CN107615117A - Optical reflectance coating - Google Patents

Abstract

Present invention offer is a kind of in the optical reflectance coating with the index layer containing water-soluble resin, and film failure is few, even if being used during long, crack produces also few optical reflectance coating.A kind of optical reflectance coating, it has base material and dielectric substance multilayer film, the dielectric substance multilayer film is configured on a surface of the base material, and formed by low-index layer and high refractive index layer alternative stacked, at least 1 layer in the low-index layer and the high refractive index layer is the layer containing water-dispersible hydrophobic resin, and the layer containing water-dispersible hydrophobic resin is containing water-soluble resin and relative to the water-dispersible hydrophobic resin that gross mass is 5~55 mass %.

Description

Optical reflectance coating

Technical field

The present invention relates to a kind of optical reflectance coating.

Background technology

In general, it is known that adjust the blooming of high refractive index layer and low-index layer respectively and them is stacked in base Material surface and the dielectric substance multilayer film formed, optionally reflect the light of specific wavelength.This dielectric substance multilayer film example Such as utilized as the window or vehicle part optical reflectance coating that are arranged at building.This optical reflectance coating makes luminous ray Through and optionally shield near infrared ray, only by adjusting the thickness or refractive index of each layer, reflection wavelength can be controlled, can be with Ultraviolet or visible ray are reflected.

Forming method as laminated body as dielectric substance multilayer film, it is however generally that, useful dry type film method is folded The method of layer, but many manufacturing costs are needed in the formation using the dielectric substance multilayer film of dry type film method, therefore be impracticable 's.As the method for practicality, for example, utilize wet mode to containing water-soluble resin and metal oxide grain The coating fluid of the mixture of son is coated to carry out the method for lamination.Particularly from the aspect of cost, preferably by simultaneously Double-layer be coated with high refractive index layer with coating fluid and low-index layer with coating fluid come the method that manufactures.

Form multilayer by being coated to the coating fluid containing water-soluble resin however, it is known that having and make them folded In the laminated body that layer forms, the adsorption/desorption of moisture easily occurs.Caused by the adsorption/desorption by moisture each layer shrink, Repetition is expanded, through crack can be produced after a while.

In order to improve the water resistance of the laminated body containing water-soluble resin, such as in Japanese Unexamined Patent Publication 2012-973 publications It is open that there are as below methods：Crosslinking agent is set to be contained in coating fluid, by making water solubility on mutual interface between adjacent layer Resin and cross-linking agents, so that interlayer is closely sealed and suppresses being mixed into for moisture.

The content of the invention

The technical problems to be solved by the invention

Such as above-mentioned Japanese Unexamined Patent Publication 2012-973 publications, by the way that crosslinking agent, Ke Yiti are applied in combination in water-soluble resin The water resistance of high laminated body.But in method described in Japanese Unexamined Patent Publication 2012-973 publications, due in coating solution The crosslinking agent of remained unreacted after drying, therefore, by the crosslinking agent through when react and caused by producing the solidify afterwards of film Shrink.Its result is learnt, the generation in crack when in high humidity environment is exposed on long-time, can be more deteriorated.In order to not anti- The mode that the crosslinking agent answered does not remain is reacted the high temperature, it is necessary to nearly 100 DEG C, because the temperature exceedes the glass of resin base material Change transition temperature, therefore be unpractical.

Therefore, the present invention is to complete in view of the foregoing, its object is to a kind of, there is provided optical reflectance coating, its In optical reflectance coating with the index layer containing water-soluble resin, film failure is few, even if being used during long, the production in crack It is raw also few.

For solving the technical scheme of technical problem

The present inventor etc. are above-mentioned in order to solve the problems, such as, have made intensive studies, and as a result distinguish：By using following proposal And realize the purpose of the present invention.

That is, above-mentioned technical problem of the invention solves by following method.

1. a kind of optical reflectance coating, it has base material and dielectric substance multilayer film,

The dielectric substance multilayer film is configured on a surface of the base material, and by low-index layer and high refractive index layer Alternative stacked forms,

At least 1 layer in the low-index layer and the high refractive index layer is to contain water-dispersible hydrophobic resin Layer, the layer containing water-dispersible hydrophobic resin are 5~55 mass %'s containing water-soluble resin and relative to gross mass Water-dispersible hydrophobic resin.

2. the optical reflectance coating as described in above-mentioned 1., wherein, the layer containing water-dispersible hydrophobic resin also contains Anionic surfactant, the water-dispersible hydrophobic resin are anionic emulsion resin.

3. the optical reflectance coating as described in above-mentioned 1. or 2., wherein, in the dielectric substance multilayer film, with contacting the base The superiors of the opposite side in the side of material are the layer containing water-dispersible hydrophobic resin.

4. such as the optical reflectance coating any one of above-mentioned 1.~3., wherein, in the dielectric substance multilayer film, with institute It is the layer containing water-dispersible hydrophobic resin to state the orlop that base material is in contact.

5. such as the optical reflectance coating any one of above-mentioned 1.~4., wherein, the superiors of the dielectric substance multilayer film And orlop is low-index layer, whole low-index layers is the layer containing water-dispersible hydrophobic resin.

6. such as the optical reflectance coating any one of above-mentioned 1.~5., wherein, it is described to contain water-dispersible hydrophobic tree The average degree of polymerization of the water-soluble resin of the layer of fat is 4000~6000.

7. the manufacture method of the optical reflectance coating as described in above-mentioned 2., it includes：Make water-soluble resin, anionic surface Activating agent and anionic emulsion resin are dissolved or dispersed in aqueous solvent to prepare the stage of coating fluid；

The stage of the layer containing water-dispersible hydrophobic resin is formed by being coated with the coating fluid.

Embodiment

Hereinafter, embodiments of the present invention are illustrated.

The mode of the present invention is a kind of optical reflectance coating, and it has base material and dielectric substance multilayer film, the dielectric substance Multilayer film is configured on a surface of the base material, and formed by low-index layer and high refractive index layer alternative stacked, described At least 1 layer in low-index layer and the high refractive index layer is the layer containing water-dispersible hydrophobic resin, described to contain water The layer of dispersed hydrophobic resin is containing water-soluble resin and relative to the water-dispersible hydrophobic that gross mass is 5~55 mass % Resin.

According to the present invention, a kind of optical reflectance coating is can obtain, it is in the light with the index layer containing water-soluble resin Learn in reflectance coating, film failure is few, even if being used during long, the generation in crack is also few.

The optical reflectance coating of the present invention contains water at least one index layer in high refractive index layer and low-index layer Soluble resin.Here, as described above, in the optical reflectance coating containing water-soluble resin, exist through that can produce after a while The problem of crack.

Therefore, the present inventor etc. is studied the crack (cracking) of optical reflectance coating, is as a result found：By with it is water-soluble Property resin be used together the water-dispersible hydrophobic resin of specified amount, it is possible to reduce the expansion of index layer, shrink, it is possible to reduce Through when crack produce.When water-dispersible hydrophobic resin is added in water-soluble resin, resin generation is fusible to be carried out making film When, compared with being added without the situation of water-dispersible hydrophobic resin, it can obtain the strong film of hydrophobicity.It is therefore contemplated that it can reduce Atmosphere moisture amount change caused by film expansion, shrink, accordingly it is possible to prevent the generation in crack.Further, since contain There are emulsion resin, coated film softness, therefore film failure can be reduced.It is especially considering that by anionic surfactant It is combined with anionic water-dispersible hydrophobic resin, in the stability in the coating fluid of water-dispersible hydrophobic resin Rise, suppress that cohesion etc. locally occurs during dried coating film, can further reduce film failure.

Here, relative to the gross mass (solid constituent quality) of the layer containing water-dispersible hydrophobic resin, moisture is dissipated The content of property hydrophobic resin is set to 5~55 mass %, and can obtain excellent crack prevents effect.In addition, film event can be reduced Barrier.When the content of water-dispersible hydrophobic resin is less than 5 mass %, water-dispersible hydrophobic resin it is mutual it is fusible tail off, nothing Method fully obtains the effect of the present invention.On the other hand, when the content of water-dispersible hydrophobic resin is more than 55 mass %, easily Hole is formed with water-soluble resin, film mist degree easily rises.In addition, the content of water-dispersible hydrophobic resin is more than 55 matter When measuring %, in water-based coating, especially while the viscosity of coating fluid is produced when double-layer is coated with to be reduced.Therefore, it is not easy to be formed uniformly Film, easily produce through when crack.In addition, also easily produce film failure.Also, because the viscosity of coating fluid reduces, Index layer mixes each other, easily produces mist degree.It is preferred that the content of water-dispersible hydrophobic resin is relative to containing moisture The gross mass for dissipating the layer of property hydrophobic resin is 10~40 mass %, more preferably 10~30 mass %.Use two or more Water-dispersible hydrophobic resin when, they, which are adjusted, makes its total amount in above range.Dissipated with more than 2 layers containing moisture During the layer of property hydrophobic resin, the content of at least 1 layer water-dispersible hydrophobic resin is whole in above range, but more preferably Layer be above range.

Hereinafter, the inscape of the optical reflectance coating of the present invention is described in detail.It should be noted that it is following, In the case of not distinguished to low-index layer and high refractive index layer, it is referred to as " index layer " as comprising both concepts.

In addition, in this specification, represent scope " X~Y " means " more than X below Y ".In addition, as long as no special theory Bright, the measure such as operation transitivity is carried out under conditions of room temperature (20~25 DEG C), relative humidity 40~50%.

[optical reflectance coating]

The optical reflectance coating of the present invention has base material and dielectric substance multilayer film, and the dielectric substance multilayer film is by low-index layer Formed with high refractive index layer alternative stacked, and the dielectric substance multilayer film is configured on a surface of the base material.

