CN1145383A - Multicolor coating composition - Google Patents
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- CN1145383A CN1145383A CN 96109205 CN96109205A CN1145383A CN 1145383 A CN1145383 A CN 1145383A CN 96109205 CN96109205 CN 96109205 CN 96109205 A CN96109205 A CN 96109205A CN 1145383 A CN1145383 A CN 1145383A
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Abstract
A multicolor coating composition and coating mehtod thereof. Said composition containing at least one kind of enamel dispersion particles prepared by dispersing in an aqueous dispersion medium, and enamel obtained by mixing and dispersing a composition comprising as essential components, (A) a copolymer having a weight average molecular weight of 20,000 to 200,000 and an acid value of not more than 2 and prepared by copolymerizing a monomer mixture containing at least 20% by weight of an acrylic monomer, (B) a pigment, and (C) an organic solvent.
Description
The present invention relates to a kind of oil-in-water-type multicolor coating composition, particularly a kind ofly contain that the enamel paint (ENAMEL) that is dispersed in the pigment in the enamel paint is dispersed in aqueous phase and the multicolor coating composition made, it can show multicoloured design, this design is that a large amount of tones is mixed, through primary coating, almost there is not taste during coating, the good and waterproof of its coating weatherability.Composition of the present invention can be used to apply building, vehicle, bridge, container, fluting board, plastic containers, office machinery, furniture, the interior outside of woodwork or the like.
Thisly form coating that the multicolour design films through primary coating and be referred to as multicolor coating and be JIS K 5667 by specific.In these coating, Japanese Patent discloses oil-in-water-type multicolor coating a kind of and that use in practice with J.C.ZORA for No. 231698, it contains and is dispersed in the water dispersion medium as the discontinuous phase that is enough to identify, the colored enamel paint that is dissolved in organic solvent, for example, it has been widely used in various purposes in Japan.Yet because the multicolor coating of most routine contains nitrocellulose, polyethylene toluene or polyhutadiene are as basic resin, and its weathering resistance is poor, result's decolouring of filming.When it is used to the outside of buildings, the foaming of filming.The organic solvent that is used to dissolve these basic resin also has problem flavoursome when applying, and the Working environment problem, because sp value (solubility parameter) that it is had relatively high expectations (Parameter of solubility) and lower boiling.
The present invention's contriver studies assiduously and improves weathering resistance with styrene-propene acyl group multipolymer as basic resin.Can not stablize and be dispersed in the water enamel paint particle, therefore can not actual use.
Above-mentioned conventional multicolor coating water-repellancy and poor durability, thereby the problem that causes is when using out of doors, overlay pattern particulate dispersant resin in filming is dissolved in the rainwater or the like, when under specific environment, using, as the open air, or the toilet, peeling off can appear between the pattern particle in the place of waters such as bathroom.Therefore, be difficult in and keep the virgin state of filming under the specific environment for a long time.In addition, another problem is to film can occur damaging through pollution.
The inventor has solved above-mentioned problem after deliberation, and find to stablize the enamel paint disperse phase, have specific monomer concentration by use, the multipolymer of acidity and molecular-weight average can reach the keeping quality (Storability) of its weathering resistance of filming and coating as the enamel paint resin.The present invention just is being based on this.
According to the present invention, it provides a kind of multicolor coating, and this coating contains at least a enamel paint discrete particles, and this particle makes through enamel paint is dispersed in the water dispersion medium, this enamel paint is through mixing and disperseing a kind of composition to make, said composition comprises (A), and a kind of molecular-weight average is 20,000 to 200,000, acid number is less than 2 multipolymer, this multipolymer contain through copolymerization at least 20% weight Acrylic Acid Monomer monomer mixture and make (B) pigment and (C) organic solvent.
Multipolymer of the present invention (A) be molecular-weight average be 20,000 to 200,000 and acid number for being not more than 2, and contain the multipolymer that the monomer mixture of the Acrylic Acid Monomer of at least 20% weight makes by copolymerization.
The example of Acrylic Acid Monomer comprises alkyl ester and the cycloalkyl ester with 1-24 carbon atom vinylformic acid and methacrylic acid, as (methyl) methyl acrylate, (first) ethyl propenoate, (just) (first) butyl acrylate, (different) (first) butyl acrylate, t-(first) butyl acrylate, 2-ethylhexyl (first) acrylate, lauryl (first) acrylate and iso-borneol (first) acrylate.They can use separately or two or morely unite use.The band hydrophilic functional groups, as carbonyl, hydroxyl, amide group or amino Acrylic Acid Monomer can be with a spot of, but the above-mentioned monomer that does not destroy enamel paint discrete particles stability is united use.
Be used for comprising vinyl aromatic compound with other monomeric example of above-mentioned Acrylic Acid Monomer copolymerization, as vinylbenzene, alpha-methyl styrene, Vinyl toluene and α-chloro-styrene; The monomer that contains alkoxysilyl, as vinyltrimethoxy silane, vinyltriethoxysilane, γ-(first) acryloyl-oxy propyl trimethoxy silicane, and γ-(first) acryloyl-oxy propyl group dimethoxy-methyl silane; Perfluoroalkyl (first) acrylate for example, perfluoro butyl ethyl (first) acrylate, the different nonyl ethyl of perfluor (first) acrylate (perfluoroisononylethyl (meth) acrylate) and perfluoro capryl ethyl (first) acrylate; By general formula CX
2=CX
2The fluoroolefin of expression, (wherein X ' s is identical or different and is selected from H, Cl, Br, F, alkyl and alkylhalide group, but at least one F in the molecular formula) for example, CF
2=CF
2, CHF=CF
2, CH
2=CF
2, CClF=CF
2Deng.Can suitably select them according to required physical property.
