CN100423855C - Method for forming brilliant coating film and coated article showing metallic effect - Google Patents
Method for forming brilliant coating film and coated article showing metallic effect Download PDFInfo
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- CN100423855C CN100423855C CNB2004800130531A CN200480013053A CN100423855C CN 100423855 C CN100423855 C CN 100423855C CN B2004800130531 A CNB2004800130531 A CN B2004800130531A CN 200480013053 A CN200480013053 A CN 200480013053A CN 100423855 C CN100423855 C CN 100423855C
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Abstract
There is provided a method for forming a brilliant coating film with an excellent brilliant appearance by using aqueous first and second base coating compositions without preheating the applied first base coating composition. In the method, the aqueous first base coating composition is applied to a substrate to form a first base coating, the aqueous second base coating composition is applied to the first base coating to form a second base coating, a clear coating composition is applied to the second base coating to form a clear coating, and then the uncured coatings formed are simultaneously heated and cured, under controlling the solid contents of the first and second base coating compositions and the ratio therebetween, or the brilliant pigment mass concentrations of the base coating compositions and the ratio therebetween, or the mass ratio, the evaporation rate, and the solubility parameter of a solvent contained in the first base coating composition.
Description
Technical field
The present invention relates to a kind of goods of filming that are used to form the method for filming of light and are coated with this light.
Background technology
The coating composition that contains the light of aluminium or splitting has been used to form the metallicity with metallicity gloss and has filmed.
The method of filming of utilizing the coating composition of light to form light comprises the method that the formation metallicity described among the JP-A-2002-35688 is filmed, and this metallicity is filmed at aspect excellent performances such as directionality, density, conversion performance (flip-flop property), brightness.In the method for this formation multilayer film, the primer composition that contains the heating curable of hydrophilic organic solvent and water is coated on bottom, the solids content on the surface of the composition that this is coated is controlled in mass ratio 70% or more (when not solidifying this coated composition), the metallic paints composition that contains hydrophilic organic solvent is coated on this surface, if necessary, can further apply transparent coating composition.
Yet, method among the JP-A-2002-35688 need be measured the influence of VOC (VOC) to environment, reason is that the metallic paints composition that contains hydrophilic organic solvent as second primer composition does not only contain organic solvent and moisture, in addition, this method comprises the step of the primer composition of the coated heating curable of preheating, so that solids content is controlled at mass ratio 70% or more and can not solidify said composition.Therefore this method circuit that need in subbing (work) is distinguished, have the complexity of preheating unit.
Therefore, the purpose of this invention is to provide a kind of method of filming that can form light and have the goods through applying of filming of this light, use the first and second moisture primer compositions to form this under the situation of this method by first primer composition that applies in not preheating and film with good bright looking.
Summary of the invention
As the result who conscientiously studies, the inventor has finished the present invention.More particularly, provide following content.
1. one kind is used for forming the bright method of filming in substrate, and this method may further comprise the steps successively:
(1) primer composition with the first moisture light is coated on substrate, so that the first order in the subbing district (floor) forms the first subbing floor;
(2) primer composition with the second moisture light is coated on the first subbing layer that obtains in the step (1), so that the second level in the subbing district (floor) forms the second subbing floor;
(3) transparent coating composition is coated on the second subbing layer that obtains in the step (2), so that in the clear dope district, form transparent dope layer; And
(4) uncured dope layer that forms in while heating steps (1), (2) and (3), so that solidify these dope layers,
Satisfy at least one among following collateral condition I, II and the III:
The condition of collateral condition I (A-1) is meant: the primer composition of first light that this is moisture has the solids content of mass ratio 10% to 45%, and the primer composition of this second moisture light has the solids content of mass ratio 10% to 40%; Condition (B-1) is meant: the ratio of the solids content of the primer composition of the solids content of the primer composition of first light that this is moisture and the second moisture light is 1.1/1 to 4/1;
The condition of collateral condition II (A-2) is meant: the primer composition of first light that this is moisture has the mass concentration of 1% to 30% bright pigment, and the primer composition of this second moisture light has the mass concentration of 5% to 40% bright pigment, and condition (B-2) is meant: the ratio of the mass concentration of the bright pigment of the primer composition of the mass concentration of the bright pigment of the primer composition of first light that this is moisture and the second moisture light is 1/4 to 1/1.1; And
The condition of collateral condition III (A-3) is meant: the primer composition of first light that this is moisture comprises at least a organic solvent and water, and the organic solvent that this is at least a and the mass ratio of water are from 5/95 to 49/51, and condition (B-3) is meant: at least a organic solvent that is used for the primer composition of the first moisture light contains the specific organic solvent of mass ratio 40% to 100%, and it has the evaporation rate (what had 25 ℃ the time based on n-butyl acetate is 100 evaporation rate) of 9.5 to 14.5 solubility parameter and 150 to 800.
2. one kind is used for forming the bright method of filming in substrate, and this method comprises the following steps: successively
(1) primer composition with the first moisture light is coated on substrate, so that the first order in the subbing district forms the first subbing floor;
(2) primer composition with the second moisture light is coated on the first subbing layer that obtains in the step (1), so that the second level in the subbing district forms the second subbing floor; And
(5) the uncured dope layer of the middle formation of heating steps (1) and (2) simultaneously, so that solidify this coating,
Satisfy at least one among following collateral condition I, II and the III:
The condition of collateral condition I (A-1) is meant: the primer composition of first light that this is moisture has the solids content of mass ratio 10% to 45%, and the primer composition of this second moisture light has the solids content of mass ratio 10% to 40%, and condition (B-1) is meant: the ratio of the solids content of the primer composition of the solids content of the primer composition of first light that this is moisture and the second moisture light is 1.1/1 to 4/1;
The condition of collateral condition II (A-2) is meant: the primer composition of first light that this is moisture has the mass concentration of 1% to 30% bright pigment, and the primer composition of this second moisture light has the mass concentration of 5% to 40% bright pigment, and condition (B-2) is meant: the ratio of the mass concentration of the bright pigment of the primer composition of the mass concentration of the bright pigment of the primer composition of first light that this is moisture and the second moisture light is 1/4 to 1/1.1; And
The condition of collateral condition III (A-3) is meant: the primer composition of first light that this is moisture comprises at least a organic solvent and water, and the organic solvent that this is at least a and the mass ratio of water are from 5/95 to 49/51, and condition (B-3) is meant: at least a organic solvent that is used for the primer composition of the first moisture light contains the specific organic solvent of mass ratio 40% to 100%, and it has the evaporation rate (what had 25 ℃ the time based on n-butyl acetate is 100 evaporation rate) of 9.5 to 14.5 solubility parameter and 150 to 800.
3. be used to form the bright method of filming according to 1 or 2, wherein this method satisfies condition (C): the primer composition of second light that this is moisture comprises at least a organic solvent and water, and the mass ratio of this at least a organic solvent and water is from 5/95 to 49/51.
According to from 1 to 3 any be used to form the light the method for filming, wherein this method satisfies condition (D): the ratio of the build of this first subbing layer and the build of the second subbing layer is 1.5/1 to 5/1.
5. according to any method of filming that is used to form light of from 1 to 4, wherein the primer composition of this second moisture light contains 0.1 to 5 mass parts based on fluorine or based on the additive of silicon in the solids content of the paint vehicle of per 100 mass parts.
6. the goods through applying of filming that comprise the light that forms according to any method of 1 to 5.
The specific embodiment
Detailed description of the present invention is as follows.
