CN102069607B - Laminating body - Google Patents
Laminating body Download PDFInfo
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- CN102069607B CN102069607B CN2010105292826A CN201010529282A CN102069607B CN 102069607 B CN102069607 B CN 102069607B CN 2010105292826 A CN2010105292826 A CN 2010105292826A CN 201010529282 A CN201010529282 A CN 201010529282A CN 102069607 B CN102069607 B CN 102069607B
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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 the 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 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: JP 2005-90042 communique.
For the problems referred to above, for example put down in writing the coating that forms by the coloring pigment that uses by high reflectance in patent documentation 1, 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 temperature ascending effect, has 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, have screening concurrently hot and transparent, described duplexer show good screening hot in, can also show the Art 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 that the combination based on this metal oxide coated particle is carried out, 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, arbitrary described duplexer according to claim 1～3 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 the Art Designs such as the performance decorative pattern of decorative layer and tone 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 layer 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 known method manufacturing.
The matrix particle is not as long as, for having the material of the transparency, be particularly limited, such as being: mica, glass, sericite, talcum, kaolin, montmorillonite, synthetic phlogopite, synthetic sericite, silica, aluminium oxide, boron nitride etc.Can use wherein more than one.The especially applicable mica of the present invention, glass, synthetic phlogopite.
The shape of matrix particle can be needle-like, spherical, flakey etc., the lepidiod shape of better use.Suitably set in the scope that the size of matrix particle (minor axis and major diameter) can be below the 0.1 above 1mm of μ m (be preferably more than 1 μ m below 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, such as being: 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, and is approximately the following left and right of the above 200nm of 50nm.
The shape of metal oxide coated particle can, for needle-like, spherical, flakey etc., wherein be preferably lepidiod shape.
When the metal oxide coated particle is flakey, its size (minor axis and major diameter) is generally below the 0.1 above 1mm of 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, further be more preferred from the above 100 μ m of 5 μ m following) left and right, its thickness is generally the above 5 μ m of 0.01 μ m following (being preferably the above 1 μ m of 0.05 μ m following) left and right.
In addition, the size of above-mentioned metal oxide coated particle and thickness, can carry out Observe and measure by SEM.
This metal oxide coated particle all has the transparency basically, but the interference effect by the catoptrical path difference based on the reverberation on metal oxide coating layer surface and matrix particle surface can send colour.
Colored form and aspect can be controlled according to the thickness such as the metal oxide coating layer etc.For example, when the thickness of metal oxide coating layer is 90nm～110nm left and right, obtain the reverberation of red colour system; When thickness is 110nm～120nm left and right, obtain the reverberation that aubergine (purple) is; When thickness is 120nm～135nm left and right, obtain the reverberation of blue series; When thickness is 135nm～155nm left and right, 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 with two or more, mixing, 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 relatively low 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.
In the present invention, by this high brightnessization, can obtain having concurrently the hot and transparent hyaline layer of screening.Especially, in order to form the form and aspect of netrual colour,, by making up colored metal oxide coated particle, can further improve effect of the present invention.
Color combinations can from purplish red (purple), blue, blue or green (water colour), green, yellow, orange, to reach the selection such as red two or more.Especially be preferably in 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 blue or green, magenta and yellow etc. 3 kinds 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 the 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 only having a kind of metal oxide coated particle that demonstrates the colored interference look, there will be the form and aspect of the colour that is formed by interference colours, thereby be easy to destroy the decorative pattern of decorative layer and tone etc.In addition, sometimes also can affect the screening hot property.
The hidden power of the metal oxide coated particle of white (silver color) is very high, can not bring into play well decorative pattern and the tone of decorative layer.In addition, also be difficult to obtain hiding fully hot property.
On the other hand, when using two or more common coloring pigment,, by subtractive colour mixture, can not form black, dark form and aspect, make the decorative pattern of decorative layer and tone by fully hidden.
Common coloring pigment exists absorbed wavelength and unabsorbed wavelength in visible-range, unabsorbed wavelength is reflected, thereby can see corresponding form and aspect therewith.For example blue pigment in visible-range, is absorbed by pigment except showing blue wavelength, and the blue wavelength of unabsorbed demonstration is reflected, thereby can see blueness.
