CN103649249A

CN103649249A - Aqueous multicolor coating composition

Info

Publication number: CN103649249A
Application number: CN201280020252.XA
Authority: CN
Inventors: 井上刚; 尾崎透; 安达顺之; 繁谷纯
Original assignee: Kansai Paint Co Ltd
Current assignee: Kansai Paint Co Ltd
Priority date: 2011-04-27
Filing date: 2012-04-23
Publication date: 2014-03-19
Anticipated expiration: 2032-04-23
Also published as: JP5873432B2; JPWO2012147693A1; WO2012147693A1; CN103649249B

Abstract

An aqueous multicolor coating composition composed of a colored coating-particle component containing a coloring agent and an aqueous resin having a carboxyl group and another cross-linked functional group, and a coating formation component containing an aqueous resin having a carboxyl group, a hydrolysable silyl group, and another cross-linked function group. The coating formation component includes a specific amount of polyvalent metal, thereby making it possible to obtain an aqueous multicolor coating composition in which the colored coating particles are not liable to be crushed during spray application as well as roller application, and that is multicolored with excellent clarity, has good adherence to cloth, and can form a multicolored coating having excellent long-term weather resistance.

Description

Aqueous colorful pattern coating composition

Technical field

The present invention relates to weathering resistance etc. excellent in te pins of durability, not only in spraying but also in roller coat, also can form the aqueous colorful pattern coating composition that the multicolour pattern colorful, clarity is excellent is filmed.

Background technology

Coating of multi-colour pattern is the coating of the pigmented coating particle that contains the multiple color being stably scattered in dispersion medium, can obtain the colorful decorative pattern of multiple color by an application, is mainly used in the application of buildings etc.

In recent years, due to various for the demand of outward appearance to the care of environment and client, therefore require people to develop the coating of multi-colour pattern of water system.

For example, a kind of water-in-water type multi-color decorative pattern paint composition is disclosed in TOHKEMY 2005-15645 communique, this water-in-water type multi-color decorative pattern paint composition is that painted gel particle is scattered in the transparent low luster coating of the pigment extender that contains water-base resin and tool specific refractive index and is formed, wherein, described painted gel particle is prepared by have water-base resin, tinting pigment, the water of reactive functional groups and the reactive compounds that can react under water exists.

Water-borne coatings is compared with solvent based coating, conventionally there are the poor tendencies of application operability such as easy sagging, people wish to develop a kind of aqueous colorful pattern coating, it can make formed filming have colorful designability, and application operability is good, particularly good to the dispersing less of surrounding environment, roller coat operability.

Under Shang Shu Zhuan Condition, the aqueous colorful pattern coating that has proposed respectively the aqueous colorful pattern coating that contains specific combination thickening material and contained specified quantitative resin bead in TOHKEMY 2007-262350 communique and TOHKEMY 2009-173770 communique.

According to these documents, this aqueous colorful pattern coating is difficult to occur trickle etc. after application, can form harsh feeling few, there is filming of colorful designability, but during roller coat operation, if coating is applied to large load, pigmented coating breakage of particles, interior bag thing oozes out from inside, occurs the feint problem of decorative pattern.

In TOHKEMY 2008-202037 communique, also record: in containing the coating composition that utilizes the water-soluble polysaccharides granulated gel obtaining with reacting of specific metallic compound and the forming component of filming, by containing specific metallic compound in the forming component that makes to film, can be suppressed at the oozing out of interior bag thing of granulated gel in coating composition manufacturing stage or storage.

But the multicolour pattern being formed by aforementioned coating composition is filmed not enough at outdoor long-term weatherability, the leeway being still improved.

Prior art document

Patent documentation:

Patent documentation 1: TOHKEMY 2005-15645 communique

Patent documentation 2: TOHKEMY 2007-262350 communique

Patent documentation 3: TOHKEMY 2009-173770 communique

Patent documentation 4: TOHKEMY 2008-202037 communique.

Summary of the invention

The problem that invention will solve

Main purpose of the present invention be to provide weathering resistance etc. excellent in te pins of durability, not only in spraying but also in roller coat, also can form the aqueous colorful pattern coating composition that the multicolour pattern colorful, clarity is excellent is filmed.

Solve the mode of problem

The inventor conducts in-depth research for achieving the above object, found that: existing by containing polyvalent metal with specified quantitative in the aqueous colorful pattern coating containing specifically film forming component and specific pigmented coating particulate component, can obtain a kind of aqueous colorful pattern coating composition, even pigmented coating particle is also difficult to break when roller coat, can form colorful, clarity is excellent, and the multicolour pattern good with the tack of substrate, long-term weatherability is excellent is filmed, thereby completed the present invention.

That is, the invention provides a kind of aqueous colorful pattern coating composition, this aqueous colorful pattern coating composition contains:

(A) pigmented coating particulate component, this pigmented coating particulate component contains water-base resin (a1) and tinting material (a2), and described water-base resin (a1) has carboxyl and other bridging property functional group in addition, and

(B) forming component of filming, this forming component of filming contains water-base resin (b1) and polyvalent metal compounds (b2), and described water-base resin (b1) has carboxyl and water-disintegrable silyl and other bridging property functional group in addition;

This aqueous colorful pattern coating composition is characterised in that: at least one party of pigmented coating particulate component (A) and the forming component of filming (B) is contained compound (c), this compound (c) in 1 molecule, at least have 2 can with water-base resin (a1) in bridging property functional group and the functional group of the bridging property functional group reactions in water-base resin (b1); In the forming component of filming (B), the carboxyl with respect to 1 equivalent in water-base resin (b1), according to the metal meter that converts, contains polyvalent metal compounds (b2) with the ratio of 0.1～0.9 equivalent.

Invention effect

According to aqueous colorful pattern coating composition of the present invention, pigmented coating particulate component (A) is firm bonding with filming that forming component (B) reacts to each other via crosslinker compound (c), simultaneously, water-disintegrable silyl in water-base resin (b1) by hydrolysis and from condensation, and by polyvalent metal compounds (b2), generate metal bridging between the carboxyl in water-base resin (a1) and water-base resin (b1), the weather resistance of weathering resistance etc. is very excellent, even carry out as roller coat coating is applied to the application of large load time, pigmented coating particle can not break yet, the situation that can form the inhomogeneous grade of generation decorative pattern is few, the multicolour pattern of clarity excellence is filmed.

In addition, according to the aqueous colorful pattern coating composition of the present invention that further contains the coating particles composition (C) that the forming component spheroidizing of filming with the transparency is formed, the depth feelings that can make formed multicolour pattern film more improves, and can obtain also can showing the so excellent effect of bag texture according to the color of pigmented coating particulate component (A).

Below, further describe the finishing of aqueous colorful pattern coating composition of the present invention and this coating composition.

Specific embodiments

< pigmented coating particulate component (A) >

Pigmented coating particulate component (A) in aqueous colorful pattern coating composition of the present invention contains water-base resin (a1) and tinting material (a2).

water-base resin (a1)

Water-base resin (a1) is solubilized or is scattered in the resin in water, this resin kind is also not particularly limited, such as enumerating: acrylic resin, silicon resinoid, polyurethanes resin, redix, phenolic resinoid, polyester resin, alkyd based resin, polycarbonate resin etc., they can be respectively separately or two or more is used in combination.In addition, these resins for example can pass through modification as urethane-modified acrylic resin, or can, through graft polymerization, can also be the forms of discrete particles.

During form that water-base resin (a1) is discrete particles, can have the multilayered structure of single layer structure (granular uniformly) or core sheath structure etc., during for core sheath structure, core and/or sheath can be cross-linked.In addition, the carboxyl that water-base resin (a1) has can be used the amines such as methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol; The alkali part of ammonia etc. or substantially neutralization completely.

From weather resistance, the weathering resistance equal angles of pigmented coating particulate component (A), consider; water-base resin (a1) is preferably acrylic resin; described acrylic resin can be enumerated: make at least a kind containing the compound of (methyl) acryl; with as required can other polymerizability unsaturated monomer of copolymerization together with, carry out (being total to) polymerization and the resin that obtains.