Be used to form the first method of filming of light
According to a particular embodiment of the invention, the first method of filming that is used to form light may further comprise the steps successively: (1) is coated on substrate with the primer composition of the first moisture light, so that the first order in the subbing district (floor) forms the first subbing floor;
(2) primer composition with the second moisture light is coated on the first subbing layer that forms in the step (1), so that the second level in the subbing district (floor) forms the second subbing floor; (3) transparent coating composition is coated on the second subbing layer that in step (2), forms, so that form transparent dope layer in the clear dope district; And (4) heat in step (1), (2) and (3) the uncured dope layer that forms simultaneously, so that solidify these dope layers, and satisfies among following collateral condition I, II and the III at least one.
Collateral condition I
Collateral condition I is meant: condition (A-1) and (B-1) be met.Condition (A-1) is: the primer composition of first light that this is moisture has the solids content of mass ratio 10% to 45%, and the primer composition of this second moisture light has the solids content of mass ratio 10% to 40%.Condition (B-1) is: the ratio of the solids content of the primer composition of the solids content of the primer composition of first light that this is moisture and the second moisture light is from 1.1/1 to 4/1.
Collateral condition II
Collateral condition II is meant: condition (A-2) and (B-2) be met.Condition (A-2) is: the primer composition of first light that this is moisture has the mass concentration (hereinafter being called " PWC ") of 1% to 30% bright pigment, and the primer composition of this second moisture light has the PWC of 5% to 40% bright pigment.Condition (B-2) is: the ratio of the PWC of the bright pigment of the primer composition of the PWC of the bright pigment of the primer composition of first light that this is moisture and the second moisture light is 1/4 to 1/1.1.
Collateral condition III
Collateral condition III is meant: condition (A-3) and (B-3) be met.Condition (A-3) is: the primer composition of first light that this is moisture comprises the solvent that contains at least a organic solvent and water, and the mass ratio of this at least a organic solvent and water is from 5/95 to 49/51.Condition (B-3) is meant: at least a organic solvent that is used for the primer composition of the first moisture light contains the specific organic solvent of mass ratio 40% to 100%, it has 9.5 to 14.5 solubility parameter and 150 to 800 evaporation rate, this moment n-butyl acetate to have in the time of 25 ℃ be 100 evaporation rate (evaporation rate 100 that has 25 ℃ the time with n-butyl acetate is as benchmark).
Be used to form the second method of filming of light
According to a particular embodiment of the invention, the second method of filming that is used to form light may further comprise the steps successively: (1) is coated on substrate with the primer composition of the first moisture light, so that the first order in the subbing district forms the first subbing floor; (2) primer composition with the second moisture light is coated on the first subbing layer that forms in the step (1), so that the second level in the subbing district forms the second subbing floor; And the uncured dope layer of (5) middle formation of heating steps (1) and (2) simultaneously, so that solidify these dope layers, and satisfy among above-mentioned collateral condition I, II and the III at least one.
Be used to form the third method of filming of light
According to a particular embodiment of the invention, the third method of filming that is used to form light is meant: first kind or the second method of satisfy condition (C), this condition (C) is: the primer composition of second light that this is moisture comprises the solvent that contains at least a organic solvent and water, and the mass ratio of this at least a organic solvent and water is from 5/95 to 49/51.
Be used to form the 4th kind of method of filming of light
According to a particular embodiment of the invention, the 4th kind of method of filming that is used to form light is meant: satisfy condition (D) first kind any in the third method, this condition (D) is: the ratio of the build of the build of this first subbing and second subbing is 1.5/1 to 5/1.
Be used to form the 5th kind of method of filming of light
According to a particular embodiment of the invention, the 5th kind of method of filming that is used to form light is meant from first kind to the 4th kind any the method, wherein the primer composition of this second moisture light is in the solids content of per 100 mass parts paint vehicles, contains 0.1 to 5 mass parts based on fluorine or based on the additive of (organic) silicon.
Substrate
According to a particular embodiment of the invention, be used to form the light the method for filming in used base material include but not limited to: metal, for example iron, aluminium, copper and alloy thereof; Inorganic material, for example glass, cement and concrete; Plastic material, for example resin (as polyvinyl resin, acrylic resin, ethylene-vinyl acetate copolymer resin, polyamide, acrylic resin, inclined to one side (two) vinyl chloride resin, polycarbonate resin, polyurethane resin, epoxy resin etc.) and FRP (fibre reinforced plastics); And natural or synthetic material, for example wood materials and textile material (as, paper, clothing etc.).
According to a particular embodiment of the invention, be used to form in the method for filming of light, if be used for the substrate of the conduction of the vehicle body of automobile or parts, so this substrate can be coated with the primary coat tunic (by chemical treatment, or film in the centre that has except this primary coat tunic electro-deposition coating etc.).If be used for nonconducting substrate of the vehicle body or the parts of automobile, so can be afterwards in chemical treatment and conductive processing (if desired), with this substrate coated with priming paint.
This primary coat tunic can play the effect that improves following performance: the filming with adhesion, covering or the covering of substrate or cover performance, corrosion resistance and the rustless property of this substrate of this light.This primary coat tunic can be by being coated with, curing and the formation of cured base coating composition.This primary coat tunic can have the build of 8 μ m to 30 μ m.This bottom coating composition not particular restricted in, but can comprise various compositions, for example cation electric deposition paint composition and anionic electrodeposition electrodeposition coating compositions.According to the type of this electrodeposition coating composition, said composition is by electro-deposition and pass through baked and cured.
Filming in this centre can be by applying midcoat composition, form in substrate or on the primary coat tunic, so that improve filming with adhesion, covering or the covering of substrate or primary coat tunic or covering this substrate or the performance and the resistance to rupture of primary coat tunic of this light.Film and can have the build of 10 μ m to 50 μ m in this centre.For example, this midcoat composition can be to comprise mylar that contains hydroxyl and/or the acrylic resin that contains hydroxyl, and the composition of the PIC of melamine formaldehyde resin (melamine resin) and/or end-blocking (sealing).According to the type of said composition, such composition is applied and dry or curing under room temperature or stoving temperature.
According to a particular embodiment of the invention, be used to form in the method for filming of light, this subbing district is the zone that the subbing floor forms, and the coat film that this subbing layer is a multilayer than internal layer (by under coating).
According to a particular embodiment of the invention, be used to form in the method for filming of light, this clear dope district is the zone that clear dope floor (or transparent area enamelled coating) forms, and outer (by last coating) of the coat film that this transparent area enamelled coating is a multilayer.
According to a particular embodiment of the invention, be used to form in the method for filming of light, this subbing floor forms in the subbing district continuously.This first subbing layer forms in the first order (layer), and (layer) forms and this second subbing layer is in the second level.In specific embodiments of the invention, different specific coating compositions is respectively applied for first and second grades, and this is very important.
Step (1)
According to a particular embodiment of the invention, in the step (1) of the method for filming that is used to form light, the first subbing floor forms by the primer composition (it can be known as the first moisture primer composition) that the first order in the subbing district applies the first moisture light.
This first moisture primer composition contains the water-base resin that forms resin as paint vehicle.This water-base resin can utilize alkaline matter by regulating and control acid number and becoming hydrophilic by the carboxyl (for example, 50% or more carboxyl) of this resin of neutralization.In specific embodiments of the invention, this water-base resin can comprise: the resin that water miscible resin, available water are disperseed, and emulsifying resins.The example of alkaline matter comprises: ammonia, methylamine, ethamine, dimethylamine, diethylamine, trimethylamine, triethylamine, dimethylethanolamine, diethanol amine, triethanolamine etc.Wherein more preferably diethanol amine, dimethylethanolamine and triethanolamine.The solvent of first primer composition that this is moisture mainly is made up of water, can also contain organic solvent.
Form resin for paint vehicle, the crosslinking agent that acrylic resin or mylar can be used as this resin with the PIC and/or the polycarbodiimide compound of amino resins and/or end-blocking.For forming this subbing layer, more preferably use acrylic resin.
