CN104073112A - Heat-insulative light extinction aqueous coating composition and method for forming heat-insulative light extinction coating - Google Patents
Heat-insulative light extinction aqueous coating composition and method for forming heat-insulative light extinction coating Download PDFInfo
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- CN104073112A CN104073112A CN201410099484.XA CN201410099484A CN104073112A CN 104073112 A CN104073112 A CN 104073112A CN 201410099484 A CN201410099484 A CN 201410099484A CN 104073112 A CN104073112 A CN 104073112A
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Abstract
The invention provides a heat-insulative light extinction aqueous coating composition and a method for forming a heat-insulative light extinction coating, wherein the composition has excellent weather resistance and/or excellent storage stability of a formed coating. A fine appearance with high heat insulating performance and light extinction harmony can be sustained for a long time, and furthermore the heat-insulative light extinction aqueous coating composition can be preferably used for the outer wall of a building. The heat-insulative light extinction aqueous coating composition comprises the components of: an aqueous resin (A) in which an acid value of a unit solid matter is in a range of 2.5-30mgKOH/g, a pigment component (B) and a non-ionic surfactant (C) with an HLB value above 10. The pigment component (B) comprises the components of: an inorganic white pigment (b1), a sheet-shaped extender pigment (b2) and an extender pigment (b3) except for (b2). The pigment volume concentration of the pigment component (B) is 45-80%. The volume ratios of the pigment (b1), the pigment (b2) and the pigment (b3) in total volume of the pigment (B) are described as follows: the volume ratio of (b1) is 60-15%; the volume ratio of (b2) is 5-70%; and the volume ratio of (b3) is 20-80%, and the content of the surfactant is 0.3-10% by mass in reference to that of the curved matter of the acqeous resin (A).
Description
Technical field
The present invention relates to thermal insulation delustring water-based paint compositions and use its thermal insulation delustring coating film-forming methods, described thermal insulation delustring water-based paint compositions can obtain harmonious meticulous outward appearance and have high thermal insulation.
Background technology
In recent years, the temperature rising causing because of thermal energy such as sunlights in order to suppress buildings and/or fabrication, people implement heat insulation processing at the coating such as roof and/or outer wall thermal insulating coating, have developed a lot of thermal insulating coatings or have used the invention such as coating process of thermal insulating coating.
A kind of coating composition is for example disclosed in patent documentation 1, it comprises following black pigment compositions, in this black pigment compositions, be mixed with two or more visible region show absorb and be more than 35% coloured pigment dyestuff near infrared region reflectivity, this black pigment compositions has the black of Munsell mark (N-1).
In addition, in patent documentation 2, disclose a kind of coating process, wherein, on outer wall material, be coated with thermal insulation whitewash, be then coated with the thermal insulation color coating obtaining by combining multiple pigmented coating.
In patent documentation 1 and 2, in the existing thermal insulating coating of record, coating process, particularly, in the situation that thickness is thinner, it is disguised poor to make sometimes, makes sometimes base material increase and cannot obtain sufficient thermal insulation ultrared absorbed dose.
In addition, these existing thermal insulating coatings are envisioned for the glossiness film of tool for being coated on such as roof etc., but people expect to develop the thermal insulating coating that can obtain the meticulous outward appearance with delustring hamony.
As the strategy of these problems, for example, the water-based paint compositions of a kind of calcium carbonate that comprises titanium dioxide, porous medium and water-base resin is disclosed in patent documentation 3.
The gloss of the water-based paint compositions of recording in patent documentation 3 is low, can obtain in addition the film with high scattered reflection rate, thereby also can, by being coated on the interior finish face of buildings, contribute to the energy-conservation of light source.But, in this coating, contain in a large number the calcium carbonate of porous medium, thereby film easily cracks, for anti-problem here, can consider to use the low resin of second-order transition temperature (Tg), but in the case of resin low Tg being applicable to the outer wall and/or roof of buildings, having and film is made dirty and damaged reflection function, or the problem of white powder and/or variable color occurs.In addition, have and be difficult for the long-term stability that keeps coating, the problem of thickening along with time process.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-20647 communique
Patent documentation 2: TOHKEMY 2002-320912 communique
Patent documentation 3: TOHKEMY 2012-92289 communique
Summary of the invention
The problem that invention will solve
The object of the invention is to propose a kind of thermal insulation delustring water-based paint compositions and use its thermal insulation delustring coating film-forming methods, weathering resistance and/or the storage stability of coating etc. of this thermal insulation delustring water-based paint compositions are good, the meticulous outward appearance can long term maintenance with thermal insulation and delustring hamony, also can preferably be used in the outer wall of buildings etc.
For the scheme of dealing with problems
The inventor etc. conduct in-depth research above-mentioned problem, found that the following fact, thereby reach the present invention: the pigment composition by compounding specific components in the water-base resin that is specified range at acid number and specific tensio-active agent, thus can obtain storage stability and well and together have the film of delustring sense and thermal insulation.
, the present invention relates to a kind of thermal insulation delustring water-based paint compositions, it is characterized in that, it is the water-base resin (A) in the acid number that the comprises unit solid substance scope that is 2.5～30mgKOH/g, pigment composition (B) and HLB value are the water-based paint compositions of more than 10 nonionic surfactants (C), pigment composition (B) comprises inorganic white pigment (b1), laminar pigment extender (b2) and the pigment extender except (b2) (b3), the pigment volume concentration (PVC) of pigment composition (B) is in 45～80% scope, inorganic white pigment (b1), laminar pigment extender (b2) and pigment extender (b3) shared volume ratio in the whole volumes of pigment composition (B) is: inorganic white pigment (b1) is 60～15%, laminar pigment extender (b2) is 5～70%, pigment extender (b3) is 20～80%, the content of nonionic surfactant (C) is taking the solid substance of water-base resin (A) as benchmark is in the scope of 0.3～10 quality %,
The invention still further relates to a kind of thermal insulation delustring coating film-forming methods, it is characterized in that, this thermal insulation delustring water-based paint compositions of application,
The invention still further relates to a kind of method that temperature that suppresses interior of building raises, thereby suppress the temperature rising of interior of building by this thermal insulation delustring water-based paint compositions of the outside wall surface application at buildings,
The invention still further relates to a kind of coated article, its coated article for obtaining by this thermal insulation delustring water-based paint compositions of application.