Contain the compound of (methyl) acryl such as enumerating: straight chain or branched (methyl) alkyl acrylate of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid Lauryl Ester, (methyl) stearyl acrylate base ester etc., ester ring type (methyl) alkyl acrylate of (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc., (methyl) vinylformic acid aralkyl ester of (methyl) vinylformic acid benzyl ester etc., (methyl) alkoxyalkyl acrylate of (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester etc., (methyl) perfluoroalkyl acrylate, as (methyl) vinylformic acid N, (methyl) vinylformic acid N of N-diethylamino ethyl ester, N-dialkyl aminoalkyl ester, (methyl) acrylamide, (methyl) vinylformic acid allyl ester, two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid triethyleneglycol ester, two (methyl) vinylformic acid Tetraglycol 99 ester, two (methyl) vinylformic acid 1, 3-butanediol ester, trimethylolpropane tris (methyl) acrylate, two (methyl) vinylformic acid 1, 4-butanediol ester, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid 1, 6-hexylene glycol ester, two (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, two (methyl) vinylformic acid glyceryl ester, 1, 1, 1-trimethylolethane two (methyl) acrylate, 1, 1, 1-trimethylolethane trimethacrylate (methyl) acrylate, 1, 1, (methyl) acryloyl monomer at least in 1 molecule of 1-trimethylolpropane tris (methyl) acrylate etc. with 2 polymerizability unsaturated groups, (methyl) acryloyl monomer of the hydroxyl of (methyl) acrylate containing polyoxyethylene chain that (methyl) vinylformic acid hydroxyalkyl acrylate of (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester etc., 6-caprolactone modification body, the molecular end of above-mentioned (methyl) vinylformic acid hydroxyalkyl acrylate are hydroxyl etc., (methyl) vinylformic acid, (methyl) acryloyl monomer containing carbonyl of (methyl) vinylformic acid acetoacetoxy groups ethyl ester, diacetone (methyl) acrylamide etc., (methyl) vinylformic acid glycidyl esters, (methyl) vinylformic acid Beta-methyl glycidyl esters, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl ethyl ester, (methyl) vinylformic acid 3, (methyl) acryloyl monomer containing epoxy group(ing) of 4-epoxy group(ing) cyclohexyl propyl ester etc., (methyl) acryloyl monomer of the isocyanato group containing of (methyl) vinylformic acid isocyanato ethyl ester etc., (methyl) acryloyl monomer containing alkoxysilyl of γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane etc., (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base propyl ester, (methyl) vinylformic acid dicyclopentenyl ester etc. containing (methyl) acryloyl monomer of oxidative cure group etc., they can be respectively separately or two or more is used in combination.

In addition, other polymerizability unsaturated monomer that can copolymerization for example can be enumerated: (methyl) vinyl cyanide; The vinyl ester compound of vinyl-acetic ester, vinyl propionate base ester etc.; The vinyl aromatic compounds of vinylbenzene, alpha-methyl styrene etc.; Many vinyl compounds at least in 1 molecule of isocyanuric acid triallyl ester, diallyl terephthalate, Vinylstyrene etc. with 2 polymerizability unsaturated groups; Allyl alcohol; The carboxylic polymerizability unsaturated monomer of toxilic acid, β-crotonic acid, propenoic acid beta-carboxy ethyl ester etc.; The polymerizability unsaturated monomer containing carbonyl of the vinyl alkyl ketone of (methyl) propenal, formyl vinylbenzene, carbonatoms 4～7 (such as ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone etc.), acetoacetyl allyl ester etc.; The polymerizability unsaturated monomer containing epoxy group(ing) of allyl glycidyl ether etc.; Between the polymerizability unsaturated monomer of isocyanato group containing of pseudoallyl-alpha, alpha-dimethylbenzyl isocyanic ester etc.; The polymerizability unsaturated monomer containing alkoxysilyl of vinyltrimethoxy silane, vinyltriethoxysilane etc.; Containing the polymerizability unsaturated monomer containing oxidative cure group of the polymerizability unsaturated monomer of epoxy group(ing) or the polymerizability unsaturated monomer of hydroxyl and the reaction product of unsaturated fatty acids etc. etc., they are can be respectively independent or two or more is used in combination.

Water-base resin of the present invention (a1) has carboxyl, makes thus resin (a1) Water-borne modification, and manufacture stability is improved.

In addition, other bridging property functional group beyond the carboxyl that water-base resin (a1) has is such as enumerating: hydroxyl, isocyanato, amino, amide group, carbonyl etc., and from the viewpoint of weathering resistance, storage stability etc., particularly preferably carbonyl.

The water-base resin (a1) with carboxyl and carbonyl for example can be manufactured as follows: use (methyl) vinylformic acid and/or foregoing other carboxylic polymerizability unsaturated monomer and foregoing (methyl) acryloyl monomer containing carbonyl and/or other the polymerizability unsaturated monomer containing carbonyl as at least a portion of monomer component, with other compound and/or other polymerizability unsaturated monomer copolymerization containing (methyl) acryl.Described (methyl) vinylformic acid and other carboxylic polymerizability unsaturated monomer and be containing (methyl) acryloyl monomer of carbonyl and the usage quantity of other the polymerizability unsaturated monomer containing carbonyl: the total quality for whole polymerizability unsaturated monomers of copolymerization is benchmark, (methyl) vinylformic acid and other carboxylic polymerizability unsaturated monomer can be 0.05～10 quality % conventionally, be preferably in the scope of 0.1～3 quality %, and conventionally can be 0.2～30 quality % containing (methyl) acryloyl monomer of carbonyl with containing the polymerizability unsaturated monomer of carbonyl, preferably in the scope of 0.3～15 quality %.

The polymerization process of above-mentioned monomer is also not particularly limited, for example can be according to conventional emulsion polymerization, by making above-mentioned monomer (being total to) polymerization carry out under the existence of emulsifying agent.This emulsifying agent can be used itself known emulsifying agent, concrete example is as enumerated: anionic emulsifier, non-ionic emulsifier, zwitter-ion emulsifying agent, can also be used reactive emulsifier that contains polymerizability unsaturated group and anionic property group or nonionic group in molecule etc.Its usage quantity can be: the total quality of whole polymerizability unsaturated monomers of take is benchmark, is generally 0.5～6 quality %, preferably in the scope of 1～4 quality %.The emulsion particle generating can have 50～500nm, preferably 100～400nm, the further preferred median size within the scope of 100～300nm conventionally.In this specification sheets, " median size " is to adopt submicron particles analyser N4 (trade(brand)name, ベッ Network マ Application コールター Co., Ltd. manufactures, particle size distribution device), by sample, with deionized water dilution, be the applicable concentration of measuring, in the lower value of measuring of normal temperature (20 ℃ of left and right).

Water-base resin (a1) conventionally can have 0.1～50mgKOH/g, is preferably 0.1～25mgKOH/g, the further preferred acid number within the scope of 0.1～20mgKOH/g, and conventionally can have 0～250mgKOH/g, preferably 0～225mgKOH/g, the further preferred hydroxyl value within the scope of 0～200mgKOH/g.And water-base resin (a1) can have 2000～5000000, preferably 10000～3000000 conventionally, the further preferred weight-average molecular weight in 50000～1000000 scopes.

In this specification sheets, " weight-average molecular weight " can be used " HLC-8120GPC " (trade(brand)name; Eastソー company manufactures) as gel permeation chromatography device, use 1 " TSKgel GMHHR-L " (trade(brand)name; Eastソー company manufactures) as post, use differential refractometer as detector, in moving phase: dimethyl formamide (containing each 10mM lithiumbromide and phosphoric acid), measure temperature: measure under the condition of 25 ℃, flow velocity: 1mL/ minute.

tinting material (a2)

The contained tinting material (a2) of pigmented coating particulate component (A) comprises tinting pigment, aura pigment, fluorescent material etc.

Tinting pigment is such as enumerating: the white pigments such as titanium dioxide; Carbon black, acetylene black, dim, bone black, graphite, iron oxide black, nigrosine ?look pigment; The yellow ultramarines such as Zh 1, titan yellow, monoazo yellow, azo condensation is yellow, azomethine is yellow, pucherite, benzimidazolone, isoindolinone, isoindoline, quinophthalone (quinophthalone), diarylide yellow, permanent yellow; Solid orange waits orange pigments forever; The red pigments such as red iron oxide, naphthols AS class azophloxine, anthanthrone, anthraquinonyl are red, perylene maroon (perylene marron), quinacridine ketone red, diketopyrrolopyrrolecocrystals, Pigment red (watching red), permanent bordeaux; The violet pigments such as cobalt violet, quinacridone violet, dioxazine violet; The blue pigmentss such as cobalt blue, phthalocyanine blue, indanthrene blue (threne blue); The Green look pigment such as phthalocyanine green etc., aura pigment is such as enumerating: the metallicity pigment such as aluminium powder, bronze powder, copper powder, glass putty, iron phosphide, zinc powder; The pearly pigments such as the mica powder of coated metal oxide, mica shape ferric oxide etc., these pigment can be respectively separately or two or more is used in combination.It is the fine titanium of 10～80nm or the functional titanium dioxide such as anatase titanium dioxide with photocatalyst activity that the above-mentioned titanium dioxide as white pigment also comprises median size.

Fluorescent material can be enumerated fluorescence or hold pigment and the dyestuff of photosensitiveness, for example, can enumerate: the organic compound of diphenylethlene Lei, oxazole class, thiazoles, imidazoles, triazole species, pyrazoles, furans, thiophene-based, peri-position dicarboxamide (peri-dicarboxylic acid amide) class, coumarins; In the metallic compounds such as zinc sulphide, strontium aluminate, calcium aluminate, add mineral-type compound that the metals such as copper, silver, manganese, europium obtain etc.These tinting materials (a2) can be according to object color component respectively separately or two or more is used in combination.