[base material]

The optical reflectance coating of the present invention contains the base material for supporting dielectric substance multilayer film etc..As base material, can use Various resin films, polyolefin film (polyethylene, polypropylene etc.), polyester film (polyethylene terephthalate can be used (PET), PEN etc.), polyvinyl chloride, cellulose triacetate etc., preferably polyester film.As polyester film (hereinafter referred to as polyester), is not particularly limited, the tool preferably using dicarboxylic acid component and diol component as main constituent There is the polyester of film formative.

As the dicarboxylic acid component of main constituent, can enumerate：Terephthalic acid (TPA), M-phthalic acid, adjacent benzene two Formic acid, 2,6 naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acids, diphenyl sulfone dicarboxylic acids, diphenyl ether dicarboxylic acids, diphenylethane dicarboxyl Acid, cyclohexane dicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfide dicarboxylic acids, diphenylketone dicarboxylic acids, phenyl indane dicarboxylic acid Deng.In addition, as diol component, can enumerate：Double (the 4- hydroxyls of ethylene glycol, propane diols, butanediol, cyclohexanedimethanol, 2,2- Phenyl) propane, 2,2- double (4- hydroxyethoxyphenyls) propane, double (4- hydroxy phenyls) sulfones, bisphenol fluorene di-hydroxyethylether, diethyls Glycol, neopentyl glycol, hydroquinones, cyclohexane diol etc..In the polyester using these materials as main constituent, from saturating Bright property, mechanical strength, dimensional stability etc. consider, as dicarboxylic acid component, as terephthalic acid (TPA) or 2,6- naphthalene dicarboxyl Acid, diol component, the polyester preferably using ethylene glycol or 1,4-CHDM as main constituent.Wherein, preferably with Polyethylene terephthalate or PEN are for the polyester of main constituent or by terephthaldehyde Copolyester that acid, 2,6 naphthalene dicarboxylic acid and ethylene glycol are formed and using the mixture of more than two kinds of these polyester as main structure Into the polyester of composition.

The thickness of base material used in the present invention is preferably 10~300 μm, particularly preferably 20~150 μm.In addition, base Material can be to overlap with the base material of 2, in this case, its species is identical or different.

For base material, the transmitance of the visible region shown in JIS R3106-1998 is preferably more than 85%, especially Preferably more than 90%.It is more than above-mentioned transmitance by base material, is shown when that stack membrane will be made by JIS R3106-1998 The transmitance of visible region be set to more than the 50% (upper limit：100%) aspect is favourable, therefore it is preferred that.

It in addition, the use of the base material for having above-mentioned resin etc. can be unstretching film, or stretched film.From improve intensity, From the aspect of suppressing thermal expansion, preferred stretched film.

Base material can be manufactured by known in general method.For example, by using extruder to as material Resin is melted, and is extruded and be quenched using annular die or T die heads, and it is essentially amorphous so as to not have that can manufacture There is the non-stretched base material of orientation.Furthermore it is possible to using uniaxial tension, stenter formula, gradually biaxial stretch-formed, stenter formula is simultaneously Method known to biaxial stretch-formed, tubular type simultaneously biaxial drawing etc., to non-stretched base material, along flowing (longitudinal axis) direction of base material, Or the direction of (transverse axis) vertical with the flow direction of base material is stretched and manufactures stretching base material.The stretching ratio of the situation can be with It is consistent with the resin as substrate material suitably to be selected, but be preferably respectively 2~10 times along y direction and X direction.

[dielectric substance multilayer film]

Dielectric substance multilayer film has the structure that alternately lamination low-index layer and high refractive index layer form, and has at least 1 The individual unit formed by low-index layer and high refractive index layer.Because dielectric substance multilayer film is containing so having different refractivity Index layer structure, in the case where the light (such as infrared light) with specified wavelength is incident, can at least reflect the light A part so as to playing shield effectiveness (and being effect of heat insulation in the case of infrared light).

In the manner, the index layer for forming dielectric substance multilayer film is low-index layer, or is high refractive index layer, according to Contrasted and judged with the refractive index of adjacent index layer.Specifically, when certain index layer being set into datum layer, If refractive index is low compared with datum layer with the index layer of datum layer adjoining, it is high refractive index layer to be judged as datum layer (adjoining course is low-index layer).On the other hand, compared with datum layer, if the refractive index of adjoining course is high, on the basis of judging Layer is low-index layer (adjoining course is high refractive index layer).Therefore, index layer is high refractive index layer or is low-index layer, is The relative height that relation between the refractive index having with adjoining course is determined, certain index layer is according between adjoining course Relation, may be high refractive index layer, it is also possible to be low-index layer.

As index layer, at least 1 layer refraction in the high refractive index layer and low-index layer of dielectric substance multilayer film is formed As long as layer of the rate layer containing water-dispersible hydrophobic resin, the layer containing water-dispersible hydrophobic resin contains water Soluble resin and relative to the index layer gross mass be 5~55 mass % water-dispersible hydrophobic resin, without spy Do not limit, the known index layer used in the technical field can be used.As known index layer, such as from manufacture From the viewpoint of efficiency, preferably using the index layer formed using film by wet method.

Also, from the viewpoint of reflection characteristic, preferably at least one of high refractive index layer and low-index layer layer contains Both layers of metal oxide particle, more preferably high refractive index layer and low-index layer contain metal oxide particle.

In addition, as described above, the present invention optical reflectance coating dielectric substance multilayer film in, in high refractive index layer and low folding Penetrate and water-soluble resin is used at least one kind of layer of rate layer.In addition, the refractive index of the optical reflectance coating formed using film by wet method Layer is preferably that the film that coating is formed has been carried out to the coating fluid (usually containing the water solvents such as water) containing water-soluble resin.By In water-soluble resin without using organic solvent, therefore, carrying capacity of environment is few, in addition, flexibility is high, therefore, film is durable during bending Property improve, therefore preferably.Water-soluble resin particularly contains at least one kind of layer of high refractive index layer and the low-index layer It is preferably used in the case of metal oxide particle.

It should be noted that " water solubility " means in this specification：At a temperature of material most dissolves, it is dissolved in water and makes When it is 0.5 mass % concentration, in the case where being filtered with G2 glass filters (maximum 40~50 μm of pore), it is separated by filtration Insoluble matter quality for addition high molecular 50 mass % within.

It is that the relation between adjacent index layer is determined as described above, being low-index layer or high refractive index layer Relative height, certain index layer may be that low-index layer may be high refractive index layer, below, to that can use respective method The composition of typical high refractive index layer and low-index layer illustrates in the index layer of formation.

(high refractive index layer)

High refractive index layer preferably comprises water-soluble resin.In addition, metal oxide particle, solidification can be contained as needed Agent, surfactant, other additives.It should be noted that by water-soluble resin and metal contained in high refractive index layer It is referred to as " the 1st water-soluble resin " and " the 1st metal oxide particle " individually below on oxide particle is convenient.

Now, the refractive index of the 1st metal oxide particle 2nd metal oxygen contained preferably than in low-index layer described later The refractive index of compound particle is high.By containing metal oxide particle, Ke Yizeng in high refractive index layer and/or low-index layer Refringence between big each index layer, by reducing lamination number, can improve the transparency of film, therefore preferably.In addition, deposit In advantages below：Play stress abirritation, improve film physical property (bendability when during bending and hot and humid) etc..Metal aoxidizes As long as thing particle contains in any index layer, but preferable mode is that at least high refractive index layer contains metal oxidation Thing particle, preferred mode are that high refractive index layer and low-index layer contain metal oxide particle.

(1) the 1st water-soluble resin

As the 1st water-soluble resin, it is not particularly limited, polyvinyl alcohol resin, gelatin, cellulose family, increasing can be used Mucopolysaccharide and the polymer with reactive functional groups.Wherein, preferably using polyvinyl alcohol resin.

Polyvinyl alcohol resin

As the polyvinyl alcohol resin, can enumerate common poly- obtained from polyvinyl acetate is hydrolyzed Vinyl alcohol (unmodified polyethylene alcohol), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, anion-modified polyvinyl Alcohol, vinyl alcohol are birdsed of the same feather flock together the modified polyvinylalcohols such as compound.It should be noted that sometimes with modified polyvinylalcohol to the closely sealed of film Property, water resistance, flexibility are improved.

Gelatin

As gelatin, can be applicable in the past can be widely used various bright in silver halide photographic sensitive material field Glue.For example,：Acid treatment gelatin；Alkali treated gelatin；The ferment treatment that ferment treatment is carried out in the manufacturing process of gelatin is bright Glue；Have in the molecule as the amino of functional group, imino group, hydroxyl, carboxyl, and the examination for the group that can be reacted with having Agent has carried out gelatine derivative obtained from handling and being modified etc..

It should be noted that in the case of using gelatin, the hard coat agent of gelatin can be added as needed on.

Cellulose family

As cellulose family, it is preferable to use water miscible cellulose derivative.For example,：Carboxymethyl cellulose The water solubility such as plain (cellulose carboxyl methyl ether), methylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose Cellulose derivative；The cellulose families containing carboxylic acid group such as carboxymethyl cellulose (cellulose carboxyl methyl ether), carboxy ethyl cellulose； The cellulose derivatives such as NC Nitroncellulose, cellulose-acetate propionate, cellulose acetate, cellulose sulfuric acid ester.

Viscosify polysaccharide

The polymer that polysaccharide is carbohydrate is viscosified, there are multiple hydrogen bond bases in intramolecular.The thickening polysaccharide is caused due to temperature Intermolecular hydrogen bonding is made a concerted effort difference, the larger characteristic of differences in viscosity during viscosity and high temperature when having low temperature.In addition, in thickening polysaccharide During middle addition metal oxide particle, cause and be considered viscosity in low temperature and caused by the hydrogen bonding of its metal oxide particle Rise.For its viscosity ascensional range, viscosity at 15 DEG C is usually more than 1.0mPas, preferably 5.0mPas with On, more preferably more than 10.0mPas.

