CN102069607A - Laminating body - Google Patents
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- CN102069607A CN102069607A CN2010105292826A CN201010529282A CN102069607A CN 102069607 A CN102069607 A CN 102069607A CN 2010105292826 A CN2010105292826 A CN 2010105292826A CN 201010529282 A CN201010529282 A CN 201010529282A CN 102069607 A CN102069607 A CN 102069607A
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Abstract
The invention provides a laminating body simultaneously with the advantages of excellent heat shielding property display and excellent decoration property. The laminating body provided by the invention contains an adhesive and metallic oxide coating particles displaying more than two colorful interference colors and contains a transparent layer and a decorative layer displaying the interference color of high brightness based on the additive color mixture of the metallic oxide coating particle combination.
Description
Technical field
The present invention relates to a kind of novel duplexer.
Background technology
Up to the present, use Chinese whites such as titanium oxide, alumina to hide hot pigment as having always.This Chinese white shows certain reflecting properties at infrared spectral range.
But this Chinese white generally all has higher hidden power.Therefore, use that Chinese white is formed films irrelevantly with the color on basis etc., under many circumstances, all can only form the filming of dullness of an adularescent substantially.
Patent documentation 1: the spy opens the 2005-90042 communique.
At the problems referred to above, for example in patent documentation 1, put down in writing the coating that constitutes by the coloring pigment that uses by high reflectance, not only can form the dull tone of an adularescent, can also produce various colors.
But filming that the technology by patent documentation 1 obtains compared with the screening hot material of Chinese white system, is difficult to obtain good screening thermal effect.
Summary of the invention
The present invention is directed to the problems referred to above, its purpose is to provide a kind of good reflecting properties that has in infra-red range, when performance suppresses on the temperature ascending effect, have the transparency, bring into play basic decorative pattern and tone etc., can give the duplexer of various color.
In addition, for decorative layer gives thermal insulation and/or infrared reflectivity, and then, by stacked thermal insulation layer and infrared-reflecting layers, obtain having the hot and ornamental duplexer of good screening
The present inventor has carried out research with keen determination in order to address the above problem, obtain a kind of duplexer that comprises hyaline layer and decorative layer, wherein hyaline layer obtains by the metal oxide coated particle that makes up two or more display color interference colours, it is hot and transparent to have screening concurrently, described duplexer show good screening hot in, can also show the decoration design of the decorative pattern that can bring into play decorative layer and tone etc., finally realize the present invention.
That is to say, the present invention relates to following duplexer:
1, a kind of duplexer, it is characterized in that comprising decorative layer and hyaline layer, hyaline layer comprises the two or more metal oxide coated particles of adhesive and display color interference colours, by the addition colour mixture of carrying out based on the combination of this metal oxide coated particle, presents the interference colours of high brightness.
2, duplexer according to claim 1 is characterized in that: the adhesive of hyaline layer comprises acrylic acid composition and silicon composition.
3, duplexer according to claim 1 and 2 is characterized in that: decorative layer has thermal insulation and/or infrared reflectivity.
4, according to arbitrary described duplexer in the claim 1～3, it is characterized in that: further by being laminated more than one deck of selecting from thermal insulation layer, infrared-reflecting layers, enhancement Layer.
The invention effect
The present invention be can demonstrate good screening hot in decoration such as the performance decorative pattern of decorative layer and tone design have a good ornamental duplexer.
Further, by giving decorative layer thermal insulation and/or infrared reflectivity, or stacked thermal insulation layer and infrared-reflecting layers, can obtain hiding hot, ornamental good duplexer.
Embodiments of the present invention below are described.
The specific embodiment
Duplexer of the present invention comprises decorative layer and hyaline layer.
＜hyaline layer 〉
Hyaline layer of the present invention is formed by adhesive and transparent coating material, and this transparent coating material comprises the two or more metal oxide coated particle that demonstrates colored interference colours.
The metal oxide coated particle that the present invention uses forms with metal oxide coated matrix particle top layer, interference of light effect by metal oxide coating laminar surface and the reflection of matrix particle surface can be sent colour, and has good infrared reflection effect.This metal oxide coated particle can use the known method manufacturing.
The matrix particle is as long as for having the material of the transparency, be particularly limited, for example can be for: mica, glass, sericite, talcum, kaolin, montmorillonite, synthetic phlogopite, synthesize sericite, silica, aluminium oxide, boron nitride etc.Can use wherein more than one.The present invention especially is suitable for mica, glass, synthetic phlogopite.
The shape of matrix particle can be needle-like, spherical, flakey etc., the lepidiod shape of preferable use.Suitably set in the scope that the size of matrix particle (minor axis and major diameter) can be below the above 1mm of 0.1 μ m (be preferably more than the 1 μ m below the 500 μ m).
This metal oxide in the coating of matrix particle top layer, as long as have high index of refraction, do not limit especially, for example can be titanium dioxide, silica, iron oxide, aluminium oxide, zirconia, cobalt oxide, zinc oxide, tin oxide, chromium oxide, nickel oxide etc.Wherein, preferably be suitable for titanium dioxide.
The thickness of metal oxide coating layer can suitably be set according to the colour that sends, be approximately the above 200nm of 50nm following about.
The shape of metal oxide coated particle can wherein be preferably lepidiod shape for needle-like, spherical, flakey etc.
When the metal oxide coated particle is flakey, its size (minor axis and major diameter) is generally below the above 1mm of 0.1 μ m and (is preferably below the above 500 μ m of 1 μ m, be more preferred from below the above 200 μ m of 2 μ m, it is following further to be more preferred from the above 100 μ m of 5 μ m) about, its thickness is generally about the above 5 μ m of 0.01 μ m following (it is following to be preferably the above 1 μ m of 0.05 μ m).
