CN1489624A - Water-based coating composition for wall paper and wall paper thereof - Google Patents
Water-based coating composition for wall paper and wall paper thereof Download PDFInfo
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- CN1489624A CN1489624A CNA018220657A CN01822065A CN1489624A CN 1489624 A CN1489624 A CN 1489624A CN A018220657 A CNA018220657 A CN A018220657A CN 01822065 A CN01822065 A CN 01822065A CN 1489624 A CN1489624 A CN 1489624A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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Abstract
A water-based coating composition for wallpapers which comprises fibrous monoclinic titanium dioxide, a reactive silicone compound, and polyvinyl alcohol as effective ingredients; and a wallpaper having a coating layer formed from the water-based coating composition. The wallpaper is excellent not only in the function of protecting interior members or in deodorizing or antibacterial performance but in decorative properties, whiteness, texture, and appearance.
Description
Technical field
The present invention relates to wallpaper use coating and wallpaper.
Background technology
Along with the marked improvement that residential environment is equipped with, add the execution of guaranteeing the housing quality promotion law, the long lifetime of strong request buildings, and the long lifetime of interior dress member.Especially, nearest dwelling house pattern is difficult to keep construction quality and maintenance originally to the wallpaper from the large space part of the airspace of doorway part, coupled living room and dining room.
In order to protect the interior dress member of buildings, a kind of wallpaper that photocatalyst coatings such as containing titanium dioxide forms coating that designed is proposed.The dress member helped long lifetime in such wallpaper was not only protected, and photocatalyst also presents the effect of anti-microbial property and deodorizing performance by indoor luminescent lamp and incandescent light, so also effective to the environmental purification of living space.
In the past,, the schemes such as organic binder bond of photocatalyst, inorganic adhesive, inorganic filler, synthetic resins etc. have been proposed to contain as the wallpaper coating that contains photocatalyst.
More specifically, for example, put down in writing in the Te Kaiping 10-183023 communique contain make diacetone (methyl) acrylamide etc. contain carbonyl α, β-ethylene unsaturated monomer, and the copolymer emulsion that aforementioned ethylene unsaturated monomer emulsion polymerization is in addition formed, hydrazide derivatives such as adipic dihydrazide, amber acid dihydrazide, citric acid three hydrazides, naphthoic acid four hydrazides, photocatalyst such as pigment composition such as active aluminium sesquioxide, atlapulgite, zeolite and titanium dioxide contain photocatalyst coating.
Te Kaiping 10-180943 communique has been put down in writing the photocatalyst coating that contains of tackiness agents such as the photocatalyst that contains titanium dioxide etc. and water glass, pure aluminium silicate, silicate base metal-salt, phosphoric acid salt, colloid silica, colloid aluminium sesquioxide.
Te Kaiping 10-251565 communique put down in writing photocatalysts such as containing titanium dioxide and, the multipolymer that contains carboxyl polymerizability unsaturated monomer and other polymerizability unsaturated monomers such as (methyl) methyl acrylate, Jia Jibingxisuanyizhi, vinylbenzene of (methyl) vinylformic acid, toxilic acid, maleic anhydride etc. contain photocatalyst coating.
Te Kaiping 10-264283 communique has been put down in writing the photocatalyst coating that contains of tackiness agents such as the water-based emulsion, film forming inorganics (colloid silica, colloid aluminium sesquioxide, saponite, hectorite, kaolin, sepiolite etc.), colloid silica composite thermoplastic macromolecule emulsion of photocatalysts such as containing titanium dioxide, thermoplastic resin (acrylic resin, styrene-propene acid copolymer, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer etc.).
Te Kaiping 11-138686 communique has been put down in writing the coating that contains two kinds of photocatalysts, a kind of is the coating that contains metal oxide sol and titanium oxide sol, and another kind is the coating that contains silicon dioxide gel, an alkyl trimethoxysilane or its hydrolysis resultant and titanium oxide sol.
Te Kaiping 11-279446 communique has been put down in writing photocatalysts such as mineral-type tackiness agent, titanium dioxide such as containing colloid silica, aluminium sesquioxide colloidal sol, saponite, hectorite, sepiolite, organic class tackiness agents such as polyvinyl alcohol and water system latex or water serial emulsion contain photocatalyst coating.