The use level of tinting material (a2) can change according to its kind in wide scope, and the quality of water-base resin (a1) of take is benchmark, can be at common 1～400 quality %, particularly 2～300 quality %, more especially in the scope of 2～250 quality %.

In pigmented coating particulate component (A), can also use pigment extender together with tinting material (a2).Its object lesson can be enumerated: barium oxide powder (バリタ powder), settleability barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon(ink), diatomite, talcum powder, magnesiumcarbonate, white lake, gloss white, silica sand, silica powder etc., can be respectively separately or two or more is used in combination.The use level of described pigment extender can change according to its kind in wide scope, and the quality of water-base resin (a1) of take is benchmark, can be at common 0～1000 quality %, particularly 0～800 quality %, more especially in the scope of 1.0～750 quality %.

Pigmented coating particulate component of the present invention (A) is preferably the composition with following grain pattern: in the water-based pigmented coating that contains water-base resin (a1) and tinting material (a2), be wrapped in the shell that the metal-salt by water-soluble polysaccharides forms.The pigmented coating particulate component (A) with described structure for example can be by making the composition that contains water-based pigmented coating and water-soluble polysaccharides (a3) contact acquisition with the aqueous medium that contains metallic compound (a4), wherein, described water-based pigmented coating contains water-base resin (a1) and tinting material (a2).

Water-soluble polysaccharides (a3) comprises following polyose: this polyose has while contacting with the metal ion of monovalence or multivalence in aqueous medium, be changed to the ability of the gel (gelation) of water-insoluble or insoluble, concrete example is as enumerated: alginic acid or its an alkali metal salt, gelling gum, carrageenan, xanthan gum, polygalactomannan derivative, alginic acid or derivatives thereof, derivatived cellulose, gelatin, casein, albumin etc., or they are passed through to oxidation, methylate, carboxymethylation, hydroxyethylation, hydroxypropylation, sulfation, phosphorylation, cationizations etc. carry out chemical modification gains etc., they can be respectively separately or two or more is used in combination.

From suppressing the interior bag thing of pigmented coating particulate component (A), flow out to aqueous medium, and few the filming of formation harsh feeling, and it is good in roller coat, to form clarity, the angle of filming having excellent weather resistance is considered, the total quality of water-base resin (a1) and tinting material (a2) of take is benchmark, water-soluble polysaccharides (a3) can be at common 0.5～10 quality %, preferred 0.7～9.0 quality %, further preferably in the scope of 1.0～8.0 quality %, use, can obtain the storage stability of pigmented coating particulate component (A) thus, reduce the harsh feeling of filming that uses aqueous colorful pattern coating composition of the present invention to form.

Above-mentioned contain water-based pigmented coating with water-soluble polysaccharides (a3) if composition contact with the aqueous medium that contains metallic compound (a4), the water-soluble polysaccharides in said composition (a3) with from the metal ion of the metallic compound in aqueous medium (a4), form the salt of water-insoluble or insoluble, make water-based pigmented coating generation granulated gel, form thus pigmented coating particulate component (A).

Above-mentioned metallic compound (a4) is can in aqueous medium, generate to form the monovalence of salt or the compound of polyvalent metal ion of water-insoluble or insoluble with water-soluble polysaccharides (a3), preferably contains metal salts of organic acids as at least a portion of its composition.

By using metal salts of organic acids as at least a portion of metallic compound (a4), do not have interior bag logistics to go out, storage stability is excellent, and by roller coat, also can easily form the pigmented coating particulate component (A) that is difficult to break, can also make the Physical properties of coating film of weathering resistance that multicolour pattern films etc. good.

From the intensity equal angles of formed pigmented coating particulate component (A), consider, the metal species in described metal salts of organic acids is preferably polyvalent metal, such as enumerating: the periodic table of elements 2 family's elements such as magnesium, calcium, strontium, barium; The periodic table of elements such as titanium, zirconium 4 family's elements; The periodic table of elements such as chromium, molybdenum 6 family's elements; The periodic table of elements such as manganese 7 family's elements; The periodic table of elements such as iron, ruthenium 8 family's elements; The periodic table of elements such as cobalt, rhodium 9 family's elements; The periodic table of elements such as nickel, palladium 10 family's elements; The periodic table of elements such as copper, silver 11 family's elements; The periodic table of elements such as zinc, cadmium 12 family's elements; The periodic table of elements such as aluminium 13 family's elements; The periodic table of elements such as cerium 16 family's elements etc., they can be respectively separately or two or more is used in combination.In addition, except above-mentioned polyvalent metal, can also and use the metal of the period of element Table I family elements such as sodium, potassium.As the metal species in above-mentioned metallic compound (a4), preferred elements cycle Table II family element, particularly calcium wherein.

Organic acid in above-mentioned metal salts of organic acids so long as above-mentioned that exemplify, can form with metal the compound of salt, be not particularly limited, such as enumerating: formic acid, acetic acid, propionic acid, butyric acid, lactic acid, oxalic acid, fumaric acid, succsinic acid, phosphoric acid, citric acid, glyconic acid etc.Wherein, from the storage stability equal angles of pigmented coating particulate component (A), consider, the organic acid of molecular weight in 50～1000, particularly 50～400, more especially 170～400 scopes is applicable to.

As metal salts of organic acids, from manufacture stability, the storage stability angle of pigmented coating particulate component (A), consider, wherein special lime acetate, calcium propionate and calcium lactate are applicable to.

Metallic compound (a4), except above-mentioned metal salts of organic acids, also preferably contains metal hydroxides.Thus, except the storage stability of pigmented coating particulate component (A), manufacture stability, the harsh feeling that the multicolour pattern that also makes to be formed by aqueous colorful pattern coating composition of the present invention is filmed reduces, and the clarity that the multicolour pattern that can make to obtain by roller coat is filmed is simultaneously more good.

The object lesson of the metal species of the metal hydroxides using for such object, except above-mentioned, also can be enumerated the basic metal that belongs to the periodic table of elements 1 family's element.

In above-mentioned metallic compound (a4), by metal salts of organic acids and metal hydroxides used time, from the storage stability of pigmented coating particulate component (A), suppress the harsh feeling that formed multicolour pattern films, the clarity equal angles that formed multicolour pattern is filmed is considered, its usage ratio, with the molar ratio computing of metal salts of organic acids/metal hydroxides, in common 99/1～10/90, particularly 90/10～15/85, more especially 85/15～20/80 scope, be applicable to.

By at least a portion of metallic compound (a4) being dissolved in the aqueous medium of water etc., can prepare the aqueous medium that contains metal ion.Now, metallic compound (a4) needn't all be dissolved in aqueous medium, can be to only have partly soluble state.

The concentration of the metallic compound in aqueous medium (a4) is strict restriction not, can be at common 0.05～20 quality %, preferably in the scope of 0.05～15 quality %.

From the storage stability of pigmented coating particulate component (A) and the viewpoint consideration of manufacturing stability, above-mentioned aqueous medium is preferably in common 4.0～13.7, preferably 7.0～13.5 scope by pH regulator.

The above-mentioned composition that contains water-based pigmented coating and water-soluble polysaccharides (a3) can carry out by the following method with for example the contacting of aqueous medium of containing from the metal ion of metallic compound (a4): said composition is added drop-wise to the method in aqueous medium by the tip of syringe; Utilize centrifugal force said composition is dispersed and be added drop-wise to the method in aqueous medium; Make said composition be added drop-wise to the method in aqueous medium by the most advanced and sophisticated atomization of fog nozzle; Said composition is joined in aqueous medium to the method being uniformly mixed with dispersion machine etc.

In the manufacture of pigmented coating particulate component (A), about above-mentioned composition and aqueous medium, storage stability from pigmented coating particulate component (A), and the multicolour pattern that suppresses to be formed by the aqueous colorful pattern coating composition of the present invention harsh feeling of filming, the clarity that multicolour pattern is filmed and weathering resistance equal angles are considered, with respect to 1 equivalent carboxyl in contained water-soluble polysaccharides (a3) in composition, according to metal conversion amount meter, metallic compound (a4) contained in aqueous medium is preferably below 1.5 equivalents, particularly in the scope more than 0.2 and lower than 1.0 equivalents, more especially the scope at 0.2～0.9 equivalent contains.

Above-mentioned water-based pigmented coating can further contain fire retardants such as the specific gravity-adjusting material, defoamer, curing catalysts, pigment dispersing agent, perfume compound, deodorizing composition, antiseptic-germicide, neutralizing agent, tensio-active agent, water-based hydrophobic agent, dispersion agent, sanitas, mould inhibitor, frostproofer, UV light absorber, photostabilizer, film coalescence aid, zinc whisker, formaldehyde adsorbent, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, aluminium hydroxide of thickening material, hollow particle etc. etc. as required.