In addition, the size of above-mentioned metal oxide coated particle and thickness can be observed mensuration by SEM.
This metal oxide coated particle all has the transparency basically, but by the interference effect based on the catoptrical path difference of the reverberation of metal oxide coating laminar surface and matrix particle surface, can send colour.
Colored form and aspect can be controlled according to the thickness of for example metal oxide coating layer etc.For example, when the thickness of metal oxide coating layer is the 90nm～110nm left and right sides, obtain the reverberation of red colour system; When thickness is the 110nm～120nm left and right sides, obtain the reverberation that aubergine (purple) is; When thickness is the 120nm～135nm left and right sides, obtain the reverberation of blue system; When thickness is the 135nm～155nm left and right sides, obtain the reverberation of green system etc.
The feature of hyaline layer of the present invention is to mix to use the two or more metal oxide coated particles that can demonstrate colored interference colours.By mixing with two or more, come from the reverberation overlaid of each metal oxide coated particle, can obtain the interference colours of high brightness by addition colour mixture.
In addition, the connotation of " high brightness " is: during to low relatively other metal oxide coated particles of metal oxide coated mix particles of brightness, compare the state that mixed brightness uprises with the brightness before mixing.
Among the present invention, can obtain having concurrently the hot and transparent hyaline layer of screening by this high brightnessization.Especially in order to form the form and aspect of netrual colour,, can further improve effect of the present invention by making up colored metal oxide coated particle.
Color combinations can from purplish red (purple), blue, blue or green (water colour), green, yellow, orange, to reach selection such as red two or more.Especially be preferably among the present invention and form purplish red (purple) and green, Lan Hehuang, green grass or young crops (water colour) and two kinds of combinations with complementary color relation such as red, perhaps red, green and blue, or 3 kinds of green grass or young crops, magenta and Huangs etc. such as make up at the more form and aspect of netrual colour.
In addition, the metal oxide coated particle has the good transparency, and is also lower than the hidden power of Chinese whites such as titanium oxide, also is difficult to become the reason of filming and worsening.Further, metal oxide coated particle of the present invention has the character that absorbs light hardly and the light that is not reflected is passed through in visible-range.
Therefore, as long as there is two or more metal oxide coated particles, although overlaid between the metal oxide coated particle, the effect by each metal oxide coated particle can improve reflected intensity.
When having only a kind of metal oxide coated particle that demonstrates the colored interference look, the form and aspect of the colour that forms by interference colours can occur, thereby be easy to destroy the decorative pattern of decorative layer and tone etc.In addition, also can influence the screening hot property sometimes.
The hidden power of the metal oxide coated particle of white (silver color) is very high, can not bring into play the decorative pattern and the tone of decorative layer well.In addition, also be difficult to be hidden fully hot property.
On the other hand, when using two or more common coloring pigment,, can not form black, dark form and aspect, make the decorative pattern of decorative layer and tone by hidden fully by subtractive colour mixture.
Common coloring pigment exists absorbed wavelength and unabsorbed wavelength in visible-range, unabsorbed wavelength is reflected, thereby can see corresponding therewith form and aspect.For example blue pigment is absorbed by pigment except that showing blue wavelength in visible-range, and the unabsorbed wavelength of blueness that shows is reflected, thereby can see blueness.
When using two kinds of such coloring pigments,, become black, dark form and aspect fully by subtractive colour mixture.This is because in the absorbing wavelength scope and reflected wavelength range that exist, all have the absorbing wavelength scope in arbitrary coloring pigment in coloring pigment separately, because wavelength is absorbed fully in this scope, so the reflected wavelength range reflected intensity can diminish.For example, during with red pigment and viridine green mixing, because they are the colors with so-called complementary color relation, therefore, red pigment absorbs and demonstrates red wavelength wavelength in addition, and viridine green absorbs the wavelength beyond the wavelength that demonstrates green, therefore, almost light all is absorbed in the whole zone in visible-range, becomes black, dark form and aspect.
The effect of material is binded in the adhesive performance in the hyaline layer of the present invention, as long as can form the coverlay with transparency, it uses does not do special qualification.This adhesive for example is water-soluble resin, water-dispersed resin, the solvable type resin of solvent, non-water-dispersion type resin, no-solvent type resin, powdex etc.Wherein, in the present invention, preferably suitable water dispersion resin and/or water-soluble resin especially preferably are suitable for the form that comprises water-dispersed resin (synthetic resin emulsifying agent).It (further is 50～300nm) that the averaged particles of synthetic resin emulsifying agent directly is preferably 30～500nm.
The kind of spendable resin for example can be silicones, vinyl, vinyl acetate resin, mylar, alkyd resins, ethylene chloride resin, epoxy resin, acrylic resin, polyurethane resin, acrylic silicon resin, acrylated polyurethane resin, fluororesin, cellulose, polyvinyl alcohol, biogum, galactomannans derivative, alginic acid derivative, cellulose derivative etc., or their compound system etc.
Adhesive in the hyaline layer of the present invention especially preferably is suitable for the adhesive that comprises acrylic acid composition and silicon composition.The weight rate of acrylic acid composition and silicon composition is preferably 100: 10 after converting by the solid composition～100: 90, is more preferred from 100: 20～100: 70.As long as use this adhesive,, can improve effect of the present invention by the difference of two or more resin refractive indexes.
The acrylic acid composition can be by the various acrylic monomers of polymerization, or obtain by the various acrylic monomers of combined polymerization and other monomers.
Acrylic monomers for example is: methyl methacrylate, EMA, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, the methacrylic acid n-pentyl ester, the metering system isoamyl valerate, the just own ester of methacrylic acid, methacrylic acid 2-Octyl Nitrite, 2-Propenoic acid, 2-methyl-, octyl ester, decyl-octyl methacrylate, lauryl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid, methacrylic acid methyl amino ethyl ester, dimethylaminoethyl methacrylate, Methacrylamide, N-(2-dimethylaminoethyl) acrylamide, N-(2-dimethylaminoethyl) Methacrylamide, the diacetone Methacrylamide, 2-hydroxyethyl methacry-late, hydroxy propyl methacrylate or methacrylonitrile etc.