The above-mentioned photocatalyst coating that contains in the past is the coating that mainly contains Powdered titanium dioxide, can bring into play good effect aspect deodorization and the antibacterial really.Yet wallpaper is decorated indoor simultaneously for dress member in protecting and is used, but the wallpaper that forms the formed coating of coating that contains photocatalysts such as titanium dioxide in the past lacks ornamental, shortage luxurious sense and attractive in appearance.In addition, exist whiteness low and by in the past the coating that photocatalyst coating forms of containing through the lower shortcoming of long-time back whiteness.
In addition, during the containing photocatalyst coatings such as titanium dioxide and be used for the polyolefins wallpaper and use base material of these past, can not form dark and beautiful embossed pattern.
In addition, international publication put down in writing for No. 98/43733 contain that monocline crystal class titania fiber and tetraethyl orthosilicate condenses constituted contain the photocatalyst wallpaper with coating (embodiment 5).But this coating can not be formed with the embossed pattern of dark line on the coating surface.This international monopoly does not point out that the combination of fibrous monocline crystal class titanium dioxide and which kind of composition can form good decorative property on the coating surface, especially the embossed pattern this point of dark line be arranged.
The object of the present invention is to provide not only has dress member function or deodorization and anti-microbial property in the protection, and ornamental, whiteness, texture and the attractive in appearance also excellent novel photocatalyst water-borne coatings that contains.
Summary of the invention
The present invention relates to fibrous oblique system titanium dioxide, reactive polysiloxane compound and polyvinyl alcohol is the wallpaper use coating of effective constituent.
In addition, the present invention relates to the wallpaper of sheet material or film with base material on the coating that forms of the above-mentioned wallpaper use coating of design be the wallpaper of feature.
The coating that wallpaper use coating of the present invention forms have with in the past to contain coating that photocatalyst coating forms equal or than the defencive function of its better internal dress member, the decomposability of disappear smelly performance, anti-microbial property and organic dirt, even and the fabulous embossed pattern of its surface formation, reduction that the whiteness height is preserved whiteness for a long time also obviously reduce, show good ornamental, high-grade texture arranged.
In addition, of the present inventionly also can form dark and beautiful embossed pattern when containing photocatalyst coating and being used for the polyolefins wallpaper with base material.
As above-mentioned before the present patent application, as with specific fibrous monocline crystal class titanium dioxide as the photocatalyst composition, and with reactive polysiloxane compound as tackiness agent, further cooperate polyvinyl alcohol more can improve the wallpaper that embossed pattern forms the composition of effect effect and do not exist fully with coating as having, and also unpredictable fully just like the coating of above-mentioned good effect.
Wallpaper use coating of the present invention as must composition being, contains fibrous monocline crystal class titanium dioxide, reactive polysiloxane compound and polyvinyl alcohol, and these compositions are dispersed in the water in right amount.
Fibrous monocline crystal class titanium dioxide is known fibrous titanium dioxide, and is for example, on the books in No. 98/43733 grade of international publication.Monocline crystal class titanium dioxide has does not need corpusculed operation, the coherency of carrying out with sand mill etc. little in the manufacturing processed of coating, and can adapt to execute changes sieve, also can form the advantage of printing rill.
The size of fibrous monocline crystal class titanium dioxide does not have particular restriction, but can use usually about fiber diameter 0.01～1 μ m, about preferred 0.05～0.5 μ m, about long 0.5～100 μ m of average fiber, about preferred 3～50 μ m, long-width ratio (average fiber length/fiber diameter) is more than 5, and is preferred more than 10.
The use level of fibrous monocline crystal class titanium dioxide does not have particular restriction, can from wide region, suitably select according to all conditions such as the kind of its size, other compositions and use levels, but if the function as photocatalyst is given full play in consideration, the embossed pattern that coating surface is formed have the whiteness of distincter dark line, coating good, prevent that coating from cracking etc., usually can be 3～30 weight % of water-borne coatings total amount of the present invention, preferred 5～20 weight %.