The effect of invention
Coating composition of the present invention has delustring sense, can form the film of excellent in heat insulating performance, thereby can obtain by being coated on such as buildings etc. the outward appearance of harmonious atmosphere, can contribute to the energy-conservation of heating and cooling equipment and/or light source etc.
In addition, the Long-term Storage excellent in stability of composition of the present invention.
And, about the film being formed by water-based flatting coating composition of the present invention, be difficult for generating the strain of film inside, break etc. even if expose without etc. also can not produce under harsh environment, attractive in appearance and heat-proof quality that can long term maintenance coated article.
Embodiment
It is more than 10 nonionic surfactants (C) that thermal insulation delustring water-based paint compositions of the present invention comprises water-base resin (A), pigment composition (B) and HLB value.
< water-base resin (A) >
Water-base resin (A) in the present invention is be dissolvable in water or be scattered in the resin in water, as this resin kind, be not particularly limited if there is the resin of film formation ability, can use existing known resin, for example list acrylic resin, silicon resinoid, polyurethanes resin, fluorine-type resin, polyvinyl acetate esters resin, redix, phenolic resinoid, polyester resin, alkyd based resin, polycarbonate resin, melamine resin etc., they can use separately respectively or combine two or more and use.In addition, about these resins, for example, can as polyurethane-modified acrylic acid resinoid, carry out modification, or the resin that also can obtain for graft polymerization, or can be also the form of discrete particles.
About water-base resin (A), in the case of the form of discrete particles, can there is the multilayered structures such as single layer structure (homogeneous granular) or core/shell structure, the in the situation that of core/shell structure, core and/or shell also can be cross-linked.
About water-base resin (A); consider from the viewpoint such as weather resistance, weathering resistance of the film that formed by water-based paint compositions of the present invention; be preferably acrylic resin; as relevant acrylic resin, can list by least one is together carried out to the resin that (being total to) polymerization obtains containing the compound of (methyl) acryl and other polymerizability unsaturated monomer that as required can copolymerization.
As the compound containing (methyl) acryl, as the compound in a part with (methyl) acryl, for example list: (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) lauryl acrylate, (methyl) stearyl acrylate base esters etc. are containing (methyl) acryl monomer of the alkyl of straight or branched, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc. are containing (methyl) acryl monomer of ester ring type alkyl, (methyl) benzyl acrylates etc. are containing (methyl) acryl monomer of aralkyl, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester etc. are containing (methyl) acryl monomer of alkoxyalkyl, fluorine-containing (methyl) acryl monomer such as (methyl) vinylformic acid hexafluoro isopropyl ester, (methyl) vinylformic acid perfluoro capryl methyl esters, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid N, (methyl) acryl monomer containing amino that N-diethylamino ethyl ester is such, (methyl) acrylamide, (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid hydroxy butyl ester, the 6-caprolactone modification body of above-mentioned (methyl) vinylformic acid hydroxyalkyl acrylate, contain (methyl) acryl monomer that molecular end is the hydroxyls such as (methyl) acrylate of the polyethylene oxide chain of hydroxyl, carboxylic (methyl) acryl monomer such as (methyl) vinylformic acid, propenoic acid beta-carboxyl ethyl ester, (methyl) vinylformic acid acetoacetoxy groups ethyl ester, diacetone (methyl) acrylamide etc. are containing (methyl) acryl monomer of carbonyl, (methyl) vinylformic acid glycidyl esters, (methyl) vinylformic acid Beta-methyl glycidyl esters, (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters, (methyl) vinylformic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl propyl ester etc. are containing (methyl) acryl monomer of epoxy group(ing), (methyl) acryl monomer that (methyl) vinylformic acid isocyanato ethyl etc. contains isocyanato, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane etc. are containing (methyl) acryl monomer of alkoxysilyl, (methyl) vinylformic acid dicyclo amylene oxygen base ethyl ester, (methyl) vinylformic acid dicyclo amylene oxygen base propyl ester, (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate etc. contain (methyl) acryl monomer of oxidative cure group etc.
As the compound in a part with at least two (methyl) acryls, for example list: (methyl) allyl acrylate, two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) vinylformic acid TEG 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, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two (methyl) vinylformic acid glycerine ester, 1, 1, 1-trihydroxy methyl ethane two (methyl) acrylate, 1, 1, 1-trihydroxy methyl ethane three (methyl) acrylate, 1, 1, 1-trihydroxy methyl propane three (methyl) acrylate etc.
These can use separately respectively containing compounds of (methyl) acryl or combine two or more and use.
In addition, as other polymerizability unsaturated monomer that can copolymerization, list: (methyl) vinyl cyanide; The vinyl ester such as vinyl-acetic ester, propionate compound; The vinyl aromatic compounds such as vinylbenzene, alpha-methyl styrene; Cyanacrylate, diallyl terephthalate, Vinylstyrene etc. have many vinyl compounds of at least two polymerizability unsaturated groups in a part; Vinyl carbinol; The carboxylic polymerizability unsaturated monomer such as toxilic acid, β-crotonic acid; Vinyl alkyl ketone (such as ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone etc.), the acetoacetoxy groups allyl ester etc. of (methyl) propenal, formyl radical vinylbenzene, carbonatoms 4～7 is containing the polymerizability unsaturated monomer of carbonyl; Allyl glycidyl ether etc. are containing the polymerizability unsaturated monomer of epoxy group(ing); Between the polymerizability unsaturated monomer of the isocyanato group containing such as pseudoallyl-alpha, alpha-dimethylbenzyl isocyanic ester; Vinyltrimethoxy silane, vinyltriethoxysilane etc. are containing the polymerizability unsaturated monomer of alkoxysilyl; The fluorovinyl ethers such as fluoroalkyl trifluoro vinyl ether, perfluoroalkyl trifluoro vinyl ether; The above-mentioned polymerizability unsaturated monomers that contain oxidative cure group containing the polymerizability unsaturated monomer of epoxy group(ing) or polymerizability unsaturated monomer and the reaction product of unsaturated fatty acids etc. of hydroxyl etc., they can use separately respectively or combine two or more and use.