Thus, can obtain the pigmented coating particulate component (A) with following grain pattern: in the water-based pigmented coating that contains water-base resin (a1) and tinting material (a2), be wrapped in the shell that the metal-salt by water-soluble polysaccharides forms.

< forming component (B) > that films

The Physical properties of coating film of the weathering resistance of filming in order to ensure formed multicolour pattern etc., aqueous colorful pattern coating composition of the present invention, except containing pigmented coating particulate component (A), also contains the forming component of filming (B).The forming component of filming (B) is the composition with self film-formed, the clarity equal angles that the multicolour pattern of the weathering resistance of filming from multicolour pattern, roller coat gained is filmed is considered, contain water-base resin (b1) and polyvalent metal compounds (b2), wherein said water-base resin (b1) has carboxyl and water-disintegrable silyl and other bridging property functional group in addition.

water-base resin (b1)

In the forming component of filming (B), contained water-base resin (b1) has carboxyl and water-disintegrable silyl and other bridging property functional group in addition.Water-base resin (b1) has carboxyl, thus can Water-borne modification, to improving the weathering resistance that multicolour pattern films, there is contribution simultaneously.And, water-base resin (b1) has water-disintegrable silyl, thus, the weathering resistance that the multicolour pattern being formed by aqueous colorful pattern coating composition of the present invention is filmed and for example, further improving with the tack of substrate (being located at the primer coating film of multicolour pattern under filming).

In this specification sheets, " water-disintegrable silyl " is to generate the group that silanol group and this silanol group dehydrating condensation form siloxane bond by hydrolysis, wherein, comprise and have with the water-disintegrable atom of monovalence of Siliciumatom Direct Bonding (by react the atom that generates silanol group with water, halogen atom for example) and with one of monovalence hydrolization group (for example, by react the group that generates silanol group, alkoxyl group with water) of Siliciumatom Direct Bonding or both silyls.

The object lesson of said hydrolyzed silyl is such as enumerating: the halogenation silyls such as Trichloromonosilane base, silicobromoform base; The trialkoxysilyl such as trimethoxysilyl, triethoxysilyl, tripropoxy-sil(ic)ane base, three butoxy silyls; The halo dialkoxies such as chloro dimethoxy, chloro diethoxy etc., wherein preferred trialkoxysilyl.

In addition, the bridging property functional group of other that water-base resin (b1) has, such as enumerating hydroxyl, isocyanato, amino, amide group, carbonyl etc., considers from weathering resistance, storage stability equal angles, particularly preferably carbonyl.

The resin that contains carboxyl, water-disintegrable silyl and carbonyl for example can be manufactured as follows: use (methyl) vinylformic acid and/or foregoing other carboxylic polymerizability unsaturated monomer, at least a portion containing the polymerizability unsaturated monomer of water-disintegrable silyl and foregoing (methyl) acryloyl monomer containing carbonyl and/or other the polymerizability unsaturated monomer containing carbonyl as monomer component, make its with foregoing other the compound that contains (methyl) acryl and/or other polymerizability unsaturated monomer copolymerization.The weathering resistance of filming from formed multicolour pattern and with the tack of primer coating film, the storage stability equal angles of coating composition consider, usage quantity about described monomer component, total quality for whole polymerizability unsaturated monomers of copolymerization is benchmark, preferably: (methyl) vinylformic acid and other carboxylic polymerizability unsaturated monomer conventionally at 0.05～10 quality %, particularly 0.03～6 quality %, be more in particular in the scope of 0.1～3 quality %; Containing the polymerizability unsaturated monomer of water-disintegrable silyl conventionally at 0.01～10 quality %, particularly 0.03～7 quality %, be more in particular in the scope of 0.05～5 quality %; Containing (methyl) acryloyl monomer of carbonyl and other the polymerizability unsaturated monomer containing carbonyl conventionally at 0.2～30 quality %, particularly 0.25～20 quality %, be more in particular in the scope of 0.3～15 quality %.

The above-mentioned polymerizability unsaturated monomer containing water-disintegrable silyl for example can be enumerated: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methyl dimethoxysilane, vinyl methyldiethoxysilane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl group methyldiethoxysilane, γ-(methyl) acryloxy propyl-triethoxysilicane, β-(methyl) acryloxy ethyl trimethoxy silane, γ-(methyl) acryloxy butyl phenyl dimethoxy silane, vinyl monohydroxy dimethoxy silane, vinyl ortho-siliformic acid etc.

The polymerization process of above-mentioned monomer is also not particularly limited, for example can be according to conventional emulsion polymerization, under the existence of emulsifying agent, by above-mentioned monomer component (being total to) polymerization is carried out.This emulsifying agent can be used itself known emulsifying agent, concrete example be as enumerated anionic emulsifier, non-ionic emulsifier, zwitter-ion emulsifying agent, also can use and in molecule, contain polymerizability unsaturated group and anionic property group or both reactive emulsifiers of nonionic group etc.The total quality of whole polymerizability unsaturated monomers of take is benchmark, and its usage quantity can be at common 0.5～6 quality %, preferably in the scope of 1～4 quality %.The emulsion particle generating can have common 50～500nm, preferably 100～400nm, the further preferred median size within the scope of 100～300nm.

In addition, during above-mentioned copolymerization, by making different monomer components divide a plurality of stage polymerizations, make water-base resin (b1) form the multilayer shape of core-sheath-type etc., thereby can make weathering resistance, film-forming properties that multicolour pattern is filmed improve.

Water-base resin (b1) can have common 0.5～100mgKOH/g, preferably 1～75mgKOH/g, the further preferred acid number within the scope of 1～50mgKOH/g, and common 0～250mgKOH/g, preferably 0～225mgKOH/g, the further preferred hydroxyl value within the scope of 1～200mgKOH/g.And that water-base resin (a1) can have is common 2000～5000000, preferably 10000～3000000, the further preferred weight-average molecular weight in 50000～1000000 scopes.

polyvalent metal compounds (b2)

The forming component of filming (B) contains polyvalent metal compounds (b2), the clarity of the decorative pattern in the time of can making thus storage stability, this coating composition of roller coat of aqueous colorful pattern coating composition of the present invention, the raisings such as weathering resistance that formed multicolour pattern is filmed.

Polyvalent metal compounds (b2) can be used the free compound of polyvalent metal ion that can make the carboxyl that can have with water-base resin (b1) form metal bridging in aqueous medium, such as enumerating the compound that contains following metallic element: the periodic table of elements 2 family's elements such as magnesium, calcium, strontium, barium; The periodic table of elements such as titanium, zirconium 4 family's elements; The periodic table of elements such as chromium, molybdenum 6 family's elements; The periodic table of elements such as manganese 7 family's elements; The periodic table of elements such as iron, ruthenium 8 family's elements; The periodic table of elements such as cobalt, rhodium 9 family's elements; The periodic table of elements such as nickel, palladium 10 family's elements; The periodic table of elements such as copper, silver 11 family's elements; The periodic table of elements 13 family's elements such as the periodic table of elements such as zinc, cadmium 12 family's elements, aluminium; The metallic elements such as the periodic table of elements such as cerium 16 family's elements, wherein, the compound that contains the periodic table of elements 2 family's element, particularly calcium is applicable to.

Polyvalent metal compounds (b2) can be enumerated organic acid salt, oxyhydroxide, oxide compound, carbonate of above-mentioned metal etc.

In the present invention, from the weathering resistance that multicolour pattern is filmed is improved, the excellent equal angles of clarity that simultaneously multicolour pattern during the good and roller coat of coating storage stability is filmed considers, preferably polyvalent metal compounds (b2) contains metal salts of organic acids as a part for its composition.Suitable choice for use in the compound exemplifying in the explanation of metallic compound (a4) that organic acid in above-mentioned metal salts of organic acids can be from pigmented coating particulate component (A).

With respect to 1 equivalent carboxyl in contained water-base resin (b1) in the forming component of filming (B), the content of polyvalent metal compounds (b2), according to metal, convert and count, be preferably generally 0.1～0.9 equivalent, be in particular 0.15～0.8 equivalent, be more in particular in the scope of 0.15～0.5 equivalent.Polyvalent metal compounds (b2) if usage quantity lower than 0.1 equivalent, roller coat operability and and the formed multicolour pattern clarity of filming not enough, if contrary, surpass 0.9 equivalent, roller coat operability, coating storage stability, the deficiencies such as weathering resistance of filming.

In the forming component of filming (B), can further contain as required tinting pigment, aura pigment, fluorescent material, pigment extender, other additive for coatings etc.Tinting pigment, aura pigment and fluorescent material can be enumerated the material that aforesaid tinting material (a2) is exemplified.In addition, this other additive for coatings is such as enumerating: the fire retardant of thickening material, resin bead, neutralizing agent, static inhibitor, tenderizer, antiseptic-germicide, essence, curing catalysts, pH adjusting agent, humextant, powdery or particulate gac, photocatalyst oxidizes titanium, water-based hydrophobic agent, dispersion agent, defoamer, sanitas, mould inhibitor, frostproofer, UV light absorber, photostabilizer, film coalescence aid, zinc whisker, curing catalyst, aldehyde sorbent material, wax, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, aluminium hydroxide etc. etc.