Reactive polysiloxane compound is mainly as tackiness agent among the present invention.As reactive polysiloxane compound, then do not have particular restriction so long as can form the polysiloxane resinoid of rubber-like elasticity film, can use known any, wherein, preferred hydroxylation polydiorganosiloxane.Do not have particular restriction as the organic radical that contains in the hydroxylation polydiorganosiloxane, but generally be C
7Following aliphatics or aromatic series monovalence alkyl.As C
7The concrete example of following monovalence alkyl can be enumerated methyl, ethyl, butyl, hexyl, phenyl etc.At least 50% of the organic radical sum is methyl in preferred its molecule of hydroxylation polydiorganosiloxane.In addition, the weight-average molecular weight of relevant hydroxylation polydiorganosiloxane (to call Mw in the following text) without limits, but Elastic Film, emulsifying stability that elongation is arranged when obtaining to have tension stress and fracture as if consideration are good etc., can use more than the Mw5000 preferred 30000～1000000 usually.Reactive polysiloxane compound can be used singly or two or more kinds thereof.
Reactive polysiloxane compound preferably uses with the form of emulsification.The emulsification of reactive polysiloxane compound can be according to known method, and emulsifying agent carries out emulsion polymerization or add emulsifying agent in reactive polysiloxane compound makes by adding in reactive polysiloxane compound monomer.As emulsifying agent, can suitably select anion surfactant, nonionogenic tenside, cats product etc. a kind or 2 kinds with on use.The addition of emulsifying agent does not have particular restriction, can be according to suitably selections from wide region such as the desired characteristics of purpose emulsification, but form good emulsifying things such as property in order to obtain emulsifying stability and Elastic Film, with respect to the emulsion reaction system can be 1～5 weight % usually, preferred 2～3 weight %.
The use level of reactive polysiloxane compound does not have particular restriction, can be according to the kind of reactive polysiloxane compound, the kind of other compositions and use level, the various conditions of the desired performance of gained water-borne coatings etc. are suitably selected from wide region, but make fibrous monocline crystal class titanium dioxide give full play to the photocatalyst function if consider, with the formation water tolerance, the coating that the stationarity of fibrous monocline crystal class titanium dioxide and wet friction fastness are good etc., can be 3～30 weight % (solids component) of water-borne coatings total amount of the present invention, preferred 5～20 weight %.
Among the present invention, more tough for the Elastic Film that reactive polysiloxane compound is formed, also can in reactive polysiloxane compound or its emulsification, add more than a kind or 2 kinds of colloid silica, linking agent, curing catalysts etc.As colloid silica, can enumerate aqueous colloidal silicon-dioxide with stabilizations such as sodium ion with 0.001～0.05 μ m particle diameter, as linking agent, can enumerate organoalkoxysilane, hydrogenated methyl diene polysiloxane.As curing catalysts, can enumerate metal fatty acid salt, organo-peroxide, inorganic peroxide of reactive polysiloxane compound depolymerization etc. not being had dysgenic dialkyl tin two acylate representatives etc.
Mainly has the effect that further raising forms the embossed pattern effect of fibrous monocline crystal class titanium dioxide demonstration as the another kind of polyvinyl alcohol that must composition of water-borne coatings of the present invention.The polyvinyl alcohol of saponification deg 70～100% in preferred these polyvinyl alcohol.The various conditions of the performance that the use level of polyvinyl alcohol can require according to kind and use level, the gained coating composition of other compositions etc. are suitably selected from wide region, but in order to obtain water tolerance, especially the coating that wet friction fastness height, film-forming properties and embossed pattern formation property is good, can be 0.5～5 weight % (solids component) of water-borne coatings total amount of the present invention, preferred 1～3 weight %.
Wallpaper use coating of the present invention in order further to improve its good characteristic, can cooperate more than a kind or 2 kinds of high melting point polyethylene wax emulsification, tackifier, nonionogenic tenside, defoamer etc.
High melting point polyethylene wax emulsification mainly contains the metal to-metal contact fastness that helps improve by the formed coating of water-borne coatings of the present invention.And, also have the advantage that does not hinder fibrous monocline crystal class titanium dioxide optical catalyst function.Do not have particular restriction as high melting point polyethylene wax, the ethene polymers that fusing point can be reached weight-average molecular weight 500～10000 usually more than 100 ℃ carries out emulsification to be used.In addition, also can use various commercially available products as high melting point polyethylene wax, for example, can enumerate Mitsui Ha イ ワ Star Network ス (Mitsui Chemicals system), ダ イ ヤ レ Application 30 (Mitsubishi Chemical's systems), day stone レ Network ス Port レ one Le (Nippon Mitsubishi Oil's system), サ Application ワ Star Network ス (Sanyo's system of changing into), Port リ レ Star Star (Chinese essential oil system), ネ オ ワ Star Network ス (ヤ ス Ha ラ ケ ミ カ Le system), ACpolyethylene (ア ラ イ De シ グ Na Le corporate system), エ Port レ Application (イ one ス ト マ Application. ケ ミ カ Le corporate system), ヘ キ ス ト ワ Star Network ス (Network ラ リ ア Application ト corporate system), A-Wax (BASF AG's system), Polywax (ペ ト ロ ラ ト corporate system), trade(brand)name: エ ス コ マ one (エ Network Application Application ケ ミ カ リ corporate system) etc.High melting point polyethylene wax can be used singly or two or more kinds thereof.The use level of high melting point polyethylene wax emulsification as 0.5～3 weight % of solids component for coating total amount of the present invention, is preferably 1～2 weight %.