Can be in the presence of the radical polymerization initiator, the method with commonly used makes the used multipolymer of the present invention as the above-mentioned monomer mixture of solution polymerization process polymerization.The example of radical polymerization initiator comprises superoxide, as benzoyl peroxide, t-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide, two different phenylpropyl alcohol hydroperoxide, t-butyl perbenzoate, lauryl peroxide, vinyl superoxide and t-butyl peroxy-2-ethylhexanoate; And azo-compound, as α, α '-azo-bis-isobutyl cyanide, α, α '-azo-2-methyl fourth cyanogen, azobisdimethylcvaleronitrile and azo bicyclohexane nitrile.
The solvent that is used for polyreaction is an aliphatic hydrocrbon, as petroleum benzene, and a kind of solvent oil (about 150-200 degree centigrade fraction) (mineral spirit) or turps; Aromatic hydrocarbon is benzene for example, toluene or dimethylbenzene; Alicyclic hydrocarbon such as hexanaphthene; Perhaps little material with the avidity of water, as ethylene dichloride, trieline, texanol, texanol isobutylate, 2-ethylhexyl alcohol, diisobutyl ketone, 2-ethylhexyl acetic ester, dibutyl phthalate or dioctyl phthalate (DOP).They can use or unite use separately.Wherein, aliphatic hydrocarbon solvent when applying from Working environment be seen as preferred it.
When adopting relatively poor solvent, as solvent, the solubility parameter sp value that it is desirable to described monomer mixture will suitably be controlled (measuring its wetting ability) to obtain good enamel paint as relatively poor aliphatic hydrocarbon solvent when polyreaction.Owing to be subjected to the influence of high hydrophilic monomer, the sp value that contains the monomer mixture of Acrylic Acid Monomer is 7.6-8.6, is preferably 7.8-8.4.Used Acrylic Acid Monomer can suitably be selected so that the sp value reaches this scope.
Calculate sp value (parameter of solubility) with each monomeric sp value as follows
Sp value: δ
δ×100＝(δ
a×A)+(δ
b×B)+(δ
c×C)+………
δ wherein
a, δ
b, δ
c... be monomer a, b, c ... the sp value, and A, B, C ... own (vinylformic acid) monomeric total weight monomer a for pressing, b, c ... the numerical value of weight percent (each monomeric sp value is J, Paint Tech., 42 (541), 176 (1970))).
Polymerization contains at least 20% weight, and the monomer mixture that is preferably the aforesaid propylene acid mono of at least 50% weight can make multipolymer (A).From weathering resistance and water-repellancy angle, this monomer mixture contains 0-50% weight, is preferably the vinylbenzene of 10-30% weight, and 20-100% weight is preferably the vinylformic acid and the 0-80% weight of 50-90% weight, is preferably other monomer of 0-40% weight.
The molecular-weight average of multipolymer (A) is 20,000-200, and 000, be preferably 50,000-150,000.If the stability of enamel paint discrete particles can descend in weathering resistance that molecular weight less than 20,000, is filmed and the coating, if its molecular weight greater than 200,000, the manufacturability of coating and the moulding property of filming all can reduce greatly.
The acid number of multipolymer (A) is preferably less than 1 less than 2.If its acid number is greater than 2, the stability of enamel paint discrete particles can descend greatly.
The second-order transition temperature (Tg) of multipolymer (A) is 0-80 degree centigrade, is preferably the 10-60 degree.If Tg is lower than 0 degree centigrade, the stability of enamel paint discrete particles and the weathering resistance of filming can reduce, and film can be easy to painted.If the Tg value is higher than 80 degrees centigrade, moulding property can reduce, and filming is easy to become fragile.
Known tinting pigment of any routine (coloring pigment) or loading pigment can both be as the present invention's pigment (B).Tinting pigment comprises titanium oxide, carbon black, red iron oxide, ferric oxide, copper phthalocyanine blue (copper phthalocyanine blue) the copper phthalein mountain valley with clumps of trees and bamboo green (copper phthalocya-nine green), benzoglyoxaline, azo pigment, quinacridone red, chrome yellow, chromic oxide, ultramarine blue, pearl pigment, metal powder or the like.Loading pigment comprises lime carbonate, clay, talcum, barium sulfate, white carbon, aluminum oxide, silicon oxide, bentonite, mica or the like.They can use separately also can unite use.The content of pigment is preferably and is no more than 70% weight in the enamel paint, and it can suitably select it according to final design, more preferably is no more than 50% weight.Surpass 70% weight as content, the physical strength of enamel paint can reduce, and the result can reduce stability and spraying adaptability when applying the enamel paint discrete particles.And then, when surpassing 50% weight as content, viscosity and proportion that will wayward enamel paint.
Any known organic solvent can be as the present invention's organic solvent (C).These organic solvents comprise aliphatic hydrocrbon, as petroleum benzene, and a kind of solvent oil (about 150-200 degree centigrade fraction) (mineral spirit) or turps; Aromatic hydrocarbon is benzene for example, toluene or dimethylbenzene; Alicyclic hydrocarbon such as hexanaphthene; Other also comprises as ethylene dichloride, trieline, texanol, texanol isobuty-late, 2-ethylhexyl alcohol, diisobutyl ketone, 2-ethylhexyl acetic ester, dibutyl phthalate or dioctyl phthalate (DOP), methyl alcohol, ethanol, butanols, acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK).They can use or unite use separately.Wherein, aliphatic hydrocarbon solvent when applying from Working environment be seen as preferred it.The content of organic solvent (C) is preferably 20-70% weight in the enamel paint.If this content is less than 20% weight, with the proportion and the viscosity of wayward enamel paint, and if this content when surpassing 70% weight can reduce the physical strength of enamel paint, the result can reduce stability and spraying adaptability when applying the enamel paint discrete particles.