Wherein, thickening material can be used itself known material in indefinite ground, and its object lesson is such as enumerating: the mineral-type compounds such as water-soluble alkali metal silicates, montmorillonite, colloidal aluminum oxide; The derivatived cellulose compounds such as methylcellulose gum, Natvosol, carboxymethyl cellulose; The polyether compounds such as Pluronic polyethers, polyethers dialkyl, polyethers dialkyl ether, the urethane-modified thing of polyethers, the epoxide modified thing of polyethers; The polyacrylic compounds such as sodium polyacrylate, polyacrylic acid (methyl) acrylate copolymer; The polyvinyl compounds such as polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyvinyl benzyl alcohol multipolymer; The protein derivatives such as sodium-caseinate, ammonium caseinate; The partial ester of vinyl methyl ether-copolymer-maleic anhydride, drying oil fatty acid allyl alcohol ester-copolymer-maleic anhydride etc., they can be respectively separately or two or more is used in combination.Wherein, thickening material is preferably used polyacrylic compounds, can make thus the clarity of the multicolour pattern that weathering resistance, roller coat operability, roller coat that multicolour pattern films form improve.

The solids component quality of aqueous colorful pattern coating composition of the present invention of take is benchmark, the usage quantity of this thickening material can common 0.01～10 quality %, preferably 0.05～5 quality %, further preferably in the scope of 0.03～7.5 quality %.

And, the appropriate dumb light sense of filming from formed multicolour pattern and clarity, the consideration of long-term weatherability equal angles, the forming component of preferably filming (B) contains resin bead.Described resin bead is such as enumerating: acrylic resin pearl, polystyrene resin pearl, polyvinyl resin pearl, acrylic resin pearl, carbamate resins pearl, silicone resin pearl, fluoro-resin pearl, vibrin pearl, polyamide resin pearl, nylon resin pearl etc.The use level of above-mentioned resin bead, the film solids component of forming component (B) of take is benchmark, common 1～100 quality %, preferably 3～75 quality %, further preferably in the scope of 5～50 quality %, be applicable to.

crosslinker compound (c)

In the present invention, the at least one party of pigmented coating particulate component (A) and the forming component of filming (B) is contained compound (c), in 1 molecule of this compound (c), at least have 2 can with water-base resin (a1) in bridging property functional group and the functional group of the bridging property functional group reactions in water-base resin (b1), result, at the multicolour pattern formation stages of filming, pigmented coating particulate component (A) and the forming component of filming (B) react to each other via crosslinker compound (c), be cross-linked securely bonding, the multicolour pattern that forms the excellences such as long-term weatherability, water tolerance is filmed.

The functional group that above-mentioned crosslinker compound (c) can have is such as enumerating hydroxyl, isocyanato, alkylether radicals, imino-, amino, amide group, carbonyl, epoxy group(ing), diazanyl, Semicarbazido, di-acetyl two hydrazone groups etc., in 1 molecule, at least there is the compound of 2 such functional groups except hydrazine derivative described later, such as can enumerate polyol compound, polyisocyanate compounds, melamine compound, polyamine compounds, polyamide compound, containing the resin of carbonyl, containing the resin of epoxy group(ing) etc.

The combination of contained functional group in the bridging property functional group having respectively as water-base resin (a1) and water-base resin (b1) and crosslinker compound (c), so long as the combination that can react to each other under the drying conditions of filming, and be not particularly limited, concrete example is as enumerated: hydroxyl and isocyanate group, hydroxyl and alkylether radicals, hydroxyl and imino-, amino and epoxy group(ing), amide group and epoxy group(ing), carbonyl and diazanyl, carbonyl and hydrazide group, carbonyl and Semicarbazido, and the combination of carbonyl and di-acetyl two hydrazone groups etc., from can the crosslinked angle of normal temperature single component considering, the particularly preferably combination of carbonyl and hydrazide group.

In aqueous colorful pattern coating composition of the present invention, coating composition for all conditions such as clarity of filming that obtain the weathering resistance that meets multicolour pattern and film, tack with primer coating film, coating storage stability, formed by roller coat simultaneously, preferably water-base resin (a1) contains carboxyl and carbonyl, and water-base resin (b1) contains carboxyl, trialkoxysilyl and carbonyl, pigmented coating particulate component (A) and/or the forming component of filming (B) contain with the hydrazine derivative of carbonyl reaction as crosslinker compound (c).

Above-mentioned hydrazine derivative is such as enumerating: two hydrazides of the saturated aliphatic carboxylic acid of the carbonatomss 2～18 such as hydrazine, hydrazine hydrate, careless acid dihydrazide, propanedioic acid two hydrazides, amber acid dihydrazide, pentanedioic acid two hydrazides, adipic dihydrazide, sebacic dihydrazide; Two hydrazides of single ethylenic unsaturated dicarboxylic acids such as Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides; Two hydrazides of phthalic acid, terephthalic acid or m-phthalic acid; Two hydrazides of pyromellitic acid, three hydrazides or four hydrazides; Nitrilotriacetic acid three hydrazides, citric acid three hydrazides, 1,2,4-benzene three hydrazides; Ethylenediamine tetraacetic acid (EDTA) four hydrazides, Isosorbide-5-Nitrae, 5,8-naphthoic acid, four hydrazides; Make the oligopolymer with carboxylic acid low alkyl group ester group react polyhydrazide forming etc. with hydrazine or hydrazine hydrate; Carbon acid dihydrazide, two (Urea,amino-) are (bis-semicarbazide); Make N, the N of N-dimethylhydrazine etc., N-replaces hydrazine or the above-mentioned hydrazides exemplifying to the vulcabond such as hexylidene diisocyanate, isophorone diisocyanate and the multifunctional Urea,amino-that obtained by its derivative polyisocyanate compounds excessive response; The multifunctional Urea,amino-of water system that makes the isocyanate group excessive response in the reactant of the active dydrogen compounds that above-mentioned two hydrazides that exemplify contain hydrophilic radical to this polyisocyanate compounds and polyether glycol class or polyalkylene glycol monoalkyl ethers etc. and obtain; This multifunctional Urea,amino-with the multifunctional Urea,amino-of water system mixture; Di-acetyl dihydrazone etc., they can be respectively separately or two or more is used in combination.

< aqueous colorful pattern coating composition and application > thereof

Aqueous colorful pattern coating composition of the present invention can be by mixing the pigmented coating particulate component (A) obtaining as mentioned above and the forming component of filming (B) and easily preparation, when both are mixed, can as required, coordinate normally used additive, water etc. in paint field.The designability of filming from the multicolour pattern of gained, weathering resistance equal angles are considered, the mixing ratio of pigmented coating particulate component (A) and forming component (B) that film, according to the solids component mass ratio meter of pigmented coating particulate component (the A)/forming component of filming (B), can common 1/99～60/40, preferably 5/95～55/45, further preferably in 10/90～50/50 scope.

< coating particles composition (C) >

In aqueous colorful pattern coating composition of the present invention, except pigmented coating particulate component (A) and the forming component of filming (B), also can further contain as required and there is transparent coating particles composition (C).Coating particles composition (C) preferably has carboxyl and other bridging property functional group in addition.

Coating particles composition (C) be can form have the transparency the coating composition of filming carry out spheroidizing and obtain.

Aqueous colorful pattern coating composition of the present invention, by further containing coating particles composition (C), can make formed depth feelings of filming more improve.

In composition of the present invention, even if do not contain coating particles composition (C), kind and the combination of the tinting material by suitable selection based on pigmented coating particulate component (A) (a2), the decorative pattern that also can form bag is filmed, but by coating particles composition (C) and pigmented coating particulate component (A) are also used, the texture of bag, material sense (material sense) significantly improve, and can obtain the appearance design close to natural stone.

Here, the term of " having the transparency " not only refers to completely transparent situation, also comprises translucent state, can be colourless can be also coloured.

Having transparent coating particles composition (C) can be by for example in the manufacture of above-mentioned pigmented coating particulate component (A), do not use tinting material (a2), even if or use, also not damage formed transparent degree of filming, the solids component of water-base resin (a1) of for example take is benchmark, with lower than 1.0 quality %, preferably the amount below 0.5 quality % is used, thereby similarly manufacture with pigmented coating particulate component (A).

In addition, about coating particles composition (C), so long as filming of being formed by the composition before spheroidizing has the transparency, can contain pigment extender.When having transparent coating particles composition (C) and containing pigment extender, it is benchmark that its content be take the solids component of contained water-base resin (b1) in coating particles composition (C), can be below 100 quality %, preferably below 80 quality %.

