CN103649249B - Aqueous colorful pattern coating composition - Google Patents

Abstract

Containing pigmented finiss particulate component and the aqueous colorful pattern coating composition of film forming component, described pigmented finiss particulate component contains and has carboxyl and the water-base resin of other cross-linking functional group in addition and coloring agent, and described film forming component contains tool carboxyl and hydrolyzable silyl group and the water-base resin of other cross-linking functional group in addition；Wherein, by containing polyvalent metal with specified quantitative in this film forming component of aqueous colorful pattern coating composition, a kind of aqueous colorful pattern coating composition can be obtained, this aqueous colorful pattern coating composition not only when spraying but also during at roller coat pigmented finiss granule be also difficult to rupture, can be formed colorful, clarity is excellent and the multi-color decorative pattern film good with the tack of substrate, long-term weatherability is excellent.

Description

Aqueous colorful pattern coating composition

Technical field

The present invention relates to weatherability etc. excellent in te pins of durability, not only also can be formed in spraying but also in roller coat colorful, The aqueous colorful pattern coating composition of the multi-color decorative pattern film that clarity is excellent.

Background technology

Coating of multi-colour pattern is the painting of the pigmented finiss granule containing the multiple color being stably scattered in disperse medium Material, can be obtained the colorful decorative pattern of multiple color, be mainly used in the application of building etc. by an application.

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

Such as, Japanese Unexamined Patent Publication 2005-15645 publication discloses a kind of water-in-water type multi-color decorative pattern paint compositions, This water-in-water type multi-color decorative pattern paint compositions is to be scattered in by coloring gel granule containing water-base resin and tool specific refractive index Extender pigment transparent low luster coating in form, wherein, described coloring gel granule is by the aqueous with reactive functional groups Prepared by resin, coloring pigment, water and the reactive compounds that can react in the presence of water.

Water paint, compared with solvent coating, generally has the tendency of the application operability differences such as easy sagging, it is desirable to A kind of aqueous colorful pattern coating of exploitation, it can make formed film have colorful design, and application operability is good Good, particularly surrounding is dispersed less, roller coating operation good.

Under above-mentioned shape, in Japanese Unexamined Patent Publication 2007-262350 publication and Japanese Unexamined Patent Publication 2009-173770 publication Propose the aqueous colorful pattern coating containing specific combination thickening agent respectively and the aqueous containing specified quantitative resin bead is many Color decorative pattern paint.

According to these documents, this aqueous colorful pattern coating is difficult to occur after application trickling etc., can form that harsh feeling is few, tool There is the film of colorful design, but during roller coating operation, if coating to be applied big load, then pigmented finiss breakage of particles, Interior bag thing oozes out from inside, the feint problem of decorative pattern occurs.

Japanese Unexamined Patent Publication 2008-202037 publication also states that: containing utilizing water-soluble polysaccharides and specific metal In granulated gel that the reaction of compound obtains and the coating composition of film forming component, film forming component contains by making There is specific metallic compound, the oozing of interior bag thing of granulated gel in coating composition fabrication stage or storage can be suppressed Go out.

But, aforementioned coating composition the multi-color decorative pattern film formed is not enough at outdoor long-term weatherability, Shang Yougai Kind leeway.

Prior art literature

Patent documentation:

Patent documentation 1: Japanese Unexamined Patent Publication 2005-15645 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2007-262350 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2009-173770 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2008-202037 publication.

Summary of the invention

The problem that invention is to be solved

The main object of the present invention is to provide the excellent in te pins of durability, of weatherability etc. not only in spraying but also in roller coat also The aqueous colorful pattern coating composition of multi-color decorative pattern film colorful, that clarity is excellent can be formed.

Solve the mode of problem

The present inventor conducts in-depth research for achieving the above object, found that: existing by containing specific film The aqueous colorful pattern coating of forming component and specific pigmented finiss particulate component contains polyvalent metal with specified quantitative, can obtain Obtain a kind of aqueous colorful pattern coating composition, even if pigmented finiss granule is also difficult to rupture when roller coat, can be formed colorful, fresh Reflecting property is excellent, and the multi-color decorative pattern film good with the tack of substrate, long-term weatherability is excellent, thus completes this Bright.

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

(A) pigmented finiss particulate component, this pigmented finiss particulate component contains water-base resin (a1) and coloring agent (a2), institute State water-base resin (a1) and there is carboxyl and other cross-linking functional group in addition, and

(B) film forming component, this film forming component contains water-base resin (b1) and polyvalent metal compounds (b2), institute State water-base resin (b1) and there is carboxyl and hydrolyzable silyl group and other cross-linking functional group in addition；

This aqueous colorful pattern coating composition is characterised by: pigmented finiss particulate component (A) and film forming component (B) at least one party contains compound (c), and this compound (c) at least has 2 in 1 molecule can be with water-base resin (a1) In cross-linking functional group and in water-base resin (b1) cross-linking functional group reaction functional group；In film forming component (B), Relative to 1 equivalent carboxyl in water-base resin (b1), according to metal conversion meter, contain multivalence with the ratio of 0.1～0.9 equivalent Metallic compound (b2).

Invention effect

According to the aqueous colorful pattern coating composition of the present invention, pigmented finiss particulate component (A) and film forming component (B) react to each other and secure bond via crosslinker compound (c), meanwhile, the hydrolyzable silyl group in water-base resin (b1) Self condensed by hydrolysis, and pass through polyvalent metal compounds between the carboxyl in water-base resin (a1) and water-base resin (b1) (b2) generating metal bridging, the durability of weatherability etc. is the most excellent, though carry out as such in roller coat coating is applied big During the application of load, pigmented finiss granule also will not rupture, and can be formed and occur that the situation of the uneven grade of decorative pattern is few, clarity is excellent Multi-color decorative pattern film.

It addition, according to the coating particles composition of the film forming component spheroidizing contained having the transparency further (C) aqueous colorful pattern coating composition of the present invention, can make the depth feelings of formed multi-color decorative pattern film more carry Height, the available effect that also can show the such excellence of bag texture according to the color of pigmented finiss particulate component (A).

Hereinafter, aqueous colorful pattern coating composition and the painting of this coating composition of the present invention are further described Dress method.

Specific embodiments

<pigmented finiss particulate component (A)>

Pigmented finiss particulate component (A) in the aqueous colorful pattern coating composition of the present invention contains water-base resin (a1) With coloring agent (a2).

Water-base resin (a1)

Water-base resin (a1) is solubilized or the resin being dispersed in water, and this resin types is also not particularly limited, such as may be used Enumerate: acrylic resin, silicon resinoid, polyurethane based resin, epoxylite, phenolic resinoid, polyester resin, alkyd Resinoid, polycarbonate resin etc., two or more can individually or be applied in combination by they.It addition, these resins such as may be used To pass through modification as urethane-modified acrylic's resin, or can be through glycerol polymerization, also [table 2]

Table 2

State.

When water-base resin (a1) is the form of discrete particles, can have single layer structure (the most granular) or core sheath structure Deng multiple structure, during for core sheath structure, core and/or sheath can cross-link.It addition, the carboxyl that water-base resin (a1) is had is permissible With amine such as methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol Class；The alkali part of ammonia etc. or neutralize the most completely.

Angularly considering from durability, the weatherability of pigmented finiss particulate component (A), water-base resin (a1) is preferably propylene Acid resin, described acrylic resin can be enumerated: makes at least one contain the compound of (methyl) acryloyl group, and as required Other copolymerizable polymerism unsaturated monomer together, carry out (co) polymerization and the resin that obtains.