When using two kinds of such coloring pigments,, by subtractive colour mixture, become black, dark form and aspect fully.This is that because wavelength in this scope is completely absorbed, so the reflected wavelength range reflected intensity can diminish 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.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 in the whole zone in visible-range, light all is absorbed, and becomes black, dark form and aspect.
In hyaline layer of the present invention, the effect of material is binded in the adhesive performance, as long as can form the coverlay with transparency, its use is not done and is particularly limited.This adhesive is such as being water-soluble resin, water-dispersed resin, solvent-soluble resin, non-aqueous 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 be suitable for the form that comprises water-dispersed resin (synthetic resin emulsifying agent).It (is further 50～300nm) that the averaged particles footpath of synthetic resin emulsifying agent is preferably 30～500nm.
The kind of spendable resin is such as thinking 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 hyaline layer of the present invention, the especially preferably applicable adhesive that comprises acrylic acid composition and silicon composition.The weight rate of acrylic acid composition and silicon composition, be 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,, by the difference of two or more resin refractive indexes, can improve effect of the present invention.
The acrylic acid composition can be by the various acrylic monomers of polymerization, or by the various acrylic monomers of combined polymerization and other monomers, obtain.
acrylic monomers, be for example: 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, 2-Ethylhexyl Methacrylate, 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 made take sodium metasilicate for example, lithium metasilicate, potassium silicate, silicate compound as raw material.Wherein, silicate compound is such as being: 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 5～100nm left and right.
In 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,, due to the difference of acrylic acid composition and silicon composition refractive index, can provide its interface glazing reflex, second, because the silicon composition in coverlay carries out regularly arranged, expanded reflected wavelength range, the 3rd, owing to forming coverlay under the existence at the silicon composition, thereby form little space, make degradation under heat conductivity.Further, also can consider to have given efficient peptizaiton etc. to the metal oxide coated particle.
In addition, in the present invention, comprise the adhesive of acrylic acid composition and silicon composition by use, can prevent hyaline layer produces after for a long time pollution, have good weatherability, suppress the hot line that is caused by pollutant and absorb.
Adhesive in the present invention is the applicable material that comprises acrylic resin emulsifying agent and silica especially preferably.Wherein, the acrylic resin emulsifying agent preferably applicable 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 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 above-mentioned composition, also can mix use with various additives.Additive is such as being: thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, algaecide, 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 as previously mentioned, is to present the interference colours of high brightness by the addition colour mixture that the combination according to the metal oxide coated particle is carried out.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 more high brightness is higher, more low-light level is lower, 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 in the present invention
*Value is more than 35 below 90, is further more than 45 below 80.In this scope, can have a good screening hot, 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 more approaching, 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.
In the present invention, a
*Value and b
*Value, { (a
*)
2+ (b
*)
2}
1/2Being particularly preferably below 30, is further below 20, is further below 15.
The transparency of hyaline layer is to see the degree of 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).In the present invention, hidden rate is particularly preferably below 60%, is further below 50%.
In addition, any one in the brightness of hyaline layer, form and aspect, the transparency can be all the coating material of 40 μ m by be coated with a pair dry film thickness on hidden rate test paper, and dried material is measured as test film.Wherein, for brightness and form and aspect, the foundation of black of using is measured as object.
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, is further the following left and right of the above 0.3mm of 0.02mm.
＜decorative layer 〉
Decorative layer of the present invention, as long as have multi color effect and/or ridge design, its application is not done and is particularly limited.In addition, the multi color effect described in the present invention refers to mix under the vision visible state decorative pattern that has at least two kinds of above colors of color.In addition, ridge design refers to have the approximately surface detail of the difference of height of 0.2～5mm left and right.
This decorative layer is such as being: the thin decoration that the decoration of stone material style is coated with coating of multi-colour pattern, the JISA6909 of material, JISK5667 is coated with material and thick decoration Tu Cai etc. and is coated with by ornamental the decorative layer that material forms.