In aqueous colorful pattern coating composition of the present invention, there is transparent coating particles composition (C) going back and use except pigmented coating particulate component (A), using in this situation as particulate component, the designability equal angles of filming from gained multicolour pattern is considered, according to the solids component mass ratio meter of pigmented coating particulate component (A)/Clear paint particulate component (C), itself and with ratio can be common 20/80～99/1, preferably 25/75～97/3, further preferably in 30/70～95/5 scope.

Aqueous colorful pattern coating composition of the present invention is by being coated on substrate surface, and the multicolour pattern that can form excellent performances such as having colorful designability, water tolerance is filmed.

The substrate surface of applicable aqueous colorful pattern coating composition of the present invention is not particularly limited, for example can enumerate: plasterboard, concrete wall, concrete blocks, wall dunnage, mortar wall, slabstone (Slate board), PC plate, ALC plate, cement calcium silicate board, timber, stone material, plastic shaping thing, ceramic ware, ceramic tile, the surface of the base materials such as metal work material, be located at the crylic acid resin on these base materials, propenoic methyl carbamate resene, polyurethane type resin, fluorine type resin, silicone resin, organosilicon acrylic resin class, vinyl acetate resin class, the coated surfaces such as epoxy resin, by polyvinyl chloride, polyolefine, paper, the wallpaper face that the materials such as cloth form etc.

Aqueous colorful pattern coating composition of the present invention can adopt itself known application means to carry out application, such as can be according to the kind of base material, purposes etc., suitable choice for use from the finishing of roller, aerial spraying, hydraulic spraying, resin spray gun, omnipotent spray gun, hairbrush, roller coating machine etc.In not damaging the scope of appearance of film, aqueous colorful pattern coating composition of the present invention can also repeatedly be coated with.

Formation is filmed dry can be according to the composition of used coating composition etc., by any means of heat drying, forced drying or Air drying, undertaken.

Can according to circumstances in advance primer base be coated on to substrate surface, and then aqueous colorful pattern coating composition of the present invention is coated on formed priming paint painting face.

Above-mentioned primer base can suitably be selected according to the kind of substrate surface, state etc., such as using seal coat (sealer), substrate to adjust the primer bases such as material.The all right common finish paint coating of application is as the substrate formation coating of aqueous colorful pattern coating composition of the present invention.

Described as substrate form with and the finish paint coating that uses such as can enumerate contain by acrylic resin, the third silicon resinoid, polyolefin resin, silicon resinoid, polyurethanes resin, redix, the water system that the resin kind such as phenolic resinoid, polyester resin, alkyd based resin, Biodegradable resin forms or the resin of solvent system are as the coating of resin glue, preferably use contains the water-borne coatings that aqueous resin forms.

Above-mentioned substrate forms can adopt itself known application means with the application of coating, such as can be according to the purposes of base material etc., suitable choice for use from the finishing of roller, aerial spraying, hydraulic spraying, resin spray gun, omnipotent spray gun, hairbrush, roller coating machine etc.Formed primer coating film dry can be according to the kind of used primer base etc., by any means of heat drying, forced drying or Air drying, is undertaken.

Also can be in application application varnish colour (clear coating) on the painting face of aqueous colorful pattern coating composition of the present invention.Described varnish colour such as can enumerate contain by acrylic resin, the third silicon resinoid, polyolefin resin, silicon resinoid, polyurethanes resin, redix, the water system that forms of the resin kind such as phenolic resinoid, polyester resin, alkyd based resin, Biodegradable resin or solvent be resin as the coating of resin glue, preferably use and contain the water-borne coatings that aqueous resin forms.Described varnish colour can as required, contain just like the tinting material being exemplified facing to look coating particles composition (A) not damage the transparent degree of filming.

The application of above-mentioned varnish colour can adopt itself known application means to carry out, such as can be according to the purposes of base material etc., and suitable choice for use from roller, aerial spraying, hydraulic spraying, resin spray gun, omnipotent spray gun, hairbrush, roller coating machine etc.Formed varnish is filmed dry can be according to the kind of used varnish colour etc., by any means of heat drying, forced drying or Air drying, undertaken.

Embodiment

Further illustrate by the following examples the present invention, but the present invention is not only defined as these embodiment." part " in following example and " % " represent respectively " mass parts " and " quality % ".

The manufacture > of < emulsion

Production Example 1: the manufacture of the emulsion (a1) containing carboxyl and carbonyl of carrying out in order to manufacture redness and white pigmented coating particulate component

In four neck flasks of 2 liters of capacity, add 285 parts of deionized waters and 1 part " ニューコー Le 707SF " (note 1), after nitrogen displacement, in 85 ℃, preserve.Add respectively wherein in the pre-emulsion that the composition emulsion of following composition is obtained 3% amount and 3 parts of ammonium persulphates are dissolved in to 41 parts in 123 parts of initiator solutions that 120 parts of deionized waters obtain, from adding, finish, after 20 minutes, with 4 hours, remaining pre-emulsion and ammonium persulfate aqueous solution to be added drop-wise in flask.

< pre-emulsion forms >

368 parts of deionized waters

150 parts of vinylbenzene

410 parts of methyl methacrylates

240 parts of n-butyl acrylates

150 parts of 2-EHAs

20 parts of diacetone-acryloamide(DAA)s

25 parts of vinylformic acid 2-hydroxy methacrylates

5 parts, vinylformic acid

" ニューコー Le 707SF " (note 1) 66 parts

After dropping finishes, it is further kept 2 hours at 85 ℃, be then cooled to 40～60 ℃.Then, with ammoniacal liquor, regulate pH, obtain solids component and be 55% emulsion (a1).The median size of emulsion (a1) is 175nm, and pH is 8.3.

(note 1) " ニューコー Le 707SF ": trade(brand)name, Japanese emulsifying agent society manufactures, and for having the anionic surfactant of polyoxyethylene chain, nonvolatile component is 30%.

Production Example 2: in order to manufacture the manufacture of the contained core sheath emulsion (a2) containing carboxyl, alkoxysilyl and carbonyl of filming forming component and carrying out in aqueous colorful pattern coating

In four neck flasks of 3 liters of capacity, add 400 parts of deionized waters and 1 part " ニューコー Le 707SF " (note 1), after nitrogen displacement, in 85 ℃, preserve.Add respectively wherein the amount that the composition of following composition is carried out in the pre-emulsion that emulsion obtains (core with) to 3% amount and 5 parts of ammonium persulphates is dissolved in 105 parts of initiator solutions that 100 parts of deionized waters obtain to 25%, after add finishing 20 minutes, with 3 hours, 50% minim in remaining pre-emulsion (core use) and ammonium persulfate aqueous solution is added in flask.

< pre-emulsion forms (core is used) >

300 parts of deionized waters

100 parts of vinylbenzene

250 parts of methyl methacrylates

230 parts of n-butyl acrylates

100 parts of 2-EHAs

13 parts of vinylformic acid 2-hydroxy methacrylates

6 parts of vinyltriethoxysilanes

1 part, vinylformic acid

" ニューコー Le 707SF " (note 1) 46 parts

After dropping finishes, by its further slaking 2 hours at 85 ℃, then with within 2 hours, dripping the amount of the composition of following composition being carried out in the pre-emulsion that emulsion obtains (sheath with) and above-mentioned ammonium persulfate aqueous solution to 25%.

< pre-emulsion forms (sheath is used) >

200 parts of deionized waters

41 parts of vinylbenzene

176 parts of methyl methacrylates

41 parts of n-butyl acrylates

15 parts of 2-EHAs

15 parts of diacetone-acryloamide(DAA)s

6 parts of Hydroxyethyl Acrylate

2 parts of vinyltriethoxysilanes

4 parts, vinylformic acid

" ニューコー Le 707SF " (note 1) 20 parts

After dropping finishes, it is further kept 2 hours at 85 ℃, be then cooled to 40～60 ℃.Then with ammoniacal liquor, regulate pH, obtain solids component and be 50% core sheath emulsion (a2).The median size of emulsion (a2) is 190nm, and pH is 8.6.

Production Example 3: in order to manufacture the manufacture of the emulsion (a3) containing carboxyl and carbonyl that there is transparent coating particles composition and carry out

In four neck flasks of 2 liters of capacity, add 285 parts of deionized waters and 1 part " ニューコー Le 707SF " (note 1), after nitrogen displacement, in 85 ℃, preserve.Add respectively wherein the composition of following composition is carried out in pre-emulsion that emulsion obtains to 3% amount and 3 parts of ammonium persulphates are dissolved in to 41 parts in 123 parts of initiator solutions that 120 parts of deionized waters obtain, from adding, finish, after 20 minutes, with 4 hours, remaining pre-emulsion and ammonium persulfate aqueous solution to be added drop-wise in flask.