Such as can enumerate containing the compound of (methyl) acryloyl group: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) amyl acrylate, (first Base) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate base The straight chain of ester etc. or branched (methyl) alkyl acrylate；(methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate Deng ester ring type (methyl) alkyl acrylate；(methyl) acrylic acid aralkyl ester of (methyl) benzyl acrylate etc.；(first Base) (methyl) alkoxyalkyl acrylate of acrylic acid 2-methoxy acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester etc.； (methyl) perfluoroalkyl acrylate；Such as (methyl) acrylic acid N of (methyl) acrylic acid N, N-diethylamino ethyl ester, N-dioxane Base aminoalkyl ester；(methyl) acrylamide；(methyl) allyl acrylate, two (methyl) acrylic acid glycol ester, two (first Base) acrylic acid triethyleneglycol ester, two (methyl) acrylic acid tetraethylene glycol (TEG) ester, two (methyl) acrylic acid 1,3 butylene glycol ester, trihydroxy methyl Propane three (methyl) acrylate, two (methyl) acrylic acid 1,4-butanediol ester, two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid 1,6-HD ester, two (methyl) acrylate, pentaerythritol, four (methyl) acrylate, pentaerythritol, two (methyl) glycerol acrylate, 1,1,1-trimethylolethane two (methyl) acrylate, 1,1,1-trimethylolethane trimethacrylate (first Base) acrylate, 1,1,1-trimethylolpropane tris (methyl) acrylate etc. 1 molecule at least there are 2 polymerisms (methyl) acryloyl monomer of unsaturated group；(methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) hydroxyalkyl acrylates of (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) hydroxy butyl acrylate etc., above-mentioned (first Base) the 6-caprolactone modification body of hydroxyalkyl acrylates, molecular end be (methyl) propylene containing polyoxyethylene chain of hydroxyl (methyl) acryloyl monomer of the hydroxyl of acid esters etc.；(methyl) acrylic acid；(methyl) acrylic acid acetoacetoxyethyl, double (methyl) acryloyl monomer containing carbonyl of acetone (methyl) acrylamide etc.；(methyl) glycidyl acrylate, (first Base) propenoic acid beta-methylglycidyl ester, (methyl) acrylic acid 3,4-expoxycyclohexyl methyl ester, (methyl) acrylic acid 3,4- (methyl) acryloyl list containing epoxy radicals of expoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4-expoxycyclohexyl propyl ester etc. Body；(methyl) acryloyl monomer of the isocyanato group containing of (methyl) acrylic acid isocyanatoethyl methacrylate etc.；γ-methacryloxy (the first containing alkoxysilyl of propyl trimethoxy silicane, γ-methacryloxypropyl etc. Base) acryloyl monomer；(methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid dicyclopentenyl epoxide propyl ester, (methyl) acryloyl monomer etc. containing oxidation curable group of (methyl) acrylic acid dicyclopentenyl ester etc., they can distinguish single Solely or two or more is applied in combination.

It addition, other copolymerizable polymerism unsaturated monomer such as can be enumerated: (methyl) acrylonitrile；Vinyl acetate base The vinyl ester compound of ester, vinyl propionate base ester etc.；The vinyl aromatic compounds of styrene, α-methyl styrene etc.；Different 1 molecule of cyanuric acid alkatriene propyl diester, diallyl terephthalate, divinylbenzene etc. at least have 2 polymerizations Many vinyl compounds of property unsaturated group；Allyl alcohol；Containing of maleic acid .beta.-methylacrylic acid, propenoic acid beta-carboxy ethyl ester etc. The polymerism unsaturated monomer of carboxyl；(methyl) acrylic aldehyde, formyl styrene, the vinyl alkyl ketone (example of carbon number 4～7 Such as ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone etc.), poly-containing carbonyl of acetoacetyl allyl ester etc. Conjunction property unsaturated monomer；The polymerism unsaturated monomer containing epoxy radicals of allyl glycidyl ether etc.；Between isopropenyl-α, The polymerism unsaturated monomer of the isocyanato group containing of α-dimethylbenzyl isocyanates etc.；Vinyltrimethoxy silane, ethylene The polymerism unsaturated monomer containing alkoxysilyl of ethyl triethoxy silicane alkane etc.；Polymerism unsaturation list containing epoxy radicals The polymerism unsaturated monomer of body or hydroxyl contains the poly-of oxidation curable group with the product etc. of unsaturated fatty acid Conjunction property unsaturated monomers etc., two or more can individually or be applied in combination by they.

The water-base resin (a1) of the present invention has carboxyl, thus makes resin (a1) Water-borne modification, and manufactures stability and obtain Improve.

It addition, other cross-linking functional group beyond the carboxyl that had of water-base resin (a1) such as can enumerate: hydroxyl, different Cyanic acid base, amino, amide groups, carbonyl etc., from the standpoint of weatherability, storage-stable etc., particularly preferred carbonyl.

The water-base resin (a1) with carboxyl and carbonyl such as can manufacture as follows: uses (methyl) acrylic acid and/or as front Other described carboxylic polymerism unsaturated monomer and foregoing (methyl) acryloyl monomer containing carbonyl and/or its At least some of as monomer component of its polymerism unsaturated monomer containing carbonyl, with other containing (methyl) acryloyl group Compound and/or other polymerism unsaturated monomer copolymerization.Described (methyl) acrylic acid and other carboxylic polymerism insatiable hunger With the usage amount of monomer and (methyl) acryloyl monomer containing carbonyl and other the polymerism unsaturated monomer containing carbonyl it is: On the basis of the total quality of whole polymerism unsaturated monomers of copolymerization, (methyl) acrylic acid and the carboxylic of other gather Conjunction property unsaturated monomer generally can be 0.05～10 mass %, in the range of preferably 0.1～3 mass %, and (the first containing carbonyl Base) acryloyl monomer and generally can be 0.2～30 mass %, preferably 0.3～15 mass % containing the polymerism unsaturated monomer of carbonyl In the range of.

The polymerization of above-mentioned monomer is also not particularly limited, such as can be according to conventional emulsion polymerization, by breast Above-mentioned monomer (co) polymerization is made to carry out in the presence of agent.This emulsifying agent can use emulsifying agent known to itself, concrete example As enumerated: anionic emulsifier, non-ionic emulsifier, amphion emulsifying agent, it is also possible to use in molecule and contain Polymerism unsaturated group and anionic property group or the reactive emulsifier etc. of nonionic group.Its usage amount is permissible It is: on the basis of the total quality of whole polymerism unsaturated monomers, usually 0.5～6 mass %, the model of preferably 1～4 mass % In enclosing.The emulsion particle generated could generally have 50～500nm, preferably 100～400nm, further preferred 100～300nm In the range of mean diameter.In this specification, " mean diameter " is to use submicron particles analyser N4 (trade name, ベ ッ Network マ ンコル タ Co., Ltd. manufactures, particle size distribution device), it is diluted to sample deionized water be suitable for the dense of mensuration Degree, the value measured under room temperature (about 20 DEG C).

Water-base resin (a1) could generally have 0.1～50mgKOH/g, is preferably 0.1～25mgKOH/g, further preferably Acid number in the range of 0.1～20mgKOH/g, and could generally have 0～250mgKOH/g, preferably 0～225mgKOH/g, enter one Hydroxyl value in the range of step preferably 0～200mgKOH/g.And, water-base resin (a1) could generally have 2000～5000000, excellent Select the weight average molecular weight in the range of 10000～3000000, further preferred 50000～1000000.

In this specification, " weight average molecular weight " can use " HLC-8120GPC " (trade name, ソ company manufactures) to make For gel permeation chromatography device, 1 " TSKgel GMHHR-L " (trade name, ソ company manufactures) is used as post, to use Differential refractometer is as detector, in flowing phase: dimethylformamide (containing each 10mM lithium bromide and phosphoric acid), mensuration temperature: 25 DEG C, flow velocity: measure under conditions of 1mL/ minute.

Coloring agent (a2)

Coloring agent (a2) contained by pigmented finiss particulate component (A) comprises coloring pigment, aura pigment, fluorescent material Deng.

Coloring pigment such as can be enumerated: the Chinese whites such as titanium dioxide；Carbon black, acetylene black, dim, bone black, graphite, ferrum Black, nigrosine isochrome pigment；Yellow iron oxide, titan yellow, monoazo yellow, azo condensation Huang, azomethine Huang, pucherite, benzene And the yellow face such as imidazolone, isoindolinone, isoindoline, quinophthalone (quinophthalone), benzidine yellow, permanent yellow Material；Forever consolidate the orange pigments such as orange；Red iron oxide, naphthols AS class azophloxine, anthanthrone, anthraquinonyl are red, purplish red (perylene marron), quinacridine ketone red, diketopyrrolopyrrolecocrystals, paratonere (watching red), forever solid The red pigment such as red；The violet pigments such as cobalt violet, quinacridone violet, diazine are purple；Cobalt blue, phthalocyanine blue, indanthrene blue (threne The blue pigment such as blue)；Phthalocyanine green isochrome pigment etc., aura pigment such as can be enumerated: aluminium powder, bronze powder, copper powder, stannum The metallic pigment such as powder, iron phosphide, zinc powder；The pearlescent pigments etc. such as the mica powder of coated metal oxide, micaceous iron oxide, this Two or more can individually or be applied in combination by a little pigment.The above-mentioned titanium dioxide as Chinese white also comprises averagely Particle diameter is the functional titanium dioxide such as the fine titanium of 10～80nm or the anatase titanium dioxide with photocatalyst activity.

Fluorescent material can enumerate fluorescence or the pigment storing photosensitiveness and dyestuff, such as, can enumerate: diphenylethlene class, azoles Class, thiazoles, imidazoles, triazole type, pyrazoles, furans, thiophene-based, peri-position dicarboxamide (peri-dicarboxylic Acid amide) class, the organic compounds of Coumarins；The metallic compounds such as zinc sulfide, strontium aluminate, calcium aluminate add The mineral-type compound etc. that the metals such as copper, silver, manganese, europium obtain.These coloring agent (a2) can according to object color component individually Or two or more is applied in combination.

The use level of coloring agent (a2) can change in the range of wide according to its kind, with the quality of water-base resin (a1) is Benchmark, can be in usual 1～400 mass %, particularly 2～300 mass %, more particularly 2～250 in the range of mass %.