Tackifier are to use for the film forming characteristics that improves water-borne coatings of the present invention.Can use known tackifier as tackifier, for example, can enumerate the alkali salt etc. that polymerization oils, hydrogenated castor oil, metallic soap class (especially soap classes such as aluminium, lead, rare earth class, calcium, zinc), dimerization acids, high-melting-point such as high polymerized linseed oil are got polyethylene kind, inorganic tackifier (wilkinite, silicon-dioxide etc.), brown alga acids, derivatived cellulose, polyacrylic ester and polymethacrylate beyond the ethylene waxes.Tackifier can be used alone or with two or more.The use level of tackifier does not have particular restriction, and the amount that can suitably select to bring into play its function according to the kind and the use level of other compositions is generally below the 3 weight % of water-borne coatings total amount of the present invention, is preferably 0.5～2 weight %.
Nonionogenic tenside is effective to the wettability that improves fibrous monocline crystal class titanium dioxide.As nonionogenic tenside, available known compound, for example, can enumerate Voranol EP 2001, polyoxyethylene alkyl phenyl ether, the akylarylformaldehyde--condensated Soxylat A 25-7, polyox-yethylene-polyoxypropylene block copolymer, the ether type of polyoxyethylene polyoxy-propylene etc., the Soxylat A 25-7 of glyceryl ester, the Soxylat A 25-7 of sorbitan ester, ether-ethers such as the Soxylat A 25-7 of sorbitol ester, cithrol, glyceryl ester, polyglycerol ester, sorbitan ester, propylene glycol ester, esters such as sucrose ester, fatty acid alkyl amide, the polyoxyethylene fatty amide, nitrogen-containing surfactants such as polyoxyethylene alkyl amine etc.Nonionogenic tenside can be used alone or with two or more.The use level of nonionogenic tenside does not have particular restriction, can suitably select to bring into play the amount of its function according to the kind and the use level of other compositions, but be generally below the 3 weight % of water-borne coatings total amount of the present invention, is preferably 0.5～2 weight %.
Defoamer can improve the defoaming of water-borne coatings of the present invention.Known defoamer can be used as defoamer, for example, the low tensio-active agent of HLB, C can be enumerated
6～C
10Alcohol, pine tar, silicon etc.
In the wallpaper use coating of the present invention, in the scope of not destroying its superperformance, can cooperate the past as more than a kind or 2 kinds of known additives of coating.As this additive, for example, titanium dioxide photocatalyst, anti-flooding agent, anti-color-separated agent, the gas checking of using among organic binder bond in the past or inorganic adhesive, the present invention in addition be can enumerate and agent, emulsifying agent, wetting agent, dispersion agent, pH regulator agent, mineral dye, pigment dyestuff, film coalescence aid, frostproofer, fire retardant, UV light absorber, static inhibitor, inhibitor, mould inhibitor, sterilant, antiseptic-germicide, sanitas etc. prevented.
Wallpaper use coating of the present invention can with general stirrer with water, above-mentioned 3 kinds must composition and as required other compositions mix manufacturing respectively in right amount.
As the wallpaper base material can use known any, for example, can enumerate vellum, glassine paper, tracing paper, Japan paper, casting paper, natural paper oar such as overlay paper paper, impregnated paper, Composite Paper, non-woven fabrics, woven fabrics, cloth, polyvinyl chloride, polyethylene terephthalate, poly-methyl methacrylate acid, polycarbonate, polyolefins (polyethylene, polypropylene, polyisoprene, polybutene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, olefin hydrocarbons thermoplasticity elastic body etc.), modified polystyrene, the shock resistance polystyrene, the plastic sheet material of ABS etc., plasterboard, glued board, particle board etc.Can use these a kind or 2 kinds compoundly used as the wallpaper base material.