Among the present invention, mix aforesaid multipolymer (A), comprise the pigment (B) of tinting pigment and organic solvent (C) and according to the method for routine, as adopt for example dispersion mixer of decollator, sand milling, roller mill or ball mill disperse, and make enamel paint (enamel).Therefore, can suitably in said composition, add additives such as for example dispersion agent, anti-whipping agent or softening agent on request.
The enamel paint discrete particles stability of the scope of the proportion of the enamel paint that as above obtains from coating is preferably 0.95-1.5 at 0.90-2.5.If proportion surpasses this scope, on discrete particles can float on the surface when depositing coating, bonding mutually easily it.Press final design and can suitably determine the viscosity of enamel paint, from the physical strength angle of enamel paint, it is generally 1Pas or bigger.
Composition of the present invention contains at least a enamel paint discrete particles (enamel dispersionparticle), and this particle result is distributed to above-mentioned enamel paint in the water dispersion medium and makes.
Any known water dispersion medium can be used as above-mentioned water dispersion medium, and it is generally suitably mixes being used for stable dispersion particulate stablizer, and their not aggegations and making.Described stablizer promptly can be also can be inorganic organically, but preferably water miscible and have a stablizer of hydrophobic part.This stablizer comprises known protective colloid, methylcellulose gum for example, ethyl cellulose, polyvinyl alcohol; casein, tragacanth gum, rhodia phthalic ester; bentonite, Natvosol, poly-first vinylformic acid; gum arabic, kuteera gum, gelatin; sodiun alginate, albumin, pectin; xanthan gum, starch, water-soluble urea formaldehyde or the like.Relative water-insoluble salt, clay for example, talcum, barium sulfate, lime carbonate, magnesiumcarbonate and diatomite can be used used as stabilizers.Yet,, it is desirable to use its nearly thin as far as possible powder because requirement is bigger than the consumption of water-soluble stablizer.
With ionogen (as sodium-chlor, sodium sulfate or sal epsom), moist agent, film coalescence aid, frostproofer, anti-whipping agent and desired dyestuff are with suitable being metered in the above-mentioned water dispersion medium, and its add-on can not be destroyed the stability of discrete particles or the like.
Disperse the method for enamel paint can adopt conventional known method in water dispersion medium, it uses common dispersion mixer mixing enamel paint and water dispersion medium, and its ratio is 1.5-0.3.Yet the preferred device that uses for example has the propeller-type mixer of two cutting knifes for mixing the device of all components with little shearing force.
In order in water dispersion medium, to disperse enamel paint, disperse the desired enamel paint of each final design, and the water dispersant of each enamel paint be mixed preparation coating.Perhaps all enamel paint of Mixed Design requirement and while are disperseed it in water dispersion medium, preparation coating.Preceding a kind of method is more commonly used from the reproducibility of pattern color.
From the reproducibility angle of pattern color, by the about 0.1mm of size of the above-mentioned enamel paint discrete particles that obtains or bigger.Granular size can be come according to final design alternative by the kind of stablizer in suitable control water dispersion medium and the composition and the viscosity of quantity and enamel paint.The enamel paint discrete particles is always not circular, but can be oval or beading shape.
Composition of the present invention contains at least a above-mentioned enamel paint discrete particles.According to design requirements, can mixed state comprise several enamel paint aqueous dispersions in the said composition.Composition of the present invention can use with common coating method, and for example brush method etc. are rolled in spraying.Particularly preferably use spraying, as aerial spraying or HVLP (heavy body low pressure) spraying, reason is can obtain uniform pattern with flexible enamel paint discrete particles hardly.Weight of coated paint is unrestricted, is generally 50-1200g/m
2, be preferably 200-700g/m
2
The present invention applies last method and comprises and use broken colour coating, dry coating and film with a transparent coating to above-mentioned.
The Clear paint that uses in the inventive method is for being dissolved in organic solvent or aqueous coating, and its dry-coated material lid end rate is 0.5 or littler, to use the feature of pattern coating film most effectively.If coating lid end rate is less than 0.5, Clear paint can be glossiness, smooth colored Clear paint and the Clear paint that contains pearl pressure.
Any known resin can use and unrestricted as the resin combination of Clear paint.Be used for the open air as Clear paint, preferably this Clear paint contains at least a acrylic resin, urethane resin, and silicone resin and fluoro-resin are as basic resin.
Preferably, Clear paint contains the organosilicon acid esters (organo sili-cate) that following general formula is represented:
(wherein R is identical or different, and it is selected from hydrogen atom and has the alkyl of 1-3 carbon atom) and/or its condensation product.The example of described organosilicate comprises tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, dimethoxy diethoxy silane or the like.The condensation product of organosilicate comprises the side chain represented by above-mentioned general formula and the condensation product of straight chain organosilicate.Operable commerical prod is ethyl silicate 40 for example, ethyl silicate 48 and methyl silicate 51 (be Colcoat Co. make) they can be separately or two or three kind of associating commerce.Because when mixing organosilicate and/or its condensation product, can will be bonded at dirt flush away on filming through rainwater of open air or the like, so the long-term commerce of filming is also apparent dirty, and can also keep its initial quality.According to 100 listed as parts by weight of coating resin solids content, the about 1-40 weight part of the overall proportion of organosilicate and/or its condensation product.