In pigmented finiss particulate component (A), it is also possible to be used together extender pigment with coloring agent (a2).Its object lesson can Enumerate: Barium monoxide powder (バ リ タ powder), settleability barium sulfate, brium carbonate, calcium carbonate, Gypsum Fibrosum, clay, white carbon, kieselguhr, cunning Stone powder, magnesium carbonate, alumina white, gloss white, silica sand, silica flour etc., can individually or be applied in combination two or more.Described body The use level of matter pigment can change in the range of wide according to its kind, on the basis of the quality of water-base resin (a1), and Ke Yi Usual 0～1000 mass %, particularly 0～800 mass %, more particularly 1.0～750 are in the range of mass %.

The pigmented finiss particulate component (A) of the present invention preferably has the composition of following grain structure: containing water-base resin (a1) it is enclosed in the shell formed by the slaine of water-soluble polysaccharides with the aqueous pigmented finiss of coloring agent (a2).Have described The pigmented finiss particulate component (A) of structure such as can be by making containing aqueous pigmented finiss and the combination of water-soluble polysaccharides (a3) Thing contacts acquisition with the aqueous medium containing metallic compound (a4), and wherein, described aqueous pigmented finiss contains water-base resin And coloring agent (a2) (a1).

Water-soluble polysaccharides (a3) comprises following polysaccharide: this polysaccharide have in an aqueous medium with monovalence or multivalence Metal ion contact time, be changed to the ability of the gel (gelation) of water-insoluble or slightly solubility, the most such as, can enumerate: algae Acid or its alkali metal salt, gellan gum, chondrus ocellatus Holmes polysaccharide, biogum, galactomannan derivant, alginic acid or derivatives thereof, fibre Dimension element derivant, gelatin, casein, albumin etc., or by them by aoxidizing, methylating, carboxy methylation, hydroxyethylation, Hydroxypropylation, sulphation, phosphorylation, cationization etc. carry out chemical modification gains etc., they can individually or by 2 kinds with On be applied in combination.

Flow out to aqueous medium from the interior bag thing of suppression pigmented finiss particulate component (A), and it is few to form harsh feeling Film, and from the point of view of the film that clarity is good, have excellent weather resistance can be formed in roller coat, with water-base resin (a1) and On the basis of the total quality of coloring agent (a2), water-soluble polysaccharides (a3) can usual 0.5～10 mass %, preferably 0.7～9.0 Quality %, further preferred 1.0～8.0 use in the range of mass %, and the storage that thus can obtain pigmented finiss particulate component (A) is steady Qualitative, minimizing uses the harsh feeling of the film of the aqueous colorful pattern coating composition formation of the present invention.

Above-mentioned containing aqueous pigmented finiss and water-soluble polysaccharides (a3) if compositions with containing metallic compound (a4) Aqueous medium contact, then the water-soluble polysaccharides in said composition (a3) with from the metallic compound (a4) in aqueous medium Metal ion form water-insoluble or the salt of slightly solubility, make aqueous pigmented finiss generation granulated gel, be consequently formed coloring Coating particles composition (A).

Above-mentioned metallic compound (a4) is can to generate in an aqueous medium can form water not with water-soluble polysaccharides (a3) The monovalence of the salt of dissolubility or slightly solubility or the compound of polyvalent metal ion, preferably comprise metal salts of organic acids as its composition At least partially.

By using at least some of as metallic compound (a4) of metal salts of organic acids, then interior bag logistics is not had to go out, Excellent storage stability, and also can be readily formed, by roller coat, the pigmented finiss particulate component (A) being difficult to rupture, it is also possible to make The Physical properties of coating film of the weatherability etc. of multi-color decorative pattern film is good.

Angularly consider from the intensity of the pigmented finiss particulate component (A) formed, the gold in described metal salts of organic acids Belong to kind and be preferably polyvalent metal, such as, can enumerate: the periodic table of elements 2 race elements such as magnesium, calcium, strontium, barium；The element such as titanium, zirconium week Qi Biao 4 race element；The periodic table of elements such as chromium, molybdenum 6 race element；The periodic table of elements such as manganese 7 race element；The periodic table of elements such as ferrum, ruthenium 8 Race's element；The periodic table of elements such as cobalt, rhodium 9 race element；The periodic table of elements such as nickel, palladium 10 race element；The periodic table of elements such as copper, silver 11 Race's element；The periodic table of elements such as zinc, cadmium 12 race element；The periodic table of elements such as aluminum 13 race element；Unit of the periodic table of elements such as cerium 16 race Elements etc., two or more can individually or be applied in combination by they.It addition, in addition to above-mentioned polyvalent metal, it is also possible to and with sodium, The metal of the period of element such as potassium Table I race element.As the metal species in above-mentioned metallic compound (a4), wherein preferred elements week Phase Table II race element, particularly calcium.

As long as the organic acid in above-mentioned metal salts of organic acids as the most above-mentioned that enumerate, the compound of salt can be formed i.e. with metal Can, be not particularly limited, such as, can enumerate: formic acid, acetic acid, propanoic acid, butanoic acid, lactic acid, oxalic acid, fumaric acid, succinic acid, phosphoric acid, Citric acid, gluconic acid etc..Wherein, angularly consider from the storage-stable of pigmented finiss particulate component (A), molecular weight 50～ 1000, the organic acid in the range of particularly 50～400, more particularly 170～400 is applicable.

As metal salts of organic acids, examine from manufacture stability, the storage-stable angle of pigmented finiss particulate component (A) Considering, wherein calcium acetate, calcium propionate and calcium lactate are applicable especially.

Metallic compound (a4), in addition to above-mentioned metal salts of organic acids, further preferably contains metal hydroxides.Thus, remove Outside the storage-stable of color coating particles composition (A), manufacture stability, also make by the aqueous colorful pattern coating of the present invention The harsh feeling of the multi-color decorative pattern film that compositions is formed reduces, the multi-color decorative pattern film that simultaneously can make to be obtained by roller coat fresh Reflecting property is the best.

The object lesson of the metal species of the metal hydroxides used for such purpose in addition to that mentioned above, is gone back The alkali metal belonging to the periodic table of elements 1 race element can be enumerated.

In above-mentioned metallic compound (a4), by metal salts of organic acids and metal hydroxides used time, from pigmented finiss The harsh feeling of the multi-color decorative pattern film that the storage-stable of particulate component (A), suppression are formed, the multi-color decorative pattern film formed Clarity angularly consider, it uses ratio, with the molar ratio computing of metal salts of organic acids/metal hydroxides, usual 99/ It is applicable in the range of 1～10/90, particularly 90/10～15/85, more particularly 85/15～20/80.

By being dissolved in metallic compound (a4) at least partially in the aqueous medium of water etc., can prepare containing gold Belong to the aqueous medium of ion.Now, metallic compound (a4) need not be fully dissolved in aqueous medium, can be that only part is molten The state solved.

The concentration of the metallic compound (a4) in aqueous medium does not has considered critical, can be in usual 0.05～20 matter Amount %, preferably 0.05～15 in the range of mass %.

From the viewpoint of the storage-stable of pigmented finiss particulate component (A) and manufacture stability, above-mentioned aqueous medium It is preferably in the range of usual 4.0～13.7, preferably 7.0～13.5 by pH regulator.

The above-mentioned compositions containing aqueous pigmented finiss and water-soluble polysaccharides (a3) with containing from metallic compound (a4) contact of the aqueous medium of metal ion such as can be carried out by the following method: by said composition by the tip of syringe The method being added drop-wise in aqueous medium；The method utilizing centrifugal force to make said composition disperse and to be added drop-wise in aqueous medium；Make this The method that compositions is added drop-wise in aqueous medium by the most advanced and sophisticated atomization of spray nozzle；Said composition is joined in aqueous medium, Method etc. with dispersion machine stirring mixing.

In the manufacture of pigmented finiss particulate component (A), about above-mentioned composition and aqueous medium, from pigmented finiss granule The multi-color decorative pattern that the storage-stable of composition (A) and suppression are formed by the aqueous colorful pattern coating composition of the present invention is coated with The harsh feeling of film, the clarity of multi-color decorative pattern film and weatherability angularly consider, relative to 1 equivalent, institute in the composition is aqueous Carboxyl in soluble polysaccharide class (a3), according to metal conversion gauge, metallic compound (a4) contained in aqueous medium preferably exists Below 1.5 equivalents, particularly 0.2 less than in the range of 1.0 equivalents, more particularly in the range of 0.2～0.9 equivalent Contain.

Above-mentioned aqueous pigmented finiss can contain the most as required thickening agent, hollow particle etc. specific gravity-adjusting material, Defoamer, curing catalysts, pigment dispersing agent, aromatic, deodorant, antibacterial, nertralizer, surfactant, water-based hydrophobic Agent, dispersant, preservative, antifungus agent, antifreezing agent, UV absorbent, light stabilizer, coalescents, zinc whisker, formaldehyde absorbing The fire retardants etc. such as agent, antimony trioxide, Antimonic oxide, aluminium hydroxide.