These wallpaper base material is with sheet material or plate, and it is known more than a kind or 2 kinds for example to contain Powdered inorganic filling material, softening agent, whipping agent, stablizer, lubricant, pigment, oxidation inhibitor, UV light absorber, fire retardant etc. as required.As Powdered inorganic filling material, for example, can enumerate aluminium hydroxide, magnesium hydroxide, hydrated barta, lime carbonate, magnesiumcarbonate, calcium sulfate, barium sulfate, ferrous hydroxide, alkaline carbonic acid zinc, basic lead white, silica sand, clay, talcum, silicon-dioxide, titanium dioxide, Magnesium Silicate q-agent etc.As softening agent, for example can enumerate phthalic esters such as dioctyl phthalate (DOP), dibutyl phthalate, butyl benzyl phthalate, phosphoric acid ester, chlorination fatty acid ester, clorafin, epoxide, polyester, adipic acid ester etc.As whipping agent, for example, can enumerate azo classes such as azodicarboamide, Diisopropyl azodicarboxylate, hydrazides classes such as tosyl group hydrazides, benzenesulfonyl hydrazides, nitrous base class such as dinitropentamethylenetetramine etc.Stablizer can use with whipping agent, is the additive that the control blowing temperature uses, and can enumerate the complex class of cadmium, barium, zinc mixture etc., plumbous class, tin class, calcium class etc.As lubricant, for example, can enumerate the macrogol ester of paraffin, low molecular weight polycaprolactone alkene, stearic acid, stearate, stearyl alcohol, Vaseline, lipid acid etc.As pigment, for example can enumerate pigment dyestuffs such as azo lake class, quinoline a word used for translation ketone, phthalocyanines, mineral dyes such as chromium titanium, red iron oxide etc.As oxidation inhibitor, for example, can enumerate phenols, Phosphorus, Hinered phenols etc.As UV light absorber, for example, can enumerate benzotriazole category, benzophenone etc.As fire retardant, for example, can enumerate phosphonitrile class, Phosphorus, fluorine-type resin etc.
In addition, among the present invention, between coating that contains photocatalyst and wallpaper base material, can establish the adhesive linkage (grappling coating) that adhesive resin forms, known resin can be used as this adhesive resin, for example, ethylene-vinyl acetate resin (EVA resin) etc. can be enumerated.
When using wallpaper use coating of the present invention to make wallpaper, can adopt known method.For example, with coating composition of the present invention according to coating coatings such as (adopt that blade coating, intaglio plate are coated with, screen cloth is coated with, carve roller coat) flexocoat, coating (adopting roller, spraying, bristle, mop, sponge, the coating of yarn first grade), impregnating known method, be coated on the wallpaper base material of sheet or film like, dry, carry out wallpaper and process with embossing.Also can carry out the foaming or the rill printing (projection printing) of wallpaper base material in the embossing first being processed.In addition, also coating composition of the present invention can be carried out moulding and be processed into film, this pellicular cascade is processed on the wallpaper base material.Stacked processing can be implemented according to known method, for example, utilizes hot-rolling to carry out under 60～200 ℃ temperature.In addition, can also use to melt extrude punch die, T punch die, multilayer extrusion die simultaneously, the glue spread of the coating of Xing Chenging does not have particular restriction like this, can suitably select from wide region, but single face is 2～30g/m usually
2, be preferably 5～20g/m
2About.
For the surface at wallpaper use coating that coating forms of the present invention is formed with the embossed pattern of good dark line, do not need to implement special operation, can pass by general wallpaper to process with embossing.
The wallpaper of the present invention that makes like this is formed with the embossed pattern of dark line on its surface, be rich in ornamental, high-grade texture arranged.Give full play to over simultaneously the photocatalyst function of confirming effect, the decomposability of smelly, the deodorizing performance of especially disappearing, anti-microbial property, organic dirt.
For the surface at wallpaper use coating that coating forms of the present invention is formed with the embossed pattern of good dark line, do not need to implement special operation, can pass by general wallpaper to process with embossing.
Embodiment
Below, enumerate embodiment, comparative example and test example, specifically describe the present invention.