It is desirable to from the weathering resistance angle, Clear paint contains UV light absorber.This UV light absorber is a benzophenone, benzotriazole, N-oxalic acid anilide (anilide oxalate), cyanoacrylate, triazine, metal oxide fine particles such as titanium oxide fine particle or the like.Can separately or unite more than two and use them.Also can use as interrupted amine photostabilizers such as (hindered amine).The ratio of the wide absorption agent of ultraviolet ray is about 0.5-3% weight.
Clear paint also can be suitably and needed fluidity improver, additive, and vulcanization accelerator, softening agent or the like mixes.Usually the method that adopts as brush, is rolled spray etc. and can both be used this coating.Weight of coated paint is preferably 100-200g/m
2
As mentioned above, the present invention's method comprises and uses and dryly use above-mentioned Clear paint on colo(u)r coating and the dried paint film more than above-mentioned.Before multicolor coating is used, a kind of main raw directly is applied on a kind of substrate can forms a substrate layer, perhaps directly use substrate coating, then main raw is used further on the substrate.
Can be used as substrate to above-mentioned substrate coating if desired, and this substrate coating with making improvements adherent purpose between substrate and the main raw layer, prevent the substrate weathering or because the inhomogeneous absorption main raw of porous substrate.Substrate coating is a kind of gasket coating, or a kind of substrate material that contains resin Composition, and described resin Composition is selected from acrylic resin at least, vinyl chloride resin, and vinyl acetate resin is crossed epoxy resins, benzene first two acid resins or the like.Substrate coating can suitably repeatedly be used the place with water, toilet for example, bathroom etc.These places all require to have very high water resistance.
This main raw can be directly used in substrate, perhaps is used for the top of substrate and is used on substrate forming one resembling fork-join spare sample, the atypic or three-dimensional arrangement of piling up, and cover crackle and defective on the substrate.This main raw can be that a kind of its composite bed is a synthetic resins emulsion in order to finish the main raw of composite bed at last, clay or polymer cement, or improved substantially coating material.Elastic coating particularly, it comprises synthetic resins emulsion, as disclosed reaction slaking vinylformic acid emulsion among the JP-A-6-190332.Also can be used to form a uneven layer to them as roller or spray gun with Painting tool commonly used.The coating amount of application is preferably 0.3-2Kg/m
2
Operable substrate comprises cement in the inventive method, plaster and slabstone; Pottery and potter's clay are for example watt; Plastics, wood, stone, metal, paper etc.Preferably, the surface of suitable finished these materials of process.
As mentioned above, according to the present invention, may obtain the stable multicolor coating composition of taking discrete particles of a kind of energy, it has and does not have taste when good storage characteristics is used, the coating weatherability that forms is good, good waterproof performance, and also can easily obtain and have multicolour design sense, adopt the colored multicolour of transferring of macro-mixing to film.By further using Clear paint on multicolour is filmed, the original condition of filming is able to secular preservation, can't produce flavescence or efflorescence in normal back of time, and can not produce owing to using it out of doors is to occur filming peeling off between the design particle.
From the angle of decorating, in order to form a kind of structure, make a substrate layer by using a kind of main raw, can improve designing properties, can obtain the degree of depth that outward appearance seems stone material through a spot of operation.A multicolor coating can very well be used to the ectonexine of buildings.
Following embodiment further explains the present invention.
The preparation of multipolymer (A)
Production example A
Select one to have thermometer, thermostatted, agitator, the reactor of reflux exchanger and dropping liquid pump.With pack into reactor and of the solvent oil (about 150-200 degree centigrade fraction) of 45 weight parts 100 degrees centigrade of stirring heating, monomer mixture and the t-butyl peroxy-2-ethylhexanoate as shown in table 1 100.4 weight parts splash into reactor, keep 100 degrees centigrade of conventional speeds to splash into three hours with the dropping liquid pump.Splash into back 100 degree down reactors kept 2 hours, continuously stirring it.Then drip other polymerization initiator (t-butyl peroxy-2-ethylhexanoate) solution of 1 hour 0.5 weight part, under 100 degree, reactor is kept finishing in 1 hour reaction then with normal speed.Reaction product is diluted with the solvent oil (about 150-200 degree centigrade fraction) of 48.8 weight parts.The copolymer solution that obtains is the solution of uniform coating, and nonvolatile component accounts for 45% weight.The molecular-weight average of this multipolymer is 98,000, and Tg is 45 degrees centigrade.
Production example B to I
The step of duplication of production embodiment A different is to use polymerization initiator composition and the monomeric mixture shown in the reaction solvent shown in the table 1 and this table, makes copolymer solution.The every kind of multipolymer that obtains and the performance of every kind of copolymer solution see Table 1.
Table 1
Annotate: the M on " reaction soln " hurdle is meant mineral spirit in the table 1, and X refers to xylene.