Thus, it is possible to obtain, there is the pigmented finiss particulate component (A) of following grain structure: containing water-base resin (a1) and The aqueous pigmented finiss of coloring agent (a2) is enclosed in the shell formed by the slaine of water-soluble polysaccharides.

<film forming component (B)>

In order to ensure the Physical properties of coating film of the weatherability etc. of the multi-color decorative pattern film formed, the aqueous colorful pattern of the present invention Coating composition is in addition to containing pigmented finiss particulate component (A), possibly together with film forming component (B).Film forming component (B) it is the composition with self film, from the weatherability of multi-color decorative pattern film, the clarity of the multi-color decorative pattern film of roller coat gained Angularly considering, containing water-base resin (b1) and polyvalent metal compounds (b2), wherein said water-base resin (b1) has carboxyl With hydrolyzable silyl group and other cross-linking functional group in addition.

Water-base resin (b1)

Water-base resin (b1) contained in film forming component (B) has carboxyl and hydrolyzable silyl group and removes this it Other outer cross-linking functional group.Water-base resin (b1) has carboxyl, thus can Water-borne modification, simultaneously to improve multi-color decorative pattern be coated with The weatherability of film has contribution.And, water-base resin (b1) has hydrolyzable silyl group, thus, by the aqueous colorful of the present invention The weatherability of multi-color decorative pattern film that pattern coating composition is formed and (being such as located under multi-color decorative pattern film with substrate Primer coating film) tack further improve.

In this specification, " hydrolyzable silyl group " is can to generate silanol group and the dehydration of this silanol group by hydrolysis Condensation and form the group of siloxane bond, wherein, comprise have with the monovalence of silicon atom Direct Bonding water-disintegrable atom (by with Water reacts and generates the atom of silanol group, such as halogen atom) and (logical with the monovalence hydrolization group of silicon atom Direct Bonding Cross with water react generate silanol group group, such as alkoxyl) one or both of silicyl.

The object lesson of said hydrolyzed silicyl such as can be enumerated: the halogen such as silicochloroform base, silicobromoform base Change silicyl；Trimethoxysilyl, triethoxysilyl, tripropoxy-silicane base, three butoxy monosilanes The trialkoxysilyl such as base；The halo dialkoxies etc. such as chloro dimethoxy, chloro diethoxy, the most preferably three alcoxyls Base silicyl.

It addition, other the cross-linking functional group that water-base resin (b1) is had such as can enumerate hydroxyl, isocyanate group, ammonia Base, amide groups, carbonyl etc., angularly consider from weatherability, storage-stable, particularly preferred carbonyl.

Resin containing carboxyl, hydrolyzable silyl group and carbonyl such as can manufacture as follows: use (methyl) acrylic acid and/ Or other carboxylic polymerism unsaturated monomer, polymerism unsaturation list containing hydrolyzable silyl group foregoing Body and foregoing (methyl) acryloyl monomer containing carbonyl and/or other the polymerism unsaturated monomer containing carbonyl At least some of as monomer component so that it is with foregoing other the compound containing (methyl) acryloyl group and/or Other polymerism unsaturated monomer copolymerization.From the weatherability of the multi-color decorative pattern film formed and with the attachment of primer coating film Property, the storage-stable of coating composition angularly consider, about the usage amount of described monomer component, whole poly-for copolymerization On the basis of the total quality of conjunction property unsaturated monomer, preferably: (methyl) acrylic acid and other carboxylic polymerism insatiable hunger With monomer generally in 0.05～10 mass %, particularly 0.03～6 mass %, be more in particular in the range of 0.1～3 mass %；Aqueous The polymerism unsaturated monomer of solution property silicyl generally in 0.01～10 mass %, particularly 0.03～7 mass %, be more in particular in In the range of 0.05～5 mass %；(methyl) acryloyl monomer containing carbonyl and other the polymerism unsaturation list containing carbonyl Body generally in 0.2～30 mass %, particularly 0.25～20 mass %, be more in particular in the range of 0.3～15 mass %.

The above-mentioned polymerism unsaturated monomer containing hydrolyzable silyl group such as can be enumerated: vinyltrimethoxy silane, VTES, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silane, γ-(methyl) third Alkene acryloxypropylethoxysilane trimethoxy silane, γ-(methyl) acryloxypropyl dimethoxysilane, γ-(methyl) third Alkene methyl diethoxy silane, γ-(methyl) acryloxypropyl triethoxysilane, β-(methyl) propylene Trimethylammonium trimethoxy silane, γ-(methyl) acryloxy butyl phenyl dimethoxysilane, vinyl monohydroxy two Methoxy silane, vinyl ortho-siliformic acid etc..

The polymerization of above-mentioned monomer is also not particularly limited, such as can be according to conventional emulsion polymerization, at emulsifying agent In the presence of, by making above-mentioned monomer component (co) polymerization carry out.This emulsifying agent can use emulsifying agent known to itself, tool Body such as can enumerate anionic emulsifier, non-ionic emulsifier, amphion emulsifying agent, it be also possible to use in molecule and contains Polymerism unsaturated group and anionic property group or the reactive emulsifier etc. both nonionic group.With all polymerizations On the basis of the total quality of property unsaturated monomer, its usage amount can be at usual 0.5～6 mass %, preferably 1～4 models of mass % In enclosing.The emulsion particle generated can have usual 50～500nm, preferably 100～400nm, further preferred 100～300nm model Enclose interior mean diameter.

It addition, during above-mentioned copolymerization, by making different monomer components divide multiple stage polymerization, make water-base resin (b1) be formed Many stratiforms of core-sheath-type etc., such that it is able to make the weatherability of multi-color decorative pattern film, film property improve.

Water-base resin (b1) can have usual 0.5～100mgKOH/g, preferably 1～75mgKOH/g, further preferred 1～ Acid number in the range of 50mgKOH/g, and usual 0～250mgKOH/g, preferably 0～225mgKOH/g, further preferred 1～ Hydroxyl value in the range of 200mgKOH/g.And, water-base resin (a1) can have usual 2000～5000000, preferably 10000～ 3000000, the weight average molecular weight in the range of further preferred 50000～1000000.

Polyvalent metal compounds (b2)

Film forming component (B) contains polyvalent metal compounds (b2), thus can make the aqueous colorful pattern of the present invention The clarity of decorative pattern during this coating composition of the storage-stable of coating composition, roller coat, the multi-color decorative pattern film formed Weatherability etc. improve.

Polyvalent metal compounds (b2) can use and can make in an aqueous medium can be had with water-base resin (b1) Carboxyl forms the compound that the polyvalent metal ion of metal bridging dissociates, such as, can enumerate the chemical combination containing following metallic element Thing: the periodic table of elements 2 race elements such as magnesium, calcium, strontium, barium；The periodic table of elements such as titanium, zirconium 4 race element；The periodic table of elements such as chromium, molybdenum 6 Race's element；The periodic table of elements such as manganese 7 race element；The periodic table of elements such as ferrum, ruthenium 8 race element；Unit of the periodic table of elements such as cobalt, rhodium 9 race Element；The periodic table of elements such as nickel, palladium 10 race element；The periodic table of elements such as copper, silver 11 race element；The periodic table of elements such as zinc, cadmium 12 race The periodic table of elements such as element, aluminum 13 race element；The metallic elements such as the periodic table of elements such as cerium 16 race element, wherein, containing element week Qi Biao 2 race element, the particularly compound of calcium are applicable.

Polyvalent metal compounds (b2) can enumerate the acylate of above-mentioned metal, hydroxide, oxide, carbonate etc..

In the present invention, improving from the weatherability making multi-color decorative pattern film, coating storage-stable is good simultaneously and during roller coat The clarity excellence of multi-color decorative pattern film angularly consider, preferably polyvalent metal compounds (b2) is made containing metal salts of organic acids A part for its composition.Organic acid in above-mentioned metal salts of organic acids can metal from pigmented finiss particulate component (A) The compound enumerated in the explanation of compound (a4) suitably selects use.

Relative to 1 the equivalent carboxyl in contained water-base resin (b1), polyvalent metal compounds in film forming component (B) (b2) content, according to metal conversion meter, be preferably generally 0.1～0.9 equivalent, specifically for 0.15～0.8 equivalent, be more in particular in In the range of 0.15～0.5 equivalent.Polyvalent metal compounds (b2) if usage amount less than 0.1 equivalent, then roller coating operation and Not enough with the clarity of the multi-color decorative pattern film formed, if contrary more than 0.9 equivalent, then roller coating operation, coating storage are surely The deficiencies such as the weatherability of qualitative, film.