Embodiment 1～8 and comparative example 1～4
1. the manufacturing of wallpaper use coating
Voranol EP 2001 (HLB=10.5 is to call " POE alkyl oxide " in the following text) is dissolved in the water in 1 liter stainless steel vessel with stirrer.Add the titanium dioxide shown in following again, mixed 30 minutes, then add the emulsion and the polyvinyl alcohol water solution of reactive polysiloxane compound, mixed 30 minutes.After using nonionic class tackifier (trade(brand)name: ネ オ ス テ Star カ one N solar corona chemistry is made) to be adjusted to viscosity 4000～5000mPas at last, make wallpaper use coating.
Following each composition of concrete use.In addition, the cooperation ratio (weight part) of each composition is shown in table 1～3.
(1) titanium dioxide
Titanium dioxide A: oblique crystal fibre-like titanium dioxide (trade(brand)name: MTW-500 ， Da mound chemistry system, fiber diameter 0.3 μ m, the long 10 μ m of average fiber, long-width ratio 33)
Titanium dioxide B: oblique crystal fibre-like titanium dioxide (trade(brand)name: MTW-200 ， Da mound chemistry system, fiber diameter 0.1 μ m, the long 3 μ m of average fiber, long-width ratio 30)
Titanium dioxide C: granular titanias (trade(brand)name: ST-01, the former industry system of stone, median size 7nm)
Titanium dioxide D: granular titanias (trade(brand)name: ST-41, the former industry system of stone, averaged particles footpath 0.2 μ m)
(2) emulsion of reactive polysiloxane compound
Polysiloxane emulsion E: contain and use Sodium dodecylbenzene sulfonate, POE alkyl oxide to carry out the polysiloxane emulsion of the about 40 weight % of the about 350000 terminal hydroxyl polydimethylsiloxanes of weight-average molecular weight (Mw) of letex polymerization.
Polysiloxane emulsion F: with above-mentioned polysiloxane emulsion E 700 weight parts, contain SiO
2About 30 weight % and with aqueous colloidal silicon-dioxide 250 weight parts of the proportion 1.21 of sodium ion stabilization, and two lauric acid dioctyl tins, 50 weight parts carry out the blended polysiloxane emulsion.
Polysiloxane emulsion G: the polysiloxane emulsion that contains the about 40 weight % of terminal methyl group polydimethylsiloxane of the weight-average molecular weight (Mw) about 200,000 of using Sodium dodecylbenzene sulfonate, POE alkyl oxide to carry out letex polymerization.
(3) polyvinyl alcohol (being called for short PVA)
PVA aqueous solution H: the polyvinyl alcohol 20 weight % aqueous solution (4% solution viscosity 30mPas) of saponification deg 90%
PVA aqueous solution I: polyvinyl alcohol 20% aqueous solution of saponification deg 75% (4% solution viscosity 15mPas)
Table 1
| Embodiment | ||||
| ??1 | ??2 | ??3 | ????4 | |
| Water | ??450 | ??480 | ??450 | ????460 |
| The POE alkyl oxide | ??10 | ??10 | ??10 | ????10 |
| Titanium oxide A | ??50 | ??100 | ??200 | ????100 |
| Titanium oxide B | ||||
| Polysiloxane emulsification E | ??300 | ??250 | ??200 | ????250 |
| Polysiloxane emulsification F | ||||
| PVA aqueous solution H | ??100 | ??100 | ??100 | |
| PVA aqueous solution I | ????100 | |||
| Nonionic class tackifier | ??90 | ??60 | ??40 | ????80 |
| Dope viscosity (mPas) | ??4500 | ??4800 | ??4400 | ????4000 |
Table 2
| Embodiment | ||||
| ????5 | ????6 | ????7 | ????8 | |
| Water | ????490 | ????470 | ????450 | ????480 |
| The POE alkyl oxide | ????10 | ????10 | ????10 | ????10 |
| Titanium oxide A | ????100 | ????100 | ||
| Titanium oxide B | ????50 | ????100 | ||
| Polysiloxane emulsification E | ????300 | ????250 | ||
| Polysiloxane emulsification F | ????250 | ????250 | ||
| PVA aqueous solution H | ????100 | ????100 | ????100 | |
| PVA aqueous solution I | ????100 | |||
| Nonionic class tackifier | ????50 | ????70 | ????90 | ????60 |
| Dope viscosity (mPas) | ????4500 | ????4100 | ????4600 | ????5000 |