| Production example | ||||||||||
| ????A | ????B | ????C | ????D | ????E | ????F | ????G | ????H | ????I | ||
| Monomer composition | Vinylbenzene | ????20 | ????10 | ????25 | ????55 | ????20 | ????40 | ????20 | ????30 | |
| Methyl methacrylate | ????30 | ????10 | ????40 | ????25 | ????10 | |||||
| The i-butyl methacrylate | ????63 | ????45 | ????60 | ????40 | ????20 | ????35 | ????63 | ????30 | ||
| The i-butyl acrylate | ????17 | ????20 | ????17 | ????10 | ||||||
| The n-butyl acrylate | ????30 | ????20 | ||||||||
| Lauryl first acrylate | ????15 | ????35 | ????25 | ????20 | ||||||
| Vinylformic acid | ????0.1 | ????0.3 | ||||||||
| The SP value of vinylformic acid influence | ????8.2 | ????8.5 | ????8.4 | ????8.0 | ????8.0 | ????8.9 | ????8.6 | ????8.2 | ????8.3 | |
| The polymerization initiator | ????0.4 | ????0.4 | ????0.4 | ????0.13 | ????0.4 | ????0.4 | ????0.4 | ????1.0 | ????0.4 | |
| Reaction soln (*) | ????M | ????M | ????M | ????M | ????M | ????X | ????M | ????M | ????M | |
| Acid number | ????0.1 | ????1.1 | ????0.2 | ????0.1 | ????0.2 | ????0.2 | ????0.2 | ????0.1 | ????2.5 | |
| Weight average molecular weight | ????98000 | ????89000 | ????92000 | ????168000 | ????91000 | ????81000 | ????97000 | ????16000 | ????92000 | |
| Tg | ????45 | ????43 | ????15 | ????6 | ????31 | ????30 | ????83 | ????45 | ????26 | |
| Non-volatile amount | ????45 | ????45 | ????45 | ????45 | ????4?5 | ????45 | ????45 | ????45 | ????45 | |
In water, disperse enamel paint
With copolymer solution, pigment and solvent are packed in 2 liters the stainless steel vessel, and its loading ratio is as shown in table 2, stirs 15 minutes with agitator.Disperse 15 minutes this solution with peeling off pearl together with the sand milling of table height subsequently, it is yellow to prepare white, redness, and black and blue enamel paint are with corresponding to each the copolymer solution A to I that obtains in the above-mentioned production example.
Then, the clear water that will contain 100 weight parts, 0.5 weight part methylcellulose gum, 0.1 the water dispersion medium of Slaoff 72N of weight part (annotating 1) and 0.1 weight part BYK-025 (annotating 2) mixes through above-mentioned each enamel paint that obtains with 100 weight parts, with blade agitators stirring at low speed 15 minutes, thereby enamel paint is distributed to a kind of like this degree, the scope that is the granular size of its enamel paint discrete particles is the 1-2 millimeter, thereby in water, make white, yellow, red, black and blue enamel paint makes it corresponding to copolymer A-I.The sanitas of (annotating 1) Slaoff 72N:Takeda Pharmaceutical Co. preparation.The anti-whipping agent that (annotating 2) BYK-025:Bic Chemy Co. produces.
Table 2
| Enamel paint | |||||
| White | Yellow | Red | Black | Blue look | |
| Copolymer solution | ??210 | ???210 | ???210 | ???210 | ???210 |
| Titanium white | ??72 | ||||
| The oxidation Huang | ???72 | ||||
| Red iron oxide | ???30 | ||||
| Carbon black | ???12 | ||||
| Phthalein is blue or green blue | ???48 | ||||
| Talcum | ??30 | ???30 | ???60 | ???72 | ???60 |
| Bentonite | ??24 | ???24 | ???24 | ???24 | ???24 |
| Solvent oil | ??234 | ???234 | ???210 | ???144 | ???162 |
| Amount to | ??570 | ???570 | ???534 | ???462 | ???504 |
The preparation of multicolor coating
Embodiment 1-8 and comparative example 1-4
White in the water for preparing to I for copolymer A, Huang, red, black and blue enamel paint dispersion liquid mixes, and its every kind multipolymer (white/yellow/red/black/orchid) blending ratio is 60/10/10/10/10, produces multicolor coating A-I.
Copolymer A ceramic whiteware lacquer dispersion liquid in water and the Huang in water of multipolymer B, red, dispersion liquid black and blue enamel paint mixes, and its blending ratio be (white/yellow/red/as to deceive/orchid) 60/10/10/10/10, prepares multicolor coating J.
Using Zoracoat No.229 (KANSAI PAINT CO. produce contain Nitrocellulose multicolor coating) and Zoratone No.17911SU (multicolor coating that contains the vinyl toluene resin that KANSAI PAINT CO. produces) respectively is multicolor coating K and L.
The coating situation of these coating sees Table 3 with film forming test and test-results
Table 3
Annotate: "-" expression test is impossible in the table 3.
| Embodiment | Comparative example | |||||||||||||
| ?1 | ?2 | ?3 | ??4 | ?5 | ?6 | ?7 | ?8 | ?1 | ?2 | ?3 | ?4 | |||
| The coating title | ?A | ?B | ?C | ??D | ?E | ?F | ?G | ?J | ?H | ?I | ?K | ?L | ||
| Forming test | The coating situation | When coating is made | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?× | ?◎ | ?◎ |
| After following 24 hours of the room temperature | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | ?× | ?◎ | ?◎ | ||
| 40 ℃ after following 1 month | ?◎ | ?○ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?× | ?- | ?◎ | ?◎ | ||
| During coating | Taste | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?- | ?× | ?○ | ||
| Pattern character | ?◎ | ?○ | ?◎ | ?○ | ?◎ | ?◎ | ?○ | ?◎ | ?△ | ?- | ?○ | ?◎ | ||
| Weathering resistance | 250 hours | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | ?- | ?○ | ?○ | |
| 1,000 hour | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | ?◎ | ?○ | ?◎ | ?× | ?- | ?× | ?× | ||
| The hot/cold round-robin test | ?◎ | ?◎ | ?○ | ?◎ | ?◎ | ?◎ | ?○ | ?◎ | ?○ | ?- | ?× | ?× | ||
Test method is as follows.(1) coating situation (keeping quality)
Preparation placed coating room temperature 24 hours behind the coating immediately, left standstill 1 month under 40 degrees centigrade then.After this, the coating in the stirred vessel is not destroyed the enamel paint discrete particles lightly, observes the situation of coating.