As usable thickening polysaccharide, it is not particularly limited, commonly known natural holosaccharide, natural compound can be enumerated Polysaccharide, synthesis holosaccharide, synthesis complex polysaccharide.On the detailed of these polysaccharide, " biochemical dictionary (second edition), east are referred to Capital chemistry is published with people ", " food industry " the 31st volumes page (1988) 21 etc..

Polymer with reactive functional groups

As the polymer with reactive functional groups, for example,：PVP class；Polypropylene Acid, AA-AN copolymerization thing, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylate copolymer, propylene The acrylic resins such as acid-acrylate copolymer；Styrene-acrylic copolymer, Styrene-methyl Acrylic Acid Copolymer, Styrene-t-acrylate copolymer, styrene-α-methylstyrene-acrylic copolymer, styrene-α-first The styrene acrylics such as base Styrene And Chloroalkyl Acrylates-acrylate copolymer；Styrene-styrene sodium sulfonate copolymers, Styrene -2- hydroxyethylmethacry,ates copolymer, styrene -2- hydroxyethylmethacry,ates-styrene sulfonic acid potassium copolymer, Styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-Malaysia Acid copolymer；Vinyl acetate-maleate copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic The vinyl acetate such as copolymer lipin polymer and their salt.Wherein, preferably using PVP class and it is contained Copolymer.

Above-mentioned water-soluble resin can be used alone, and can also mix two or more and use.

The weight average molecular weight of 1st water-soluble resin is preferably 1000~200000, and more preferably 3000~40000.Need Illustrate, in this specification, the value of " weight average molecular weight " uses the value measured using gel permeation chromatography (GPC).

Relative to the mass % of solid state component 100 of high refractive index layer, the content of the 1st water-soluble resin is preferably 5~50 matter Measure %, more preferably 10~40 mass %.

(2) the 1st metal oxide particles

As the 1st metal oxide particle, it is not particularly limited, preferred index is 2.0~3.0 metal oxide grain Son.Specifically, can enumerate：Titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, colloidal alumina, lead titanates, red lead, chrome yellow, Zinc chromate, chromium oxide, iron oxide, iron oxide black, cupric oxide, magnesia, magnesium hydroxide, strontium titanates, yittrium oxide, niobium oxide, europium oxide, Lanthana, zircon, tin oxide etc..Wherein, from the viewpoint of transparent and high refractive index high refractive index layer is formed, the 1st metal Oxide particle is preferably titanium oxide, zirconium oxide, from the viewpoint of weatherability is improved, more preferably rutile-type (regular crystal Shape) titanium oxide.

In addition, titanium oxide can be the mode that the core-shell particle that cladding forms is carried out with siliceous hydrous oxide.Should Core-shell particle has following structure：As core Titanium particles surface by as the shell bag comprising siliceous aqua oxidation Cover.The volume average particle size of the Titanium particles as core segment now is preferably more than 1nm and is less than 30nm, more preferably Less than more than 4nm 30nm.By containing this core-shell particle, passing through the siliceous hydrous oxide and water-soluble resin of shell Interaction, the interlayer mixing of high refractive index layer and low-index layer can be suppressed.

The 1st above-mentioned metal oxide particle can be used alone, and can also mix two or more and use.

For the content of the 1st metal oxide particle, from the viewpoint of becoming big with the refringence of low-index layer, Relative to the mass % of solid constituent 100 of high refractive index layer, more preferably preferably 15~80 mass %, 20~77 mass %, More preferably 30~75 mass %.

In addition, the volume average particle size of the 1st metal oxide particle is preferably below 30nm, more preferably 1~30nm, enter One step is preferably 5~15nm.When volume average particle size is below 30nm, mist degree is few and visible light permeability is excellent, therefore preferably. It should be noted that in this specification, the value of " volume average particle size " uses the value determined by following method.It is specific and Speech, is observed with any 1000 particles in section or surface of the electron microscope to appearing in index layer and determines grain Footpath, being respectively present n1, n2 in the particle of the particle diameter respectively with d1, d2 ... di ... dk ..., ni ... nk metals aoxidize In the group of thing particle, in the case where the volume of every 1 particle is set into vi, volume average particle size is calculated using following formula (mv)。

[mathematical expression 1]

Mv={ ∑ (vidi)/(∑ (vi)) }

(3) curing agent

Curing agent has the 1st water-soluble resin (being preferably polyvinyl alcohol resin) reaction with containing in high refractive index layer And form the function of the network of hydrogen bond.

As curing agent, as long as curing reaction occurs with the 1st water-soluble resin, it is not particularly limited, it is however generally that, Can enumerate with can from water-soluble resin react group compound or promote water-soluble resin with different groups that This compound reacted.

As concrete example, in the case where using polyvinyl alcohol resin as the 1st water-soluble resin, preferably using boric acid And its salt is as curing agent.Further, it is possible to use the known curing agent beyond boric acid and its salt.

It should be noted that boric acid and its salt mean the oxyacid and its salt of the atom centered on boron atom.Specifically, Ortho-boric acid, hypoboric acid, metaboric acid, tetraboric acid, five boric acid, eight boric acid and their salt can be enumerated.

Relative to the mass % of solid state component in high refractive index layer 100, the content of curing agent is preferably 1~10 mass %, more Preferably 2~6 mass %.

Total usage amount of curing agent during especially with polyvinyl alcohol resin as 1 water-soluble resin, preferably phase It is 1~600mg for polyvinyl alcohol resin 1g, is 10~600mg more preferably relative to polyvinyl alcohol resin 1g.

Surfactant

As surfactant, it is not particularly limited, can enumerates：Amphoteric ionic surfactant, cationic table Face activating agent, anionic surfactant, anionic surfactant, fluorine class surfactant and silicon class surface-active Agent.Wherein, acrylic surfaces activating agent, silicon class surfactant or fluorine class surfactant can be used.As surface-active Agent, the surfactant of chain alkyl is preferably comprised, the surfactant of the alkyl more preferably with carbon number 6~20.

As amphoteric ionic surfactant, can enumerate：Alkyl betaine, alkyl amine oxide, coconut oleoyl amine third Base glycine betaine, lauroylamidopropyl betaine, palm kernel oil fatty acid amide propyl glycine betaine, cocoyl both sexes acetic acid Na, the moon Osmanthus acyl both sexes guanidine-acetic acid Na, dodecanamide propyl hydroxy betaines, dodecanamide propyl amine oxide, myristamide propyl group amine Oxide, hydroxy alkyl (C12-14) hydroxyethyl methyl amimoacetic acid.

As cationic surface active agent, alkylamine salt, quaternary ammonium salt can be enumerated.

Anionic surfactant be hydrophilic group ionize in aqueous be anion surfactant, as the moon from Subtype surfactant, it can enumerate：Sulfuric acid, sulfonate, carboxylate, phosphate ester salt etc..Such as alkylsurfuric acid can be used Ester salt, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene aryl ether sulfuric acid, alkylbenzenesulfonate, soap, polyoxy Vinyl alkyl ether phosphate, alkenyl succinic acid dipotassium.As commercially available anionic surfactant, such as sulfuric ester Salt, it can enumerate：The EMAL (registration mark) of Kao Corp's manufacture, the HITENOL (notes of the first Industrial Co., Ltd manufacture Volume trade mark) NF-08, HITENOL NF-0825, HITENOL NF-13, HITENOL NF-17 (be polyoxyethylene styrene Phenyl ether ammonium sulfate) etc., as sulfonate, NEOPELEX (registration mark), the PELEX of Kao Corp can be enumerated (registration mark).As carboxylate, the NEO-HITENOL (registration mark) of Di-ichi Kogyo Seiyaku Co., Ltd. can be enumerated, As phosphate ester salt, PLYSURF (registration mark) of Di-ichi Kogyo Seiyaku Co., Ltd. etc. can be enumerated.In the present invention, from From the viewpoint of the Combination of liquid, preferably sulfuric acid or sulfonate.

As nonionic surface active agent, can enumerate：Polyoxyethylene alkyl ether (such as Kao Corp's system Emulgen (registration mark)), polyoxyethylene sorbitan fatty acid ester (such as Kao Corp RHEODOL (registration Trade mark) TW series), fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine, alkyl chain triacontanol acid amides.Or Person, as polyoxyethylene alkyl ether, polyoxyethylene single 2-ethyl hexyl ether, polyoxyethylene decyl ethers (such as the first work can be used Industry Pharmaceutical Co., Ltd Noigen (registration mark) XL-40, NoigenXL-50, NoigenXL-60 etc.).

As fluorine class surfactant, can enumerate：SURFLON S-211、SURFLON S-221、SURFLON S- 231st, SURFLON S-241, SURFLON S-242, SURFLON S-243, S-420 (AGC SEIMI CHEMICAL strain formula meetings Society's system), MEGAFACE F-114, MEGAFACE F-410, MEGAFACE F-477, MEGAFACE F-553 (Dainippon Ink Chemicals System), MEGAFACE FC-430, MEGAFACE FC-4430, MEGAFACE FC-4432 (3M societies system).

As silicon class surfactant, can enumerate：BYK-345、BYK-347、BYK-348、BYK-349(BYK- Chemie Japan Co. Ltd. systems).