< pre-emulsion forms >

368 parts of deionized waters

200 parts of vinylbenzene

400 parts of methyl methacrylates

300 parts of n-butyl acrylates

69 parts of 2-EHAs

20 parts of diacetone-acryloamide(DAA)s

10 parts of vinylformic acid 2-hydroxy methacrylates

1 part, vinylformic acid

" ニューコー Le 707SF " (note 1) 66 parts

After dropping finishes, it is further kept 2 hours at 85 ℃, be then cooled to 40～60 ℃.Then with ammoniacal liquor, regulate pH, obtain solids component and be 55% emulsion (a3).The median size of emulsion (a3) is 190nm, and pH is 8.1.

Production Example 4: for comparative example not containing the manufacture of the emulsion (a4) of water-disintegrable silyl

< pre-emulsion forms >

368 parts of deionized waters

150 parts of vinylbenzene

400 parts of methyl methacrylates

360 parts of n-butyl acrylates

67 parts of 2-EHAs

10 parts of diacetone-acryloamide(DAA)s

10 parts of vinylformic acid 2-hydroxy methacrylates

3 parts, vinylformic acid

" ニューコー Le 707SF " (note 1) 66 parts

After dropping finishes, it is further kept 2 hours at 85 ℃, be then cooled to 40～60 ℃.Then with ammoniacal liquor, regulate pH, obtain solids component and be 55% emulsion (a4).The median size of emulsion (a4) is 180nm, and pH is 8.0.

The manufacture > of < white pigment slurry

Production Example 5

In 1 liter of stainless steel vessel, pack following compositions into, with stirrer, be uniformly mixed 30 minutes, obtain thus white pigment slurry (b1).

225 parts, water

" スラオ Off 72N " (note 2) 15 parts

30 parts of " DISPER BYK-190 " (notes 3)

" SN デフォーマー 380 " (note 4) 15 parts

500 parts of " TITANIX JR-605 " (notes 5)

(note 2) " スラオ Off 72N ": trade(brand)name, military field pharmaceutical industries (strain) is manufactured, sanitas;

(note 3) " DISPER BYK-190 ": trade(brand)name, BYK-Chemie company manufactures, pigment dispersing agent;

(note 4) " SN デ Off ォーマー 380 ": trade(brand)name, sannopco company (サ Application ノプコ society) manufactures, defoamer;

(note 5) " TITANIX JR-605 ": trade(brand)name, tayca company (テイカ society) manufactures, titanium white.

The manufacture > of < sorrel pigment slurry

Production Example 6

In 1 liter of stainless steel vessel, pack following compositions into, with stirrer, be uniformly mixed 60 minutes, obtain thus sorrel pigment slurry (b2).

400 parts, water

" スラオ Off 72N " (note 2) 15 parts

48 parts of " DISPER BYK-190 " (notes 3)

" SN デフォーマー 380 " (note 4) 15 parts

240 parts of ferric oxide.

The manufacture > of < pigmented coating particle use coating composition (white)

Production Example 7

In container, coordinate successively following compositions, be uniformly mixed and make them even, obtain pigmented coating particle use coating composition (A-1).

250 parts of 55% emulsions (a1)

White pigments slurry (b1) 154 parts

20 parts of " TEXANOL " (notes 6)

" SN デフォーマー 380 " (note 4) 2 parts

" SN シックナー 612 " (note 7) 2 parts

2% 280 parts of the sodiun alginate aqueous solution

(note 6) " TEXANOL ": trade(brand)name, Eastman Chemical company manufactures, single isopropylformic acid 2,2,4-neopentyl glycol ester, film coalescence aid;

(note 7) " SN シッ Network Na ー 612 ": trade(brand)name, sannopco company manufactures, polyurethane polyureas ethers viscosity modifier.

The manufacture > of < pigmented coating particle use coating composition (sorrel)

Production Example 8

In container, coordinate successively following compositions, be uniformly mixed and make them even, obtain pigmented coating particle use coating composition (A-2).

250 parts of 55% emulsions (a1)

276 parts of reddish brown pigment slurrys (b2)

20 parts of " TEXANOL " (notes 6)

" SN デフォーマー 380 " (note 4) 2 parts

" SN シックナー 612 " (note 7) 2 parts

2% 280 parts of the sodiun alginate aqueous solution.

The manufacture > of < Clear paint particle use coating composition

Production Example 9

In container, coordinate successively following compositions, be uniformly mixed and make them even, obtain Clear paint particle use coating composition (A-3).

250 parts of 55% emulsions (a3)

20 parts of " TEXANOL " (notes 6)

" SN デフォーマー 380 " (note 4) 2 parts

" SN シックナー 612 " (note 7) 2 parts

2% 280 parts of the sodiun alginate aqueous solution.

The manufacture > of < pigmented coating granule manufacture use medium

Production Example 10

In the stainless steel vessel of 4 liters of capacity, pack 7.0 parts of lime acetate monohydrates and 2,000 parts of deionized waters into, be stirred to evenly, manufacture thus the aqueous medium (B-1) that contains lime acetate.

Production Example 11～12

In above-mentioned Production Example 10, formula is consisted of shown in following table 1, in addition similarly manufacture aqueous medium (B-2)～(B-3) with Production Example 10.

Table 1

。

The manufacture > of < pigmented coating particulate component

Production Example 13

In the stainless steel vessel of 4 liters of capacity, pack 1 into, the aqueous medium (B-1) of 300 parts of above-mentioned Production Example 10 gained, use has the agitating vane of 75mm diameter, with revolution 2,000rpm lentamente to the water-based paint compositions (A-1) that drips 650 parts of above-mentioned Production Example 7 gained in container, generates pigmented coating particle while stirring.Then, then with same rotational speed, liquid in container is stirred 15 minutes, then use 200 object wire netting leachings, obtain pigmented coating particle (C-1).The solids component of the pigmented coating particle (C-1) of gained is 20%.

Production Example 14～20

In above-mentioned Production Example 13, by the formula change of the water-based paint compositions of aqueous medium and dropping, be shown in table 2, in addition same with above-mentioned Production Example 13, manufacture pigmented coating particle (C-2)～(C-8).And in aqueous medium, contained metallic compound carrys out the equivalence ratio (when a plurality of compounds and while being used as metallic compound, being the equivalence ratio of total amount) of the carboxyl of sodium alginate with respect to 1 equivalent shown in table 2.Here, the molecular weight of sodiun alginate is made as 90000.

Table 2

。

The manufacture > of < Clear paint particle

Production Example 21

In the stainless steel vessel of 4 liters of capacity, pack 1 into, the aqueous medium (B-1) of 300 parts of above-mentioned Production Example 10 gained, use has the agitating vane of 75mm diameter, with revolution 2,000rpm lentamente to the water-based paint compositions (A-3) that drips 510 parts of above-mentioned Production Example 9 gained in container, generates Clear paint particle while stirring.Then, then with same rotational speed, liquid in container is stirred 15 minutes, then use 200 object wire netting leachings, obtain Clear paint particle (C-9).The solids component of the Clear paint particle (C-9) of gained is 22%.

The film manufacture > of forming component use varnish colour of <

Production Example 22

In the stainless steel vessel of 2 liters of capacity, pack successively following compositions into, with stirrer, be uniformly mixed 30 minutes until evenly, obtain thus water varnish coating (D-1).

750 parts of 50% emulsions (a2)

55 parts of " TEXANOL " (notes 6)

10 parts of " BYK-028 " (notes 8)

" プライマ Le ASE60 " (note 9) 3 parts

0.7 part of lime acetate

(note 8) " BYK-028 ": trade(brand)name, BYK-Chemie company manufactures, defoamer

(note 9) " プライマ Le ASE60 ": trade(brand)name, Rhom and Hass (ロー system ア Application De ハース society) manufactures, polyacrylic viscosity modifier.

Production Example 23～30

In above-mentioned Production Example 22, formula is formed and to be made as following table 3, in addition same with Production Example 22, obtain water varnish coating (D-2)～(D-9).

(note 10) " MBX-15 ": trade(brand)name, ponding changes into product industry society and manufactures, methyl-methacrylate resin pearl, median size 15 μ m.

The manufacture > of < aqueous colorful pattern coating

Embodiment 1～10 and comparative example 1～4

In the stainless steel vessel of 500 milliliters of capacity, pack successively while stirring the composition shown in following table 4 into, be then stirred to evenly, manufacture thus aqueous colorful pattern coating (E-1)～(E-14).

。

< performance evaluation >

Embodiment 11～20 and comparative example 5～8

At the upper roller coat " EP シーラー is transparent " of slabstone (600 * 900 * 3mm) (Northwest paint company (Northwest ペイント society) is manufactured, trade(brand)name, water system ACRYLIC EMULSION class seal coat), glue spread is 100g/m ², dry, roller coat " アレスア Network アグロス is white " (Northwest paint company is manufactured, trade(brand)name, ACRYLIC EMULSION class coating) then, glue spread is 100g/m ², under the condition of 20 ℃ of temperature, relative humidity 60%, be dried 1 day, using it as by coated plate, each aqueous colorful pattern coating obtaining in above-described embodiment and comparative example is supplied with to following test.Result as described in Table 5.