Acrylic resin can be the copolymer of the unsaturated monomer of acrylic monomers and other alkene.The example that can be used for the acrylic monomers of copolymer comprises: acrylate or methacrylate, as the ester of methyl, ethyl, propyl group, normal-butyl, isobutyl group, the tert-butyl group, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-ethoxy or 2-hydroxypropyl; The acrylic monomers that contains amide groups, as acrylamide, Methacrylamide, N,N-DMAA, N, N-dimethylmethacryl amide, N, N-dibutyl acrylamide and N, N-dibutylmethyl acrylamide; The adduct of the caprolactone open loop of acrylic acid 2-hydroxyl ethyl ester or methacrylic acid 2-hydroxyl ethyl ester; (methyl) acrylate of polyalcohol etc.Can comprise with other the example of unsaturated monomer of alkene of acrylic monomers copolymerization: styrene, AMS, itaconic acid, maleic acid, vinyl acetate etc.
The example of mylar comprises: the mylar of the not oil-containing that the condensation by polyalcohol and polyacid obtains, and by the react mylar of oil-modification of obtaining of the oil component with polyalcohol and polyacid and one or more aliphatic acid, this aliphatic acid is the aliphatic acid of castor oil, dehydrated castor oil, tung oil, safflower oil, soya-bean oil, Linseed oil, tall oil, cocounut oil etc.
As crosslinking agent, can use the PIC or the polycarbodiimide compound of amino resins and/or end-blocking, more preferably use amino resins.The instantiation of crosslinking agent comprises: two-, three-, four-, five-or six-methylol melamine and alkyl ether thereof, wherein alkyl is methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group etc.; Urea-formaldehyde condensation products; Urea-melamine cocondensation product etc.More preferably melamine resin is used as crosslinking agent.
The polyisocyanate compounds of end-blocking is the polyisocyanate compounds by end of the chain sealed knot agent (end-capping reagent, sealer) end-blocking.End-blocking part in the polyisocyanate compounds of end-blocking is dissociated under heating condition.The example of polyisocyanate compounds comprises: the aliphatic diisocyanate compound, as trimethylene diisocyanate, hexamethylene diisocyanate and trimethylene diisocyanate; Aromatic diisocyanate compounds is as phenylene vulcabond and naphthalene diisocyanate; The aliphatic-aromatic vulcabond is as toluenediisocyanate and toluylene group diisocyanate; Three-or more polyisocyanate compounds, as the trimethylphenyl triisocyanate; The dimer of toluylene group diisocyanate or trimer; Deng.The example of this end-capping reagent comprises: alcohol, as methyl alcohol and ethanol; Tertiary amine is as diethanol amine; Lactams is as caprolactam; Oxime, as methyl ethyl ketone oxime: etc.
This polycarbodiimide compound has at least two carbodiimide-baseds (N=C=N-yl).The particular instance of this polycarbodiimide compound comprises: poly-(4,4 '-xylyl carbodiimides), poly-(3,3 '-dimethyl-4,4 '-xylyl carbodiimides), poly-(tolyl carbodiimides), poly-(to the phenylene carbodiimides), poly-(-the phenylene carbodiimides), poly-(3,3 '-dimethyl-4,4 '-xylyl carbodiimides), poly-(naphthylene carbodiimides), poly-(1,6-hexa-methylene carbodiimides), poly-(4,4 '-methylene dicyclohexyl carbodiimide), poly-(1,4-tetramethylene carbodiimides), poly-(1,3-cyclohexylidene carbodiimides), poly-(1,4-cyclohexylidene carbodiimides), poly-(1,3-diisopropyl phenylene carbodiimides), poly-(1-methyl-3,5-diisopropyl phenylene carbodiimides), poly-(1,3,5-triethyl group phenylene carbodiimides), poly-(triisopropyl phenylene carbodiimides) etc.
In the paint vehicle of this first moisture primer composition, the mass ratio that this paint vehicle forms resin and crosslinking agent is such so that the content of this paint vehicle formation resin is mass ratio 50% to 90%, and the content of this crosslinking agent is mass ratio 10% to 50%, to such an extent as to preferred mass ratio is that such this paint vehicle formation resin content is a mass ratio 60% to 85%, and the content of this crosslinking agent is mass ratio 15% to 40%.When the content of this crosslinking agent is less than mass ratio 10% (when maybe the content that forms resin when this paint vehicle is more than mass ratio 90%), this is crosslinked may to be inadequate.On the other hand, when the content of this crosslinking agent during more than mass ratio 50% (maybe when the content of the resin of this formation paint vehicle is less than mass ratio 50%), the storage stability of this coating composition reduces, and curing degree increases, and causes the bad outward appearance of this coating thus.
This first moisture primer composition contains bright pigment (flitter), can also further contain color pigment and extender pigment if desired.This light pigment can preferably include at least a bright pigment, and this light pigment is selected from: aluminium powder (kaolin) pigment, the alumina silicate pigment of metal oxide-coated, the silica flake pigment of metal oxide-coated, graphite pigment, interfere (type) pigments, mica, colored pigments, mica, Titanium sheet pigment, stainless steel sheet pigment, the iron oxide flake pigment, the glass flake pigment of plating, the glass flake pigment of coated metal oxide (a metal oxide-coated platedglass flake pigment), holographic pigment (hologram pigment), and the flake pigment that comprises cholesteric liquid crystal polymer.This bright pigment can preferably include: aluminium powder (alumina silicate) pigment, the alumina silicate pigment of metal oxide-coated, the silica flake pigment of metal oxide-coated, graphite pigment, interfere pigments, mica, colored pigments, mica, Titanium sheet pigment, stainless steel sheet pigment, the iron oxide flake pigment, the glass flake pigment of plating, the glass flake pigment of coated metal oxide, holographic pigment, and the flake pigment that comprises cholesteric liquid crystal polymer, perhaps its composition.
The example of this color pigment comprises: organic pigment, as azo lake pigment, insoluble type AZOpigments, condensed type AZOpigments, phthalocyanine color, indigo pigment, perylene pigment (perynone pigment), perylene pigment, phthalein ketone pigment, triazine dioxin pigment, quinacridone pigment, isoindolinone pigment, benzimidazolone pigment, diketopyrrolo-pyrrole pigment (diketopyrrolopyrrole) and metal complex pigment; And inorganic pigment, as iron oxide yellow, iron oxide red, carbon black and titanium dioxide.The example of this extender pigment comprises: talcum, calcium carbonate, blanc fixe, silica etc.
This first moisture primer composition provides usually by this way, so that mentioned component can dissolve or be scattered in the water (or deionized water) as solvent (or dispersant).The composition that comprises the hydrophilic organic solvent of place of water also can be included in wherein.In the mixed system of water and organic solvent, the content of water can be from mass ratio 51% to 100% in the whole solvent, and organic solvent content can be from mass ratio 0% to 49%, and the content of water can be higher than the content of organic solvent like this.
This organic solvent can comprise the solvent that is generally used for coating composition.The example of this organic solvent can comprise: hydrocarbon, as toluene and dimethylbenzene; Ketone is as acetone and methyl ethyl ketone (butanone); Ester is as ethyl acetate, butyl acetate, cellosolve acetate and butyl cellosolve; And alcohol.Preferred organic solvent comprises the hydrophily alcoholic solvent
The example of this hydrophily alcoholic solvent can comprise: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, ethylene glycol, 1,2-propane diols, 1,3-butanediol, 2,3-butanediol, hexylene glycol, 2,5-hexylene glycol, DPG etc.