High refractive index layer can contain other additives.As other additives, amino acid, lithium compound can be enumerated Deng.Further, it is possible to use Japanese Unexamined Patent Application 57-74193 publications, Japanese Unexamined Patent Application 57-87988 publications, Japanese Unexamined Patent Application Ultra-violet absorber described in 62-261476 publications；Japanese Unexamined Patent Application 57-74192 publications, Japanese Unexamined Patent Application 57- No. 87989 publications, Japanese Unexamined Patent Application 60-72785 publications, Japanese Unexamined Patent Application 61-146591 publications, Japanese Unexamined Patent Publication 1- Anti-fading agent described in No. 95091 publications, Japanese Unexamined Patent Publication 3-13376 publications etc.；Japanese Unexamined Patent Application 59-42993 public affairs Report, Japanese Unexamined Patent Application 59-52689 publications, Japanese Unexamined Patent Application 62-280069 publications, Japanese Unexamined Patent Application 61-242871 public affairs Fluorescent whitening agent described in report, Japanese Unexamined Patent Publication 4-219266 publications etc.；Sulfuric acid, phosphoric acid, acetic acid, citric acid, hydroxide The pH adjusting agents such as sodium, potassium hydroxide, potassium carbonate；Defoamer；The lubricants such as diethylene glycol；Preservative；Mould inhibitor；Antistatic agent； Delustering agent；Heat stabilizer；Antioxidant；Fire retardant；Nucleating Agent；Inorganic particulate；Organic filler；Viscosity reductant；Lubricant；Infrared ray Absorbent；Pigment；Various additives etc. known to pigment etc. are used as other additives.

(low-index layer)

In addition, low-index layer preferably comprises water-soluble resin.Further according to need can contain metal oxide particle, Curing agent, surfactant, other additives.It should be noted that by water-soluble resin contained in low-index layer and It is referred to as " the 2nd water-soluble resin " and " the 2nd metal oxide particle " individually below on metal oxide particle is convenient.

(1) the 2nd water-soluble resin

As the 2nd water-soluble resin, the material same with the 1st water-soluble resin can be used.

Now, high refractive index layer and low-index layer use as the 1st water-soluble resin and the 2nd water-soluble resin In the case of polyvinyl alcohol resin, respectively preferably using the different polyvinyl alcohol resin of saponification degree.Thus, interface is suppressed Mixing, reflectivity (such as infrared reflectivity (infrared shielding rate)) become better, and mist degree can step-down.It should be noted that this " saponification degree " means (to be derived from the thing of the vinyl acetate of raw material relative to the propionyloxy in polyvinyl alcohol resin in specification Matter) and hydroxyl total hydroxyl ratio.

Relative to the mass % of solid state component in low-index layer 100, the content of the 2nd water-soluble resin is preferably 3~60 matter Measure %, more preferably 10~45 mass %.

(2) the 2nd metal oxide particles

As the 2nd metal oxide particle, it is not particularly limited, preferably using synthesis non-crystalline silica, colloidal state two The silica such as silica (silica), more preferably using acid colloidal silica sol.In addition, rolled over from more reducing Penetrate from the viewpoint of rate, as the 2nd metal oxide particle, can use and have cuniculate hollow minute particle in the inside of particle, Particularly preferably use the hollow minute particle of silica (silica).

Cataloid can be that cation-modified material has been carried out to its surface, alternatively, it is also possible to be with Al, The material that Ca, Mg or Ba etc. are handled.

In addition, the 2nd metal oxide particle can be coated to composition using surface carries out surface coating.

The average grain diameter of the 2nd contained metal oxide particle (preferably silica) in the low-index layer of the present invention (number is average；Diameter) it is preferably 3~100nm, more preferably 3~50nm.It should be noted that in this specification, with regard to metal Oxide particle " (number is average for average grain diameter；Diameter) " for, in itself or refraction appeared in particle with electron microscope The section of rate layer or the particle on surface are observed, and determine the particle diameter of 1,000 Arbitrary Particles, (individual as its simple average value Number is average) obtain.Here, the particle diameter of respective particle is represented with the diameter for assuming the bowlder equal with its projected area.

Relative to the mass % of total solid content 100 of low-index layer, the 2nd metal oxide particle in low-index layer Content be preferably 0.1~70 mass %, more preferably 30~70 mass %, more preferably 45~65 mass %.

It can be used alone from viewpoint, the 2nd above-mentioned metal oxides such as adjustment refractive indexes, 2 kinds can also be combined Use above.

Curing agent, surfactant, other additives

As curing agent, surfactant, other additives, the material same with high refractive index layer can be used, therefore, In this description will be omitted.

(layer containing water-dispersible hydrophobic resin)

The optical reflectance coating of the present invention is as described above, in the high refractive index layer and low-index layer of composition dielectric substance multilayer film At least 1 layer be the layer containing water-dispersible hydrophobic resin containing water-soluble resin and water-dispersible hydrophobic resin, phase For the gross mass (solid state component quality) of the layer containing water-dispersible hydrophobic resin, contain 5~55 mass % (solids Composition quality) water-dispersible hydrophobic resin.

As long as water dispersible of the layer containing water-dispersible hydrophobic resin containing water-soluble resin and specified amount The layer of hydrophobic resin, can be high refractive index layer, or low-index layer.Dredged as described containing water dispersible The layer of water-base resin, in addition to containing water-dispersible hydrophobic resin described later with specified amount, it can use and be rolled over above-mentioned height Penetrate rate layer and the same technical scheme of low-index layer.In general, water-dispersible hydrophobic resin is that (1.5 is left for low-refraction It is right), therefore, in the case where remaining not fusible water-dispersible hydrophobic resin, it is possible to due to the refraction of high refractive index layer Rate and cause mist degree to rise, therefore, the layer containing water-dispersible hydrophobic resin is preferably low-index layer.

In addition, as long as the optical reflectance coating of the present invention is formed in the high refractive index layer and low-index layer of dielectric substance multilayer film At least 1 layer be the layer containing water-dispersible hydrophobic resin, the orlop preferably to connect with base material or opposite with base material The superiors of side are the layer containing water-dispersible hydrophobic resin.Further preferably described orlop and the whole of the superiors Low-index layer be the layer containing water-dispersible hydrophobic resin.

Water-dispersible hydrophobic resin

Water-dispersible hydrophobic resin suitable for the present invention is the hydrophobic polymer for being scattered in aqueous solvent in optics The resin for carrying out deposition during the film forming of the index layer in the manufacturing process of reflectance coating and being formed.

The water-dispersible hydrophobic resin can be emulsion resin.Emulsion resin is in an aqueous medium with resin emulsion State is dispersed with the resin particle that small such as average grain diameter is less than 2.0 μm, is made using dispersants such as macromolecule dispersing agents Oil-soluble monomer carries out emulsion polymerization and obtained.

It oil-soluble monomer can be used to be not particularly limited, can enumerate：Ethene, propylene, butadiene, vinyl acetate and Its partial hydrolystate, vinyl ethers, acrylicacidandesters class, methacrylic acid and its esters, acrylamide and its derivative, first Base acrylamide and its derivative, styrene, divinylbenzene, vinyl chloride, vinylidene chloride, maleic acid, vinyl pyrrolidone, The diisocyanates such as 1,6- hexamethylene diisocyanates, Polyisocyanate esters, glycols, polyalcohols, omega-dicarboxylic acids etc..

In addition, workable dispersant is not particularly limited, for example, alkylsulfonate, alkylbenzenesulfonate, diethyl The so low molecular dispersant of amine, ethylene diamine, quaternary ammonium salt, in addition, can be enumerated：Ethylene nonyl phenyl ether, gather Ethoxyethylidene laurate ether, hydroxy ethyl cellulose, macromolecule dispersing agent as PVP.

As the resin of above-mentioned carry out emulsion polymerization, for example,：Acrylic resin, styrene-butadiene Resin, vinyl acetate resins, polyurethane resin, phenolic resin, acrylate etc..

As emulsion resin, commercially available emulsion resin can be used, for example,：Mowinyl 718A、 Mowinyl 710A, Mowinyl 731A, Mowinyl LDM7582, Mowinyl 5450, (the Japan's synthesis of Mowinyl 6960 Chemical industry Co., Ltd. manufacture), SUPERFLEX (registration mark) 150,170,300,500M (the first industrial pharmaceutical strain formula meetings Society manufacture), ADEKA BONTIGHTER HUX-232, HUX-380, HUX-386, HUX-830, HUX-895 (Co., Ltd. ADEKA manufacture), AE-116, AE-120A, AE-200A, AE-336B, AE-981A, AE-986B (E. TEC Co., Ltd's manufacture), ETERNACOLLUW-1005E, UW-5002, UW-5034E, UE-5502 (Ube Industries, Ltd's manufacture) and UV curable Silicone-Acrylic Polymer(アクリット)UW-309、UV curable Silicone-Acrylic Polymer(アクリット)UW-319SX、UV curable Silicone-Acrylic Polymer(アクリット)UW-520 (manufacture of great achievement fine chemistry Co., Ltd.) etc..

Anionic emulsion resin, cation type emulsion resin, the equal of anionic emulsion resin are used as emulsion resin And use, but in the layer containing water-dispersible hydrophobic resin in the optical reflectance coating of the present invention, preferably by anionic Emulsion resin is applied in combination with anionic surfactant.

Think due to making inorganic particulate as metal oxide particle, water-soluble resin and surfactant-dispersed In the coating fluid that aqueous solvent forms, anionic emulsion resin is added, is further made using anionic surfactant For surfactant, the structural viscosity of coating fluid stabilizes, and dispersity becomes rising that is good and suppressing viscosity.As a result, Film failure, the film failure of special fine strip shape are significantly improved, the yield of product can be greatly improved.

Here, as anionic emulsion resin, preferably using Polyurethane Emulsion of Negative-ion Type resin, anionic third Olefin(e) acid class emulsion resin, anionic Styrene And Chloroalkyl Acrylates copolymer emulsion resin etc.., can as anionic surfactant To use material similar to the above.

The particle diameter of emulsion resin is not particularly limited, and average grain diameter is preferably 1~100nm, more preferably 5~60nm.It is logical Crossing emulsion resin has above-mentioned average grain diameter, reduces the obtained mist degree of optical reflectance coating, can improve the transparency.Emulsion resin Average grain diameter can be measured using dynamic light scattering method.