The silicon composition can be silica, silicone etc., wherein preferably is suitable for silica.
This silica can be that raw material is made with for example sodium metasilicate, lithium metasilicate, potassium silicate, silicate compound.Wherein, silicate compound for example can be tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, tetraisobutoxy-silicane alkane, four sec-butoxy silane, four tert-butoxy silane, tetraphenoxy-silicane alkane etc. or their condensation product etc.Can use catalyst etc. during fabrication.In addition, can be in manufacture process and after manufacturing, by the metal that comprises in removal catalyst such as ion-exchange treatment etc.The particle diameter of silica is generally 1～200nm, is preferably about 5～100nm.
Among the present invention, the adhesive raising that comprises acrylic acid composition and silicon composition by use hides hot.Its reason it be unclear that, but can consider following situation: first, because the difference of acrylic acid composition and silicon composition refractive index can provide its interface glazing reflex, second, because the silicon composition in the coverlay carries out regularly arranged, expanded reflected wavelength range, the 3rd, owing in the presence of the silicon composition, form coverlay, thereby form little space, make degradation under the heat conductivity.Further, also can consider to have given efficient peptizaiton etc. to the metal oxide coated particle.
In addition, among the present invention, comprise the adhesive of acrylic acid composition and silicon composition by use, can prevent the pollution that hyaline layer produces after for a long time, have good weatherability, the hot line that suppresses to be caused by pollutant absorbs.
Adhesive among the present invention especially preferably is suitable for the material that comprises acrylic resin emulsifying agent and silica.Wherein, the acrylic resin emulsifying agent preferably be suitable for can with the material of silicon dioxde reaction.Particularly, preferably can with the emulsifying agent with (being preferably water-disintegrable silicyl) functional groups such as hydroxy, water-disintegrable silicyls of the silanol radical reaction that exists in the silica.By using this adhesive, can further improve effect of the present invention.
The blending ratio of adhesive and metal oxide coated particle is not particularly limited, but preferably with respect to solid composition 100 weight portions of adhesive, the total amount of metal oxide coated particle is below above 300 weight portions of 0.1 weight portion, be more preferred from below above 200 weight portions of 0.5 weight portion, further be more preferred from below above 100 weight portions of 1.0 weight portions, the best is below above 30 weight portions of 2.0 weight portions.By this blending ratio, be easy to obtain having concurrently the hot and transparent hyaline layer of screening.
Transparent coating material of the present invention as required, except that above-mentioned composition, also can mix use with various additives.Additive for example can be for: thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, anti-algae agent, antiseptic, dispersant, defoamer, adsorbent, fiber, pull out aqua, bridging agent, ultra-violet absorber, delustering agent, antioxidant, catalyst, conditioning agent, low pollutionization agent, fire retardant, do not fire agent etc.In addition, can significantly not damaging in the scope of effect of the present invention, also can comprise the metal oxide coated particle.
Hyaline layer of the present invention is the interference colours that present high brightness by the addition colour mixture of carrying out according to the combination of metal oxide coated particle as previously mentioned.The brightness of hyaline layer can adopt the color colour difference meter to measure, can be by CIE1976L
*a
*b
*L in the colour space
*Value is estimated.That is to say L
*Be worth that high brightness is high more more, low-light level is low more more, by to mixing the L when two or more
*The L of value when only mixing a kind
*Value compares to be estimated.
Be preferably L among the present invention
*Value is more than 35 below 90, further is more than 45 below 80.In this scope, it is hot to have a good screening, the decorative pattern of performance decorative layer and tone etc.
The form and aspect of hyaline layer can be measured by the color colour difference meter, by CIE1976L
*a
*b
*A in the colour space
*Value, b
*Value is estimated.That is to say a
*Value and b
*Value Ga 0 is approaching more, then is be evaluated as the form and aspect of netrual colour more.Particularly, by relatively mixing a when two or more
*Value, b
*The a of value when only mixing a kind
*Value, b
*Value is estimated.
Among the present invention, a
*Value and b
*Value, { (a
*)
2+ (b
*)
2}
1/2Being particularly preferably below 30, further is below 20, further is below 15.
The transparency of hyaline layer is to see the degree of the decorative pattern and the tone of decorative layer.Particularly, the transparency of hyaline layer can be estimated by using the color colour difference meter to measure hidden rate.This mensuration can be carried out based on JISK5600-4-1 " the general test method (hidden power) of coating " method B (hidden rate test paper).Among the present invention, hidden rate is particularly preferably below 60%, further is below 50%.
In addition, each in the brightness of hyaline layer, form and aspect, the transparency can be the coating material of 40 μ m by be coated with a pair dry film thickness on hidden rate test paper all, and dried matter is measured as test film.Wherein, for brightness and form and aspect, measure as object with the foundation of black.
The thickness of hyaline layer of the present invention can suitably be selected according to purposes, but is generally below the above 0.5mm of 0.01mm, further be the above 0.3mm of 0.02mm following about.
＜decorative layer 〉
Decorative layer of the present invention, as long as have multi color effect and/or ridge design, it is used and is not done special qualification.In addition, the multi color effect described in the present invention is meant and mixes the decorative pattern that has at least two kinds of above colors of color under the vision visible state.In addition, ridge design is meant the surface detail with the difference of height about about 0.2～5mm.
This decorative layer for example can be coated with material and thick decoration Tu Cai etc. for the thin decoration that: the decoration of stone material style is coated with coating of multi-colour pattern, the JISA6909 of material, JISK5667 and be coated with the decorative layer that material forms by ornamental.