Condition (A-3): the organic solvent of the solvent in the first moisture primer composition/water ratio
According to a particular embodiment of the invention, in satisfying the method for filming that is used to form light of collateral condition III, be comprised in solvent in this first moisture primer composition and have from 5/95 to 49/51 the organic solvent and the mass ratio (being known as " ratio of organic solvent/water ") of water.When the ratio of this organic solvent/water less than 5/95 the time, the decentralization of the composition in this coating composition especially should light dispersing of pigments degree, may reduce, and can not reach outstanding outward appearance thus.When the ratio of this organic solvent/water worked energetically 49/51, the content of this VOC (VOC) may increase.
Condition (B-3): the specific organic solvent that is used for the first moisture primer composition
According to a particular embodiment of the invention, in satisfying the method for filming that is used to form light of collateral condition III, the above-mentioned organic solvent that is used for the solvent that the bottom of this first moisture light films contains the specific organic solvent of mass ratio 40% to 100%.This specific organic solvent has 150 to 800 evaporation rate, and the evaporation rate that has 25 ℃ the time with n-butyl acetate is 100 as benchmark.In addition, this specific organic solvent has 9.5 to 14.5 solubility parameter.
When the evaporation rate of the specific organic solvent that is used for this first moisture primer composition less than 150 the time, this specific organic solvent evaporates from coating with low-down speed, so that drippage performance and outward appearance may be impaired.When the evaporation rate of this specific organic solvent greater than 800 the time, the bin stability of this coating composition may reduce, reason is that volatile quantity is bigger.This evaporation rate more preferably from 200 to 750.
When the solubility parameter of the specific organic solvent that is used for this first moisture primer composition less than 9.5 the time, this specific organic solvent may be separated from coating composition.When this solubility parameter greater than 14.5 the time, the speed that this specific organic solvent volatilizees from coating is lower.This solubility parameter more preferably from 9.7 to 14.5.
The disadvantage that contains the organic solvent of the specific organic solvent that is less than mass ratio 40% is: the directionality of the material that this is bright is impaired etc.This organic solvent preferably contains the specific organic solvent of mass ratio 50% to 100%.
The evaporation rate of this specific organic solvent is a relative value, and this value is measured by gravimetry, and the prerequisite of this method is: the evaporation rate of supposition n-butyl acetate in the time of 25 ℃ is 100, it is at Paul Nylen, et al., Modern Surface Coatings, the value of describing in 1965.The solubility parameter of this specific organic solution is based on C.M.Hansen.Ind.Eng.Chem.Prod.Res Develop., 8[1] values described in 2 (1969) determine.
The evaporation rate and the solubility parameter of typical organic solvent that is generally used for the coating composition field is as described below.This typical organic solvent comprises: hydrocarbon, as toluene (evaporation rate 195, solubility parameter 8.9) and dimethylbenzene (evaporation rate 68, solubility parameter 8.8); Ketone is as acetone (evaporation rate 720, solubility parameter 9.8) and methyl ethyl ketone (evaporation rate 465, solubility parameter 9.3); Ester is as ethyl acetate (evaporation rate 525, solubility parameter 9.1) and butyl acetate (evaporation rate 100, solubility parameter 8.5); And alcohol, as methyl alcohol (evaporation rate 370, solubility parameter 14.5), ethanol (evaporation rate 203, solubility parameter 13.0), isopropyl alcohol (evaporation rate 205, solubility parameter 11.5), n-butanol (evaporation rate 49, solubility parameter 11.3), propane diols (evaporation rate 1, solubility parameter 14.8) and butoxy ethanol (evaporation rate 10, solubility parameter 10.2).
This first moisture primer composition can also contain additive except mentioned component, the example of additive comprises: antiprecipitant, curing catalysts, ultra-violet absorber, antioxidant, levelling agent, surperficial controlling agent (as silicone and organic polymer), anti-dripping agent, thickener, defoamer, lubricant and crosslinked polymer particle (or microgel).
Step (2)
According to a particular embodiment of the invention, be used to form in the step (2) of the method for filming of light, the second subbing floor by the second level in the subbing district will the second moisture light primer composition (it can be known as the second moisture primer composition) be coated on the first subbing floor of the middle formation of step (1) and form.
The second moisture primer composition used in the second level in this subbing district can comprise paint vehicle, pigment, solvent and the additive that can be used for the first moisture primer composition.
Condition (C): the water-organic solvent ratio of the solvent in the second moisture primer composition
According to a particular embodiment of the invention, be used to form in the third method of filming of light, filming of this light is to form under the situation of (C) that satisfies condition, and this condition (C) is: be included in the ratio that solvent in this second moisture primer composition has organic solvent/water of from 5/95 to 49/51.Therefore, the solvent of this second moisture primer composition contains than the more water of organic solvent.When the ratio of this organic solvent/water less than 5/95 the time, the decentralization of the composition of the light of this coating composition may reduce, and can not reach outstanding outward appearance thus.When the mass ratio of this organic solvent/water greater than 49/51 the time, from the viewpoint of VOC, said composition is not particularly preferred.The mass ratio of this organic solvent/water more preferably from 10/90 to 45/55.
Be used for the second moisture primer composition based on fluorine or based on the amount of the additive of silicon (organosilicon)
According to a particular embodiment of the invention, be used to form in the 5th kind of method of filming of light, this second moisture primer composition is in the paint vehicle solids content of per 100 mass parts, contain 0.1 mass parts to 5 mass parts based on fluorine or based on the additive of silicon, the surface tension of said composition is minimized thus, thereby has improved the wetability with this first moisture subbing layer.
This example based on the additive of fluorine can comprise: fluorinated alkyl carboxylate, fluorinated alkyl alkoxide and fluorinated alkyl esters.
This example based on the additive of silicon can comprise: the poly-methyl alkyl siloxane of polyether-modified poly-methyl alkyl siloxane, polyether-modified dimethyl silicone polymer, the poly-methyl alkyl siloxane of polyester modification, silicone modified polypropylene (polyacryl) and aralkyl-modification.
When this was less than 0.1 mass parts based on fluorine or based on the quantity of the additive of silicon in the paint vehicle solids content of 100 parts of every quality, surface tension may descend fully.When this quantity during more than 5 mass parts, this performance of filming may be impaired.Should be based on fluorine or based on more preferably 0.2 to 2 mass parts of the quantity of the additive of silicon.
Condition (A-1): the solids content of the first and second moisture primer compositions
According to a particular embodiment of the invention, satisfy in the method for filming that is used to form light of collateral condition I, this first moisture primer composition has the solids content of mass ratio 10% to 45%, and this second moisture primer composition has the solids content of mass ratio 10% to 40%.When the solids content of this first moisture primer composition is less than mass ratio 10%, for formation has the dope layer of expecting thickness, use relatively large said composition, cause bad coating efficiency.When the solids content of this first moisture primer composition during more than mass ratio 45%, the appearance damage of coating.This first moisture primer composition preferably has the solids content of mass ratio 15% to 40%.When the solids content of this second moisture primer composition is less than mass ratio 10%, for formation has the dope layer of expecting thickness, use relatively large said composition, cause bad coating efficiency.When the solids content of this second moisture primer composition during more than mass ratio 40%, the directionality of the pigment that this is bright is impaired.This second moisture primer composition preferably has the solids content of mass ratio 11% to 30%.When said composition was coated, every kind of coating composition all had above-mentioned solids content, and the heating residue content that this solids content obtains after equaling by the heating said composition volatile ingredient to be removed.In the present invention, this heating residue content be by 105 ℃ with before the said composition heating 3 hours and the difference between the mass value of this coating composition of measuring afterwards obtain.