(the stone material style is decorated and is coated with material)
The stone material style is decorated and is coated with material for forming according to the aggregate color material that is coated with of multi color effect, and its composition is to bind material and aggregate as necessary composition.
Bind material such as being: water-soluble resin, water-dispersed resin, solvent-soluble resin, non-aqueous dispersion type resin, no-solvent type resin, powdex etc., the especially preferably applicable form that comprises water-dispersed resin (synthetic resin emulsifying agent).In addition, the kind of resin is not particularly limited, such as using: 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, usually use the aggregate of particle diameter 0.05～5mm.Described aggregate can preferably use natural aggregates such as crushed material from natural stone, natural stone, and the artificial aggregate such as painted aggregate select at least a more than.Particularly, such as being: marble, imperial 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 the 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, with solid composition 100 weight portions with respect to binding material, is generally 100～4000 weight portions, 150～3000 weight portions, and the ratio that is more preferred from 200～2000 weight portions mixes.The blending ratio of aggregate in this scope, preferably is applicable to form film ornamental, prevents the aspects such as crack.
Can be coated with in material the composition that mixes except above-mentioned by stone material style decoration.This composition is such as being: coloring pigment, extender pigment, thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, algaecide, 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.
In the situation that according to the stone material style, decorate and to be coated with material and to form decorative layer, can use such as, sprayer, roller, trowel, bristle, reciprocating engine, coating machine, pour into the device such as machine, also can overlapping one or more be coated with material and form decorative layer.Decorate and be coated with material by this stone material style, 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 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 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 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 dispersion medium the 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 solvent-soluble resin and/or non-aqueous dispersion type resin, obtain the solvent-borne type pigmented finiss, it is distributed in the aqueous dispersion matchmaker coating of multi-colour pattern that namely becomes oil type in water (O/W type).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 aqueous dispersion matchmaker coating of multi-colour pattern that namely becomes water mid-water type (W/W type).
Coloring pigment in pigmented finiss generally can use the material that can coordinate with coating.particularly, can be for example: 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, molybdic acid is yellow, permanent bordeaux, forever solid purplish red, anthraquinone is red, perylene is red, quinacridone is red, yellow iron oxide, titan yellow, first yellow (First Yellow), benzimidazolone yellow, reddish brown, chrome green, cobalt green, phthalocyanine green, ultramarine, dark purple, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine is purple, aluminium pigment, pearl pigment etc., can use one or more in these.
Can suitably use known additive for coatings in pigmented finiss.This additive is such as being: thickener, coalescents, dye leveller, wetting agent, plasticizer, antifreezing agent, PH conditioning agent, anticorrisive agent, mould inhibitor, algaecide, 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 make method that pigmented finiss disperses etc. in comprising the aqueous dispersion matchmaker of dispersion stabilizer etc.
Dispersion stabilizer is to make pigmented finiss thoroughly stabilize to granular composition, and kind that can corresponding pigmented finiss etc. is selected.Composition that the object lesson of dispersion stabilizer plays a role such as the bridging agent that can think as pigmented finiss etc.This composition is such as using: 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 and adjust with respect to 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, aqueous dispersion matchmaker's viscosity etc.
The particle diameter of look grain is not particularly limited, but be generally 0.01～10mm, (is preferably about 0.1～5mm).
When according to coating of multi-colour pattern, forming decorative layer, can use the devices such as sprayer, roller, bristle.
(thin decoration is coated with the thick decoration of material and is coated with material)
the thin decoration of stipulating in 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, algaecide, 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, with respect to solid composition 100 weight portions that bind material, is generally 1～300 weight portion (being preferably 2～200 weight portions) left and right.
Extender pigment is mainly brought into play the effect of extender, is filming of thick film to be formed the composition of 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, with respect to solid composition 100 weight portions that bind material, is generally 10～1000 weight portions (being preferably 20～500 weight portions) left and right.
Aggregate for example can use with (stone material style decorate be coated with material) in illustrative identical material.The blending ratio of aggregate, with respect to solid composition 100 weight portions that bind material, is generally 10～2000 weight portions (being preferably 30～1500 weight portions) left and right.