The refractive index of emulsion resin is it is not also specifically limited, preferably 1.3~1.7, more preferably 1.4~1.6.If Above range, then close to the refractive index of water-soluble resin, therefore, the obtained mist degree of optical reflectance coating can be reduced.

For above-mentioned emulsion resin, from the viewpoint of flexibility is improved, glass transition temperature (Tg) is preferably Less than 20 DEG C, more preferably -30~10 DEG C.

Metal oxide particle

Layer containing water-dispersible hydrophobic resin can contain metal oxide particle.Metal oxide particle can be used The material same with above-mentioned high refractive index layer and low-index layer.

Water-soluble resin

The layer containing water-dispersible hydrophobic resin in the optical reflectance coating of the present invention contains water-soluble resin.As water Soluble resin, the material same with above-mentioned high refractive index layer and low-index layer can be used.

It is preferred that the average degree of polymerization of water-soluble resin in the layer containing water-dispersible hydrophobic resin for 1500~ 6000, more preferably 4000~6000.The average of water-soluble resin in the layer containing water-dispersible hydrophobic resin gathers Right more preferably 4000~5000, it is still more preferably 4500~5000.If the average polymerization of water-soluble resin Spend for more than 1500, then in the case of using double-layer rubbing method is coated simultaneously, water-soluble resin can also be suppressed Spread and produce mist degree.In addition, if the average degree of polymerization of water-soluble resin is less than 6000, then the viscosity of coating fluid will not mistake In rise, therefore, suitable for the making of the dielectric substance multilayer film carried out based on coating.Contain water-dispersible hydrophobic tree with multilayer In the case of the layer of fat, the average polymerization of the water-soluble resin in preferably at least 1 layer of layer containing water-dispersible hydrophobic resin Spend for above range, the average degree of polymerization of the water-soluble resin in more preferably whole layers containing water-dispersible hydrophobic resin For above range.

In addition, the water-soluble resin in the layer containing water-dispersible hydrophobic resin is preferably polyvinyl alcohol tree Fat.Thus, the dispersiveness stabilisation of water-dispersible hydrophobic resin, can suppress the rising of mist degree.The soap of polyvinyl alcohol resin Change degree is, for example, 70~99.5 moles of %, and from the viewpoint of further suppression mist degree, preferably 80~95 moles of % are more excellent Elect 85~90 moles of % as.It should be noted that the average degree of polymerization of water-soluble resin is viscosity average polymerization degree, polyvinyl alcohol The average degree of polymerization of resinoid can be with JIS JISK6726：It is measured on the basis of 1994.

Also, the preferred embodiment of the present invention is forms in the index layer of dielectric substance multilayer film, with contacting base material The superiors of the opposite side of side are the layer containing water-dispersible hydrophobic resin.It is more preferably now described to be dissipated containing moisture Property hydrophobic resin layer in water-soluble resin average degree of polymerization be 4000~6000.It is described to contain water-dispersible hydrophobic The average degree of polymerization of water-soluble resin in the layer of resin is more preferably 4000~5000, still more preferably for 4500~ 5000.Now, as long as the layer containing water-dispersible hydrophobic resin contains anionic emulsion resin and anionic table Face activating agent, then it can significantly more obtain the effect of the present invention.

As described above, in the optical reflectance coating of the present invention, as long as forming the high refractive index layer of dielectric substance multilayer film and low At least 1 layer in index layer is the layer containing water-dispersible hydrophobic resin, but the superiors' example of dielectric substance multilayer film It is such as Nian Jie with glass matrix via adhesive layer and as optical reflector in use, moisture in generation environment is adsorbed, taken off Expansion from caused layer, when shrinking, caused stress is easily concentrated therewith.Therefore, the weatherability of optical reflectance coating is being improved Aspect, the absorption of the moisture in the superiors' configuration can suppress environment, the layer containing water-dispersible hydrophobic resin departed from are Effectively.

In the case of making dielectric substance multilayer film by being coated with the coating fluid containing water-soluble resin, if water-soluble tree The average degree of polymerization of fat is, for example, more than 1500, is preferably more than 4000, then is applied even in using double-layer rubbing method simultaneously In the case of cloth, water-soluble resin diffusion can also be suppressed and produce mist degree.In addition, if the average degree of polymerization of water-soluble resin For less than 6000, then the viscosity of coating fluid does not raise excessively, therefore, suitable for the system of the dielectric substance multilayer film carried out based on coating Make.More preferably the average degree of polymerization of water-soluble resin is 4000~5000, more preferably 4500~5000.

In addition, in index layer of the embodiment of present invention further optimization for composition dielectric substance multilayer film, with base The orlop that material connects is the layer containing water-dispersible hydrophobic resin.In generation environment moisture absorption, depart from caused by Layer expansion, shrink when, the orlop of dielectric substance multilayer film compared with the layer of inner side easily concentrate therewith by caused stress Layer, it is therefore preferable that orlop is set into the layer containing water-dispersible hydrophobic resin.More preferably the superiors and undermost it is Layer containing water-dispersible hydrophobic resin.Now, as long as the layer containing water-dispersible hydrophobic resin contains anion Type emulsion resin and anionic surfactant, then it can significantly more obtain the effect of the present invention.

The preferred embodiment of the present invention is the superiors of the dielectric substance multilayer film and orlop is low-index layer, Whole low-index layers are the layer containing water-dispersible hydrophobic resin.So, Jie for having water-soluble resin is being used In electric body multilayer film, it can further reduce with the variation of the amount of moisture in environment and the absorption of moisture occurs, departs from, because This, is exposed to the generation in crack when under high humidity during can further reducing length.Now, containing water-dispersible hydrophobic resin When the average degree of polymerization of water-soluble resin in layer is set to 4000~6000, contain moisture in the low-index layer of whole In the case of dissipating property hydrophobic resin, it is also difficult to produce the rising of mist degree.

The thickness of layer containing water-dispersible hydrophobic resin is not particularly limited, and contains water-dispersible hydrophobic resin When layer is high refractive index layer, its every 1 layer thickness is preferably 20~800nm, more preferably 50~500nm.In addition, contain moisture When the layer for dissipating property hydrophobic resin is low-index layer, its every 1 layer thickness is preferably 20~800nm, more preferably 50~ 500nm。

[optical characteristics]

In the case of infrared shielding film of the optical reflectance coating for reflection infrared light of the present invention, from can be with less layer From the viewpoint of number improves infrared reflectivitys, being preferably designed makes the specific refractivity of low-index layer and high refractive index layer be It is larger.In the manner, at least one for the hierarchical element being made up of low-index layer and high refractive index layer, adjacent low folding The specific refractivity for penetrating rate layer and high refractive index layer is preferably more than 0.1, more preferably more than 0.3, more preferably 0.35 More than, particularly preferably more than 0.4.In the case of the laminated body with multiple high refractive index layers and low-index layer, preferably The specific refractivity of high refractive index layer and low-index layer in whole laminated bodies is in above-mentioned preferable scope.But close Can be outside above-mentioned preferable scope in the superiors or undermost index layer that form sensing multilayer film in this case Form.

As the optical characteristics of the optical reflectance coating of the manner, the transmission of the visible region shown in JIS R3106-1998 Rate is preferably more than 50%, more preferably more than 75%, more preferably more than 85%.Additionally, it is preferred that wavelength 900nm~ 1400nm region has the region more than reflectivity 50%.

As the number of plies (total number of plies of high refractive index layer and low-index layer) of the index layer of dielectric substance multilayer film, from upper From the viewpoint of stating, for example, 6~500 layers, preferably 6~300 layers.In addition, situation about particularly being made of film by wet method Under, preferably 6~50 layers, more preferably 8~40 layers, more preferably 9~30 layers, particularly preferably 11~31 layers.Dielectric In above range excellent heat-proof quality and the transparency can be achieved, film is peeled off or chap in the number of plies of the index layer of body multilayer film Suppression split etc., therefore it is preferred that.It should be noted that there is multilayer high refractive index layer and/or low-refraction in dielectric substance multilayer film In the case of layer, each high refractive index layer and/or each low-index layer can be identical respectively, can also be different.

Every 1 layer of thickness of high refractive index layer is preferably 20~800nm, more preferably 50~500nm.In addition, low refraction Every 1 layer of thickness of rate layer is preferably 20~800nm, more preferably 50~500nm.

Here, during the thickness of every 1 layer of measure, sometimes without clear and definite in the border of high refractive index layer and low-index layer Interface, composition continuously change.In this interface zone for forming and continuously changing, maximum refraction is set to During rate-minimum refractive index=Δ n, regard the minimum refractive index of 2 interlayers+Δ n/2 position as bed boundary.

, can be with it should be noted that in the case where high refractive index layer and low-index layer contain metal oxide particle Above-mentioned composition is observed according to the concentration distribution of the metal oxide particle.Metal oxide concentration distribution can be by using splashing Penetrate method to be etched from surface to depth direction, using XPS surface analysis apparatus, most surface is set to 0nm, with 0.5nm/min Speed sputtered, determine atomic composition ratio and observed.Alternatively, it is also possible to by cutting off stack membrane, to section XPS Surface analysis apparatus determines atomic composition ratio to confirm.

XPS surface analysis apparatus is not particularly limited, and any machine can use.As the XPS surface analysis apparatus, Such as the ESCALAB-200R that VGScientifics companies can be used to manufacture.Mg is used in x-ray anode, with output work Rate 600W (accelerating potential 15kV, emission current 40mA) is measured.

[adhesive layer]

The optical reflectance coating of the present invention can have adhesive layer.The adhesive layer is generally arranged at the base with dielectric substance multilayer film On the surface of the opposite side of material, and known peeling paper or barrier film can be further set.As the technical scheme of adhesive layer, do not have There is special limitation, such as dry lamination agent, wet type laminating agent, adhesive, sealant, hot solvent etc. can be used.