Condition (B-1): the solids content ratio between the first and second moisture primer compositions
According to a particular embodiment of the invention, satisfy in the method for filming that is used to form light of collateral condition I, the solids content of first primer composition that this is moisture is from 1.1/1 to 4/1 with the solids content ratio of the solids content of the second moisture primer composition.Therefore, the solids content of this first moisture primer composition is more than the solids content of the second moisture primer composition.When this solids content ratio was not in above-mentioned scope, the directionality of the pigment that this is bright can be impaired.More preferably, this solids content ratio can from 1.3/1 to 2.5/1.
Condition (D): the build ratio between the first and second moisture subbings
According to a particular embodiment of the invention, be used to form in the 4th kind of method of filming of light, the build of this first subbing layer is from 1.5/1 to 5/1 with the build ratio of the build of the second subbing layer.Therefore, the build of this first moisture subbing layer is greater than the build of the second moisture subbing layer.When the build between this first and second subbing layer than less than 1.5/1 the time, the directionality of this light pigment can be impaired.If this build ratio is greater than 5/1, brightness can become inhomogeneous so.This build is than more preferably from 1.5/1 to 3/1.
This first moisture subbing layer preferably has the build of 5 μ m to 15 μ m, and the second moisture subbing layer preferably has the build of 2 μ m to 8 μ m.
Condition (A-2): the PWC of the bright pigment of the first and second moisture primer compositions
According to a particular embodiment of the invention, satisfy in the method for filming that is used to form light of collateral condition II, this first moisture primer composition has the PWC of 1% to 30% bright pigment, and this second moisture primer composition has the PWC of 5% to 40% bright pigment.When the PWC of the bright pigment of this first moisture primer composition less than 1% the time, hiding performance can be not enough.When the PWC of the bright pigment of this first moisture primer composition greater than 30% the time, paintability may be impaired.This first moisture primer composition more preferably has the PWC of 3% to 25% bright pigment.When the PWC of the bright pigment of this second moisture primer composition less than 5% the time, brightness may be not enough.When the PWC of the bright pigment of this second moisture primer composition greater than 40% the time, the directionality of the pigment that this is bright may be impaired, applies outward appearance thereby reduce.This second moisture primer composition more preferably has the PWC of 7% to 30% bright pigment.This bright pigment preferably has conversion performance (flip-flopproperty), this means intensity of reflected light angle (perhaps light-receiving angle) and changing according to the observation.
Condition (B-2): the PWC ratio of the bright pigment of the first and second moisture primer compositions
According to a particular embodiment of the invention, satisfy in the method for filming that is used to form light of collateral condition II, the PWC of the bright pigment of first primer composition that this is moisture and the PWC of the bright pigment of the PWC of the bright pigment of the second moisture primer composition are from 1/4 to 1/1.1 than (rate).Therefore, the PWC of the bright pigment of this second moisture primer composition is greater than the PWC of the bright pigment of the first moisture primer composition.When this bright pigment PWC than less than 1/4 the time, it is inhomogeneous that brightness can become.On the other hand, when the PWC of this light pigment than greater than 1/1.1 the time, the directionality of this light pigment may be not enough.More preferably, the PWC of this light pigment ratio can from 1/1.5 to 1/3.5.
These first and second moisture subbing layers preferably form by spraying coating process.Particularly, the first moisture subbing layer of formation can stand to place, and bumps wet mode coated with the second moisture subbing layer with wet subsequently.The second moisture subbing layer that forms can stand to place in 2 minutes, subsequently if necessary, 40 ℃ to 80 ℃ with drying oven with its preheating 1 to 10 minute, so that obtain uncured subbing.
In spraying process, the cup-shaped coating unit of rotating spraying type or air-atomizing type coating unit are preferably used as spray gun.For example, metal revolves a glass G1-COPES bell (ABB Industry OY) and can be used as the cup-shaped coating unit of rotating spraying type.When using this rotating spraying type coating unit, rotary speed is preferably from 2 * 10
4Rpm to 4 * 10
4Rpm. and emission index preferably from 80cc/min to 250cc/min.
Step (3)
According to a particular embodiment of the invention, be used to form in the step (3) of the bright method of filming, by forming the clear dope floor on the second moisture subbing floor that in the clear dope district, transparent coating composition is coated in formation in the step (2).
According to the specific embodiment of this method, should be noted that the second method of filming that is used to form light comprises step (1), (2) and (5), step (3) and (4) have been omitted like this.
In step (3), the second uncured bottom that this clear dope floor obtains in step (2) in the clear dope district is filmed to go up and is formed.This transparent coating can be not hide the water white transparency that bottom films to film, or translucent, and promptly so-called colored transparent is filmed.The transparent coating of filming as top transparent forms on filming in the bottom, and its brightness can improve like this, and is derived from the outstanding pigment of filming the bottom and can be hidden by this transparent coating.
The coating composition that is generally used for the cover coating can be as the clear coating composition that is used to transparent coating.For example, the mixture of above mentioned crosslinking agent and at least a heat-setting resin can be used as clear coating composition, and this resin is selected from: acrylic resin, mylar, fluororesin, epoxy resin, polyurethane resin, polyether resin and modified resin thereof.In addition, at least a heat-setting resin (it can be mixed with above mentioned crosslinking agent), can be selected from following group: acrylic resin, mylar, fluororesin, epoxy resin, polyurethane resin, polyether resin and modified resin thereof, the mixture of selected like this resin and this reagent can be used as transparent coating composition.
This transparent coating composition can contain additive, and as color pigment, extender pigment, modifier, ultra-violet absorber, levelling agent, dispersant and defoamer, condition is the transparency that this additive does not damage said composition.The composition of describing in JP-B-8-19315 (it comprises polymer that contains carboxyl and the polymer that contains epoxy radicals) from the viewpoint of antiacid rain, can preferably be used as clear coating composition.This clear coating composition can be organic solvent type, water type, powder-type etc.This organic solvent type or water type clear coating composition can be the composition of single component type or the composition of two kinds of component types, as the polyurethane resin coating composition of two kinds of component types.
This transparent coating preferably has the build of 10 μ m to 60 μ m.When build is not in this scope, the outward appearance of transparent coating meeting defectiveness, and the formability of filming has infringement.This build more preferably from 20 μ m to 50 μ m.
Step (4)
According to a particular embodiment of the invention, be used to form in the step (4) of the bright first method of filming, uncured the filming that forms in step (1), (2) and (3) heated simultaneously and solidified.
In the dry section adjacent with clear dope (work) district, uncured the filming that forms in step (1), (2) and (3) is dried or solidifies the predefined time period with predefined temperature, so that form the filming of light of multilayer in this substrate.The temperature and time section that is used for drying or curing can be determined according to this first moisture primer composition, this second moisture primer composition and the type of this clear coating composition.
Step (5)
According to a particular embodiment of the invention, in the step (5) of the second method of filming that is used to form light, uncured the filming that forms in step (1) and (2) heated simultaneously and solidified.
In the dry section of suitably arranging, uncured the filming that forms in step (1) and (2) is dried or solidifies the predefined time (section) with predefined temperature, so that the light of formation multilayer films in this substrate.The temperature and time section that is used for drying or curing can be determined according to the type of these first and second moisture primer compositions.
Goods through applying
According to a particular embodiment of the invention, the goods (coated article) through applying comprise filming of the light that forms by any method in aforesaid first kind to the 5th kind method.Utilizing under the situation of first method, the goods through applying are included at least one the step (1) that satisfies among collateral condition I, II and the III in (4), the filming of the light that forms in substrate.Utilizing under the situation of second method, the goods through applying are included at least one the step (1), (2) and (5) that satisfies among collateral condition I, II and the III, the filming of the light that forms in substrate.Utilizing under the situation of the third method, the goods through applying are included under the situation of satisfy condition (C), the filming of the light that forms in substrate based on first kind or second method.Under the situation of utilizing the 4th kind of method, the goods through applying are included under the situation of satisfy condition (D), based on first kind of filming to any light that forms in substrate of the third method.Under the situation of utilizing the 5th kind of method, goods through applying comprise filming of light, this film be by utilizing this second moisture light primer composition (this coating composition the paint vehicle solids content kind of per 100 mass parts contain 0.1 to 5 mass parts based on fluorine or based on the additive of silicon), form in substrate based on any in first kind to the 4th kind method.