Film forming component (B) can contain coloring pigment, aura pigment, fluorescent material, body the most further Matter pigment, other additive for coatings etc..Coloring pigment, aura pigment and fluorescent material can be enumerated aforesaid coloring The material that agent (a2) is enumerated.It addition, other additive for coatings such as can be enumerated: thickening agent, resin bead, nertralizer, Antistatic additive, softening agent, antibacterial, essence, curing catalysts, pH adjusting agent, conditioning agent, powdery or particulate activated carbon, Photocatalyst titanium oxide, water-based hydrophobic agent, dispersant, defoamer, preservative, antifungus agent, antifreezing agent, UV absorbent, light Stabilizer, coalescents, zinc whisker, curing accelerator, aldehyde adsorbent, wax, antimony trioxide, Antimonic oxide, aluminium hydroxide etc. Fire retardant etc..

Wherein, thickening agent can use material known to itself in indefinite ground, and its object lesson such as can be enumerated: water solublity The mineral-type compounds such as alkali silicate, montmorillonite, colloidal aluminium oxide；Methylcellulose, hydroxyethyl cellulose, carboxymethyl The cellulose derivative compounds such as cellulose；Pluronic polyethers, polyethers dialkyl, polyethers dialkyl ether, polyethers amino The polyether compounds such as formic acid esters modifier, the epoxide modified thing of polyethers；Sodium polyacrylate, polyacrylic acid (methyl) acrylate are common The polyacrylic compounds such as polymers；The poly-second such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl benzyl alcohol copolymer Thiazolinyl compounds；The protein derivatives such as sodium caseinate, ammonium caseinate；Vinyl methyl ether-copolymer-maleic anhydride Partial ester, drying oil fatty acid allyl alcohol ester-copolymer-maleic anhydride etc., two or more combination can individually or be made by they With.Wherein, thickening agent is preferably used polyacrylic compounds, and the weatherability of multi-color decorative pattern film, roller coat thus can be made to grasp The clarity of the multi-color decorative pattern that the property made, roller coat are formed improves.

On the basis of the solid constituent quality of the aqueous colorful pattern coating composition of the present invention, the usage amount of this thickening agent Can be in usual 0.01～10 mass %, preferably 0.05～5 mass %, further preferred 0.03～7.5 in the range of mass %.

And, angularly consider from appropriate dumb light sense and clarity, the long-term weatherability of the multi-color decorative pattern film formed, Preferably film forming component (B) contains resin bead.Described resin bead such as can be enumerated: acrylic resin pearl, polystyrene resin Pearl, polyvinyl resin pearl, acrylic resin pearl, carbamate resins pearl, silicones pearl, fluororesin pearl, polyester resin pearl, poly- Amide resin pearl, nylon resin pearl etc..The use level of above-mentioned resin bead, on the basis of the solid constituent of film forming component (B), It is applicable in usual 1～100 mass %, preferably 3～75 mass %, further preferred 5～50 in the range of mass %.

Crosslinker compound (c)

In the present invention, at least one party of pigmented finiss particulate component (A) and film forming component (B) contains compound (c), At least having 2 in 1 molecule of this compound (c) can be with the cross-linking functional group in water-base resin (a1) and water-base resin (b1) functional group of the cross-linking functional group's reaction in is as a result, at multi-color decorative pattern film formation stages, pigmented finiss particulate component (A) react to each other via crosslinker compound (c) with film forming component (B), cross-link bonding securely, form long-term weatherability Property, multi-color decorative pattern film that resistance to water etc. is excellent.

The functional group that above-mentioned crosslinker compound (c) can have such as can enumerate hydroxyl, isocyanate group, alkylether radicals, Asia Amino, amino, amide groups, carbonyl, epoxy radicals, diazanyl, Semicarbazido, biacetyl two hydrazone group etc., at least have 2 in 1 molecule The compound of such functional group in addition to hydrazine derivate described later, such as, can enumerate polyol compound, polyisocyanate esterification Compound, melamine compound, polyamine compounds, polyamide compound, the resin containing carbonyl, the resin etc. containing epoxy radicals.

The cross-linking functional group being respectively provided with as water-base resin (a1) and water-base resin (b1) and crosslinker compound (c) The combination of the functional group contained by, as long as the combination that can react to each other under the drying condition of film, limits the most especially Fixed, the most such as can enumerate: hydroxyl and NCO, hydroxyl and alkylether radicals, hydroxyl and imino group, amino and epoxy radicals, Amide groups and epoxy radicals, carbonyl and diazanyl, carbonyl and hydrazide group, carbonyl and Semicarbazido and carbonyl and biacetyl two hydrazone group etc. Combination, from can be from the point of view of the crosslinking of room temperature one pack system, the combination of particularly preferred carbonyl and hydrazide group.

In the aqueous colorful pattern coating composition of the present invention, meet the weather-proof of multi-color decorative pattern film to obtain simultaneously The coating of all conditions such as property and the tack of primer coating film, coating storage-stable, the roller coat clarity of film that formed Compositions, preferably water-base resin (a1) contain carboxyl and carbonyl, and water-base resin (b1) is containing carboxyl, trialkoxysilyl With carbonyl, pigmented finiss particulate component (A) and/or film forming component (B) contain the hydrazine derivate with carbonyl reaction as friendship Connection immunomodulator compounds (c).

Above-mentioned hydrazine derivate such as can be enumerated: hydrazine, hydrazine hydrate, grass acid dihydrazide, acid dihydrazide, succinic acid two acyl Two acyls of the saturated aliphatic carboxylic acid of the carbon numbers 2～18 such as hydrazine, glutaric, adipic dihydrazide, sebacic dihydrazide Hydrazine；Two hydrazides of the Mono-olefinic unsaturated dicarboxylics such as Malaysia acid dihydrazide, fumaric acid two hydrazides, itaconic acid two hydrazides；Adjacent benzene Two hydrazides of dioctyl phthalate, p-phthalic acid or M-phthalic acid；Two hydrazides of PMA, three hydrazides or four hydrazides；Nitrilo three Acetic acid three hydrazides, citric acid three hydrazides, 1,2,4-benzene three hydrazides；Ethylenediaminetetraacetic acid four hydrazides, 1,4,5,8-naphthoic acid four acyl Hydrazine；Make the polyhydrazide etc. that the oligomer with lower alkyl carboxylic ester base reacts with hydrazine or hydrazine hydrate；Carbon acid dihydrazide, double (semicarbazides) (bis-semicarbazide)；The N, N-making N, N-dimethylhydrazine etc. replaces hydrazine or the above-mentioned hydrazides enumerated to Asia The diisocyanate such as hexyl diisocyanate, isophorone diisocyanate and the polyisocyanate compounds mistake derived by it The multifunctional semicarbazides that quantitative response obtains；Make above-mentioned two hydrazides enumerated to this polyisocyanate compounds and polyether polyols alcohols Or polyalkylene glycol monoalkyl ethers etc. is containing the NCO excess in the reactant of the active dydrogen compounds of hydrophilic radical The multifunctional semicarbazides of water system reacted and obtain；This multifunctional semicarbazides with the multifunctional semicarbazides of water system mixture；Biacetyl Dihydrazone etc., two or more can individually or be applied in combination by they.

<aqueous colorful pattern coating composition and application thereof>

The aqueous colorful pattern coating composition of the present invention can be by the pigmented finiss particulate component that will obtain as mentioned above (A) mix with film forming component (B) and easily prepare, when both being mixed, paint field can be coordinated as required In normally used additive, water etc..Angularly considering from the design of multi-color decorative pattern film of gained, weatherability, coloring is coated with Material particulate component (A) and the mixing ratio of film forming component (B), according to pigmented finiss particulate component (A)/film forming component (B) solid constituent mass ratio meter, can usual 1/99～60/40, preferably 5/95～55/45, further preferred 10/90～ In the range of 50/50.

<coating particles composition (C)>

Except pigmented finiss particulate component (A) and film forming component in the aqueous colorful pattern coating composition of the present invention (B), outside, the coating particles composition (C) with the transparency can also be contained the most further.Coating particles composition (C) is preferred There is carboxyl and other cross-linking functional group in addition.

Coating particles composition (C) is the coating composition that can form the film with the transparency to be carried out spheroidizing and obtains.

The aqueous colorful pattern coating composition of the present invention, by containing coating particles composition (C) further, can make institute The depth feelings of the film formed more improves.

In the compositions of the present invention, even if not containing coating particles composition (C), by suitably selecting based on pigmented finiss The kind of the coloring agent (a2) of grain composition (A) and combination, it is also possible to form the decorative pattern film of bag, but by coating particles is become Dividing (C) and pigmented finiss particulate component (A) use, the texture of bag, material sense (material sense) significantly improve, it is possible to obtain close Appearance design in natural stone.

Here, the term of " having the transparency " refers not only to fully transparent situation, also comprises translucent state, Ke Yishi Colourless can also be coloured.

The coating particles composition (C) with the transparency can be by such as at above-mentioned pigmented finiss particulate component (A) In manufacture, do not use coloring agent (a2), even if or using, not damage the degree of the transparency of formed film, example yet As on the basis of the solid constituent of water-base resin (a1), to use less than the amount below 1.0 mass %, preferably 0.5 mass %, from And manufacture in the same manner as pigmented finiss particulate component (A).