Table 3
| Comparative example | ||||
| ????1 | ????2 | ????3 | ????4 | |
| Water | ????480 | ????480 | ????470 | ????460 |
| The POE alkyl oxide | ????10 | ????10 | ????10 | ????10 |
| Titanium oxide A | ????100 | ????100 | ||
| Titanium oxide B | ||||
| Titanium oxide C | ????100 | |||
| Titanium oxide D | ????100 | |||
| Polysiloxane emulsification E | ????250 | ????250 | ????300 | |
| Polysiloxane emulsification G | ????250 | |||
| PVA aqueous solution H | ????100 | ????100 | ????100 | |
| PVA aqueous solution I | ||||
| Nonionic class tackifier | ????60 | ????60 | ????120 | ????80 |
| Dope viscosity (mPas) | ????4800 | ????4300 | ????4000 | ????4100 |
2. the making of wallpaper
Be provided with at thick 0.125mm discipline state system paper (strain) system wallpaper on the base material of ethylene-vinyl acetate resin (EVA) coating behind Yong Tsuji well formula automatic printing machine screen cloth coating (#700 ベ ) above-mentioned water-borne coatings that makes, predrying (100 ℃ * 1 minute) with body paper, carry out embossing processing at 150 ℃, make wallpaper of the present invention and relatively use wallpaper.
Test example 1
Estimate the various performances of the wallpaper that embodiment 1～8 and comparative example 1～4 make according to method shown below.Be further used as comparative example 5, the wallpaper that is not coated with water-borne coatings is also carried out same performance test with base material.Show the result in table 4～5.
(1) dirt decomposability (armpit look)
Be coated with the ethanolic soln (10ppm) of methylenum coeruleum (MB) with brush, pressing JIS L-0824 shone 63 ℃ * 20 hours 60 ℃ * 1 hour exsiccant test portion with the carbon fadeometer, use ミ ノ Le CM-3700d colour examining machine to measure the test portion b value (blue degree) of UV rayed front and back, formula is calculated armpit colourity calculated as described below.
Armpit colourity (%)=(x/y) * 100
B value after the b value one UV rayed after X:MB is painted
B value before b value one MB after Y:MB is painted is painted
(2) friction fastness
According to JIS L-0849, use and learn vibration shape frictional testing machines, judge the state of dry type friction 25 times, 2 (loading 200g) backs of wet friction coated face.Well: 5 grades～bad: 1 grade.
(3) coating
Whether the visual observation coating time is split (Ha ジ キ) or is coated with irregular etc.
3 grades: evenly coating is not split or is coated with irregular.
2 grades: have slightly and split or be coated with irregular.
1 grade: split or be coated with irregular serious, inhomogeneous.
(4) tear cracking when curved open
Whether visual observation is bent into 180 degree with wallpaper and chaps.The evaluation of be full of cracks is as follows.Moreover, cracking only is shown in the table 3.
3 grades: do not chap fully.
2 grades: chap slightly in the surface.
1 grade: seriously chap.
(5) designability
It is as follows to estimate designability with the clarity of the whiteness on wallpaper surface, embossing processing back and embossed pattern.
Whiteness: with ミ ノ Le CM-3700d colour examining machine, measure Hunter whiteness index (H.W.I), the bigger meaning whiteness of HWI value is higher.
Clarity: carry out visual judgement with following standard.
3 grades: rill is dark, pattern is distinct.
2 grades: rill, pattern are all general.
1 grade: rill is shallow and pattern is not distinct.
(6) photocatalyst coherency
Filter the water-borne coatings made from the #1600 yarn, observe the occurrence degree of titanium dioxide condensation product, estimate as follows.
3 grades: do not produce condensation product fully.
2 grades: produce a small amount of condensation product.
1 grade: produce a large amount of condensation products.