This being coated with in material, can form various ridge designs, such as sand wall shape, orange peel shape, fibre wall shape, carefully wavy, plucking (stucco) shape, concavo-convex, month planar, comb draw the 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.
Give method such as the method that can think making gap in decorative layer of thermal insulation etc.For example,, as the ornamental composition that is coated with material,, by with mixing such as hollow-particle and/or Porous particles, can make gap in decorative layer, give thermal insulation, thereby obtain the heat-insulating decorative layer.
Hollow-particle is such as thinking hollow ceramic particle, hollow resin particle etc.Form the ceramic constituents of hollow ceramic particle such as being: water soda glass, aluminosilicate glass, sodium borosilicate glass, coal ash, alumina, white sand, obsidian etc.Form the resin composition of hollow resin particle such as being: acrylic resin, styrene resin, acrylic acid-styrene copolymerized resin, AA-AN copolymerization 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 footpath of hollow-particle is generally 0.1～200 μ m (being preferably 1～150 μ m) left and right.In addition, the density of hollow-particle is generally 0.01～1g/cm
3(be preferably 0.01～0.8g/cm
3) left and right.
The Porous particle is such as being: 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 resin particle etc.Wherein, the Porous resin particle can use the crushed materials such as polyurethane foam, styrenic foams etc.The averaged particles footpath of Porous particle is generally 0.1～5.0mm left and right.In addition, the specific area of Porous particle is preferably 100m
2More than/g.In addition, specific area is the value of measuring by the BET method.
By to decorative layer, giving infrared reflectivity, interact with the infrared reflection effect of hyaline layer, can give more excellent infrared reflectivity, raising hides hot.
Give the method for infrared reflectivity such as thinking method that the above-mentioned ornamental composition that is coated with material is mixed with infrared reflection powder etc. etc., by with infrared reflection powder etc., mixing, can obtain giving the infrared reflection decorative layer of infrared reflectivity.
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, is further the following left and right of the above 5.0mm of 0.1mm.
Further, duplexer of the present invention when having decorative layer and hyaline layer, also can carry out stacked more than optional one deck from thermal insulation layer, infrared-reflecting layers, enhancement Layer.
＜thermal insulation layer 〉
In 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 is such as being formed by the heat-barrier material that comprises hollow-particle and/or Porous particle, bonding material etc.
Hollow-particle, Porous particle, 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, algaecide, 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 the 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, is further the following left and right of the above 5.0mm of 0.1mm.
＜infrared-reflecting layers 〉
In the present invention,, by stacked infrared-reflecting layers, with the infrared reflection effect of hyaline layer, interact, can give more excellent infrared reflectivity, raising hides hot.
Infrared-reflecting layers is such as thinking 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 the 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, algaecide, 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, coloring pigment, extender pigment, aggregate etc. can be mixed ornamental to give, hollow-particle can be mixed and/or the Porous particle gives thermal insulation.
The thickness of infrared-reflecting layers of the present invention, can suitably select according to purposes, is generally below the above 3.0mm of 0.01mm, is further the following left and right of the above 2.0mm of 0.05mm.
＜enhancement Layer 〉
In the present invention, by stacked enhancement Layer, the intensity of raising duplexer, thermal insulation etc., further as described later, while using on being laminated in base substrate, can prevent the duplexer dislocation, performance seal texts.
Cellulosic thin slices such as enhancement Layer can use such as weaving cotton cloth, nonwoven, silk screen etc.
Fiber such as can think, the fiber 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 the 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, better 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 from folded hyaline layer of surperficial concordant, decorative layer, thermal insulation layer, infrared-reflecting layers, enhancement Layer.
(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, form 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 comprise an infrared-reflecting layers that the transparency is arranged between hyaline layer and decorative layer.
The manufacture method of duplexer is not particularly limited, and can adopt wet method, dry method or their combined method suitably to make.Such as can use sprayer, roller, trowel, bristle, reciprocating engine, coating machine, pour into the device such as machine and suitably make, also can be by regulating temperature etc. to promote its sclerosis.