In the present invention, the acid number of the unit solid substance of above-mentioned water-base resin (A), in the scope of 2.5～30mgKOH/g, is preferably 3～25mgKOH/g.
When the not enough 2.5mgKOH/g of the acid number of the unit solid substance of water-base resin (A), in the time of Long-term Storage water-based paint compositions, produce agglutinator, or colour stability variation while having mixed multiple color, so not preferred.
On the other hand, when the acid number of unit solid substance exceedes 30mgKOH/g, the poor water resistance of film, therefore not preferred.
As giving the acidic group of water-base resin (A) with acid number, list carboxyl, sulfonic group, phosphate etc., be wherein preferably carboxyl.
In addition, these acidic groups also can be for being carried out a part or neutralized the material obtaining in fact completely by alkali such as amine and ammonia such as methylamine, dimethyl amine, Trimethylamine 99, ethamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol.
Other functional group except acidic group having as above-mentioned water-base resin (A), for example list hydroxyl, isocyanato, amino, amide group carbonyl etc., the viewpoint of the weathering resistance from room etc. under harsh condition considers particularly preferably have carbonyl.
In the situation that water-base resin (A) has carboxyl and carbonyl; for example; can be by use (methyl) vinylformic acid and/or as foregoing other carboxylic polymerizability unsaturated monomer with as foregoing (methyl) acryl monomer containing carbonyl and/or other polymerizability unsaturated monomer containing carbonyl; as at least a portion of monomer component; carry out copolymerization with other compound and/or other polymerizability unsaturated monomer containing (methyl) acryl, thereby manufacture water-base resin (A).
About relevant (methyl) vinylformic acid and other carboxylic polymerizability unsaturated monomer and containing (methyl) acryl monomer and other consumption containing the polymerizability unsaturated monomer of carbonyl of carbonyl, taking the total mass of whole polymerizability unsaturated monomers that is supplied in copolymerization as benchmark, (methyl) vinylformic acid and other carboxylic polymerizability unsaturated monomer are generally 0.05～10 quality %, can be preferably in the scope of 0.1～3 quality %, and be generally 0.2～30 quality % containing (methyl) acryl monomer of carbonyl with containing the polymerizability unsaturated monomer of carbonyl, can be preferably in the scope of 0.3～15 quality %.
The polymerization process of above-mentioned monomer is not particularly limited, for example, can be by according to general emulsion polymerization, under the existence of polymerization starter, emulsifying agent, above-mentioned monomer is carried out (being total to) thus polymerization carry out.
In (being total to) polymerization of monomer, also can use as required chain-transfer agent, pH adjusting agent, solvent.
As this emulsifying agent, can use himself known emulsifying agent, particularly, for example list anionic surfactant, nonionic surfactant, zwitterionics, in addition, also can use and in molecule, contain the two reactive surfactant etc. of polymerizability unsaturated group and anionic property group or nonionic group.
Its consumption is taking the total mass of whole polymerizability unsaturated monomers as benchmark, conventionally in the scope of 0.5～6 quality %, and can be preferably in the scope of 1～4 quality %.The emulsion particle generating has the median size in the scope of 50～500nm conventionally, can preferably have the median size in the scope of 100～400nm, can further preferably have the median size in the scope of 100～300nm.
In addition, in water-base resin (A), also can comprise the water-soluble macromolecular compounds such as polyvinyl alcohol, Polyvinylpyrolidone (PVP), Natvosol, methylcellulose gum, hydroxypropylcellulose, sodium polyacrylate, ethene-copolymer-maleic anhydride etc.
In this manual, the median size of water-base resin (A) is: utilize submicron particles analyzer N4 (trade(brand)name, Beckman Coulter, Inc. system, particle size distribution device), utilizing deionized water is the concentration that is suitable for mensuration by sample dilution, the value of measuring at normal temperature (20 DEG C of left and right).
This polymerization starter is under the existence of heat or reductive agent, to carry out free radical decomposition and the polymerization starter of trigger monomer addition polymerization, can use any in mineral-type initiator, organic initiator.
< pigment composition (B) >
The pigment composition (B) using in water-based paint compositions of the present invention comprises inorganic white pigment (b1), laminar pigment extender (b2) and the pigment extender except (b2) (b3).
In the present invention, inorganic white pigment (b1) is in order to give the film being formed by water-based paint compositions of the present invention with the necessary composition of thermal insulation, specifically list titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, weisspiessglanz, zirconium white, aluminium nitride, boron nitride, white lead (zinc carbonate) etc., they can be used alone or combine two or more and use.
As laminar pigment extender (b2), for example list talcum, mica, glass flake etc., they can be used alone or combine two or more and use.
By utilizing this laminar pigment extender (b2), thereby there is following effect: even still can obtain without etc. the thermal insulation delustring film of fracture-resistant excellence under harsh condition.
Pigment extender (b3) except (b2) is to form in order to give the pigment extender that film uses with delustring sense, can use known pigment extender as pigment extender, specifically list calcium carbonate, silicon-dioxide, barium sulfate, kaolin clay etc., they can be used alone or combine two or more and use.
In addition, above-mentioned pigment composition (B) can comprise known other pigment except pigment (b1), (b2) and (b3) as required.This is to feel with required tone and/or light because can give being derived from the delustring film of the light colour that the white of the pigment (b1) in the present invention is keynote.