It addition, about coating particles composition (C), as long as the film formed by the compositions before spheroidizing has transparent Property, extender pigment can be contained.When having transparent coating particles composition (C) containing extender pigment, its content is to be coated with On the basis of the solid constituent of water-base resin (b1) contained in material particulate component (C), can be below 100 mass %, preferably 80 matter Amount below %.

In the aqueous colorful pattern coating composition of the present invention, going back and apparatus in addition to pigmented finiss particulate component (A) There is the coating particles composition (C) of the transparency, in the case of particulate component, from the design of gained multi-color decorative pattern film Angularly considering, according to the solid constituent mass ratio meter of pigmented finiss particulate component (A)/clear dope particulate component (C), it is also Can be in the range of usual 20/80～99/1, preferably 25/75～97/3, further preferred 30/70～95/5 with ratio.

The aqueous colorful pattern coating composition of the present invention, by being coated on substrate surface, can be formed and have colorful setting The multi-color decorative pattern film of the excellent performances such as meter property, resistance to water.

The substrate surface of the aqueous colorful pattern coating composition of the applicable present invention is not particularly limited, such as, can lift Go out: plasterboard, concrete wall, concrete block, skirting, mortar wall, slabstone (Slate board), PC plate, ALC plate, water The surface of the base materials such as mud calcium silicate plate, timber, stone material, plastic shaping thing, ware, ceramic tile, metal working material, is located at these Crylic acid resin on base material, propenoic methyl carbamate resinae, polyurethane type resin, fluorine type resin, silicones, silicon third The coated surfaces such as resinae, vinyl acetate resin class, epoxy resin, are formed by materials such as polrvinyl chloride, polyolefin, paper, cloth Wallpaper face etc..

The aqueous colorful pattern coating composition of the present invention can use application means known to itself to carry out application, example As can be according to the kind of base material, purposes etc., from roller, aerial spraying, airless spraying, resin spray gun, omnipotent spray gun, hairbrush, roller The finishing of painting machine etc. suitably selects use.Not damaging in the range of appearance of film, the aqueous colorful pattern of the present invention is coated with Feed composition can also repeatedly be coated with.

Form being dried of film by heat drying, to force to do according to the composition etc. of the coating composition used Dry or normal temperature drying any means is carried out.

According to circumstances in advance primer base can be coated on substrate surface, the most again by the aqueous colorful pattern of the present invention Coating composition is coated on formed priming paint painting face.

Above-mentioned primer base suitably can select according to the kind of substrate surface, state etc., such as, can use seal coat (sealer), substrate adjusts the primer bases such as material.Can be using the common topcoat paint of application as the aqueous colorful of the present invention The substrate formation coating of pattern coating composition.

The described topcoat paint forming use as substrate and use such as can be enumerated containing by acrylic resin, the third silicon class Resin, polyolefin resin, silicon resinoid, polyurethane based resin, epoxylite, phenolic resinoid, polyester resin, alkyd Water system that the resin types such as resinoid, Biodegradable resin is formed or the resin of solvent system as the coating of resin binder, Water paint containing aqueous resin is preferably used.

The application of above-mentioned substrate formation coating can use application means known to itself, such as can be according to base material Purposes etc., from the finishing of roller, aerial spraying, airless spraying, resin spray gun, omnipotent spray gun, hairbrush, roll coater etc. suitably Select to use.Being dried of the primer coating film formed can be according to the kind etc. of the primer base used, by heat drying, by force System is dried or any means of normal temperature drying is carried out.

Also can on the painting face of aqueous colorful pattern coating composition being coated with the present invention application varnish paint (clear coating).Described varnish paint such as can be enumerated containing by acrylic resin, the third silicon resinoid, polyolefin resin, silicon Resinoid, polyurethane based resin, epoxylite, phenolic resinoid, polyester resin, alkyd based resin, biological degradability tree The water system of the resin types formation such as fat or solvent system resin, as the coating of resin binder, are preferably used containing aqueous resin The water paint become.Described varnish paint can as required, with do not damage film the transparency degree contain as facing to color The coloring agent that coating particles composition (A) is enumerated.

The application of above-mentioned varnish paint can use application means known to itself to carry out, such as can be according to the use of base material Ways etc., suitably select to use from roller, aerial spraying, airless spraying, resin spray gun, omnipotent spray gun, hairbrush, roll coater etc.. The varnish film formed be dried can according to the kind etc. of the varnish paint used, by heat drying, force drying or Any means of normal temperature drying is carried out.

Embodiment

It is further elaborated with the present invention by the following examples, but the present invention not shall be limited only to the extent these embodiments.Under " part " and " % " of stating in example represents " mass parts " and " quality % " respectively.

<manufacture of emulsion>

Manufacture example 1: carry out to manufacture the red and pigmented finiss particulate component of white containing carboxyl and the breast of carbonyl The manufacture of liquid (a1)

285 parts of deionized waters and 1 part " ニ ュ U Le 707SF " (note 1) is added in the four-neck flask of 2 liters of capacity, Preserve in 85 DEG C after nitrogen displacement.Add in the pre-emulsion obtained by the ingredient emulsion of following composition 3% the most respectively Measure and 3 parts of Ammonium persulfate .s are dissolved in 41 parts in 123 parts of initiator solutions that 120 parts of deionized waters obtain, from adding After terminating 20 minutes, with 4 hours, remaining pre-emulsion and ammonium persulfate aqueous solution are added drop-wise in flask.

<pre-emulsion composition>

Deionized water 368 parts

Styrene 150 parts

Methyl methacrylate 410 parts

N-butyl acrylate 240 parts

2-EHA 150 parts

N-[2-(2-methyl-4-oxopentyl) 20 parts

Acrylic acid 2-hydroxy methacrylate 25 parts

5 parts of acrylic acid

" ニ ュ U Le 707SF " (note 1) 66 parts

After completion of dropwise addition, it is kept 2 hours further at 85 DEG C, is then cooled to 40～60 DEG C.Then, ammonia is used Regulation pH, obtains the emulsion (a1) that solid constituent is 55%.The mean diameter of emulsion (a1) be 175nm, pH be 8.3.

(note 1) " ニ ュ U Le 707SF ": trade name, emulsifying agent society of Japan manufactures, for having polyoxyethylene chain Anionic surfactant, nonvolatile component is 30%.

Manufacture example 2: carry out to manufacture in aqueous colorful pattern coating contained film forming component containing carboxyl, alkane The manufacture of core sheath emulsion (a2) of epoxide silicyl and carbonyl

400 parts of deionized waters and 1 part " ニ ュ U Le 707SF " (note 1) is added in the four-neck flask of 3 liters of capacity, Preserve in 85 DEG C after nitrogen displacement.Add the most respectively and the composition of following composition is carried out the lo-tionized pre-emulsion obtained In (core with) 3% amount and 5 parts of Ammonium persulfate .s are dissolved in 105 parts of initiator solutions that 100 parts of deionized waters obtain The amount of 25%, after adding end 20 minutes, with 3 hours by remaining pre-emulsion (core is used) and ammonium persulfate aqueous solution 50% Amount be added drop-wise in flask.

<pre-emulsion composition (core is used)>

Deionized water 300 parts

Styrene 100 parts

Methyl methacrylate 250 parts

N-butyl acrylate 230 parts

2-EHA 100 parts

Acrylic acid 2-hydroxy methacrylate 13 parts

VTES 6 parts

1 part of acrylic acid

" ニ ュ U Le 707SF " (note 1) 46 parts

After completion of dropwise addition, ripening 2 hours at 85 DEG C further by it, then with dropping in 2 hours by the one-tenth of following composition Divide and carry out the amount of 25% in the lo-tionized pre-emulsion (sheath is used) obtained and above-mentioned ammonium persulfate aqueous solution.

<pre-emulsion composition (sheath is used)>

Deionized water 200 parts

Styrene 41 parts

Methyl methacrylate 176 parts

N-butyl acrylate 41 parts

2-EHA 15 parts

N-[2-(2-methyl-4-oxopentyl) 15 parts

Hydroxyethyl Acrylate 6 parts

VTES 2 parts

4 parts of acrylic acid

" ニ ュ U Le 707SF " (note 1) 20 parts

After completion of dropwise addition, it is kept 2 hours further at 85 DEG C, is then cooled to 40～60 DEG C.Then ammonia is used Regulation pH, obtains core sheath emulsion (a2) that solid constituent is 50%.The mean diameter of emulsion (a2) be 190nm, pH be 8.6.