With reference to embodiment and comparative example method of the present invention is described in more detail below, but its scope that is not intended to limit the invention.Except as otherwise noted, the quantity of component is with mass ratio (mass fraction) expression, and the trade name of using raw material, coating composition and installing.
Embodiment 1 to 16 and comparative example 1 to 5
Substrate 1 and 2 preparation
With length is that 300mm, width are that 100mm and thickness are that the matt steel plate of 0.8mm is handled with trbasic zinc phosphate.Subsequently, (Ltd.) electro-deposition and is cured 30 minutes at 160 ℃ with it to this tarnish steel plate for POWERTOP V-50, Nippon Paint Co., so that obtain having the electrodeposition coating of the build of 25 μ m with cation electric deposition paint composition.By the aerial spraying method with midcoat composition (ORGAP-5 Sealer, Nippon Paint Co., Ltd.) be coated on this electrodeposition coating, and it was cured 30 minutes at 140 ℃, film so that form the centre of the build with 40 μ m, preparation (preparation) goes out substrate 1 like this.
With length is that 300mm, width are that 100mm and thickness are flushing of plastics polypropylene board and the degreasing of 3.0mm.Subsequently, with the plate after this degreasing priming paint (RB116Primer, Nippon Bee Chemical Co., Ltd.) spraying, be dried 10 minutes then under 80 ℃ surface temperature, the film of this priming paint has the build of 10 μ m like this, prepares out substrate 2 thus.
Step (1): the formation of the first subbing layer
The first moisture primer composition of the color pigment of the necessity that will contain the bright pigment of quantity as shown in table 1 (this table 1 is divided into three parts (1), (2) and (3)) and will mix, be coated on this substrate 1 or 2, so that form the first subbing layer, film so that this substrate 1 or 2 first order in the subbing district are coated with first bottom with build as shown in table 1.Here, by utilizing propylene (acyl) base-melamine resin (acryl-melamine resin) coating composition (AQUAREX AR2100, NipponPaint Co., Ltd.) as this first moisture primer composition of raw material preparing, so that the character of this subbing of control as shown in table 1.On the other hand, in embodiment 11, (KX-0077, Nippon BeeChemical Co. Ltd.) are used as raw material (base material) to moisture melamine-carbodiimides-acrylic coating composition.
Step (2): the formation layer of second subbing
After this first moisture subbing stands to place 2 minutes, in the second level in this subbing district (floor), to contain the bright pigment (mixed colors pigment in case of necessity) of quantity as shown in table 1 and the second moisture primer composition of additive, apply thereon with the wet wet condition that bumps, so that form the second subbing layer with build as shown in table 1.Here, utilize acrylic-melamine resin coating composition (AQUAREXAR2100, Nippon Paint Co., Ltd.) this contains the second moisture primer composition of bright pigment as raw material preparing, so that the character of this subbing of control as shown in table 1.On the other hand, in embodiment 11, (KX-0077, Nippon Bee Chemical Co. Ltd.) is used as raw material to moisture melamine-carbodiimides-acrylic coating composition.
Step (3): the formation of clear dope layer (the formation method of filming of first kind of light)
This second subbing stood to put 2 minutes, and is coated with following clear coating composition in the clear dope district subsequently 80 ℃ of preheatings 3 minutes, so that formed clear dope has the build of 35 μ m.Solution-type clear coating composition (SUPERLAC O-100 Clear based on acrylic resin, Nippon Paint Co., Ltd.) be used as clear coating composition 1, and by polymer that contains carboxyl and mixture of polymers (the MACFLOW O-330 Clear that contains epoxy radicals, Nippon Paint Co., Ltd.) the solution-type clear coating composition of Zu Chenging is used as clear coating composition 2.(Ltd.) spraying is so that this clear dope layer has the build of 30 μ m for R290 Clear, Nippon Bee ChemicalCo. by acrylic (acid)-polyurethane transparent coating composition 3 in this substrate 2.
Step (4): the heat cure of uncured dope layer (the formation method of filming of first kind of light)
This clear dope layer at room temperature stood to put 10 minutes, cured 30 minutes at 140 ℃ of quilts subsequently.Under the situation of substrate 2, this clear dope layer was at room temperature put 10 minutes, cured 20 minutes at 80 ℃ of quilts subsequently.Assess the brightness of the multilayer film that obtains thus by following appraisal procedure.The results are shown in the table 1.
Step (5): the heat cure of uncured dope layer (the formation method of filming of second kind of light): embodiment 12
Formed subbing layer cured 30 minutes at 140 ℃ of quilts.Assess the brightness of the multilayer film that obtains by following appraisal procedure.The results are shown in the table 1.
Appraisal procedure
Outward appearance behind the cover (after finishing): from about front (the brightest part) and film from about 15 degree angle (shade) observation samples, so that from visually assessing flash effect, this effect has showed the quality of metallicity appearance of film and the outward appearance of this coating.What the flash effect that is observed was low more films, and estimates high more.
◎ (fabulous): do not have flash effect.Do not observe the directionality of uneven brightness or reduction.This film has the outward appearance behind the fabulous metallicity cover.
Zero (good): do not have flash effect.This film has the outward appearance behind the metallicity cover.
△ (generally): flash effect is arranged on shade.
* (poor): flash effect is all arranged on the brightest part and shade.This film has (interrupted) metallicity outward appearance successively.Observe the directionality of uneven brightness or reduction.
FF effect (flip-flop effect, transition effects):, and estimate this difference from difference near observation brightness between positive (the brightest part) and the about 15 degree angles (shade).Conversion performance is meant the difference of reflection density when viewing angle (or light-receiving angle) changes.
◎ (fabulous): between different angles, have great brightness difference.
Zero (good): between different angles, have bigger brightness difference.
△ (generally): between different angles, have less brightness difference.
* (poor): between different angles, almost do not have the brightness difference.Intermittence metallicity outward appearance.
Used at following bright pigment, color pigment and the additive shown in the table 1.
Light pigment
1: aluminium powder pigment; Aluminum Paste MH-8801 (ASAHI KASEICORPORATION).
2: aluminium powder pigment; Aluminum Paste 91-0562 (TOYO ALUMINIUMK.K.).
3: the interfere type pigments, mica; Xirallic T60-23WIII (Merck Ltd., Japan).
Color pigment
1: charcoal blacks; MA-100 (MITSUBISHI CHEMICALCORPORATION).
2: phthalocyanine blue pigment; Cyanine Blue G314 (SANYO COLOR WORKS, Ltd.).
Additive
1: the fluorinated alkyl carboxylate; Florade FC-129 (SUMITOMO 3MLIMITED).
2: organically-modified polysiloxanes; BYK-341 (BYK-Chemie JAPAN).
Table 1 in specification and below table 2 and table 3 in, each embodiment or comparative example are described from the following aspect: the ratio of the solids content of substrate, bright pigment (type and quantity (PWC)), solvent, coating composition, build, organic solvent/water, the solids content between first and second coating compositions than the PWC of the bright pigment between, first and second coating compositions than, first and second the builds between filming than, transparent (surface layer) coating composition and to the assessment of outward appearance after finishing and FF effect.
Embodiment 17 to 30 and comparative example 6 to 10
Substrate 1 and 3 preparation
Adopt and prepare substrate 1 and 2 as same method used among the embodiment 1 to 16.