Two circles: do not observe particles coalesce
Individual pen: observe some particles coalesce
Fork: taste and pattern quality when observing a large amount of particles coalesce (2) coating
Adopt spray gun with 300-400g/m
2Amount be sprayed on the sheet tin taste that produces by following criterion evaluation.
Two circles: also do not have taste when almost not having taste and use
Individual pen: almost do not have taste during coating, be retained in upward about 1 or 2 weeks of filming but apply the back taste.
Fork: taste is big, will be with protective mask during coating.
By the pattern quality (pattern quality) of filming after the following standard visual assessment coating.
Two circles: the clear 5 meters external enwergys identification of particle pattern.
Individual pen: the small part of visible particle pattern, 5 meters outer difficult identifications.
Triangle: some is out of shape pattern, can see the many linear part of pattern.
Fork: particle pattern is badly deformed and can not sees anything.(3) weathering resistance
Alelholder G (water substrate layer improving agent, KANSAI PAINT CO. produces) is used on the thin plate of 70 * 150 * 4 millimeters sizes of roller round brush to, and its round brush amount is 800-1,000kg/m
2, drying at room temperature was made a test board in 7 days then.Every kind of coating all is sprayed on this test board, and its quantity for spray is 300-400g/m
2, the plate that applied is tested in one of drying at room temperature preparation in 7 days then.
With sunlight weather survey meter (sunshine Weather-O-meter) test of the test board after the coating that obtains after 250 hours and 1000 hours, is detected its weathering resistance, the situation of visual assessment coated surface.
Two circles: do not have and on coated surface, do not see crackle, peel off, decolouring and efflorescence.
Individual pen: visible slight decolouring or efflorescence.
Fork: visible crack on coated surface, peel off decolouring or significantly decolouring and efflorescence.(4) hot/cold circulation
Test board after the coating for preparing in (3) identical mode is carried out ten hot/cold round-robin tests, hot/cold round-robin test according to JIS A 6909, each round-robin test comprises in 18 hours the water floods, in the isothermal device, handled 3 hours for negative 20 degrees centigrade, in the isothermal device, handled 5 hours for 50 degrees centigrade.The coated surface of the coated test plate of visual inspection after above-mentioned test.
Two circles: coated surface is not seen crackle, peels off decolouring.
Individual pen: coated surface is visible crack a little, peels off a kind of performance of decolouring.
Fork: the obvious visible crack of coated surface, peel off a kind of performance of decolouring.
Coating
The preparation of Clear paint
Ratio in (solids content) shown in the table 4 prepares Clear paint I-IV.Notes 3 to 6 are as follows in the table.
Annotate the acryloyl isocyanic ester sulfuration solvent-borne type Clear paint (acryl isocyanate curing solvent type clearcoating) that 3 Alesrethane Clear:KANSAI PAI NT CO. produce.
Annotate the UV light absorber that 4 Tinubin 1130:Chiba Geigy Co. produce.
Annotate the photostabilizer that 5 Sanduvor 3050:Sand Co. produce.
Annotate the organosilicate condensing agent that 6 Ethyl Silicate 40:Colcoat Co. produce.
Table 4
| Clear paint | ||||
| ????I | ????II | ??III | ???IV | |
| Alesrethane clear coating (annotating 3) | ???100 | ????100 | ??100 | ???100 |
| Tinubin 1130 (annotating 4) | ??1.5 | ???1.5 | ||
| Sanduvor 3050 (annotating 5) | ??1.0 | ???1.0 | ||
| Ethyl silicate (annotating 6) | ????20 | ????20 | ||
Embodiment 9-13 and comparative example 5-7
Multicolor coating A, C, K and L spray to (5 * 70 * 150 millimeters) on several slabstones, and consumption is 400g/m
2Drying at room temperature one day.Subsequently, Clear paint I-IV is sprayed on above the film of multicolor coating separately as shown in table 5, its consumption is 80-100g/m
2, room temperature was placed one day.Then, Clear paint I-IV is sprayed on separately above the multicolor coating film, its consumption is 80-100g/m again
2, drying at room temperature seven days gets several piece and applies slabstone.
Embodiment 15-19 and comparative example 8-11
With on roller roller coating to a slabstone (5 * 70 * 150 millimeters), capacity is 1Kg/m with Alesholder G (the white elastic substrate material of the water reaction sulfuration resin that Kansai Paint Co. produces)
2, drying at room temperature one day (as substrate material HG).Subsequently, press and use multicolor coating and Clear paint shown in the table 5, obtain the slabstone after the coating with embodiment 9 identical steps.
Embodiment 14 and comparative example 12
VP Sealer Transparent (the solvent-borne type vinyl chloride resin encapsulant that Kansai Paint Co. produces) is applied on the slabstone of one 5 * 7 * 150 millimeters sizes with the roller roller coating, and its consumption is 80-100g/m for its consumption
2, drying at room temperature one day.Cosmo Clean (the water reaction sulfuration acryloyl resin surface layer coating that kansai Paint Co. produces) is administered to the surface of exsiccant paint film with roller, and its amount of application is about 120-150g/m
2, and drying at room temperature one day (as substrate material VP).Subsequently, use multicolor coating and Clear paint to be coated to the surface of exsiccant paint film as shown in table 5, obtain the slabstone after the coating with embodiment 9 identical steps.
Coated board is made a service test.It the results are shown in Table 5.
