use airless spraying, be coated with by wet-wet mode, be coated on the topcoat compositions 1 obtained in production example 21, make build be 30 μm-40 μm, to obtain wet top coat.Keep under being allowed to condition at room temperature after 10 minutes, by its dry (force drying) in 30 minutes at 80 DEG C, to obtain the duplex coating with fixing build.Obtain the film that build is two types of 60-80 μm.
embodiment 2
As summary description in embodiment 1, obtain duplex coating, difference is, behind at room temperature 3 minutes intervals, by obtained wet priming coat at 80 DEG C dry 2 minutes in advance, is coated with topcoat compositions 1 subsequently.
embodiment 3-14 and comparative example 1-4
As summary description in embodiment 1, obtain duplex coating, difference is, changes the kind of bottom coating composition and topcoat compositions and exists and do not exist dry in advance after painting bottom coating composition, as shown in table 4 and 5.
As summary description in embodiment 1, carry out comparative example 2, difference is, coating topcoat compositions 1 instead of bottom coating composition 1, and again applies topcoat compositions 1.
The following evaluation mentioned is carried out to the duplex coating of above-mentioned embodiment and comparative example.Result is also shown in table 4 and 5.
the weatherability accelerated
The weatherability test accelerated, according to the xenon lamp method described in JISK5600-7-7, is waited meter SX2-75 (being manufactured by SugaTestInstrumentsCo., Ltd.) by super xenon and is carried out.Measured the gloss number of coating after 500 h testing period by multi-angle glossmeter GS-4K (being manufactured by SugaTestInstrumentsCo., Ltd.), and before testing, usage rate (gloss retention rate) evaluates gloss number.When 60 ° of gloss numbers are the gloss retention rate of 80% or more, are 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 that length is 10cm.According to the sprinkling method of testing for neutral brine patience described in JISK5600-7-1 (JISZ2371), test machine ST-11L is sprayed (by SugaTestInstrumentsCo. by salt solution, Ltd. manufacture), salt solution is sprayed test and carry out 240 hours.Subsequently, based on basis described below, the rust of visual valuation distance cross-cut part and the generation of bubble.
A: the rust of generation or the Breadth Maximum distance cross-cut part of bubble are less than 2mm.
B: the rust of generation or the Breadth Maximum distance cross-cut part of bubble are 2mm or more and are less than 4mm.
C: the rust of generation or the Breadth Maximum distance cross-cut part of bubble are 4mm or more.
secondary bonding
Along the cross-cut for anticorrosion character, the plate of coating adheres to a slice glassine paper adhesive tape, is peeled off subsequently, and the stripping width of measuring distance cross-cut.When stripping width is in 1mm, is evaluated as and passes through.
water proofing property
According to JISK5600-6-2, by sample submergence 96 hours in the water of 23 DEG C, based on the following basis mentioned, visual valuation.
A: do not have defect.
B: partially observable crack and stripping.
C: major part observes crack and stripping.
layer mixed nature
Based on the following basis mentioned, visual valuation after being just coated with topcoat compositions, the outward appearance of wet duplex coating.
A: do not have defect.
B: observe part reversion and observe priming coat.
C: observe major part reversion and observe priming coat.
the outward appearance (wrinkling) of coating
Based on the following basis mentioned, visual valuation after being just coated with topcoat compositions, the outward appearance of wet duplex coating.
A: do not have defect.
B: observe a part wrinkling.
C: observe major part wrinkling.
the outward appearance (gloss) of coating
By multi-angle glossmeter GS-4K (being manufactured by SugaTestInstrumentsCo., Ltd.), measure the gloss number (60 ° of gloss numbers) of the duplex coating obtained.When 60 ° of gloss numbers are 80 or more, are evaluated as and pass through, 85 or more be evaluated as excellent.
dust compatibility
Based on the following basis mentioned, the state of the rough surface that visual valuation is caused by dust when being coated with.
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 following basis mentioned, evaluate and forming the coating efficiency in duplex coating.
A: after coating bottom coating composition, do not have heating process, the process of such as preheating or heat cure, coating topcoat compositions.
B: at coating bottom coating composition after preheating, coating topcoat compositions, condition is the process that this process does not comprise heat cure.
C: after the process applying bottom coating composition and heat cure, coating topcoat compositions.