Step (1): the formation of the first subbing layer
The first order in the subbing district is coated on this substrate 1 or 2 with the first moisture primer composition, makes this first subbing layer have build as shown in table 2, and this table is divided into three parts (1), (2) and (3).This first moisture primer composition contains the pigment of light of quantity shown in the table 2 and the color pigment of necessity as required.(AQUAREXAR2100, Nippon Paint Co. is Ltd.) as this first moisture primer composition of raw material preparing, so that the performance of this subbing layer of control as shown in table 2 to utilize propylene (acyl) base-melamine resin coating composition here.On the other hand, in embodiment 27, (KX-0077, Nippon Bee Chemical Co. Ltd.) is used as raw material to moisture melamine-carbodiimides-propylene (acyl) based coating composition.
Step (2): the formation of the second subbing layer
After this first subbing layer is placed 2 minutes, the second level in this subbing district, to contain the pigment, necessary color pigment of light of following type of quantity as shown in table 2 and the second moisture primer composition of necessary additive and apply, so that this second subbing has build as shown in table 2 with the wet wet condition that bumps.(AQUAREX AR2100, Nippon PaintCo. is Ltd.) as this second moisture primer composition of raw material preparing, so that the character of this subbing of control as shown in table 2 to utilize acrylic-melamine resin coating composition here.On the other hand, in embodiment 27, (KX-0077, NipponBee Chemical Co. Ltd.) is used as raw material to moisture melamine-carbodiimides-propylene (acyl) based coating composition.
Step (3): the formation of clear dope (the formation method of filming of first kind of light)
This second subbing layer was placed 2 minutes, and is coated with following clear coating composition in the clear dope district subsequently 80 ℃ of preheatings 3 minutes, so that the clear dope layer that forms has the build of 35 μ m.Use clear coating composition 1: based on solution-type transparent composition (the SUPERLAC O-100 Clear of acrylic resin, Nippon Paint Co., Ltd.), and clear coating composition 2: by polymer that contains carboxyl and mixture of polymers (the MACFLOW O-330 Clear that contains epoxy radicals, Nippon Paint Co., Ltd.) the transparent solution-based paint composition of Zu Chenging.(Ltd.) spraying is so that this clear dope layer has the build of 30 μ m to these substrate 2 usefulness acrylic-polyurethane coating compositions for R290 Clear, Nippon Bee Chemical Co..
Step (4): the heat cure of uncured dope layer (the formation method of filming of first kind of light)
The clear dope layer was at room temperature placed 10 minutes, cured 30 minutes at 140 ℃ of quilts subsequently.Under the situation of utilizing substrate 3, this clear dope layer was at room temperature placed 10 minutes, cured 20 minutes at 80 ℃ of quilts subsequently.Adopt the brightness of the multilayer film that obtains thus with the used same method assessment of embodiment 1 to 16.The results are shown in the table 2.Those used among bright pigment, color pigment and additive shown in the table 2 and the embodiment 1 to 16 materials are identical.
Step (5): the heat cure of uncured dope layer (the formation method of filming of second kind of light): embodiment 28
The second subbing layer that forms was at room temperature placed 10 minutes, and cured 30 minutes at 140 ℃ of quilts.Adopt the brightness of the multilayer film that obtains thus with the used same method assessment of embodiment 1 to 16.The results are shown in the table 2.
Embodiment 31 to 46 and comparative example 11 to 14
Substrate 1 and 2 preparation
Adopt and prepare this substrate 1 and 2 as same method used among the embodiment 1 to 30.
Step (1): the formation of the first subbing layer
The first order in the subbing district is coated on this substrate 1 or 2 with the first moisture primer composition, so that this first subbing layer has build as shown in table 3, this table is divided into three parts (1), (2) and (3).This first moisture primer composition contains the bright pigment of quantity shown in the table 3 and the solvent shown in table 3 and the table 4, if necessary can further contain color pigment.(AQUAREX AR2100, Nippon Paint Co. is Ltd.) as this first moisture primer composition of raw material preparing, so that the character of this subbing layer of control as shown in table 3 to utilize propylene (acyl) base-melamine resin coating composition.On the other hand, in embodiment 43, (KX-0077, Nippon Bee Chemical Co. Ltd.) is used as raw material to moisture melamine-carbodiimides-propylene (acyl) based coating composition.
Here, the numbering of every kind of solvent determines that by its component it can comprise deionized water, methyl alcohol, isopropyl alcohol, acetone, 2-butoxy-ethanol (2-butoxy-ethan), dimethylbenzene, toluene or its composition in the table 4.By evaporation rate as shown in table 4 and every kind of organic principle of solubility parameter assessment.Every kind of solvent is assessed with the mass ratio of specific organic solvent.
Step (2): the formation of the second subbing layer
After this first subbing layer was placed 2 minutes, the second level in this subbing district applied the second moisture primer composition, so that this second subbing layer has build as shown in table 3 with the wet wet condition that bumps.Here, this second moisture primer composition contains the bright pigment of quantity as shown in table 3 and the solvent shown in table 3 and table 4, and necessary color pigment and the additive of necessity as required.
(AQUAREX AR2100, Nippon Paint Co. is Ltd.) as this second moisture primer composition of raw material preparing, and the character of this subbing layer of control as shown in table 3 to utilize propylene (acyl) base-melamine resin coating composition.On the other hand, in embodiment 43, (KX-0077, Nippon Bee Chemical Co. Ltd.) is used as raw material to moisture melamine-carbodiimides-propylene (acyl) based coating composition.
Step (3): the formation of clear dope layer (the formation method of filming of first kind of light)
This second subbing layer was placed 3 minutes, and is coated with following clear coating composition in the clear dope district subsequently 80 ℃ of preheatings 3 minutes, so that the clear dope layer that forms has the build of 35 μ m.Use clear coating composition 1: based on solution-type clear coating composition (the SUPERLAC O-100 Clear of acrylic resin, Nippon PaintCo., Ltd.), and clear coating composition 2: the polymer and mixture of polymers (the MACFLOW O-330 Clear that contains epoxy radicals that contain carboxyl, Nippon Paint Co., Ltd.) the solution-type clear coating composition of Zu Chenging.(Ltd.) spraying is so that this clear dope layer has the build of 30 μ m to these substrate 2 usefulness propylene (aldehyde) base-polyurethane transparent coating compositions for R290 Clear, Nippon Bee Chemical Co..
Step (4): the heat cure of uncured dope layer (the formation method of filming of first kind of light)
Clear dope was at room temperature placed 10 minutes, cured 30 minutes at 140 ℃ of quilts subsequently.Under the situation of substrate 2, this clear dope of formation was at room temperature placed 10 minutes, cured 20 minutes at 80 ℃ of quilts subsequently.Adopt the brightness of the multilayer film that obtains thus with the used same method assessment of embodiment 1 to 30.The results are shown in the table 3.Used those are identical among the pigment of the light shown in the table 3, color pigment and additive and the embodiment 1 to 30.
Step (5): the heat cure of uncured dope layer (the formation method of filming of second kind of light): embodiment 44
The second subbing layer that forms was at room temperature placed 10 minutes, cured 30 minutes at 140 ℃ of quilts subsequently.Adopt the brightness of the multilayer film that obtains thus with the used same method assessment of embodiment 1 to 30.The results are shown in the table 3.
Arrive shown in the table 3 as table 1, the filming of light of the embodiment that method by according to a particular embodiment of the invention forms has following feature: surface smoothness is good, the metallicity outward appearance that almost do not have granular substance, is formed by aluminium powder pigment etc. and do not have uneven brightness, have metallicity gloss and the conversion performance of the raising that formed by interfere type pigments, mica etc.On the other hand, this comparative example's film does not show these useful effects.