(the stone material style is decorated and is coated with material)
The stone material style is decorated and is coated with material for forming the material that is coated with of multi color effect according to the aggregate color, and its composition is necessary composition to bind material and aggregate.
Bind material for example can for: water-soluble resin, water-dispersed resin, the solvable type resin of solvent, non-water-dispersion type resin, no-solvent type resin, powdex etc. especially preferably are suitable for the form that comprises water-dispersed resin (synthetic resin emulsifying agent).In addition, the kind of resin is not particularly limited, and for example can use: silicones, vinyl, vinyl acetate resin, mylar, alkyd resins, ethylene chloride resin, epoxy resin, acrylic resin, polyurethane resin, acrylic silicon resin, acrylated polyurethane resin, fluororesin, cellulose, polyvinyl alcohol, biogum, galactomannans derivative, alginic acid derivative, cellulose derivative etc.In addition, they also can be the material that can be built bridge by curing agent and hardening catalyst.
About aggregate, use the aggregate of particle diameter 0.05～5mm usually.Described aggregate can preferably use natural aggregates such as crushed material from natural stone, natural stone, and artificial aggregate such as painted aggregate select at least a more than.Particularly, for example can be for: marble, drive shadow stone, serpentinite, granite, fluorite, gypsum rubrum, feldspar, lime stone, silica, silica sand, rubble, mica, siliceous shale, and their crushed material, pottery chinaware crushed material, ceramic powder mince, glass dust minces, bead, resin-oatmeal mince, resin bead, micelle, clipped wire etc.In addition, can use crushed materials such as shell, coral, timber, carbon, activated carbon.Further, can use by adopting pigment, dyestuff, glaze etc. their surface to be carried out the material etc. of the painted coating of surface-treated.The two or more appropriate combination of carrying out of this aggregate can be used to show various multi color effects.
Aggregate is generally 100～4000 weight portions with respect to solid composition 100 weight portions that bind material, 150～3000 weight portions, and the ratio that is more preferred from 200～2000 weight portions mixes.The blending ratio of aggregate preferably is applicable to form film ornamental in this scope, prevents aspects such as crack.
Can be coated with the composition that mixes in the material except that above-mentioned by stone material style decoration.This composition for example can be for: coloring pigment, extender pigment, thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, anti-algae agent, antiseptic, dispersant, defoamer, adsorbent, fiber, pull out aqua, bridging agent, ultra-violet absorber, delustering agent, antioxidant, catalyst, conditioning agent, low pollutionization agent, fire retardant, do not fire agent etc.In addition, can significantly not damaging in the scope of effect of the present invention, also can mix coloring pigment, extender pigment and aggregate etc.
Be coated with under the situation that material forms decorative layer decorating, for example can using, sprayer, roller, trowel, bristle, reciprocating engine, coating machine, pour into device such as machine, also can overlapping one or more be coated with material and form decorative layer according to the stone material style.Be coated with material by this stone material style decoration, can give various ridge designs.
(coating of multi-colour pattern)
Coating of multi-colour pattern is with the outstanding turbid material that forms in dispersion medium of the look grain more than the aqueous or gelatinous dichromatism.They can be divided into oil type (O/O type) in oil type in (1) water (O/W type), (2) water in oil (w/o type), (3) oil, (4) water mid-water type (W/W type).Wherein, for the coating of multi-colour pattern of oil type in the water (O/W type) and water mid-water type (W/W type), the dispersion medium of each is water-based, and is very satisfactory at aspects such as environment faces.
Look grain in the coating of multi-colour pattern be with comprise the pigmented finiss that binds material and coloring pigment and corresponding required various additives etc. with granular be scattered in the dispersion medium material that forms.
Bind material and for example can use illustrated identical material in (the stone material style is decorated and is coated with material).
In addition, when above-mentioned resin is solvable type resin of solvent and/or non-water-dispersion type resin, obtain the solvent-borne type pigmented finiss, it is distributed to the coating of multi-colour pattern that promptly becomes oil type in the water (O/W type) in the water-based dispersion medium.In addition, when above-mentioned resin is water-soluble resin and/or water-dispersed resin, obtain the water-based pigmented finiss, it is scattered in the coating of multi-colour pattern that promptly becomes water mid-water type (W/W type) in the water-based dispersion medium.
Coloring pigment in the pigmented finiss generally can use the material that can cooperate with coating.Particularly, for example can be titanium oxide, zinc oxide, carbon black, dim, boneblack (bone black), graphite, black iron oxide, copper-chrome black, cobalt black, copper ferromanganese is black, di-iron trioxide, the molybdic acid Huang, permanent bordeaux, solid forever purplish red, the red perylene of anthraquinone is red, quinacridone is red, yellow iron oxide, titan yellow, first yellow (First Yellow), the benzimidazolone Huang, reddish brown, chrome green, cobalt green, phthalocyanine green, ultramarine, dark purple, cobalt blue, phthalocyanine blue, quinacridone violet, the dioxazine purple, aluminium pigment, pearl pigments etc. can use in these one or more.
Can suitably use known coating additive in the pigmented finiss.This additive for example can be for: thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, anti-algae agent, antiseptic, dispersant, defoamer, adsorbent, fiber, pull out aqua, bridging agent, ultra-violet absorber, delustering agent, antioxidant, catalyst, conditioning agent, low pollutionization agent, fire retardant, do not fire agent etc.In addition, can significantly not damaging in the scope of effect of the present invention, also can comprise the metal oxide coated particle.
Be not particularly limited with the granular method that pigmented finiss is disperseed, can adopt known method.Particularly, can adopt and in comprising the water-based dispersion medium of dispersion stabilizer etc., make method that pigmented finiss disperses etc.