As adhesive, such as polyester adhesive, polyurethane binding, the bonding of polyvinyl acetate esters can be used Agent, acrylic adhesives, nitrile rubber etc..

In the case that the optical reflectance coating of the present invention fits in glass pane, from reconfigure, the viewpoint such as position correction, It is preferred that use the patch method to window water spray, the glass surface for making the adhesive layer of optical reflectance coating fit under wetting state, i.e., it is so-called Water and fitted method.Therefore, under moistening existing for water, preferably using the weak acrylic adhesives of bonding force.

Used acrylic adhesives can be solvent and any kind of type of latex type, but improve bonding from easy Power etc. consideration, preferred solvent class adhesive, wherein, the solvent adhesive preferably obtained by polymerisation in solution.As profit Raw material during this solvent acrylic adhesives, such as the principal monomer as skeleton, Ke Yiju are manufactured with polymerisation in solution Go out the acrylate such as ethyl acrylate, butyl acrylate, 2-EHA, 2-ethyl hexyl acrylate, as solidifying for improving Collect the comonomer of power, vinyl acetate, acrylonitrile, styrene, methyl methacrylate etc. can be enumerated, promote as further Enter and be crosslinked and assign stable bonding force, in addition to even if the bonding force also kept in presence of water to a certain degree, as Monomer containing functional group, methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, metering system can be enumerated Acid glycidyl ester etc..In adhesive layer, as host polymer, it is accordingly required in particular to it is high tackiness, therefore, there is butyl acrylate etc. The material of such low glass transition temperature (Tg) is particularly useful.

As the commercially available product of aforesaid propylene acrylic binder, for example,：COPONYL (registration mark) series (days This synthetic chemical industry Co., Ltd. manufactures) etc..

In the adhesive layer, such as stabilizer, surfactant, ultra-violet absorber, fire retardant, antistatic can be contained Agent, antioxidant, heat stabilizer, lubricant, filler, colouring agent, then regulator etc. is used as additive.Especially as window Patch is used in use, addition ultra-violet absorber can be efficiently used for the deterioration of optical reflectance coating caused by suppressing ultraviolet.

As the coating method of adhesive, it is not particularly limited, arbitrary known method, such as preferred row can be used Lift stick coating method, dispensing coating process, unfilled corner wheel coating process, intaglio plate roll coater method, scraper plate coating machine method, flush coater method, air knife coating Method, dip coating method, transfer printing etc., can be used alone or combine and use, but from the aspect of economy and productivity ratio, it is excellent Choosing is continuously carried out with roll-type.For these methods, it can suitably use and solution is made so that the solvent of adhesive can be dissolved, Or them is carried out the scattered coating fluid formed and be coated, it can use known material as solvent.

In addition, from viewpoints such as bonding effect, rate of dryings, the thickness of adhesive layer is preferably generally 1~100 μm or so Scope.

For bonding force, the peel strength that measures of 180 ° of disbonded tests recorded using JISK6854 is preferably 2~ 30N/25mm, more preferably 4~20N/25mm.

Being formed for adhesive layer can utilize application pattern to be above applied directly on dielectric substance multilayer film, in addition, also may be used In stripping film and it is dried with primary coating, then, is bonded dielectric substance multilayer film and transfers adhesive.Just dry temperature now For degree, preferably residual solvent is as few as possible, therefore, drying temperature or time do not have it is specific, preferably in 50~150 DEG C of temperature The lower drying time for setting 10 seconds~5 minutes.

[hard conating]

The optical reflectance coating of the present invention, can be to warm or purple containing utilizing as the sealer for improving wearability The hard conating for the resin that outside line etc. is solidified carries out lamination.For example, as a preferably example, can enumerate in substrate surface On lamination is carried out to dielectric substance multilayer film, adhesive layer successively, further with lamination by the opposite side in the side of these layers The mode of hard conating is coated with substrate surface.

As the solidified resin used in hard conating, thermohardening type resin or ultraviolet curing resin can be enumerated, From the aspect of shaping easily, preferred ultraviolet curing resin, wherein, more preferably pencil hardness is that at least 2H ultraviolet is consolidated Change type resin.This gel-type resin can be used alone, or so that two or more is combined and is used.

As ultraviolet curing resin, can enumerate：(methyl) acrylate, urethane acrylate, polyester Acid esters, epoxy acrylate, epoxy resin, oxetane resin, these materials can also be as the resin groups of no-solvent type Compound uses.

In the case of using above-mentioned ultraviolet curing resin, in order to promote to solidify, Photoepolymerizationinitiater initiater is preferably added.

As Photoepolymerizationinitiater initiater, acetophenones, benzophenone, ketal class, Anthraquinones, thioxanthene ketone class, idol can be used Nitrogen compound, peroxide, 2,3- dialkyl group dione compounds class, disulfide compound class, thiuram compound class, fluorine amine Compound etc..As the concrete example of Photoepolymerizationinitiater initiater, have：2,2 '-diethoxy acetophenone, to dimethyl acetophenone, 1- hydroxyls Butylcyclohexyl phenyl ketone, 1- hydroxyl 3,5-dimethylphenyls ketone, 2- methyl -4 '-methyl thio -2- morpholinopropanones, 2- benzyls -2- two Methylamino -1- (4- morphlinophenyls)-butanone -1 grade acetophenones, benzoin methylether, benzoin ethyl ether, benzoin isopropyl The benzoin class such as ether, benzyl dimethyl ketal, benzophenone, 2,4 '-dichloro benzophenone, 4,4 '-dichloro benzophenone, to chlorine The benzophenones such as benzophenone, 2,4,6- trimethylbenzoyls diphenyl phosphine oxide, Anthraquinones, thioxanthene ketone class etc..These light Polymerization initiator can be used alone, or two or more combination is fused and mixed compound.Particularly from solidification compound Stability or polymerisation reactivity etc. consider, preferably using acetophenones.

This Photoepolymerizationinitiater initiater can use commercially available product, such as be illustrated as preferred, and for example, BASF IRGACURE (registration mark) 819, IRGACURE 184, IRGACURE 907, the IRGACURE of Japan Co., Ltd. manufacture 651 etc..

From the viewpoint of the transparency for improving hard painting propert and raising optical reflectance coating, the thickness of hard conating is preferably 0.1 ~50 μm, more preferably 1~20 μm.

The forming method of hard conating is not particularly limited, and for example, the hard conating prepared containing above-mentioned each composition painting Cloth liquid, then, using applied coating solutions such as bars, solidify coating fluid using heat and/or UV, method for forming hard conating etc..

[other layers]

The optical reflectance coating of the present invention can have the layer (other layers) beyond above-mentioned layer.For example, as other Layer, can set intermediate layer.Here, " intermediate layer " means the layer between base material and dielectric substance multilayer film, or base material and hard conating Between layer.As the constituent material in intermediate layer, can enumerate：Polyester resin, polyvinyl alcohol resin, polyvinyl acetate tree Fat, polyvinyl acetal resin, acrylic resin, polyurethane resin etc., the compatibility of preferable additives, Tg low material, As long as meeting the condition, then any resin can be used.As long as the glass transition temperature (Tg) in intermediate layer is 30~120 DEG C, Sufficient weatherability is then can obtain, therefore preferably, more preferably 30~90 DEG C of scope.

[manufacture method of optical reflectance coating]

The manufacture method of the optical reflectance coating of the present invention is not particularly limited, as long as at least 1 can be formed on base material The individual unit being made up of high refractive index layer and low-index layer, at least 1 layer in high refractive index layer or low-index layer is set to The above-mentioned layer containing water-dispersible hydrophobic resin, then any method is all usable.

Specifically, high refractive index layer and low-index layer are preferably alternately coated with and is dried and forms laminated body (dielectric substance multilayer film).Specifically, following mode can be enumerated, can be enumerated：(1) high refractive index layer is coated with base material Coating fluid is simultaneously dried and forms high refractive index layer, then, is coated with low-index layer coating fluid and is dried and is formed low Index layer, the method for forming optical reflectance coating；(2) low-index layer coating fluid is coated with base material and is dried and is formed Low-index layer is right, then, is coated with high refractive index layer coating fluid and is dried and forms high refractive index layer, form optical reflection The method of film；(3) alternately gradually double-layer is coated with high refractive index layer coating fluid and low-index layer coating fluid on base material, so enters Row drying, the method for forming the optical reflectance coating containing high refractive index layer and low-index layer；(4) on base material simultaneously double-layer Coating high refractive index layer coating fluid and low-index layer coating fluid are simultaneously dried, and formation contains high refractive index layer and low refraction Method of the optical reflectance coating of rate layer etc..Wherein, preferably as simpler manufacturing process above-mentioned (4) method.That is, this hair The manufacture method of bright optical reflectance coating is preferably comprised using double-layer rubbing method simultaneously to the high refractive index layer and the low folding Penetrate rate layer and carry out lamination.

It is overlapping with the progress of undried liquid in the case of carrying out double-layer coating simultaneously, therefore, it is easier to cause interlayer to mix Close etc..But when water-soluble resin is polyvinyl alcohol resin, the soap of contained polyvinyl alcohol resin in high refractive index layer The saponification degree of change degree and polyvinyl alcohol resin contained in low-index layer is not also, it is known that the different polyvinyl alcohol of saponification degree The compatibility of resinoid is low.Therefore, each layer meeting when high refractive index layer and low-index layer overlapping with undried liquid The a little mixing of generation, when being concentrated in the drying process as the water volatilization of solvent, the different polyvinyl alcohol tree of saponification degree Fat is separated each other, the area of each bed boundary is worked for minimum power, therefore, suppresses alternate mixing, interface it is disorderly Disorderly also diminish.Therefore, can obtain desired wavelength region reflective character is excellent and optical reflectance coating that mist degree is less.