Manufacture example 3: in order to manufacture have the transparency coating particles composition and carry out containing carboxyl and the emulsion of carbonyl (a3) manufacture

285 parts of deionized waters and 1 part " ニ ュ U Le 707SF " (note 1) is added in the four-neck flask of 2 liters of capacity, Preserve in 85 DEG C after nitrogen displacement.Add the most respectively and the composition of following composition is carried out in the lo-tionized pre-emulsion obtained The amount of 3% and 3 parts of Ammonium persulfate .s are dissolved in 41 parts in 123 parts of initiator solutions that 120 parts of deionized waters obtain, from Add after terminating 20 minutes, with 4 hours, remaining pre-emulsion and ammonium persulfate aqueous solution are added drop-wise in flask.

<pre-emulsion composition>

Deionized water 368 parts

Styrene 200 parts

Methyl methacrylate 400 parts

N-butyl acrylate 300 parts

2-EHA 69 parts

N-[2-(2-methyl-4-oxopentyl) 20 parts

Acrylic acid 2-hydroxy methacrylate 10 parts

1 part of acrylic acid

" ニ ュ U Le 707SF " (note 1) 66 parts

After completion of dropwise addition, it is kept 2 hours further at 85 DEG C, is then cooled to 40～60 DEG C.Then ammonia is used Regulation pH, obtains the emulsion (a3) that solid constituent is 55%.The mean diameter of emulsion (a3) be 190nm, pH be 8.1.

Manufacture example 4: for the manufacture of the emulsion (a4) without hydrolyzable silyl group of comparative example

285 parts of deionized waters and 1 part " ニ ュ U Le 707SF " (note 1) is added in the four-neck flask of 2 liters of capacity, Preserve in 85 DEG C after nitrogen displacement.Add the most respectively and the composition of following composition is carried out in the lo-tionized pre-emulsion obtained The amount of 3% and 3 parts of Ammonium persulfate .s are dissolved in 41 parts in 123 parts of initiator solutions that 120 parts of deionized waters obtain, from Add after terminating 20 minutes, with 4 hours, remaining pre-emulsion and ammonium persulfate aqueous solution are added drop-wise in flask.

<pre-emulsion composition>

Deionized water 368 parts

Styrene 150 parts

Methyl methacrylate 400 parts

N-butyl acrylate 360 parts

2-EHA 67 parts

N-[2-(2-methyl-4-oxopentyl) 10 parts

Acrylic acid 2-hydroxy methacrylate 10 parts

3 parts of acrylic acid

" ニ ュ U Le 707SF " (note 1) 66 parts

After completion of dropwise addition, it is kept 2 hours further at 85 DEG C, is then cooled to 40～60 DEG C.Then ammonia is used Regulation pH, obtains the emulsion (a4) that solid constituent is 55%.The mean diameter of emulsion (a4) be 180nm, pH be 8.0.

<manufacture of Chinese white slurry>

Manufacture example 5

In 1 liter of rustless steel container, load following compositions, with blender stirring mixing 30 minutes, thus obtain Chinese white Slurry (b1).

225 parts of water

" ス ラ オ Off 72N " (note 2) 15 parts

" DISPER BYK-190 " (note 3) 30 parts

" SN デ Off ォ マ 380 " (note 4) 15 parts

" TITANIX JR-605 " (note 5) 500 parts

(note 2) " ス ラ オ Off 72N ": trade name, military field pharmaceutical industries (strain) manufactures, preservative；

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

(note 4) " SN デ Off ォ マ 380 ": trade name, sannopco company (サ ンノプコ society) manufactures, froth breaking Agent；

(note 5) " TITANIX JR-605 ": trade name, tayca company (テ イ カ society) manufactures, titanium white.

<manufacture of bronzing graining paste>

Manufacture example 6

In 1 liter of rustless steel container, load following compositions, with blender stirring mixing 60 minutes, thus obtain bronzing face Slip (b2).

400 parts of water

" ス ラ オ Off 72N " (note 2) 15 parts

" DISPER BYK-190 " (note 3) 48 parts

" SN デ Off ォ マ 380 " (note 4) 15 parts

Ferrum oxide 240 parts.

<manufacture of pigmented finiss particles with water coating composition (white)>

Manufacture example 7

Coordinate following compositions, stirring mixing to make them uniform the most successively, obtain pigmented finiss particles with water and be coated with Feed composition (A-1).

55% emulsion (a1) 250 parts

White pigments slurry (b1) 154 parts

" TEXANOL " (note 6) 20 parts

" SN デ Off ォ マ 380 " (note 4) 2 parts

" SN シ ッ Network Na 612 " (note 7) 2 parts

2% sodium alginate aqueous solution 280 parts

(note 6) " TEXANOL ": trade name, Eastman Chemical company manufactures, single isopropylformic acid. 2,2,4-trimethyl penta Diol ester, coalescents；

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

<manufacture of pigmented finiss particles with water coating composition (bronzing)>

Manufacture example 8

Coordinate following compositions, stirring mixing to make them uniform the most successively, obtain pigmented finiss particles with water and be coated with Feed composition (A-2).

55% emulsion (a1) 250 parts

Reddish brown graining paste (b2) 276 parts

" TEXANOL " (note 6) 20 parts

" SN デ Off ォ マ 380 " (note 4) 2 parts

" SN シ ッ Network Na 612 " (note 7) 2 parts

2% sodium alginate aqueous solution 280 parts.

<manufacture of clear dope particles with water coating composition>

Manufacture example 9

Coordinate following compositions, stirring mixing to make them uniform the most successively, obtain clear dope particles with water and be coated with Feed composition (A-3).

55% emulsion (a3) 250 parts

" TEXANOL " (note 6) 20 parts

" SN デ Off ォ マ 380 " (note 4) 2 parts

" SN シ ッ Network Na 612 " (note 7) 2 parts

2% sodium alginate aqueous solution 280 parts.

<manufacture of pigmented finiss granule manufacture aqueous medium>

Manufacture example 10

7.0 parts of calcium acetate monohydrates and 2,000 part of deionized water, stirring is loaded in the rustless steel container of 4 liters of capacity To uniformly, thus manufacture the aqueous medium (B-1) containing calcium acetate.

Manufacture example 11～12

In above-mentioned manufacture example 10, make formula consist of shown in table 1 below, in addition manufacture in the same manner as manufacturing example 10 Aqueous medium (B-2)～(B-3).

[table 1]

Table 1

。

<manufacture of pigmented finiss particulate component>

Manufacture example 13

In the rustless steel container of 4 liters of capacity, load the aqueous medium (B-1) of 1,300 parts of above-mentioned manufacture example 10 gained, make With having the stirring vane of 75mm diameter, with revolution 2,000rpm drips 650 parts of above-mentioned systems the most lentamente in container Make the water-based paint compositions (A-1) of example 7 gained, generate pigmented finiss granule.Then, then with same rotational speed by liquid in container Stir 15 minutes, then use the wire netting leaching of 200 mesh, obtain pigmented finiss granule (C-1).The pigmented finiss granule of gained (C-1) solid constituent is 20%.

Manufacture example 14～20

In above-mentioned manufacture example 13, it is shown in table 2 by the formula change of aqueous medium and the water-based paint compositions of dropping, removes Outside this as above-mentioned manufacture example 13, manufacture pigmented finiss granule (C-2)～(C-8).And, aqueous medium shown in table 2 In contained metallic compound carry out the equivalent proportion of carboxyl of sodium alginate relative to 1 equivalent (when multiple compounds and be used as gold When belonging to compound, it is the equivalent proportion of total amount).Here, the molecular weight of sodium alginate is set to 90000.

[table 2]

Table 2

。

<manufacture of clear dope granule>

Manufacture example 21

In the rustless steel container of 4 liters of capacity, load the aqueous medium (B-1) of 1,300 parts of above-mentioned manufacture example 10 gained, make With having the stirring vane of 75mm diameter, with revolution 2,000rpm drips 510 parts of above-mentioned systems the most lentamente in container Make the water-based paint compositions (A-3) of example 9 gained, generate clear dope granule.Then, then with same rotational speed by liquid in container Stir 15 minutes, then use the wire netting leaching of 200 mesh, obtain clear dope granule (C-9).The clear dope granule of gained (C-9) solid constituent is 22%.

<manufacture of water varnish coating of film forming component>

Manufacture example 22

It is sequentially loaded into following compositions, with blender stirring mixing 30 minutes until all in the rustless steel container of 2 liters of capacity Even, thus obtain water varnish coating (D-1).

50% emulsion (a2) 750 parts

" TEXANOL " (note 6) 55 parts

" BYK-028 " (note 8) 10 parts

" プ ラ イ マ Le ASE60 " (note 9) 3 parts

Calcium acetate 0.7 part

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

(note 9) " プ ラ イ マ Le ASE60 ": trade name, Rhom and Hass's (ロ system ア ンドハ ス society) manufactures, Polyacrylic viscosity modifier.

Manufacture example 23～30

In above-mentioned manufacture example 22, formula composition is set to Table 3 below, in addition as manufacturing example 22, obtains water Property varnish paint (D-2)～(D-9).