Dispersion stabilizer is to make pigmented finiss thoroughly stabilize to particulate constituents, and kind that can corresponding pigmented finiss etc. is selected.The composition that the object lesson of dispersion stabilizer for example can play a role for the bridging agent as pigmented finiss etc.This composition for example can use: epoxies, isocyanic acid salt, amine, alkoxyl silicone alkanes, organic titanate class, aluminium chelate compound class, magnesium salts, calcium salt class, barium salt class, aluminium salt, sodium salt class, sylvite class, borate family, phosphoric acid salt etc.In addition, dispersion stabilizer can use: polyvinyl alcohol, polyacrylic acid, polyethylene oxide, methylcellulose, ethyl cellulose, hydroxyethylcellulose, carboxymethyl cellulose, casein, cellulose acetate phthalic acid ester, bentonite, gelatin, sodium alginate, Arabic gum, agar-agar, xanthans, starch etc.
The particle diameter of look grain and shape can suitably be set.The shape of stirring arm that particularly, can be when making, stirring arm are suitably selected with respect to the viscosity of the adding method of the viscosity of the rotary speed of the size of tank diameter and position, stirring arm, pigmented finiss, dispersion stabilizer and concentration, water-based dispersion medium etc. and are adjusted.
The particle diameter of look grain is not particularly limited, and (is preferably about 0.1～5mm) but be generally 0.01～10mm.
When forming decorative layer, can use devices such as sprayer, roller, bristle according to coating of multi-colour pattern.
(thin decoration is coated with the thick decoration of material and is coated with material)
The thin decoration of stipulating among the JISA6909 is coated with material and thick decoration, and to be coated with material can be with the bonding material, coloring pigment, extender pigment, aggregate, and other mixed agent (thickeners, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, the PH conditioning agent, anticorrisive agent, mould inhibitor, anti-algae agent, antiseptic, dispersant, defoamer, adsorbent, fiber, pull out aqua, bridging agent, ultra-violet absorber, delustering agent, antioxidant, catalyst, conditioning agent, low pollutionization agent, fire retardant, do not fire agent etc.) evenly mix and the material that obtains.
Bind material and for example can use illustrative identical material in (the stone material style is decorated and is coated with material).
Coloring pigment for example can use illustrative identical material in (coating of multi-colour pattern).The blending ratio of coloring pigment is generally about 1～300 weight portion (being preferably 2～200 weight portions) with respect to solid composition 100 weight portions that bind material.
Extender pigment is mainly brought into play the effect of extender, is the composition that filming of thick film is formed the performance practical function.The concrete example of extender pigment is: powdered whiting, slight property calcium carbonate, kaolin, clay, potter's clay, china clay, diatomite, moisture micro mist silicic acid, talcum, blanc fixe, barium sulfate, settleability barium sulfate, brium carbonate, magnesium carbonate, silicon dioxide powder, water aluminium oxide etc.The particle diameter of described extender pigment is generally 50 μ m with interior (being preferably in the above 50 μ m of 0.5 μ m).The blending ratio of extender pigment is generally about 10～1000 weight portions (being preferably 20～500 weight portions) with respect to solid composition 100 weight portions that bind material.
Aggregate for example can use with (stone material style decorate be coated with material) in illustrative identical material.The blending ratio of aggregate is generally about 10～2000 weight portions (being preferably 30～1500 weight portions) with respect to solid composition 100 weight portions that bind material.
This being coated with in the material can form various ridge designs, for example sand wall shape, orange peel shape, fibre wall shape, carefully wavy, plucking (stucco) shape, concavo-convex, month planar, comb draw decorative patterns such as shape, worm food shape.
Decorative layer further can give thermal insulation and/or infrared reflectivity.
By for decorative layer gives thermal insulation, can suppress the heat conduction, the temperature that suppresses the duplexer back side rises, and raising hides hot.
The method that gives thermal insulation for example can be for the method for making the gap in decorative layer etc.For example,,, can in decorative layer, make the gap, give thermal insulation, thereby obtain the heat-insulating decorative layer by with mixing such as hollow-particle and/or porous plasmid as the ornamental composition that is coated with material.
Hollow-particle for example can be hollow ceramic particle, hollow resin particle etc.The ceramic constituents of forming the hollow ceramic particle for example can be water soda glass, aluminosilicate glass, sodium borosilicate glass, coal ash, alumina, white sand, obsidian etc.The resin composition of forming the hollow resin particle for example can be acrylic resin, styrene resin, acrylic acid-styrene copolymerized resin, acrylic acid-acrylonitrile compolymer resin, acrylic acid-styrene-acrylonitrile copolymer resin, acrylonitrile-methacrylonitrile copolymer resin, acrylic acid-acrylonitrile-methacrylonitrile copolymer resin, protochloride vinyl-acrylonitrile compolymer resin etc.Hollow-particle can obtain these composition foaming by adopting known method.The averaged particles of hollow-particle directly is generally about 0.1～200 μ m (being preferably 1～150 μ m).In addition, the density of hollow-particle is generally 0.01～1g/cm
3(be preferably 0.01～0.8g/cm
3) about.
Porous plasmid for example can be silica dioxide gel, zeolite, sodium sulphate, alumina, allophane, diatomite, siliceous shale, sepiolite, attapulgite, montmorillonite, eakleite, imogolite, large space between muscles stone flour, atlapulgite, carbon, activated carbon, wood powder, porous matter resin particle etc.Wherein, porous matter resin particle can use crushed materials such as polyurethane foam, styrenic foams etc.The averaged particles of porous plasmid directly is generally about 0.1～5.0mm.In addition, the specific area of porous plasmid is preferably 100m
2More than/the g.In addition, specific area is the value of measuring by the BET method.
By giving infrared reflectivity to decorative layer, the infrared reflection effect interaction with hyaline layer can give more excellent infrared reflectivity, and raising hides hot.