As coating method, such as preferably using roller coating process, rod coating process, air knife coating process, spraying process, curtain coating The slip pearl using hopper described in method or No. 2,761,791 U.S. Patent No. 2,761,419, identical publication applies Cloth method, extrusion coating method etc..

Solvent for preparing high refractive index layer coating fluid and low-index layer coating fluid is not particularly limited, preferably water, Organic solvent or its mixed solvent.In the present invention, in order that with water-soluble resin, aqueous solvent can be used.Aqueous solvent Compared with the situation using organic solvent, it is not necessary to large-scale production equipment, therefore, in terms of productivity ratio preferably, in addition, In terms of environmental preservation it is also preferred that.

As the organic solvent, for example,：The alcohols such as methanol, ethanol, 2- propyl alcohol, n-butyl alcohol, ethyl acetate, The esters such as acetic acid butyl, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, diethyl ether, propylene glycol monomethyl ether, The amide-types such as the ethers such as ethylene glycol monoethyl ether, dimethylformamide, 1-METHYLPYRROLIDONE, acetone, methyl ethyl ketone, levulinic Ketones such as ketone, cyclohexanone etc..These organic solvents can be used alone, or two or more mixes and used.In terms of environment, behaviour Simplicity of work etc. considers, as the solvent of coating fluid, preferably aqueous solvent, more preferably water, or more preferably water and first The mixed solvent of alcohol, ethanol or ethyl acetate, particularly preferred water.

During using the mixed solvent of water and a small amount of organic solvent, mixed solvent is integrally set to 100 mass %, the mixing The content of water in solvent is preferably 80~99.9 mass %, more preferably 90~99.5 mass %.Here, because, lead to Cross and be set to more than 80 mass %, it is possible to reduce volume caused by the volatilization of solvent changes, and operation improves, in addition, by being set to Below 99.9 mass %, homogenieity when can obtain liquid addition increases, stable liquid physical property.

The concentration of water-soluble resin in high refractive index layer coating fluid is preferably 0.5~10 mass %.In addition, high index of refraction The concentration of metal oxide particle in layer coating fluid is preferably 1~50 mass %.

The concentration of water-soluble resin in low-index layer coating fluid is preferably 0.5~10 mass %.In addition, low-refraction The concentration of metal oxide particle in layer coating fluid is preferably 1~50 mass %.

The preparation method of high refractive index layer coating fluid and low-index layer coating fluid is not particularly limited, for example, The method that metal oxide particle, water-soluble resin, curing agent etc. are made an addition to aqueous solvent and be stirred.Now, The order of addition of each composition, can also one it is not also specifically limited, can stir while add each composition successively and mix Side stirring is disposably added and mixed on one side.

When at least 1 layer in high refractive index layer is set into the layer containing water-dispersible hydrophobic resin, as described above Water-dispersible hydrophobic resin is added in high refractive index layer coating fluid so that final solid component concentration turns into the model specified Enclose, making the layer coating fluid containing water-dispersible hydrophobic resin, (high refractive index layer containing water-dispersible hydrophobic resin applies Cloth liquid).By being coated to the above-mentioned layer coating fluid containing water-dispersible hydrophobic resin and making its drying, can obtain To the layer containing water-dispersible hydrophobic resin to be worked as high refractive index layer.

Similarly, when at least 1 layer in low-index layer being set into the layer containing water-dispersible hydrophobic resin, as above Water-dispersible hydrophobic resin is added in described low-index layer coating fluid so that final solid component concentration, which turns into, specifies Scope, make coating fluid (the low refraction containing water-dispersible hydrophobic resin of the layer containing water-dispersible hydrophobic resin Rate layer coating fluid).By being coated to the above-mentioned layer coating fluid containing water-dispersible hydrophobic resin, dry, can be with Obtain the layer containing water-dispersible hydrophobic resin to be worked as low-index layer.

In addition, in the coating fluid of the layer containing water-dispersible hydrophobic resin, the concentration of water-dispersible hydrophobic resin does not have There is special limitation, with the content (solid constituent of the water-dispersible hydrophobic resin in the layer containing water-dispersible hydrophobic resin Content) it is adjusted as the mode of above-mentioned scope.

As described above, the preferable mode of the optical reflectance coating of the present invention is in the layer containing water-dispersible hydrophobic resin Include anionic emulsion resin and anionic surfactant.It is therefore preferable that the optical reflectance coating of the present invention includes：Make water Soluble resin, anionic based surfactants and anionic emulsion resin are dissolved or dispersed in aqueous solvent and prepare coating The stage of liquid；The stage of the layer containing water-dispersible hydrophobic resin is formed by being coated with the coating fluid.

In the case of using pearl coating method is slided, the high refractive index layer coating fluid and low during double-layer coating simultaneously is carried out The temperature of index layer coating fluid is preferably the temperature range of 25~60 DEG C of temperature range, more preferably 30~45 DEG C.In addition, make In the case of with curtain coating mode, the temperature range of preferably 25~60 DEG C of temperature range, more preferably 30~45 DEG C.

The viscosity of high refractive index layer coating fluid and low-index layer coating fluid during progress double-layer coating simultaneously is not special Limitation.But in the case of using pearl coating method is slided, it is excellent in the scope of the preferable temperature of above-mentioned coating fluid Elect 5~160mPas scope, more preferably 60~140mPas scope as.In addition, using curtain coating mode In the case of, in the scope of the preferable temperature of above-mentioned coating fluid, preferably 5~1200mPas scope is further excellent Elect 25~500mPas scope as.If the scope of this viscosity, then it can effectively carry out while double-layer is coated with.

In addition, viscosity during 15 DEG C as coating fluid, preferably more than 100mPas, more preferably 100~30, 000mPas, more preferably 2,500~30,000mPas.

The condition of coating and drying means is not particularly limited, for example, gradually in the case of rubbing method, first, will heat On base material and carried out to any coating solution of 30~60 DEG C of high refractive index layer coating fluids and low-index layer coating fluid Dry and forming layer, then, another coating solution on the layer and is dried and forms stack membrane precursor (unit). Secondly, gradually it is coated, is dried thereby using required for desired optical reflection performance is shown by methods described Unit number carries out lamination so as to obtain stack membrane precursor.When drying, preferably the film of formation is dried more than 30 DEG C.Example Such as, preferably it is dried in the range of 5~50 DEG C of wet-bulb temperature, 5~100 DEG C of film surface temperature (preferably 10~50 DEG C), for example, Blow 40~60 DEG C of warm wind 1~5 second and be dried.As drying means, warm air drying, infra-red drying, microwave can be used to do It is dry.In addition, compared with the drying in single technique, the preferably drying of multistage technology, the temperature of constant rate of drying portion is more preferably set to The temperature of ＜ falling rate of drying portion.This when the temperature range of constant rate of drying portion be preferably set to 30~60 DEG C, the temperature of falling rate of drying portion Degree scope is preferably set to 50~100 DEG C.

In addition, the condition of the coating and drying means when carrying out double-layer coating simultaneously preferably by high refractive index layer coating fluid and Low-index layer coating fluid is heated to 30~60 DEG C, and high refractive index layer coating fluid and low-index layer coating fluid are carried out on base material While double-layer be coated with, then, the temperature of the film of formation is temporarily cooled to preferably 1~15 DEG C (fixation), thereafter with 10 DEG C It is dried above.More preferably drying condition is 5~50 DEG C of wet-bulb temperature, the condition for the scope that 10~50 DEG C of film surface temperature.Example Such as, blow 40~80 DEG C of warm wind 1~5 second and be dried.In addition, as the type of cooling after firm coating, from what is formed From the viewpoint of the uniformity of film improves, preferably carried out with horizontal fixed form.

Here, the fixation means, by the means such as reduce temperature such as blow a cold wind over to film, to improve coating composition Viscosity, the process for making the mobility of each interlayer and the material in each layer reduce or be additionally carried out gelation.Will be to coated film from table Face is blown a cold wind over, press...with one's finger the surface for being pressed in coated film when finger on be not smeared with the state of any material and be defined as fixed end State.

It is preferably within 5 minutes to the time (set time) that end is fixed of blowing a cold wind over from the time of coating, it is more excellent Elect as within 2 minutes.In addition, the time of lower limit is not particularly limited, it is preferred to use the time of more than 45 seconds.Need what is illustrated It is that, as long as promptly causing the high resiliency in the intermediate layer between high refractive index layer and low-index layer, can be not provided with being consolidated Fixed process.

The adjustment of set time can by adjust the concentration of polyvinyl alcohol resin or the concentration of metal oxide particle, Or add other compositions such as the various known gelating agents such as gelatin, pectin, agar, carragheen, gellan gum and be adjusted.

The temperature of cold wind is preferably 0~25 DEG C, more preferably 5~10 DEG C.In addition, film depends on exposed to the time of cold wind In the transporting velocity of film, but preferably 10~360 seconds, more preferably 10~300 seconds, more preferably 10~120 seconds.

High refractive index layer coating fluid and low-index layer coating fluid are coated, their coating thickness is turned into above-mentioned Thickness when shown preferable dry.

＜ optical reflectors ＞

The optical reflectance coating of the present invention can apply to the field of broadness.Therefore, an embodiment of the invention is upper The optical reflector that the optical reflectance coating stated is arranged at least one surface of matrix and formed.For example, built as fitting in The outdoor window of thing or automotive window isometric period assign the hot line of hot line reflecting effect in the equipment (matrix) of sunshine The patch window such as reflectance coating film, agricultural vinyl house film etc., are mainly used with improving the purpose of weatherability.The light of the present invention Learn portion of the reflectance coating particularly suitable for the matrix such as glass is fitted in via above-mentioned adhesive layer or replaces the resin of glass Part.