As the object lesson of other pigment, list ferric oxide, perylene dye, azo pigment, yellow plumbous, red iron oxide, cinnabar, titanium is red, cadmium red, quinacridone is red, isoindolinone, Benzimidazolinone, phthalocyanine green, phthalocyanine blue, cobalt blue, indanthrene blue, ultramarine, and the tinting pigment such as barba hispanica, aluminium pigment, copper, zinc, brass, nickel, the aluminum oxide being covered by titanium oxide and/or ferric oxide, the mica being covered by titanium oxide and/or ferric oxide, the bright pigment such as holography pigment, zinc phosphate, phosphorus zinc silicate, aluminum phosphate zinc, calcium phosphate zinc, calcium phosphate, aluminum pyrophosphate, Calcium Pyrophosphate, aluminium dihydrogen tripolyphosphate, aluminium metaphosphate, calcium metaphosphate, zinc oxide, phospho-molybdic acid zinc, the rust-stabilising pigments such as phospho-molybdic acid aluminium etc., they can be used alone or combine two or more and use.
In addition, do not comprise carbon black in other pigment, or its content is for example suppressed, for trace (being below 5% according to pigment volume concentration (PVC), in particular for ratio such below 1%), it is essential that this viewpoint from the thermal insulation of film is considered.
The pigment volume concentration (PVC) of pigment composition (B) is 45～80%, preferably in 50～75% scope in the present invention.
When pigment volume concentration (PVC) less than 45%, extinction effect will become insufficient, in film, produce and will break, or find pigment sedimentation in the time of Long-term Storage water-based paint compositions of the present invention, so not preferred while exceeding 80% on the other hand.
In this manual, " pigment volume concentration (PVC) " be all resins composition in coating with whole solid substances of whole pigment among the shared volume ratio of this pigment composition.
In calculating pigment volume, be the specific gravity of pigment obtaining based on " coating raw material handbook the 6th edition " (Corporation's Japanese coating industry meeting) as basic specific gravity of pigment, in addition, the ratio of resin solid substance be reset to approximate 1 value.
In addition, in the present invention, pigment composition (B) comprises above-mentioned pigment (bl), (b2) and (b3), and comprise nonionic surfactant described later (C), thereby can comprise pigment composition (B) is stabilized to and becomes the above such amount of critical pigment volume concentration.
In this manual, critical pigment volume concentration refers to, in the time that pigment and resin is mixed, the volumetric concentration of pigment when resin fills up the gap between pigment just, utilizes following formula to calculate.
Volume × the l00/ (volume of the pigment composition (B) in the oil number+coating of the pigment composition (B) in coating) of the pigment composition (B) in critical pigment volume concentration=coating
In addition, oil number (ml/100g) refers to and utilizes the method specifying in JIS K5101-13-2:2004 and the value of obtaining is the value being represented by the ml that boils Toenol 1140 being absorbed in pigment 100g.
In addition, as inorganic white pigment (b1), laminar pigment extender (b2) and pigment extender (b3) shared volume ratio in the whole volumes of pigment composition (B),
Inorganic white pigment (b1) is 60～15%, can be preferably in 50～20% scope,
Laminar pigment extender (b2) is 5～70%, can be preferably in 10～60% scope,
Pigment extender (b3) is 20～80%, can be preferably in 30～65% scope,
Other pigment is 0～25%, can be preferably in 0～20% scope.
This be because, by making pigment (b1), (b2) and (b3) within the scope of this, thus colour stability, the weather resistance of film, thermal insulation, disguised excellent while making storage stability, the toning of water-based paint compositions of the present invention.
< nonionic surfactant (C) >
It is more than 10 nonionic surfactants (C) that water-based paint compositions of the present invention comprises HLB value.By comprising this tensio-active agent (C), thereby improve the wettability to pigment, can be suppressed at the aggegation when water-based paint compositions of the present invention that comprises in a large number pigment is preserved, in addition, the colour stability can improve toning time.
As the object lesson of such nonionic surfactant (C), list the polyoxyethylene alkyl phenyl ether such as polyoxyethylene nonylplenyl ether, polyoxyethylene propylene oxide octyl phenyl ether; The polyoxyalkylene alkyl such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; The polyoxyethylenes such as polyoxyethylene toluylene phenyl ether encircle phenyl ether more; Polyoxyethylene alkylamide; Glycerine alkyl ester; Alkyl sorbitol dehydration esters etc., they can be used alone or combine two or more and use.
In the present invention, the HLB value of above-mentioned nonionic surfactant (C) is more than 10, preferably in 11～18 scope.
HLB value in this specification sheets is the wetting ability of non-ionic species tensio-active agent and the index of hydrophobic balance, can be obtained by lattice Lifei formula (Griffin equation).Specifically: the value obtaining divided by all molecular weight of nonionic class tensio-active agent by the molecular weight that makes the hydrophilic portion such as oxo alkylidene group is multiplied by 20 values that obtain.
In addition, as the content of nonionic surfactant (C), taking the solid substance of water-base resin (A) in the scope of benchmark in 0.3～10 quality %, preferably in the scope of 0.5～6 quality %.
Nonionic surfactant (C) when the quantity not sufficient 0.3 quality %, pigment composition (B) is poor to the fusion of coating, storage stability and/or colour stability when coating is mixed colours reduce.On the other hand, while exceeding 10 quality %, the water tolerance of film reduces, thereby not preferred.
In water-based paint compositions of the present invention, particularly in the situation that aforementioned water-base resin (A) has carbonyl, even even for obtain that under the condition of Air drying film also can be cross-linked and also harsh condition without under also excellent thermal insulation delustring film of long durability, preferably comprise hydrazine derivative.