The method that gives infrared reflectivity for example can be method that the above-mentioned ornamental composition that is coated with material is mixed with infrared reflection powder etc. etc.By mixing, can obtain giving the infrared reflection decorative layer of infrared reflectivity with infrared reflection powder etc.
The infrared reflection powder for example can use: aluminum slice, titanium oxide, barium sulfate, zinc oxide, calcium carbonate, silica, magnesia, zirconia, yittrium oxide, indium oxide, alumina, iron-chromium composite oxides, manganese-bismuth composite oxide, manganese-yttrium composite oxides, manganese-iron-cobalt composite oxide perylene dye, AZOpigments, quinacridone pigment, di-iron trioxide, Zhu, titanium is red, cadmium red, isoindolone, isoindoline, benzimidazolone, phthalocyanine green, phthalocyanine blue, cobalt blue, indanthrene blue, ultramarine, dark purple etc., can use wherein one or more.In addition, also can use aforementioned metal oxide coating particle.
The thickness of decorative layer of the present invention can suitably be selected according to purposes, is generally below the above 10.0mm of 0.05mm, further be the above 5.0mm of 0.1mm following about.
Further, duplexer of the present invention also can carry out stacked from thermal insulation layer, infrared-reflecting layers, enhancement Layer when having decorative layer and hyaline layer more than optional one deck.
＜thermal insulation layer 〉
Among the present invention, by stacked thermal insulation layer, can suppress the heat conduction, the temperature that suppresses the duplexer back side rises, and raising hides hot.
Thermal insulation layer for example can be formed by the heat-barrier material that comprises hollow-particle and/or porous plasmid, bonding material etc.
Hollow-particle, porous plasmid, bonding material can use aforementioned substances etc., in addition, can mix various additives (thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, anti-algae agent, antiseptic, dispersant, defoamer, adsorbent, fiber, pull out aqua, bridging agent, ultra-violet absorber, delustering agent, antioxidant, catalyst, conditioning agent, low pollutionization agent, fire retardant, do not fire agent) and obtain heat-barrier material.
In addition, in addition, can mix coloring pigment, extender pigment, aggregate etc. and give ornamentally, mix the infrared reflection powder and give infrared reflectivity.
In addition, thermal insulation layer can use foamed materials such as polyurethane foam, styrenic foams.
The thickness of thermal insulation layer of the present invention can suitably be selected according to purposes, is generally below the above 10.0mm of 0.05mm, further be the above 5.0mm of 0.1mm following about.
＜infrared-reflecting layers 〉
Among the present invention, by stacked infrared-reflecting layers, the infrared reflection effect interaction with hyaline layer can give more excellent infrared reflectivity, and raising hides hot.
Infrared-reflecting layers for example can be for from comprising the infrared reflection powder and binding the material that forms the infrared reflection material of material etc. etc.
Infrared reflection powder, bonding material can use materials such as aforementioned, in addition, mix various additives (thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, anti-algae agent, antiseptic, dispersant, defoamer, adsorbent, fiber, pull out aqua, bridging agent, ultra-violet absorber, delustering agent, antioxidant, catalyst, conditioning agent, low pollutionization agent, fire retardant, do not fire agent) and can obtain the infrared reflection material.
In addition, it is ornamental to give to mix coloring pigment, extender pigment, aggregate etc., can mix hollow-particle and/or porous plasmid gives thermal insulation.
The thickness of infrared-reflecting layers of the present invention can suitably be selected according to purposes, is generally below the above 3.0mm of 0.01mm, further be the above 2.0mm of 0.05mm following about.
＜enhancement Layer 〉
By stacked enhancement Layer, the intensity of raising duplexer, thermal insulation etc. further as described later, when using, can prevent the duplexer dislocation on being laminated in base substrate among the present invention, effects such as performance seal.
Cellulosic thin slices such as enhancement Layer can for example use and weave cotton cloth, nonwoven, silk screen etc.
Fiber for example can be fibers such as, paper pulp fiber, polyester fiber, polyacrylic fibre, aramid fiber, vinylon fiber, polyethylene fibre, polyarylate fiber, pbo fiber, nylon fiber, acrylic fiber, vinyl chloride fiber, cellulose fibre, asbestos, glass fibre, silicon dioxide fibre, silica-alumina fiber, carbon fiber, silicon carbide fibre and metal fines such as iron, copper etc.
＜duplexer 〉
Duplexer of the present invention comprises decorative layer and hyaline layer, further can be for comprising from duplexers more than three layers more than selection one deck such as thermal insulation layer, infrared-reflecting layers, enhancement Layers.
As long as the stacked composition of this duplexer can obtain effect of the present invention, be not particularly limited, preferable stacked composition is expressed as follows as embodiment.
(embodiment 1)
Embodiment 1 is the duplexer from surperficial stacked above one another hyaline layer, decorative layer.
(embodiment 2)
Embodiment 2 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, thermal insulation layer.
(embodiment 3)
Embodiment 3 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, infrared-reflecting layers.
(embodiment 4)
Embodiment 4 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, enhancement Layer.
(embodiment 5)
Embodiment 5 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, thermal insulation layer, enhancement Layer.
(embodiment 6)
Embodiment 6 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, infrared-reflecting layers, enhancement Layer.
(embodiment 7)
Embodiment 7 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, thermal insulation layer, infrared-reflecting layers.
(embodiment 8)
Embodiment 8 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, infrared-reflecting layers, thermal insulation layer.
(embodiment 9)
Embodiment 9 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, enhancement Layer, infrared-reflecting layers.
(embodiment 10)
Embodiment 10 is from surperficial stacked above one another hyaline layer, decorative layer, thermal insulation layer, enhancement Layer, infrared-reflecting layers and the duplexer that forms.