Table 4
| The dirt decomposability | Friction fastness | Coating | |||
| B value armpit colourity | Dry type | Wet type | |||
| Embodiment | ????1 | ????70.5 | ????4-5 | ????4-5 | ????3 |
| ????2 | ????76.6 | ????4-5 | ????4-5 | ????3 | |
| ????3 | ????88.0 | ????4 | ????4 | ????3 | |
| ????4 | ????76.4 | ????4-5 | ????4-5 | ????3 | |
| ????5 | ????76.0 | ????5 | ????5 | ????3 | |
| ????6 | ????76.2 | ????5 | ????5 | ????3 | |
| ????7 | ????70.3 | ????4-5 | ????4-5 | ????3 | |
| ????8 | ????75.6 | ????4-5 | ????4-5 | ????3 | |
| Comparative example | ????1 | (80.8 flavescence) | ????4 | ????4 | ????1 |
| ????2 | ????62.5 | ????4 | ????4 | ????1 | |
| ????3 | ????75.2 | ????3 | ????3 | ????2 | |
| ????4 | ????75.8 | ????2 | ????1 | ????3 | |
| ????5 | ????30.9 | ????1 | ????4 | ????- | |
Table 5
| The look fragility | Designability | The photocatalyst coherency | |||
| ???H.W.I. | Clarity | ||||
| Embodiment | ????1 | ????3 | ????86.1 | ????3 | ????3 |
| ????2 | ????3 | ????88.9 | ????3 | ????3 | |
| ????3 | ????3 | ????91.6 | ????2 | ????3 | |
| ????4 | ????3 | ????88.2 | ????3 | ????3 | |
| ????5 | ????3 | ????88.4 | ????3 | ????3 | |
| ????6 | ????3 | ????88.1 | ????3 | ????3 | |
| ????7 | ????3 | ????86.7 | ????3 | ????3 | |
| ????8 | ????3 | ????88.5 | ????3 | ????3 | |
| Comparative example | ????1 | ????2 | ????83.4 | ????1 | ????1 |
| ????2 | ????2 | ????87.5 | ????1 | ????1 | |
| ????3 | ????1 | ????88.0 | ????2 | ????3 | |
| ????4 | ????1 | ????87.8 | ????1 | ????3 | |
| ????5 | ????- | ????85.4 | ?????- | ????- | |
By table 4～5 as can be seen, wallpaper whiteness of the present invention is than wallpaper height in the past, and because its surface is formed with the embossed pattern of dark line, so demonstrate good ornamental significantly.Conclude photocatalyst functions such as wallpaper dirt decomposability of the present invention in addition.
The coating that forms by wallpaper use coating of the present invention; have with the past contain coating that photocatalyst coating forms identical or than it better in the defencive function, the decomposability of disappear smelly performance, anti-microbial property and organic dirt of dress member; and at the fabulous floral pattern of its surface formation; demonstrate the whiteness height; even it is well ornamental that the reduction of prolonged preservation whiteness also obviously reduces, high-grade texture is arranged.
In addition, of the present inventionly also can form dark and beautiful embossed pattern when containing photocatalyst coating and being used for the polyolefins wallpaper with base material.
Claims (6)
1. a wallpaper use coating is characterized in that, with fibrous monocline crystal class titanium dioxide, reactive polysiloxane compound, and polyvinyl alcohol as effective constituent.
2. the described wallpaper use of claim 1 coating is characterized in that, contains fibrous monocline crystal class titanium dioxide 3～30 weight %, reactive polysiloxane compound 3～30 weight %, and polyvinyl alcohol 0.5～5 weight %.
3. claim 1 or 2 described wallpaper use coating is characterized in that reactive polysiloxane compound is the emulsification of hydroxylation polydiorganosiloxane.
4. claim 1 or 2 described wallpaper use coating is characterized in that the saponification deg of polyvinyl alcohol is 70～100%.
5. a wallpaper is characterized in that, the wallpaper of sheet or film like with base material on the coating that forms by the wallpaper use coating of claim 1 of design.
6. the described wallpaper of claim 5 is characterized in that, the wallpaper base material is the polyolefins base material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP397203/2000 | 2000-12-27 | ||
| JP2000397203A JP4863180B2 (en) | 2000-12-27 | 2000-12-27 | Water-based paint and wallpaper for wallpaper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1489624A true CN1489624A (en) | 2004-04-14 |
| CN1221616C CN1221616C (en) | 2005-10-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01822065 Expired - Fee Related CN1221616C (en) | 2000-12-27 | 2001-12-26 | Water-based coating composition for wall paper and wall paper thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4863180B2 (en) |
| CN (1) | CN1221616C (en) |
| WO (1) | WO2002053657A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2002206073A (en) | 2002-07-26 |
| CN1221616C (en) | 2005-10-05 |
| WO2002053657A1 (en) | 2002-07-11 |
| JP4863180B2 (en) | 2012-01-25 |
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