Test method is as follows.(1) weathering resistance
After the weathering resistance of the test board test after with sunlight weather survey meter (sunshine Weather-O-meter) each being applied 300 hours and 1000 hours, the situation of visual assessment coated surface, and according to the Gridiron tape method of JIS K-5400 assessment viscosity.(situation of coated side)
Two circles: coated surface is not seen crackle, peels off decolouring and efflorescence.
Triangle: as seen coated surface decolours or efflorescence.
Fork: the coated surface visible crack, peel off, obviously decolouring and efflorescence.(adhesive tape bond test)
Two circles: do not see and peel off.
Individual pen: see slightly and peel off.
Fork: as seen obviously peel off.(2) outward appearance pollution condition
Each coated board was placed on Hiratsuka and Kanagawa (city) outdoor exposure 3 months, the pollution level of visual assessment coated side and level.
Two circles: do not see pollution.
Individual pen: see pollution slightly, but keep the quality of its original design.
Fork: obviously pollute.(3) designing quality
The designing quality of each coated board of visual assessment.
Two circles: design has tangible 3 dimension effects, its degree of depth image-stone material.
Individual pen: design the 3 dimension effects of some, its degree of depth image-stone material.
Triangle: be designed to multicolour, but do not have depth perception.
Fork: can not clearly see the multicolour pattern.
Table 5
| Embodiment | |||||||||||||
| ?9 | ???10 | ???11 | ?12 | ??13 | ???14 | ???15 | ??16 | ??17 | ?18 | ??19 | |||
| Substrate coating | ?- | ???- | ???- | ?- | ???- | ???VP | ???HG | ??HG | ??HG | ?HG | ??HG | ||
| Multicolor coating | ?A | ???A | ???A | ?A | ???C | ????A | ????A | ???A | ???A | ?A | ???C | ||
| Clear paint | ?I | ???II | ??III | ?IV | ???I | ????I | ????I | ??II | ?III | ?IV | ??II | ||
| Weathering resistance | 300 hours | Viscosity | ?◎ | ???◎ | ???◎ | ?◎ | ??◎ | ???◎ | ???◎ | ??◎ | ??◎ | ?◎ | ??◎ |
| Coated side | ?◎ | ???◎ | ???◎ | ?◎ | ??◎ | ???◎ | ???◎ | ??◎ | ??◎ | ?◎ | ??◎ | ||
| 1,000 hour | Viscosity | ?◎ | ???◎ | ???◎ | ?◎ | ??◎ | ???◎ | ???◎ | ??◎ | ??◎ | ?◎ | ??◎ | |
| Coated side | ?◎ | ???◎ | ???◎ | ?◎ | ??◎ | ???◎ | ???◎ | ??◎ | ??◎ | ?◎ | ??◎ | ||
| Pollution condition | ?○ | ???◎ | ???○ | ?◎ | ??○ | ???○ | ???○ | ??◎ | ??○ | ?◎ | ??◎ | ||
| Design character | ?○ | ???○ | ???○ | ?○ | ??○ | ???○ | ???◎ | ??◎ | ??◎ | ?◎ | ??◎ | ||
Table 5 (continuing)
| Comparative example | ||||||||||
| ????5 | ???6 | ????7 | ????8 | ????9 | ????10 | ????11 | ????12 | |||
| Substrate coating | ???- | ???- | ????- | ???HG | ????HG | ????HG | ????HG | ????VP | ||
| Multicolor coating | ???L | ???K | ????K | ????L | ????K | ????A | ????L | ????A | ||
| Clear paint | ??I | ???- | ????IV | ????I | ????- | ????- | ???IV | ????- | ||
| Weathering resistance | 300 hours | Viscosity | ??◎ | ??△ | ???◎ | ???◎ | ???△ | ???◎ | ???◎ | ???◎ |
| Coated side | ??○ | ??× | ???◎ | ???○ | ???× | ???○ | ???◎ | ???○ | ||
| 1,000 hour | Viscosity | ??× | ??× | ???△ | ???△ | ???× | ???◎ | ???△ | ???◎ | |
| Coated side | ??× | ??× | ???△ | ???△ | ???× | ???○ | ???△ | ???○ | ||
| Pollution condition | ??○ | ??◎ | ???○ | ???○ | ???× | ???× | ???○ | ???× | ||
| Design character | ??○ | ??× | ???△ | ???◎ | ???△ | ???△ | ???◎ | ???△ | ||
Claims (10)
1. multicolor coating composition, it contains at least a enamel paint discrete particles, this particle makes through enamel paint is dispersed in the water dispersion medium, and this enamel paint is through mixing and disperseing a kind of composition to make, and said composition comprises as basal component (A), a kind of weight average molecular weight is 20,000 to 200,000, acid number is less than 2 multipolymer, this multipolymer makes through the monomer mixture that copolymerization contains the Acrylic Acid Monomer of 20% weight at least, (B) pigment and (C) organic solvent.
2. multicolor coating composition as claimed in claim 1, the copolymerization of wherein said multipolymer (A) process contains the vinylbenzene of 0-50% weight, and other monomeric monomer mixture of the Acrylic Acid Monomer of 20-100% weight and 0-80% weight makes.
3. multicolor coating composition as claimed in claim 1, the copolymerization of wherein said multipolymer (A) process contains the vinylbenzene of 10-30% weight, and other monomeric monomer mixture of the Acrylic Acid Monomer of 50-90% weight and 0-40% weight makes.
4. as any one described multicolor coating composition of claim 1-3, the second-order transition temperature of wherein said multipolymer (A) is 0-80 degree centigrade.
5. as any one described multicolor coating composition of claim 1-4, the sp value that all Acrylic Acid Monomers influenced that contains in the wherein said multipolymer (A) is 7.6-8.6.