(embodiment 11)
Embodiment 11 is the duplexers from surperficial stacked above one another hyaline layer, decorative layer, infrared-reflecting layers, enhancement Layer, thermal insulation layer.
(embodiment 12)
Embodiment 12 is the duplexers that form along stacked hyaline layer, decorative layer, thermal insulation layer, infrared-reflecting layers, enhancement Layer from the surface.
(embodiment 13)
Embodiment 13 is from surperficial stacked above one another hyaline layer, decorative layer, infrared-reflecting layers, thermal insulation layer, enhancement Layer and the duplexer that forms.
(embodiment 14)
Embodiment 14 is the duplexers that form from surperficial stacked above one another hyaline layer, decorative layer, enhancement Layer, decorative layer and enhancement Layer.
In addition, embodiment 1～14th forms from surperficial stacked above one another hyaline layer and decorative layer, when decorative layer has the transparency, and also can be from surperficial stacked above one another decorative layer (transparency) and hyaline layer.In addition, also can between hyaline layer and decorative layer, comprise an infrared-reflecting layers that the transparency is arranged.
The manufacture method of duplexer is not particularly limited, and can adopt wet method, dry method or their combined method suitably to make.For example can use sprayer, roller, trowel, bristle, reciprocating engine, coating machine, pour into device such as machine and suitably make, also can be by regulating temperature etc. to promote its sclerosis.
In addition, it is suitably stacked also can to adopt identical method to carry out in infrared-reflecting layers, thermal insulation layer, the enhancement Layer.
Duplexer of the present invention, external except the building civil structure, also can preferably be applicable to household electrical appliances vehicle etc., for example can be used to be layered in base substrate.
About base substrate, get final product so long as can be used for the material of building civil structure body, household electrical appliances vehicle etc., be not particularly limited, for example can sneak into cement plate, cement calcium silicate board, rock ballast cement perlite plate, ALC plate, side plate, be extruded into template, steel plate, plastic plate, plank, glass plate, Polypropylence Sheet, film etc. for plasterboard, glued board, cement, mortar, ceramic tile, fiber.
Method at the folded body of base substrate top laminate is not particularly limited, can on base substrate, paste the method for paying by engaging material etc., for example can form decorative layer in addition, and then be coated with pair method of stacked aforementioned transparent coating material formation hyaline layer etc. thereon on base substrate, being coated with pair stacked aforementioned ornamental material that is coated with.
Embodiment
Following further clear and definite feature of the present invention shown in the example by experiment.
(manufacturing of transparent coating material)
According to the cooperation shown in the table 1,2, adopt usual method evenly to mix each raw material and make transparent coating material.
In addition, the hidden rate and the form and aspect of each transparent coating material are as follows.
Transparent coating material A:L
*Value: 49.9, a
*Value: 1.1, b
*Value :-11.3, { (a
*)
2+ (b
*)
2}
1/2: 11.4, hidden rate: in 50%
Transparent coating material B:L
*Value: 50.3, a
*Value: 1.5, b
*Value :-12.3, { (a
*)
2+ (b
*)
2}
1/2: 12.3, hidden rate: in 50%
Transparent coating material C:L
*Value: 63.3, a
*Value: 1.0, b
*Value :-10.7, { (a
*)
2+ (b
*)
2}
1/2: 10.7, hidden rate: in 50%
Transparent coating material D:L
*Value: 51.9, a
*Value: 1.7, b
*Value :-3.5, { (a
*)
2+ (b
*)
2}
1/2: 3.9, hidden rate: in 50%
Transparent coating material E:L
*Value: 50.2, a
*Value :-0.3, b
*Value :-8.4, { (a
*)
2+ (b
*)
2}
1/2: 8.4, hidden rate: in 50%
Transparent coating material F:L
*Value: 49.7, a
*Value: 1.4, b
*Value: 0.8, { (a
*)
2+ (b
*)
2}
1/2: 1.6, hidden rate: in 50%
Transparent coating material G:L
*Value: 67.7, a
*Value: 0.5, b
*Value :-10.0, { (a
*)
2+ (b
*)
2}
1/2: 10.0, hidden rate: in 50%
Transparent coating material H:L
*Value: 67.9, a
*Value: 0.2, b
*Value :-10.3, { (a
*)
2+ (b
*)
2}
1/2: 10.3, hidden rate: in 50%
Transparent coating material I:L
*Value: 68.0, a
*Value: 0.1, b
*Value :-10.4, { (a
*)
2+ (b
*)
2}
1/2: 10.4, hidden rate: in 50%
Transparent coating material J:L
*Value: 68.1, a
*Value :-0.2, b
*Value :-9.5, { (a
*)
2+ (b
*)
2}
1/2: 9.5, hidden rate: in 50%
Transparent coating material K:L
*Value: 44.8, a
*Value: 1.4, b
*Value :-5.0, { (a
*)
2+ (b
*)
2}
1/2: 5.2, hidden rate: in 50%
Transparent coating material L:L
*Value: 38.7, a
*Value :-0.4, b
*Value :-1.4, { (a
*)
2+ (b
*)
2}
1/2: 1.5, hidden rate: in 50%
Transparent coating material M:L
*Value: 81.7, a
*Value :-1.7, b
*Value :-3.5, { (a
*)
2+ (b
*)
2}
1/2: 3.9, hidden rate: more than 50%
Transparent coating material N:L
*Value: 50.1, a
*Value :-2.2, b
*Value :-5.6, { (a
*)
2+ (b
*)
2}
1/2: 6.0, hidden rate: in 50%
Transparent coating material O:L
*Value: 31.3, a
*Value: 21.3, b
*Value :-17.4, { (a
*)
2+ (b
*)
2}
1/2: 27.5, hidden rate: in 50%
Transparent coating material P:L
*Value: 31.3, a
*Value: 4.4, b
*Value :-27.5, { (a
*)
2+ (b
*)
2}
1/2: 27.8, hidden rate: in 50%
Transparent coating material Q:L
*Value: 45.4, a
*Value :-13.6, b
*Value: 0.3, { (a
*)
2+ (b
*)
2}
1/2: 13.6, hidden rate: in 50%
Transparent coating material R:L
*Value: 48.7, a
*Value :-2.5, b
*Value: 21.5, { (a
*)
2+ (b
*)
2}
1/2: 21.6, hidden rate: in 50%
Transparent coating material S:L
*Value: 36.5, a
*Value: 15.6, b
*Value: 1.8, { (a
*)
2+ (b
*)
2}
1/2: 15.7, hidden rate: in 50%
Transparent coating material T:L
*Value: 21.5, a
*Value: 0.2, b
*Value: 0.8, { (a
*)
2+ (b
*)
2}
1/2: 0.8, hidden rate: in 50%
In addition, about the mensuration of hidden rate, form and aspect, being coated with a pair dry film thickness with membrane applicator on hidden rate test paper is each transparent coating material of 40 μ m, under 23 ℃ of temperature, humidity 50%RH (hereinafter referred to as: " standard state ") keep forming in 48 hours and test body;
By use film on the black matrix on color colour difference meter " CR-300 " (Minolta Co., Ltd's system) the determination test body and white background on the visual reflection rate of filming calculate hidden rate, calculate L by measuring the visual reflection rate of filming on the black matrix
*Value, a
*Value, b
*Value.