As relevant hydrazine derivative, for example, list two hydrazides of the representative examples of saturated aliphatic carboxylic 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 the monoene formula 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, three hydrazides or four hydrazides of pyromellitic acid; Nitrilo base nitrilotriacetic 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 low-grade polymer with carboxylic acid low alkyl group ester group react polyhydrazide forming etc. with hydrazine or hydrazine hydrate (hydrazine hydrate); Carbon acid dihydrazide, two Urea,amino-; Make N, the N such as N-dimethylhydrazine, N-replaces the vulcabond such as hydrazine and/or above-mentioned illustrative hydrazides and hexamethylene diisocyanate, isophorone diisocyanate and carries out excessive response and the multifunctional Urea,amino-that obtains by its derivative polyisocyanate compound; The multifunctional Urea,amino-of water system that makes isocyanate group in the reactant of the active dydrogen compounds that above-mentioned illustrative two hydrazides and, this polyisocyanate compound and polyether glycol class and/or polyalkylene glycol monoalkyl ethers etc. comprise hydrophilic radical carry out excessive response and to obtain; This multifunctional Urea,amino-with the multifunctional Urea,amino-of water system mixture; Diacetyl group dihydrazone etc., they can use separately respectively or combine two or more and use.
In water-based paint compositions of the present invention, can further comprise as required hollow particle, alkyl silicate, aggregate, fiber, softening agent, levelling agent, prevent sagging dose, white dyes, silane coupling agent, thickening material, neutralizing agent, static inhibitor, tenderizer, antiseptic-germicide, spices, curing catalysts, pH adjusting agent, humextant, powdery or particulate gac, photocatalyst oxidizes titanium, watery water-proofing agent, dispersion agent, defoamer, sanitas, mould inhibitor, frostproofer, UV light absorber, Photostabilised dose, membrane producing promoter, zinc whisker, curing catalyst, aldehyde sorbent material, wax, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, the known additive for coatings such as fire retardant such as aluminium hydroxide.
As the hollow particle among them, list hollow inorganic particles, hollow resin particle.
By making water-based paint compositions of the present invention comprise hollow particle, thereby can make film more reflect sunshine etc., or can there is effect of heat insulation, thereby there is the effect of the temperature rising that suppresses base material.
As the inorganic substance that form hollow inorganic particles, for example list the glass such as water soda glass, aluminum silicate glass, canopy water soda glass, flying dust, aluminum oxide, zirconium white, titanium oxide or titanium dioxide, silicon boride, white sand (シ ラ ス), obsidian etc.
As the resinous principle that forms hollow resin particle, for example, list acrylic resin, styrene resin, acrylic acid or the like-styrene copolymerized resin, acrylic acid or the like-acrylonitrile compolymer resin, acrylic acid or the like-styrene-acrylonitrile resin, vinyl cyanide-methacrylonitrile copolymer resins, acrylic acid or the like-vinyl cyanide-methacrylonitrile copolymer resins, vinylidene chloride-acrylonitrile compolymer resin etc.
In above-mentioned hollow particle, can be air, any one in gas, vacuum except air.
As the median size of hollow particle, consider from the viewpoint of appearance of film, Physical properties of coating film, effect of heat insulation, be preferably 5～150 μ m.
About the median size of hollow particle, can, by taking transmission electron microscope photo (TEM), measure the particle diameter of 50 particles, averaged and obtained.
In the situation that comprises hollow particle, as its content, taking resin solid substance contained in water-based paint compositions as benchmark, be 2～50 quality %, preferably, in the scope of 5～30 quality %, it is suitable that this viewpoint from the fracture-resistant of coating storage stability, film is considered.
In addition, in the present composition, will give and form film using stain resistance as object, can comprise alkyl silicateization containing thing.
As alkyl silicate compound, for example list the compound shown in following formula, with and partial hydrolysis and condenses,
Si(-OR
1)
4
(in formula, R
1the identical or different monovalence alkyl of selecting from alkyl, aryl and aralkyl).
In above-mentioned formula, R
1be preferably the alkyl of carbonatoms 1～4.
As the example of alkyl silicate compound, list tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, tetraisobutoxy-silicane alkane, four tert.-butoxy silane and their combination arbitrarily and their partial hydrolysis and condenses.In addition, further with polyoxyalkylene compounds etc. using these illustrative compounds carry out modification and the compound that obtains also as alkyl silicate compound and involved.
In addition, in the situation that comprising abovementioned alkyl silicate ester compound, also can and use the catalyzer such as organo-tin compound, organic titanate compound, phosphate cpd, acid anhydrides, amine.
In addition, in the situation that water-based paint compositions of the present invention comprises abovementioned alkyl silicate ester compound, preferably: coating composition is made as to double-formulation, before being about to use the composition that comprises this alkyl silicate compound, carries out compounding with composition in addition.
In the situation that water-based paint compositions of the present invention comprises alkyl silicate compound, consider from forming the stain resistance of film and the viewpoint of fracture-resistant, as its content, taking resin solid substance contained in coating as benchmark, can be made as in the scope of 3～20 quality %, can preferably be made as in the scope of 5～15 quality %.
< has used the coating film-forming methods > of thermal insulation delustring water-based paint compositions
By thermal insulation delustring water-based paint compositions of the present invention is coated on to substrate surface, can form the delustring film of excellent in heat insulating performance.
The substrate surface of applicable water-based paint compositions of the present invention is not particularly limited, but for example can list plasterboard, concrete slab, concrete blocks, decorative plate of outer wall, Mortar Plates, slate plate, PC plate, ALC plate, cement calcium silicate board, brick, glass, timber, stone material, plastic shaping thing, pottery chinaware, chinaware ceramic tile, iron material, the surface of the base materials such as metal work material such as aluminium frame, be arranged at the acrylic resin class on these base materials, acrylic acid or the like polyurethane type resin, polyurethane type resin, fluorine type resin, silicone resin, silica acrylic acid resinoid class, vinyl acetate resin class, the coated surface of epoxy resin etc., by polyvinyl chloride, polyolefine, the wallpaper face that the materials such as paper cloth form etc.
These substrate surfaces also can be anticipated by encapsulant etc.
Water-based paint compositions of the present invention can be by using himself known application means to carry out application, for example can be according to kind, the purposes etc. of base material from roller, air-atomizing, use without suitably selecting the finishings such as gas blowout mist, sand-blasting gun, omnipotent rifle (universal gun), brush, roller coating machine.In addition, also water-based paint compositions of the present invention can be coated with repeatedly repeatedly in the scope of not damaging appearance of film.