Embodiment 21

The aqueous colorful pattern coating of roller coat embodiment 1 gained, glue spread is 250g/m ², under the condition of 23 ℃ of temperature, relative humidity 60%, be dried 1 day, then at this, be coated with the varnish colour that face top roll is coated with Production Example 22 gained, glue spread is 100g/m ², under the condition of 23 ℃ of temperature, relative humidity 60%, be dried 7 days, the test coated plate of gained is carried out to following (* 2) design test and the evaluation test of (* 6) weathering resistance.The results are shown in following table 5.

In embodiment 21, about the result of (* 1) roller operability, (* 4) level and smooth sense and the test of (* 5) Storage, identical with embodiment 11.

。

(* 1) roller operability

According to following benchmark, evaluate above-mentioned by coated plate on each aqueous colorful pattern coating of roller coat, glue spread be 250g/m ²time operability.

◎: during roller coat, pigmented coating particle does not break, operability is very good;

Zero: during roller coat, pigmented coating particle is difficult to break, and operability is good;

△: during roller coat, pigmented coating particle has and breaks, and operability is slightly bad;

*: during roller coat, pigmented coating breakage of particles is more, and operability is bad.

(* 2) designability

With roller above-mentioned by coated plate on each aqueous colorful pattern coating of application, glue spread is 250g/m ², under the condition of 23 ℃ of temperature, relative humidity 60%, be dried 7 days, then visual observation is coated with face, according to following benchmark evaluation designability.

◎: the decorative pattern clarity that each pigmented coating particle produces is very good;

Zero: the decorative pattern clarity that each pigmented coating particle produces is good;

△: the decorative pattern clarity that each pigmented coating particle produces is slightly bad;

*: the decorative pattern that each pigmented coating particle produces is not distinct.

(* 3) texture

Above-mentioned by each aqueous colorful pattern coating of application on coated plate to be sprayed on, glue spread is 250g/m ², under the condition of 23 ℃ of temperature, relative humidity 60%, be dried 7 days, then visual observation is coated with face, according to following benchmark evaluation texture.

◎: texture is excellent, has colorful sense and depth feelings;

Zero: have texture, have colorful sense;

△: texture is poor, colorful sense is fuzzy;

*: there is no texture, do not experience colorful sense.

(* 4) are smoothly felt

According to following benchmark, evaluate with hand touch in above-mentioned (* 2) design test, use respectively test coated plate time sense of touch.

◎: the level and smooth sense of filming is good;

Zero: the level and smooth sense of filming slightly well;

△: some harsh feelings of having filmed;

*: the significant harsh feeling of having filmed.

(* 5) Storage

The mayonnaise bottle that each aqueous colorful pattern coating of embodiment and comparative example gained is packed into 250ml, visual observation is the state after 1 month at 40 ℃, according to following benchmark evaluation.

◎: unchanged before and after storage;

Zero: before and after storage, colloidal viscosity slightly changes, but there is no to wrap in pigmented coating particle the outflow of thing;

△: the outflow of bag thing in some pigmented coating particles as seen;

*: in pigmented coating particle, the outflow of bag thing is remarkable.

(* 6) weathering resistance

The a part of cutting of respectively testing coated plate using in above-mentioned (* 2) design test is become to 70 * 150 * 3mm size, use the weather-proof instrument of xenon lamp (キセノ Application ウェザオメーター) to carry out the atmospheric exposure test of 4000 hours, then visual observation is coated with surface state, according to following benchmark evaluation.

◎: identical with the test coated plate before test, do not change;

Zero: compare with the test coated plate before test, gloss is in a slight decrease, but has colorful sense, no problem;

△: the visible albefaction of a part or xanthochromia, to compare with the test coated plate before test, colorful sense is slightly poor;

*: whole visible albefaction or xanthochromia, compare with the test coated plate before test, be changed significantly.

(* 7) tack

Use cut-off knife, the central authorities of the test coated plate using in above-mentioned (* 2) designability cut out the tool marks of the Shen Da basic unit of the angular cross that is mutually 30 degree, then, Continuous pressing device for stereo-pattern on 2 tool marks of Self-crossover, do not produce bubble, make adhesive tape and film to adhere to completely, moment peels off, and according to following benchmark, evaluates.

〇: there is no furfur (Ha ガレ);

△: at tool marks peripheral part, be coated with intermembranous a little furfur that has at priming paint/multicolour pattern;

*: at priming paint/multicolour pattern place of filming, there is significant furfur.

Industrial applicability

According to aqueous colorful pattern coating composition provided by the present invention by being coated on the substrate surfaces such as iron portion of the metope such as buildings, various building materials, door etc., can make substrate surface there is colorful designability, can give the multicolour pattern of the excellent performances such as its water tolerance and film.

Claims

1. aqueous colorful pattern coating composition, this aqueous colorful pattern coating composition contains:

(B) forming component of filming, this forming component of filming contains water-base resin (b1) and polyvalent metal compounds (b2), and described water-base resin (b1) has carboxyl and water-disintegrable silyl and other bridging property functional group in addition,

This aqueous colorful pattern coating composition is characterised in that:

At least one party of pigmented coating particulate component (A) and the forming component of filming (B) is contained compound (c), in 1 molecule of described compound (c), at least have 2 can with water-base resin (a1) in bridging property functional group and the functional group of the bridging property functional group reactions in water-base resin (b1)

In the forming component of filming (B), the carboxyl with respect to 1 equivalent in water-base resin (b1), according to the metal meter that converts, contains polyvalent metal compounds (b2) with the ratio of 0.1～0.9 equivalent.

2. the aqueous colorful pattern coating composition of claim 1, wherein, water-base resin (a1) and water-base resin (b1) have respectively carbonyl, as the functional group that can react.

3. claim 1 or 2 aqueous colorful pattern coating composition, wherein, pigmented coating particulate component (A) is the composition with following grain pattern: in the water-based pigmented coating that contains water-base resin (a1) and tinting material (a2), be wrapped in the particle being formed by water-soluble polysaccharides metal-salt.

4. the aqueous colorful pattern coating composition of any one in claim 1～3, wherein, pigmented coating particulate component (A) is that described water-based pigmented coating contains water-base resin (a1) and tinting material (a2) by making the composition that contains water-based pigmented coating and water-soluble polysaccharides (a3) contact and obtain with the aqueous medium that contains metallic compound (a4).

5. the aqueous colorful pattern coating composition of claim 4, wherein, metallic compound (a4) contains metal salts of organic acids as a part for its composition.

6. claim 4 or 5 aqueous colorful pattern coating composition, wherein, in pigmented coating particulate component (A), the carboxyl with respect to 1 equivalent in water-soluble polysaccharides (a3), according to metal conversion amount meter, with 1.5 equivalents, contain below metallic compound (a4).

7. the aqueous colorful pattern coating composition of any one in claim 1～6, wherein, water-disintegrable silyl is trialkoxysilyl.

8. the aqueous colorful pattern coating composition of any one in claim 1～7, wherein, polyvalent metal compounds (b2) is calcium containing compound.

9. the aqueous colorful pattern coating composition of any one in claim 1～8, wherein, polyvalent metal compounds (b2) contains metal salts of organic acids as a part for its composition.

10. the aqueous colorful pattern coating composition of any one in claim 1～9, wherein, in the forming component of filming (B), carboxyl with respect to 1 equivalent in water-base resin (b1), according to metal, convert and count, the scope at 0.1～0.9 equivalent contains polyvalent metal compounds (b2) conventionally.

The aqueous colorful pattern coating composition of any one in 11. claims 1～10, wherein, the forming component of filming (B) further contains thickening material.

The aqueous colorful pattern coating composition of any one in 12. claims 1～10, wherein, the forming component of filming (B) further contains resin bead.

The aqueous colorful pattern coating composition of any one in 13. claims 1～11, wherein, compound (c) has hydrazide group.

The aqueous colorful pattern coating composition of 14. claims 1, wherein, water-base resin (a1) contains carboxyl and carbonyl, water-base resin (b1) contains carboxyl, trialkoxysilyl and carbonyl, and at least one party of pigmented coating particulate component (A) and the forming component of filming (B) is contained with the hydrazine derivative of carbonyl reaction as compound (c).

The aqueous colorful pattern coating composition of any one in 15. claims 1～14, said composition, except pigmented coating particulate component (A) and the forming component of filming (B), further contains and has transparent coating particles composition (C).

16. coating processs, is characterized in that: on coated surface, across or the aqueous colorful pattern coating composition of any one in primer coating film ground application claim 1～15 not.

17. coating processs, is characterized in that: on coated surface, across or the not aqueous colorful pattern coating composition of any one, then application varnish colour on this painting face in primer coating film ground application claim 1～15.