In addition, also can adopt identical method to carry out in infrared-reflecting layers, thermal insulation layer, enhancement Layer suitably stacked.
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 for being 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, such as thinking that plasterboard, glued board, cement, mortar, ceramic tile, fiber 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.
Method at the folded body of base substrate top laminate is not particularly limited, can paste the method for paying on base substrate by engaging material etc., for example can form decorative layer for be coated with pair stacked aforementioned ornamental material that is coated with on base substrate in addition, and then be coated with pair method of stacked aforementioned transparent coating material formation hyaline layer etc. thereon.
Embodiment
Following further clear and definite feature of the present invention shown in example by experiment.
(manufacturing of transparent coating material)
, according to the cooperation shown in table 1,2, adopt usual method evenly to mix each raw material and make transparent coating material.
In addition, 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, mensuration about hidden rate, form and aspect, being coated with on hidden rate test paper with membrane applicator and paying dry film thickness 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 on the black matrix on color colour difference meter " CR-300 " (Minolta Co., Ltd's system) determination test body film and white background on the visual reflection rate of filming calculate hidden rate, calculate L by measuring the visual reflection rate of filming on black matrix
*Value, a
*Value, b
*Value.
Table 1
Table 2
Numeral all represents 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 apply 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, and (400mm * 200mm * 6mm) upper glass nonwoven cloth cover with acrylic acid series cement subsides pair duplexer obtains testing body at slabstone.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 % by 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) hide 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.Take blank (comparative example 10) as 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 compared with the D that is designated as of blank temperature raising, estimate.Result is as shown in table 3.
(embodiment 2～10, comparative example 1～10)
Beyond transparent coating material shown in table 3, use the method identical with embodiment 1 to make the test body, carry out the test identical with embodiment 1.Result is as shown in table 3.
In embodiment 2～10, by the ornamental decoration that is coated with material A clearly, demonstrate good decoration.
In comparative example 1,3, the band adularescent, the ornamental decoration that is coated with material A is fully unclear.
In comparative example 5～9, metal oxide coated particle color separately is identified, and ornamental to be coated with the original color of material fully unclear.
Claims (3)
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, the addition colour mixture of being undertaken by the combination based on this metal oxide coated particle, present the interference colours of high brightness, described adhesive comprises acrylic acid composition and silicon composition, the weight rate of acrylic acid composition and silicon composition is 100: 10～100: 90, described acrylic acid composition is the emulsion acrylic resin with water-disintegrable silicyl, described silicon composition is the silica of particle diameter 1～200nm.
2. duplexer according to claim 1, it is characterized in that: decorative layer has thermal insulation and/or infrared reflectivity.
3. duplexer according to claim 1 and 2, 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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| CN103313853B (en) * | 2011-06-29 | 2016-10-12 | F顾问株式会社 | Laminate |
| 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 |
| US20140162520A1 (en) * | 2011-08-05 | 2014-06-12 | 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 |
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| CN1746236A (en) * | 2005-08-25 | 2006-03-15 | 复旦大学 | High-performance organic-inorganic resin coating material with hybrid acrylic ester and production thereof |
| CN1903950A (en) * | 2004-07-27 | 2007-01-31 | 默克专利股份有限公司 | Mixture of interference pigments |
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| KR100324458B1 (en) * | 1999-12-03 | 2002-02-27 | 하나와 요시카즈 | Coating Structure |
| US9499697B2 (en) * | 2007-10-02 | 2016-11-22 | Ppg Industries Ohio, Inc. | Coating composition and a reflective coating system including same |
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| CN1903950A (en) * | 2004-07-27 | 2007-01-31 | 默克专利股份有限公司 | Mixture of interference pigments |
| CN1746236A (en) * | 2005-08-25 | 2006-03-15 | 复旦大学 | High-performance organic-inorganic resin coating material with hybrid acrylic ester and production thereof |
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| Title |
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| 徐扬群.珠光颜料的制造加工与应用.《珠光颜料的制造加工与应用》.2005, * |
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