Forming the dry of film can be undertaken by Air drying, but also can, according to component, the painting environment etc. of used coating composition, carry out heat drying or forced drying.
Dry film thickness can suitably be adjusted according to applicable base materials and/or painting environment, but in order to obtain sufficient thermal insulation, thereby be generally 35～5000 μ m, be preferably 50～3000 μ m.
Thereby a kind of method that the present invention provides temperature that suppresses interior of building by above-mentioned water-based paint compositions being coated on to the outside wall surface of buildings to raise in addition.
Water-based paint compositions of the present invention can form the film that has thermal insulation and have appropriate delustring sense, thereby can be given buildings outer wall with harmonious outward appearance and be given heat insulating function by this material of application.
Outside the building in the object lesson of wall, for example can exemplify the outside wall surface of the various buildingss such as building, house, facility, warehouse, as the material that forms this outside wall surface, can enumerate general outer wall materials, for example, the mineral-type exterior materials such as ceramic Side fascia, mortar, concrete, slate, or the metal species exterior material such as iron, aluminium, metal outer wall material, or the wooden class exterior material such as natural wood, glued board etc., be also included within surface and be provided with the material of old coating film.
About water-based paint compositions of the present invention, can, according to circumstances in advance at substrate surface application bottom-coating, then be coated on formed primary coat painting face.
As above-mentioned bottom-coating, can suitably select according to kind and/or the state etc. of substrate surface, for example can enumerate by comprising aqueous resin or solvent is the coating that resin forms as resin glue, described aqueous resin or solvent are that resin is to contain acrylic resin, acryl silicon resinoid, fluorine resin, polyvinyl acetate esters resin, polyolefin resin, silicon resinoid, polyurethanes resin, redix, phenolic resinoid, polyester resin, alkyd based resin, trimeric cyanamide resinoid, aqueous resin or the solvent of the resin kinds such as biodegradable resin are resin, preferably use the water-borne coatings forming by the resin that comprises water system.
Particularly when known thermal insulating coating, can further improve the heat-proof quality of substrate surface being used as bottom-coating together with the film obtaining based on water-based paint compositions of the present invention.
Above-mentioned substrate form with the application of coating can be by using himself known application means to carry out, for example can according to the purposes of base material etc. from roller, air-atomizing, without the finishings such as gas blowout mist, sand-blasting gun, omnipotent rifle, brush, roller coating machine suitably selection use.The dry Air drying that is preferably of the primary coat film forming, but can carry out heat drying or forced drying according to kind and/or the painting environment etc. of bottom-coating.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not limited only to these embodiment.In addition, " part " in following example and " % " represent respectively " mass parts " and " quality % ".
the manufacture of aqueous resin dispersion
Production Example 1
There is thermometer to possessing, add 35 parts of deionized waters, 1 part of Newcol707SF (note 1) in the reaction vessel of thermostatted, agitator and Dropping feeder, in stream of nitrogen gas, be uniformly mixed, and be warmed up to 85 DEG C.Then 10 parts of 3% part by the composition of following composition being carried out to the pre-emulsion that emulsion forms and 2.5% ammonium persulfate aqueous solutions are made an addition in reaction vessel, kept 20 minutes at 85 DEG C.
, spend 4 hour remaining pre-emulsion and 2.5% ammonium persulfate aqueous solution 20 part dripped in reaction vessel in, drip after finishing and carried out slaking in 2 hours thereafter., be cooled to 30 DEG C, use ammoniacal liquor and deionized water, adjust according to the mode that solid substance is 50%, pH is 8.0 thereafter.Then, utilize 200 object nylon cloths to filter while discharge, thereby obtain median size 180nm and (use Beckman Coulter, Inc. the submicron particle size measure of spread device " COULTER N4 type " of system, is diluted and is determined at 20 DEG C by deionized water), the aqueous resin dispersion (A-1) of the acid number 13mgKOH/g of unit solid substance.
(note 1) Newcol707SF: trade(brand)name, Japanese emulsifying agent company system, has anionic surfactant, the nonvolatile component 30% of polyethylene oxide chain.
Production Example 2～5
In above-mentioned Production Example 1, monomer component is made as to the formula shown in following table 1, in addition, similarly operate with Production Example 1 and synthesize, acquisition aqueous resin dispersion (A-2)～(A-5).
Table 1
the manufacture of colo(u)rant dispersion paste
Production Example 6
To add in turn the each composition shown in following in stainless steel container made under whipped state, utilize PRIMIX company homogenous disperse machine processed to continue to stir 30 minutes until become evenly, obtain colo(u)rant dispersion paste (B-1).
(note 2) Suraoff72N: trade(brand)name, Japan EnviroChemicals, Ltd. system, sanitas,
(note 3) SP-600: trade(brand)name, Daicel Chemical Industries, Ltd system, Natvosol class thickening material,
(note 4) DISPER BYK-190: trade(brand)name, BYK-Chemie company system, pigment dispersing agent,
(note 5) BYK-028: trade(brand)name, BYK-Chemie company system, defoamer,
(note 6) TI-PURE R-706: trade(brand)name, E.I.Du Pont Company's system, titanium dioxide, proportion 4.0, oil number 14 (ml/100g),
(note 7) Super S: trade(brand)name, Maruo Calcium Co., Ltd. system, water-ground limestone, proportion 2.7, oil number 23 (ml/100g),
(note 8) MS-P: trade(brand)name, Nippon Talc Co., Ltd. system, talcum, proportion 2.7, oil number 28 (ml/100g).
Production Example 7～11
In above-mentioned Production Example 6, pigment component is made as to the formula shown in following table 2, in addition, similarly operate with Production Example 6 and obtained colo(u)rant dispersion paste (B-2)～(B-6).