[table 4]
RT represents room temperature
[table 5]
RT represents room temperature
Each embodiment can form weatherability and the excellent duplex coating of secondary bonding, anticorrosion character and water proofing property.In addition, the score of embodiment 1-6 in dust compatibility comprising mylar at both priming coat and top coat is A, and they are very good.
Comparative example 1 is the experiment wherein not comprising acrylic resin in topcoat compositions.In this case, the outward appearance (gloss) of coating and weatherability deterioration.
Comparative example 2 is that wherein topcoat compositions 1 is used 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 is that wherein topcoat compositions does not comprise the experiment of surface conditioner.In this case, the △ γ (mN/m) between priming coat and top coat reduces (0.2), then layer mixed nature and the deterioration of dust compatibility.
Comparative example 4 is the experiment of hexane tolerance reduction (120ml) of wherein bottom coating composition.In this case, layer mixed nature deterioration.
According to the present invention, be coated with by wet-wet mode, the duplex coating with good appearance, excellent weatherability and anticorrosion character can be formed.The duplex coating formed in the present invention also has the characteristic that can be formed without thermal cure step.Therefore, it has following industrial advantage: do not need to provide firing equipment, and the investment for coating apparatus can reduce and application step can shorten.The method forming duplex coating is particularly suitable for being coated with the base material with extensive and large thermal capacitance, such as 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 obtained wet priming coat and the drying simultaneously of 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 isocyanate compound D-1 of epoxy resin C, 20-60% quality of acrylic resin A-1,5-30% quality of 25-70% 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 isocyanate compound D-2 of acrylic resin A-2,20-60% quality of 30-70% quality and the surface conditioner E-2 of 0.01-5% quality, and
Value △ γ (γ
1-γ
2) be 2-8mN/m, this value represents the capillary value γ from described bottom coating composition
1in deduct the capillary value γ of described topcoat compositions
2.
2. the method for the formation duplex coating of claim 1, wherein acrylic resin A-1 and the solid content hydroxy value both acrylic resin A-2 are 50-250mgKOH/g, and the epoxide equivalent of epoxy resin C is 100-1000g/eq.
3. the method for the formation duplex coating of claim 1 or 2, the described film-forming resin be 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: the isocyanate compound D-1 of epoxy resin C, 20-50% quality of mylar B-1,5-25% quality of acrylic resin A-1,5-30% quality of 25-50% quality and the surface conditioner E-1 of 0.01-5% quality
The described film-forming resin be 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 isocyanate compound D-2 of mylar B-2,20-50% quality and the surface conditioner E-2 of 0.01-5% quality of acrylic resin A-2,5-35% quality of 30-60% quality.
4. the method for the formation duplex coating of claim 3, wherein mylar B-1 and the solid content hydroxy value both mylar B-2 are 80-350mgKOH/g.
5. the method for the formation duplex coating of claim 1 or 2, wherein the hexane tolerance of surface conditioner E-1 is not less than 150ml, and the tolerance of the hexane of surface conditioner E-2 is in 50-150ml scope.
6. the method for the formation duplex coating of claim 1 or 2, wherein said surface conditioner E-1 comprises acrylic surface conditioning agent 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 claim 1 or 2, the painting work wherein in the step forming described priming coat and the interval time between the painting work in the step forming described top coat are 0-60 minute.
8. the method for the formation duplex coating of claim 1 or 2, 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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| CN103906577B true CN103906577B (en) | 2015-11-25 |
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| 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 |
| TWI689111B (en) * | 2016-09-13 | 2020-03-21 | 迎輝科技股份有限公司 | Quantum dot film and its manufacturing 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 |
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| JPS6031858A (en) * | 1983-07-29 | 1985-02-18 | Nippon Oil & Fats Co Ltd | Formation of paint film from aqueous paint |
| JPH0634965B2 (en) * | 1986-04-30 | 1994-05-11 | 日本ペイント株式会社 | Method for forming multilayer coating film |
| JPS63310673A (en) * | 1987-06-10 | 1988-12-19 | Kansai Paint Co Ltd | Formation of paint 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 |
| JPH06262131A (en) * | 1993-03-09 | 1994-09-20 | Sumitomo Metal Ind Ltd | Coating method |
| 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 |
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| CN103906577A (en) | 2014-07-02 |
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