According to the present invention, filming of formed multilayer light can have fabulous brightness, so that they can be more preferably used in wherein that brightness is preferred those fields, for example the parts of the shell of automobile and motorcycle and automobile (tire, bumper bar etc.).
Claims (8)
1. one kind is used for forming the bright method of filming in substrate, may further comprise the steps:
(1) primer composition with the first moisture light is coated on substrate, so that the first order in the subbing district forms the first subbing floor;
(2) under the situation of described first subbing of not preheating the primer composition of the second moisture light being coated on the first subbing layer, so that the second level in the subbing district forms the second subbing floor;
(3) transparent coating composition is coated on the second subbing layer that forms in the step (2), so that in the clear dope district, form transparent dope layer; And
(4) uncured dope layer that forms in while heating steps (1), (2) and (3), so that solidify described dope layer,
And satisfy at least one among following collateral condition I, II and the III, and further satisfy following condition (D):
The condition of collateral condition I (A-1) is meant: the primer composition of described moisture first light has the solids content of mass ratio 10% to 45%, and the primer composition of described moisture second light has the solids content of mass ratio 10% to 40%, and condition (B-1) is meant: the ratio of the solids content of the primer composition of the solids content of the primer composition of described moisture first light and the second moisture light is 1.1/1 to 4/1;
The condition of collateral condition II (A-2) is meant: the primer composition of described moisture first light has the mass concentration of 1% to 30% bright pigment, and the primer composition of described moisture second light has the mass concentration of 5% to 40% bright pigment, and condition (B-2) is meant: the ratio of the mass concentration of the bright pigment of the primer composition of the mass concentration of the bright pigment of the primer composition of described moisture first light and the second moisture light is 1/4 to 1/1.1;
The condition of collateral condition III (A-3) is meant: the primer composition of described moisture first light comprises at least a organic solvent and water, and the mass ratio of described at least a organic solvent and water is from 5/95 to 49/51, and condition (B-3) is meant: described at least a organic solvent comprises the specific organic solvent of mass ratio 40% to 100%, it has 9.5 to 14.5 solubility parameter and 150 to 800 evaporation rate, and what described evaporation rate was had 25 ℃ the time based on n-butyl acetate is 100 evaporation rate; And
Condition (D): the ratio of the build of the build of the described first subbing layer and the second subbing layer is 1.5/1 to 5/1.
2. the method for filming that is used to form light according to claim 1, wherein said method satisfies condition (C): the primer composition of described moisture second light comprises at least a organic solvent and water, and the mass ratio of described at least a organic solvent and water is from 5/95 to 49/51.
3. the method for filming that is used to form light according to claim 1, the primer composition of wherein said moisture second light contain 0.1 to 5 mass parts based on fluorine or based on the additive of silicon in per 100 mass parts paint vehicle solids contents.
4. the goods through applying of filming that comprise the light that method according to claim 1 forms.
5. one kind is used for forming the bright method of filming in substrate, comprises following step:
(1) primer composition with the first moisture light is coated on substrate, so that the first order in the subbing district forms the first subbing floor;
(2) under the situation of described first subbing of not preheating, the primer composition of the second moisture light is coated on the first subbing layer that forms in the step (1), so that the second level in the subbing district forms the second subbing floor; And
(5) the uncured dope layer of the middle formation of heating steps (1) and (2) simultaneously, so that solidify described dope layer,
And satisfy at least one among following collateral condition I, II and the III, and further satisfy following condition (D):
The condition of collateral condition I (A-1) is meant: the primer composition of described moisture first light has the solids content of mass ratio 10% to 45%, and the primer composition of described moisture second light has the solids content of mass ratio 10% to 40%, and condition (B-1) is meant: the ratio of the solids content of the primer composition of the solids content of the primer composition of described moisture first light and the second moisture light is 1.1/1 to 4/1;
The condition of collateral condition II (A-2) is meant: the primer composition of described moisture first light has the mass concentration of 1% to 30% bright pigment, and the primer composition of described moisture second light has the mass concentration of 5% to 40% bright pigment, and condition (B-2) is meant: the ratio of the mass concentration of the bright pigment of the primer composition of the mass concentration of the bright pigment of the primer composition of described moisture first light and the second moisture light is 1/4 to 1/1.1;
The condition of collateral condition III (A-3) is meant: the primer composition of described moisture first light comprises at least a organic solvent and water, and the mass ratio of described at least a organic solvent and water is from 5/95 to 49/51, and condition (B-3) is meant: described at least a organic solvent comprises the specific organic solvent of mass ratio 40% to 100%, it has 9.5 to 14.5 solubility parameter and 150 to 800 evaporation rate, and what described evaporation rate was had 25 ℃ the time based on n-butyl acetate is 100 evaporation rate; And
Condition (D): the ratio of the build of the build of the described first subbing layer and the second subbing layer is 1.5/1 to 5/1.。
6. the method for filming that is used to form light according to claim 5, wherein said method satisfies condition (C): the primer composition of described moisture second light comprises at least a organic solvent and water, and the mass ratio of described at least a organic solvent and water is from 5/95 to 49/51.
7. the method for filming that is used to form light according to claim 5, the primer composition of wherein said moisture second light comprise 0.1 to 5 mass parts based on fluorine or based on the additive of silicon in per 100 mass parts paint vehicle solids contents.
8. the goods through applying of filming that comprise the light that method according to claim 5 forms.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003155609A JP4670069B2 (en) | 2003-05-30 | 2003-05-30 | Glittering film forming method and painted product |
| JP155610/2003 | 2003-05-30 | ||
| JP155609/2003 | 2003-05-30 | ||
| JP155611/2003 | 2003-05-30 |
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| CN1787882A CN1787882A (en) | 2006-06-14 |
| CN100423855C true CN100423855C (en) | 2008-10-08 |
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| CNB2004800130531A Active CN100423855C (en) | 2003-05-30 | 2004-05-28 | Method for forming brilliant coating film and coated article showing metallic effect |
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| JP (1) | JP4670069B2 (en) |
| CN (1) | CN100423855C (en) |
Cited By (1)
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| CN109475899A (en) * | 2016-05-19 | 2019-03-15 | 威士伯有限公司 | Candy colored paint material and method for repairing and mending |
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| US7910211B2 (en) * | 2005-06-20 | 2011-03-22 | E.I. Du Pont De Nemours And Company | Process for the production of multi-layer coatings |
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| CA2572900C (en) * | 2006-01-23 | 2011-03-15 | Kansai Paint Co., Ltd. | Method of forming multi-layered patterned coating film |
| DE102007023539A1 (en) * | 2007-05-18 | 2008-11-20 | Basf Coatings Ag | Aqueous, pigmented coating compositions, process for their preparation and their use for the production of multicoat paint systems |
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| JP5939604B2 (en) * | 2009-12-18 | 2016-06-22 | 関西ペイント株式会社 | Coating composition and coating film forming method |
| JP5456496B2 (en) * | 2010-01-25 | 2014-03-26 | トヨタ自動車株式会社 | Method for forming high-saturation multilayer coating film and painted product |
| CN107708878B (en) * | 2015-07-31 | 2021-03-23 | 关西涂料株式会社 | Method for forming multilayer coating film |
| JPWO2017111112A1 (en) * | 2015-12-25 | 2018-10-11 | 関西ペイント株式会社 | Multi-layer coating formation method |
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| WO2019141823A1 (en) * | 2018-01-18 | 2019-07-25 | Basf Coatings Gmbh | Process for coating fiber composite panels at low baking temperatures |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1787882A (en) | 2006-06-14 |
| JP4670069B2 (en) | 2011-04-13 |
| JP2004351389A (en) | 2004-12-16 |
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