Table 1
Table 2
Numeral is all represented weight portion.
Table 3
(embodiment 1)
At glass nonwoven (thickness 0.4mm, level ground amount 50g/m
2) on, coating 5.0kg/m
2The ornamental material A that is coated with further applies 0.1kg/m
2Transparent coating material A, drying is 60 minutes under 80 ℃, obtains duplexer (thickness of decorative layer: 3.5mm, the thickness of hyaline layer: 40 μ m).
Resulting duplexer is downcut 400mm * 200mm, at slabstone (400mm * 200mm * 6mm) upward paste the glass nonwoven cloth cover of paying duplexer to obtain testing body with the acrylic acid series cement.The decoration of resulting test body, decorative layer (the ornamental material A that is coated with) clearly has good ornamental.
The ornamental material A that is coated with: acrylic resin emulsifying agent (solid composition 50 weight %) 200 weight portions, water 150 weight portions, painted aggregate (yellow is painted silica sand: the painted silica sand of red colour system=50: 50 (weight ratio), average grain diameter 50～500 μ m) 600 weight portions, double glazing particle (average grain diameter 40 μ m, density 0.45g/cm
3) 4 weight portions, thickener 5 weight portions, dispersant 2 weight portions, defoamer 5 weight portions
In addition, resulting test body is carried out following test.
(1) hides hot test
To resulting test body, (250W) shines from the distance of 40cm with infrared lamp, shines the temperature of using the contact tehermometer determination test body back side after 1 hour.With blank (comparative example 10) be benchmark, with temperature minimum be designated as A, below order be designated as A ', B, B ', C, C ', and more do not change with blank or estimate compared with the D that is designated as of blank temperature raising.The result is as shown in table 3.
(embodiment 2～10, comparative example 1～10)
Beyond the transparent coating material shown in the table 3, use the method identical to make the test body, carry out the test identical with embodiment 1 with embodiment 1.The result is as shown in table 3.
Among the embodiment 2～10, by the ornamental decoration that is coated with material A clearly, demonstrate good decoration.
In the comparative example 1,3, have white, the ornamental decoration that is coated with material A is unclear fully.
In the comparative example 5～9, metal oxide coated particle color separately is identified, and ornamental to be coated with the original color of material unclear fully.
Claims (4)
1. duplexer, it is characterized in that comprising decorative layer and hyaline layer, hyaline layer comprises the two or more metal oxide coated particles of adhesive and display color interference colours, by the addition colour mixture of carrying out based on the combination of this metal oxide coated particle, presents the interference colours of high brightness.
2. duplexer according to claim 1 is characterized in that: the adhesive of hyaline layer comprises acrylic acid composition and silicon composition.
3. duplexer according to claim 1 and 2 is characterized in that: decorative layer has thermal insulation and/or infrared reflectivity.
4. according to arbitrary described duplexer in the claim 1～3, it is characterized in that: further by being laminated more than one deck of selecting from thermal insulation layer, infrared-reflecting layers, enhancement Layer.
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| CN2010105292826A CN102069607B (en) | 2009-10-27 | 2010-10-22 | Laminating body |
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| CN200910207062 | 2009-10-27 | ||
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| WO2013020261A1 (en) * | 2011-08-05 | 2013-02-14 | Construction Research & Technology Gmbh | Water-proof coating system for reflecting solar radiation and water-borne coating for forming decorative and reflective layer in coating system |
| CN103313853A (en) * | 2011-06-29 | 2013-09-18 | F顾问株式会社 | Laminate body |
| JP2014529517A (en) * | 2011-08-05 | 2014-11-13 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハーＣｏｎｓｔｒｕｃｔｉｏｎ Ｒｅｓｅａｒｃｈ ＆ Ｔｅｃｈｎｏｌｏｇｙ ＧｍｂＨ | Waterproof coating system for reflecting solar radiation and aqueous coating for forming decorative and reflective layers in the coating system |
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| JP2014529517A (en) * | 2011-08-05 | 2014-11-13 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハーＣｏｎｓｔｒｕｃｔｉｏｎ Ｒｅｓｅａｒｃｈ ＆ Ｔｅｃｈｎｏｌｏｇｙ ＧｍｂＨ | Waterproof coating system for reflecting solar radiation and aqueous coating for forming decorative and reflective layers in the coating system |
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