[table 3]

(note 10) " MBX-15 ": trade name, hydrops finished industrial society manufactures, polymethyl methacrylate resin pearl, averagely Particle diameter 15 μm.

<manufacture of aqueous colorful pattern coating>

Embodiment 1～10 and comparative example 1～4

In the rustless steel container of 500 milliliters of capacity, it is sequentially loaded into the composition shown in table 4 below while stirring, then stirs To uniformly, thus manufacture aqueous colorful pattern coating (E-1)～(E-14).

[table 4]

<performance evaluation>

Embodiment 11～20 and comparative example 5～8

At upper roller coat " EP シ ラ the is transparent " (Northwest paint company (Northwest ペ イ Application ト of slabstone (600 × 900 × 3mm) Society) manufacture, trade name, water system acrylic emulsion class seal coat), coating weight is 100g/m², it is dried, then roller coat " ア レ ス ア ア グ ロ ス is white for Network " (Northwest paint company manufactures, trade name, acrylic emulsion class coating), coating weight is 100g/m², at gas It is dried 1 day under conditions of temperature 20 DEG C, relative humidity 60%, as by coated plate, by what above-described embodiment and comparative example obtained Each aqueous colorful pattern coating supplies following test.Result is as described in Table 5.

Embodiment 21

The aqueous colorful pattern coating of roller coat embodiment 1 gained, coating weight is 250g/m², at temperature 23 DEG C, relative humidity Being dried under conditions of 60% 1 day, then on this painting face, roller coat manufactures the varnish paint of example 22 gained, and coating weight is 100g/m², It is dried 7 days under conditions of temperature 23 DEG C, relative humidity 60%, the test coated plate of gained is carried out following (* 2) design test The evaluation test of (* 6) weatherability.Result is shown in table 5 below in the lump.

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

[table 5]

(* 1) roller operability

According to following benchmark, evaluate above-mentioned be 250g/ by each aqueous colorful pattern coating of roller coat on coated plate, coating weight m²Time operability.

◎: during roller coat, pigmented finiss granule does not ruptures, operability is the best；

Zero: during roller coat, pigmented finiss granule is difficult to rupture, and operability is good；

△: during roller coat, pigmented finiss granule has and ruptures, and operability is the worst；

×: during roller coat, pigmented finiss breakage of particles is more, and operability is bad.

(* 2) design

With roller above-mentioned by each aqueous colorful pattern coating of application on coated plate, coating weight is 250g/m², temperature 23 DEG C, Being dried under conditions of relative humidity 60% 7 days, then visualization is coated with face, according to following benchmark evaluation design.

The decorative pattern clarity that ◎: each pigmented finiss granule produces is the best；

Zero: the decorative pattern clarity that each pigmented finiss granule produces is good；

The decorative pattern clarity that △: each pigmented finiss granule produces is the worst；

×: the decorative pattern that each pigmented finiss granule produces is the distinctest.

(* 3) texture

Above-mentioned by each aqueous colorful pattern coating of application on coated plate to be sprayed on, coating weight is 250g/m², at temperature 23 DEG C, be dried under conditions of relative humidity 60% 7 days, then visualization is coated with face, according to following benchmark evaluation texture.

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

Zero: have texture, there is colorful sense；

△: texture is poor, colorful sense obscures；

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

(* 4) smooth sense

According to following benchmark, touching when evaluation hands touches each test coated plate used in above-mentioned (* 2) design test Sense.

The smooth sense of ◎: film is good；

Zero: the smooth sense of film is the best；

△: film has some harsh feelings；

×: film has significant harsh feeling.

(* 5) Storage

Each aqueous colorful pattern coating of embodiment and comparative example gained is loaded the mayonnaise bottle of 250ml, visualization State after 1 month at 40 DEG C, according to following benchmark evaluation.

◎: unchanged before and after storage；

Zero: before and after storage, colloidal viscosity varies slightly, but the outflow of bag thing in not having pigmented finiss granule；

△: the outflow of bag thing in more visible pigmented finiss granules；

×: in pigmented finiss granule, the outflow of bag thing is notable.

(* 6) weatherability

Become 70 × 150 × 3mm big a part of cutting of each test coated plate used in above-mentioned (* 2) design test Little, use the atmospheric exposure test that the weather-proof instrument of xenon lamp (キ セ ノ Application ウ ェ ザ オ メ タ) is carried out 4000 hours, the most visually Observe and be coated with surface state, according to following benchmark evaluation.

◎: identical with the test coated plate before test, is not changed in；

Zero: compared 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, compared with the test coated plate before test, colorful sense is slightly worse；

×: whole visible albefaction or xanthochromia, compared with the test coated plate before test, it is changed significantly.

(* 7) tack

Using cut-off knife, the central authorities of the test coated plate used in above-mentioned (* 2) design cut out the angle friendship being mutually 30 degree The tool marks as deep as basic unit of fork, then, Continuous pressing device for stereo-pattern on 2 tool marks of Self-crossover, do not produce bubble, make adhesive tape and film Adhering to completely, moment peels off, and is evaluated according to following benchmark.

: there is no desquamation (Ha ガ レ)；

△: at tool marks peripheral part, is coated with at priming paint/multi-color decorative pattern and intermembranous has a little desquamation；

×: at priming paint/multi-color decorative pattern film, there is significant desquamation.

Industrial applicability

According to aqueous colorful pattern coating composition provided by the present invention by being coated on the metope of such as building, each The substrate surfaces such as the ferrum portion of kind building materials, door etc., can make substrate surface have colorful design, can give its resistance to water etc. The multi-color decorative pattern film of excellent performance.

Claims (15)

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

(A) pigmented finiss particulate component, this pigmented finiss particulate component contains water-base resin (a1) and coloring agent (a2), described water Property resin (a1) has carboxyl and carbonyl, and

(B) film forming component, this film forming component contains water-base resin (b1) and polyvalent metal compounds (b2), described water Property resin (b1) has carboxyl and hydrolyzable silyl group and carbonyl,

This aqueous colorful pattern coating composition is characterised by:

At least one party of pigmented finiss particulate component (A) and film forming component (B) contains compound (c), described compound (c) 1 molecule at least there are 2 can be with the official of the carbonyl reaction in the carbonyl in water-base resin (a1) and water-base resin (b1) Can roll into a ball,

In film forming component (B), relative to 1 equivalent carboxyl in water-base resin (b1), according to metal conversion meter, with 0.1 ～0.9 the ratio of equivalent contain polyvalent metal compounds (b2).

2. the aqueous colorful pattern coating composition of claim 1, wherein, pigmented finiss particulate component (A) is to have following The composition of kernel structure: the aqueous pigmented finiss containing water-base resin (a1) and coloring agent (a2) is enclosed in by water soluble polysaccharide eka-gold Belong in the granule of salt formation.

3. the aqueous colorful pattern coating composition of claim 1, wherein, pigmented finiss particulate component (A) be by make containing Aqueous pigmented finiss contacts with the aqueous medium containing metallic compound (a4) with the compositions of water-soluble polysaccharides (a3) and obtains , described aqueous pigmented finiss contains water-base resin (a1) and coloring agent (a2).

4. the aqueous colorful pattern coating composition of claim 3, wherein, metallic compound (a4) is made containing metal salts of organic acids A part for its composition.

5. the aqueous colorful pattern coating composition of claim 3, wherein, in pigmented finiss particulate component (A), works as relative to 1 Amount carboxyl in water-soluble polysaccharides (a3), according to metal conversion gauge, to contain metallic compound below 1.5 equivalents (a4)。

6. the aqueous colorful pattern coating composition of claim 1, wherein, hydrolyzable silyl group is tri-alkoxy monosilane Base.

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

8. the aqueous colorful pattern coating composition of claim 1, wherein, polyvalent metal compounds (b2) contains organic acid metal Salt is as a part for its composition.

9. the aqueous colorful pattern coating composition of claim 1, wherein, film forming component (B) contains thickening agent further.

10. the aqueous colorful pattern coating composition of claim 1, wherein, film forming component (B) contains resin further Pearl.

The aqueous colorful pattern coating composition of 11. claim 1, wherein, compound (c) has hydrazide group.

The aqueous colorful pattern coating composition of 12. claim 1, wherein, water-base resin (a1) contains carboxyl and carbonyl, aqueous Resin (b1) is containing carboxyl, trialkoxysilyl and carbonyl, pigmented finiss particulate component (A) and film forming component (B) At least one party contain the hydrazine derivate with carbonyl reaction as compound (c).

Aqueous colorful pattern coating composition any one of 13. claim 1～12, said composition is except pigmented finiss granule Outside composition (A) and film forming component (B), contain the coating particles composition (C) with the transparency further.

14. coating process, it is characterised in that: on coated surface, across or not across primer coating film ground application claim 1～13 Any one of aqueous colorful pattern coating composition.

15. coating process, it is characterised in that: on coated surface, across or not across primer coating film ground application claim 1～13 Any one of aqueous colorful pattern coating composition, then application varnish paint on this painting face.