Table 2
the manufacture of water-borne coatings
Embodiment 1～8 and comparative example 1～7
In stainless steel container made, under whipped state, add in turn the each composition shown in following table 3, utilize PRIMIX company homogenous disperse machine processed to continue to stir 15 minutes until become evenly, acquisition water-borne coatings (C-1)～(C-15).
(note 9) CS-12: trade(brand)name, Chisso Corporation system, 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate, membrane producing promoter,
(note 10) Emulgen A-90: trade(brand)name, Kao Corporation system, polyoxyethylene toluylene phenyl ether, nonionic surfactant, HLB value 14.5,
(note 11) Emulgen103: trade(brand)name, Kao Corporation system, polyoxyethylene lauryl ether, nonionic circle are drawn promoting agent, HLB value 8.1,
(note 12) Silicate45: trade(brand)name, Duo Mo chemical industrial company system, the partial hydrolysis condenses of tetraethoxysilane, low pollution agent,
(note 13) S38: trade(brand)name, Sumitomo3M Limited system, glass hollow microsphere, median size 40 μ m,
(note 14) SN Thickener612N: trade(brand)name, SAN NOPCO LIMITED system, polyurethane associative thickener.
evaluation test
By the water-borne coatings being obtained by embodiment and comparative example for following evaluation.To the results are shown in table 3.
(* 1) storage stability
By each evaluation coating put into 1L with lid vial, in the thermostatic bath of 40 DEG C, place 30 days, by Visual Confirmation storage after coating state.
◎: there is no pigment sedimentation, do not have viscosity to change yet,
Zero: there is no pigment sedimentation, slightly confirm that viscosity changes,
△: although there is pigment sedimentation, if stirred, restore,
×: find pigment sedimentation, even if stir also non-restoring and residual agglutinator.
(* 2) appearance of film
Upper at flexible board (according to JIS A5430), be 100g/m according to coating amount
2mode use bristle application " Eco Cation Sealer " (Kansai Paint Co., Ltd. system, water system cation emulsion class encapsulant), under the condition of 23 DEG C of temperature, relative humidity 50%, be dried 18 hours, be then 100g/m according to coating amount each time
2mode use bristle within 4 hours, will evaluate coating with overlay painting interval to be repeatedly coated with secondary.Thereafter, under the condition of 23 DEG C of temperature, relative humidity 50% dry 24 hours and by visual observation the state of film coated surface.
◎: lackluster inhomogeneous, fully there is harmonious delustring sense,
Zero: lackluster inhomogeneous, there is delustring sense and still slightly confirm reflecting feel,
△: confirm glossy inhomogeneous,
×: confirm significant lustre lacking uniformity, break, dwindle, pin hole etc. is abnormal.
(* 3) colour stability
To evaluating in coating 200g, by UNIRANT77 (trade(brand)name, Yokohama changes into company's system, the color paste (color paste) that water-borne coatings is used) khaki color paste and red rust paste add respectively 2g, utilize PRIMIX company homogenous disperse machine processed to stir 5 minutes, then dilute according to the mode water that the viscosity based on stormer viscosity meter (Stormer Viscometer) is 75KU at 25 DEG C, obtain the toning product of evaluating coating.Then, upper at flexible board (according to JIS A5430), become 100g/m according to coating amount
2mode use bristle and application " Eco Cation Sealer " (Kansai Paint Co., Ltd. system, water system cation emulsion class encapsulant), under the condition of 23 DEG C of temperature, relative humidity 50%, be dried on the coated plate of 18 hours, the evaluation coating that in utilization, hair wool roller completes the toning of having diluted carries out whole 1 application, under the condition of 23 DEG C of temperature, relative humidity 50%, has been dried 4 hours.Then, about secondary application, half is used bristle and application, remain hair wool roller in half use and application, then under the condition of 23 DEG C of temperature, relative humidity 50% dry 24 hours, and difference and the aberration of the application part of carrying out based on bristle by visual observation and the finish department that carries out based on the roller reflecting feel between dividing.
◎: the variation of lackluster sense and aberration, cannot confirm border,
Zero: the variation of lackluster sense, but slightly there is aberration,
△: the variation of lackluster sense, but there is aberration,
×: being changed significantly of reflecting feel and aberration, can clearly confirm border.
(* 4) promote weathering resistance
Upper at flexible board (according to JIS A5430), be 100g/m according to coating amount
2mode use bristle and application " Eco Cation Sealer " (Kansai Paint Co., Ltd. system, water system cation emulsion class encapsulant), under the condition of 23 DEG C of temperature, relative humidity 50%, be dried 18 hours, be then 100g/m according to coating amount each time
2mode use bristle within 4 hours, will evaluate coating with overlay painting interval to be repeatedly coated with secondary., under the condition of temperature 23 DEG C, relative humidity 50% be dried 7 day, make and promote atmospheric exposure test plate, utilize the xenon lamp method specifying in JIS K5600-7-7, irradiating after 1000 hours by the state of visual observation film coated surface thereafter.In following benchmark, about white chalk rating, evaluate according to the regulation of JIS K5600-8-6.
◎: white chalk rating is below 1, does not expand, peels off, breaks etc., comparatively speaking there is no large colour-change with sample panel,
Zero: white chalk rating is below 2, do not expand, peel off, break etc., with the comparatively speaking coloured variation of tool slightly of sample panel,
△: white chalk rating is 3, does not expand, peels off, breaks etc., large with the compare variation of color of sample panel,
×: white chalk rating is more than 4, with the sample panel coloured variation of remarkable tool of comparing, or confirms to expand, peels off, breaks etc. extremely.
(* 5) stain resistance
Upper at flexible board (according to JIS A5430), be 100g/m according to coating amount
2mode use bristle and application " Eco Cation Sealer " (Kansai Paint Co., Ltd. system, water system cation emulsion class encapsulant), under the condition of 23 DEG C of temperature, relative humidity 50%, be dried 18 hours, be then 100g/m according to coating amount each time
2mode use bristle within 4 hours, will evaluate coating with overlay painting interval to be repeatedly coated with secondary.Dry after 7 days under the condition of 23 DEG C of temperature, relative humidity 50%,, painting is 30 ° towards tilting and carries out exposure test outside 12 months rooms towards the south in Ben Ping mound city, the stain of the painting face after testing by visual valuation.