6. as any one described multicolor coating composition of claim 1-5, the amount of the organic solvent that wherein said enamel paint contains is a 20-70% weight.
7. as any one described multicolor coating composition of claim 1-6, the proportion of wherein said enamel paint is 0.9-2.5.
8. the method for a coating coating comprises the steps:
Apply and dry multicolor coating composition, said composition contains at least a enamel paint discrete particles, this particle makes through enamel paint is dispersed in the water dispersion medium, this enamel paint is through mixing and disperseing a kind of composition to make, said composition comprises as basal component (A), a kind of weight average molecular weight is 20,000 to 200,000, acid number is less than 2 multipolymer, this multipolymer makes through the monomer mixture that copolymerization contains the Acrylic Acid Monomer of 20% weight at least, (B) pigment and (C) organic solvent; With
A kind of Clear paint is coated on the described dried coating.
9. the method that coating as claimed in claim 8 applies wherein saidly is coated with the organosilicon acid esters that coating contains has following general formula to represent:
Wherein R is identical or different, and it is selected from hydrogen atom and has the alkyl of 1-3 carbon atom, and/or its condensation product.
10. dope applying method as claimed in claim 8 or 9, the wherein said coating that is coated with contains UV light absorber.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP192700/1995 | 1995-07-28 | ||
| JP192700/95 | 1995-07-28 | ||
| JP19270095 | 1995-07-28 | ||
| JP15732196A JP3180287B2 (en) | 1995-07-28 | 1996-05-16 | Multi-color paint composition |
| JP157321/96 | 1996-05-16 | ||
| JP157321/1996 | 1996-05-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1145383A true CN1145383A (en) | 1997-03-19 |
| CN1118526C CN1118526C (en) | 2003-08-20 |
Family
ID=26484815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96109205 Expired - Fee Related CN1118526C (en) | 1995-07-28 | 1996-07-29 | Multicolor coating composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3180287B2 (en) |
| CN (1) | CN1118526C (en) |
| TW (1) | TW425421B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151476A (en) * | 2017-06-08 | 2017-09-12 | 宜都市晶典艺术品有限公司 | A kind of painting and calligraphy pigment and preparation method thereof |
| CN109294296A (en) * | 2018-09-27 | 2019-02-01 | 湖南松井新材料股份有限公司 | Aqueous one-component vitreous enamel coating of super resistant and preparation method thereof and construction technology |
| CN114106614A (en) * | 2021-03-15 | 2022-03-01 | 万华生态科技有限公司 | Flexible colloid protective agent for producing colorful stone-like paint |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100409161B1 (en) * | 1995-12-29 | 2004-03-18 | 고려화학 주식회사 | Method for preparing multi-color paints |
| JP5121094B2 (en) * | 2000-03-30 | 2013-01-16 | エスケー化研株式会社 | Finishing method of concrete exposed surface |
| JP2003226863A (en) * | 2002-02-05 | 2003-08-15 | Kansai Paint Co Ltd | Water-based sealer for inorganic building material and method for forming coating film |
| JP4971651B2 (en) * | 2006-03-01 | 2012-07-11 | 関西ペイント株式会社 | Water-based colorful pattern paint and painting method |
| JP5547367B2 (en) * | 2007-09-12 | 2014-07-09 | 関西ペイント株式会社 | Water-based colorful pattern paint |
| CN103421395A (en) * | 2013-08-19 | 2013-12-04 | 南通市通州区俊朗建筑工程有限公司 | Water-in-water multicolor paint |
| KR20160100908A (en) * | 2013-12-18 | 2016-08-24 | 요코하마 고무 가부시키가이샤 | Ultraviolet ray-curable resin composition, and laminate |
| KR102189291B1 (en) | 2014-12-09 | 2020-12-14 | 포-캉 린 | Yellow backlight system and yellow backlight method |
| CN104745033A (en) * | 2015-03-16 | 2015-07-01 | 长沙市紫荆花涂料有限公司 | Anti-crack water-based colourful paint and preparation method thereof |
| WO2017195665A1 (en) * | 2016-05-13 | 2017-11-16 | サンノプコ株式会社 | Particle stabilizer for multicolor coating material |
| JP7382696B2 (en) * | 2016-09-30 | 2023-11-17 | 株式会社日本触媒 | Resin emulsion for paint |
| RU174981U1 (en) * | 2017-01-16 | 2017-11-14 | Публичное акционерное общество "Челябинский трубопрокатный завод" (ПАО "ЧТПЗ") | DEVICE FOR WELDING JOINED PARTS |
-
1996
- 1996-05-16 JP JP15732196A patent/JP3180287B2/en not_active Expired - Fee Related
- 1996-07-24 TW TW85109022A patent/TW425421B/en not_active IP Right Cessation
- 1996-07-29 CN CN 96109205 patent/CN1118526C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151476A (en) * | 2017-06-08 | 2017-09-12 | 宜都市晶典艺术品有限公司 | A kind of painting and calligraphy pigment and preparation method thereof |
| CN109294296A (en) * | 2018-09-27 | 2019-02-01 | 湖南松井新材料股份有限公司 | Aqueous one-component vitreous enamel coating of super resistant and preparation method thereof and construction technology |
| CN114106614A (en) * | 2021-03-15 | 2022-03-01 | 万华生态科技有限公司 | Flexible colloid protective agent for producing colorful stone-like paint |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3180287B2 (en) | 2001-06-25 |
| TW425421B (en) | 2001-03-11 |
| JPH09100426A (en) | 1997-04-15 |
| CN1118526C (en) | 2003-08-20 |
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