◎: there is no discovery stain,
Zero: slightly find stain,
△: there is stain,
×: stain is remarkable.
(* 6) fracture-resistant
Upper at flexible board (according to JIS A5430), be 100g/m according to coating amount
2mode use bristle and application " Eco Cation Sealer " (Kansai Paint Co., Ltd. system, water system cation emulsion class encapsulant), under the condition of 23 DEG C of temperature, relative humidity 50%, be dried 18 hours, be then 100g/m according to coating amount each time
2mode use bristle within 4 hours, will evaluate coating with overlay painting interval to be repeatedly coated with secondary.Thereafter, under the condition of 23 DEG C of temperature, relative humidity 50%, be dried 7 days, according to JIS A6909, be supplied in the following cold repetition test of temperature that is altogether made as a circulation for 24 hours: be immersed in the water of 20 DEG C 18 hours, then in the thermostatic bath of-20 DEG C cooling 3 hours immediately, then in the thermostatic bath of 50 DEG C, heat 3 hours.By the state of the film coated surface after five circulations of visual observation.
◎: completely do not confirm and break,
Zero: slightly confirm and break, but unclear while watching away from 50cm,
△: confirm and break, even also clear away from 50cm,
×: confirm significantly and break at whole face.
(* 7) thermal insulation
According to JIS K5602-2008, on white black hidden rate test pater according to dry film thickness become 80 μ m mode application evaluation coating.The reflectivity of the film that the blackboard that then, uses spectrophotometer (UV-3100: company of Shimadzu Seisakusho Ltd. system) to measure white black hidden rate test pater in the scope of wavelength 300～2500nm divides.Thereafter, according to JIS K5602-2008, according to calculating the reflectivity at sunshine in this wavelength region may in the summation of the spectral reflectivity (spectral reflectance) at wavelength 300～2500nm place and the product of weight coefficient (weighting coefficients), thermal insulation is evaluated.
Claims (8)
1. a thermal insulation delustring water-based paint compositions, it is characterized in that, it is that water-base resin (A), pigment composition (B) and the HLB value of acid number in the scope of 2.5～30mgKOH/g that comprises unit solid substance is the water-based paint compositions of more than 10 nonionic surfactants (C)
Wherein, pigment composition (B) comprises inorganic white pigment (b1), laminar pigment extender (b2) and the pigment extender except (b2) (b3), the pigment volume concentration (PVC) of pigment composition (B) is in 45～80% scope, inorganic white pigment (b1), laminar pigment extender (b2) and pigment extender (b3) shared volume ratio in the whole volumes of pigment composition (B) is: inorganic white pigment (b1) is 60～15%, laminar pigment extender (b2) is 5～70%, pigment extender (b3) is 20～80%, the content of nonionic surfactant (C) is taking the solid substance of water-base resin (A) as benchmark is in the scope of 0.3～10 quality %.
2. thermal insulation delustring water-based paint compositions according to claim 1, is characterized in that, the pigment volume concentration (PVC) of pigment composition (B) is more than critical pigment volume concentration.
3. thermal insulation delustring water-based paint compositions according to claim 1 and 2, it further comprises hollow particle.
4. according to the thermal insulation delustring water-based paint compositions described in any one in claim 1～3, it further comprises hydrazine derivative, and wherein, water-base resin (A) is the water-base resin with carbonyl.
5. according to the thermal insulation delustring water-based paint compositions described in any one in claim 1～4, it further comprises alkyl silicate compound.
6. a thermal insulation delustring coating film-forming methods, is characterized in that, the thermal insulation delustring water-based paint compositions in substrate surface application claim 1～5 described in any one.
7. suppress a method for the temperature rising of interior of building, thereby suppress the temperature rising of interior of building by the thermal insulation delustring water-based paint compositions described in any one in the outside wall surface application claim 1～5 of buildings.
8. a coated article, the coated article that it obtains for the method for utilizing described in claim 6 or 7.
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| CN104263348A (en) * | 2014-08-26 | 2015-01-07 | 吉林大学 | Water-based visible light photochromic material for vehicle film and preparation method of photochromic material |
| CN104402245A (en) * | 2014-10-31 | 2015-03-11 | 田琳琳 | Heat-insulating shockproof glass membrane |
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| CN108779029A (en) * | 2016-03-14 | 2018-11-09 | 圣戈班普拉科公司 | Plasterboard |
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| CN110402264A (en) * | 2017-03-23 | 2019-11-01 | 蓝宝迪有限公司 | Aqueous polyurethane dispersion |
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| CN104263348A (en) * | 2014-08-26 | 2015-01-07 | 吉林大学 | Water-based visible light photochromic material for vehicle film and preparation method of photochromic material |
| CN104402245A (en) * | 2014-10-31 | 2015-03-11 | 田琳琳 | Heat-insulating shockproof glass membrane |
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| CN108779029B (en) * | 2016-03-14 | 2021-07-20 | 圣戈班普拉科公司 | Plaster slab |
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| CN110402264A (en) * | 2017-03-23 | 2019-11-01 | 蓝宝迪有限公司 | Aqueous polyurethane dispersion |
| CN110402264B (en) * | 2017-03-23 | 2021-12-10 | 蓝宝迪有限公司 | Aqueous polyurethane dispersions |
| CN109135556A (en) * | 2018-07-19 | 2019-01-04 | 宁波帝杨电子科技有限公司 | A kind of air-cleaning function water paint and preparation method thereof |
| CN109135556B (en) * | 2018-07-19 | 2021-05-25 | 福建涂丽士漆业有限公司 | Water-based paint with air purification function and preparation method thereof |
| CN115785747A (en) * | 2022-12-01 | 2023-03-14 | 江西龙正科技发展有限公司 | Novel water-based transparent woodware primer |
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| JP2014189580A (en) | 2014-10-06 |
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