As the instantiation of matrix, for example,：Glass, polycarbonate resin, polysulfone resin, acrylic compounds tree Fat, vistanex, polyether resin, polyester resin, polyamide, polysulfide ether resin, unsaturated polyester resin, asphalt mixtures modified by epoxy resin It is fat, melmac, phenolic resin, diallyl phthalate resin, polyimide resin, polyurethane resin, poly- Vinyl acetate resin, polyvinyl alcohol resin, styrene resin, vinyl chloride resin, metallic plate, ceramics etc..The species of resin can Think thermoplastic resin, heat-curing resin, ionizing radiation curable resin it is any, can also be by these material groups Close two or more and use.Matrix can be used known in extrusion molding, calendaring molding, injection molded, hollow forming, compression molding etc. Method manufacture.The thickness of matrix is not particularly limited, usually 0.1mm~5cm.

The adhesive layer that optical reflectance coating and matrix are bonded is set to be preferably provided with optical reflectance coating when fitting in glass pane etc., It is located at daylight (hot line) incident surface side.In addition, when optical reflectance coating is held between glass pane and base material, can be by water The ambient gas that grades seals, in terms of durability preferably.Even if the optical reflectance coating of the present invention is arranged at outdoor or car outer Side (outer patch use), it may have environment durability, therefore it is preferred that.

Embodiment

Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited by embodiment.Need what is illustrated It is in embodiment, to use the expression of " part " or " % ", but as long as without specified otherwise, represents " mass parts " or " quality % ".Separately Outside, carried out as long as no specified otherwise, each operation under room temperature (25 DEG C).

《The making of optical reflectance coating》

(embodiment 1)

The preparation ＞ of ＜ high refractive index layers coating fluid 1

High refractive index layer coating fluid 1 is prepared according to following steps.

(preparation for being attached with the TiO 2 sol of silica)

First, the silica attachment TiO 2 sol containing rutile titanium dioxide is prepared as follows.

In 15.0 mass % titanium oxide sol (SRD-W, volume average particle sizes：5nm, rutile titanium dioxide particle, Sakai Chemical industry Co., Ltd. manufactures) mass parts of pure water 2 are added in 0.5 mass parts, then, it is heated to 90 DEG C.Then, slowly add Silicate aqueous solution is added (to be diluted silicic acid No. soda4 (Nippon Chemical Ind manufactures) so that SiO with pure water₂It is dense Spend for 0.5 mass % solution) 0.5 mass parts, then carry out heating for 18 hours in autoclave, at 175 DEG C, cooling Afterwards, concentrated with ultrafiltration membrane, thus obtain making solid component concentration relative to the SiO that titanium dioxide is 6 mass %₂Attachment TiO 2 sol (TiO 2 sol for being hereinafter referred to as attached with silica) (volume average particle size in surface：9nm).

(preparation of high refractive index layer coating fluid 1)

The silica obtained with respect to above-mentioned step adheres to TiO 2 sol (20 mass %) 113 mass Part, aqueous citric acid solution (1.92 mass %) 48 mass parts are added, add polyvinyl alcohol (Kuraray Co., Ltd.'s manufacture, PVA- 117th, average degree of polymerization 1700, saponification degree：97.5~99 moles of %, 8 mass %) 113 mass parts and it is stirred, it is eventually adding The 5 mass % aqueous solution (SOFTZOLINE LSB-R, the manufacture of Chuan Yan fine chemistries Co., Ltd.) 0.4 mass of surfactant Part, prepare high refractive index layer coating fluid 1.

The refractive index that the film to be formed is coated to above-mentioned high refractive index layer coating fluid 1 is 1.80.It should be noted that folding The assay method for penetrating rate is (following same) as described below.

The measure ＞ of the monofilm refractive index of each layers of ＜

In order to determine refractive index, it is produced on base material and above-mentioned high refractive index layer coating fluid 1 is coated to obtain with individual layer Sample, by the sample shear into after 10cm × 10cm, refractive index is obtained according to following methods.Use the light splitting of Hitachi Photometer U-4100 (solid sample measurement system), to surface (back side) the progress asperities with aspect of measure opposite side of each sample Change is handled, and then, is carried out light absorbs processing with the spraying of black and is prevented the back side from carrying out the reflection of light, the condition of the normal reflection at 5 ° The measure of the lower reflectivity for carrying out visible region (400nm~700nm), refractive index is obtained by result.

The preparation ＞ of ＜ low-index layers coating fluid 1

By the 10 mass % aqueous solution (SNOWTEX (registration mark) OXS, one of the acidic colloidal silica of 31 mass parts Secondary particle diameter：5.4nm, Nissan Chemical Ind Ltd's manufacture) 40 DEG C are heated to, add the mass of the 3 mass % aqueous solution of boric acid 3 Part, further at 40 DEG C successively addition as water-soluble resin 39 mass parts polyvinyl alcohol the 6 mass % aqueous solution (PVA-224, average degree of polymerization：2400th, saponification degree：87~89 moles of %, Kuraray Co., Ltd. manufacture) and 1 mass parts table The 5 mass % aqueous solution (SOFTZOLINE LSB-R, the manufacture of Chuan Yan fine chemistries Co., Ltd.) of face activating agent, prepare low refraction Rate layer coating fluid 1.

The refractive index for being coated with the film that above-mentioned low-index layer coating fluid 1 obtains is 1.50.

＜ contains the preparation ＞ of the low-index layer coating fluid 1 of water-dispersible hydrophobic resin

By the 10 mass % aqueous solution (SNOWTEX (registration mark) OXS, one of the acidic colloidal silica of 13 mass parts Secondary particle diameter：5.4nm, Nissan Chemical Ind Ltd's system) make and be heated to 40 DEG C, add the mass of the 3 mass % aqueous solution of boric acid 3 Part, further at 40 DEG C successively addition as water-soluble resin 35 mass parts polyvinyl alcohol the 6 mass % aqueous solution (PVA-224, average degree of polymerization：2400th, saponification degree：87~89 moles of %, Kuraray Co., Ltd. manufacture), the water of 3 mass parts The mass % aqueous solution (ADEKA BONTIGHTER HUX-830, average grain diameter=100nm, ADEKA strain of dispersed polyurethane resin 6 Formula commercial firm manufactures) and 1 mass parts anionic surfactant the 5 mass % aqueous solution it is (NoigenXL-40, first industrial Pharmaceutical Co., Ltd manufactures), prepare the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin.

It should be noted that it is anionic resin to determine Z current potentials and confirm above-mentioned water dispersible polyurethane resin.Specifically Assay method is as described below.

Device：Malvern companies zetasizer-nano ZSP

Mensuration mode：Electrophoretic light scattering method

Sample adjusts：Measure is by water-dispersible hydrophobic resins dilute to be calculated as with quality % 1% solution.

The refraction of obtained film is coated to the above-mentioned low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Rate is 1.50.

The making ＞ of ＜ optical reflectance coatings 1

The slip hopper apparatus being coated with using 19 layers of double-layer can be carried out, respectively will be above-mentioned in the high refraction that is prepared Rate layer coating fluid 1, low-index layer coating fluid 1 and the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin are adjusted To 40 DEG C.Using the 160mm width as the base material for being heated to 40 DEG C in the polyethylene terephthalate film (east of 50 μm of thickness The A4300 of paj manufacture：The easy following layer in two sides) on, orlop and the superiors are set to low-index layer, will be the 11st from substrate side Layer is set to the low-index layer containing water-dispersible hydrophobic resin, in addition, weight while being alternately carried out amounting to 19 layers respectively Layer coating so that the thickness during drying of low-index layer and the low-index layer containing water-dispersible hydrophobic resin is each layer 150nm, each layer of high refractive index layer are 130nm.Just after coating, blowing 10 DEG C of cold wind makes it fix (thickening).

After fixed (thickening) terminates, blow 60 DEG C of warm wind and be dried, make the light by amounting to 19 layers of embodiment 1 formed Learn reflectance coating 1.

It should be noted that for the measure (confirmation) of thickness, optical reflectance coating sample is cut off, to section XPS tables Surface analysis device measure high-index material (TiO₂) and low-index material (SiO₂) amount, it is possible thereby to confirm to ensure The thickness of above layers.

(embodiment 2)

＜ contains the preparation ＞ of the low-index layer coating fluid 2 of water-dispersible hydrophobic resin

The 10 mass % aqueous solution of acidic colloidal silica are set to 18 mass parts, by 6 mass % water of polyvinyl alcohol Solution is set to 6 mass parts, the mass % aqueous solution of water dispersible polyurethane resin 6 is set into 47 mass parts, in addition, with containing water The low-index layer coating fluid 1 of dispersed hydrophobic resin similarly operates, and prepares containing the low of water-dispersible hydrophobic resin Index layer coating fluid 2.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 2 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 2

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 2 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 2.

(embodiment 3)

＜ contains the preparation ＞ of the low-index layer coating fluid 3 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 19 mass parts, and the 6 mass % aqueous solution of polyvinyl alcohol are set into 38 mass parts, The mass % aqueous solution of water dispersible polyurethane resin 6 is set to 18 mass parts, in addition, operated similarly to Example 1, is prepared Low-index layer coating fluid 3 containing water-dispersible hydrophobic resin.

The refraction of obtained film is coated to the above-mentioned low-index layer coating fluid 3 containing water-dispersible hydrophobic resin Rate is 1.50.

The making ＞ of ＜ optical reflectance coatings 3

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 3 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 3.

(embodiment 4)

＜ contains the preparation ＞ of the low-index layer coating fluid 4 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 19 mass parts, and the 6 mass % aqueous solution of polyvinyl alcohol are set into 38 mass parts, The mass % aqueous solution of water dispersible polyurethane resin 6 is set to 18 mass parts, by the 5 of the anionic surfactant of 1 mass parts Live on the anionic surface that the quality % aqueous solution (NoigenXL-40, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture) is set to 1 mass parts Property agent the 5 mass % aqueous solution (HITENOL NF-08, Di-ichi Kogyo Seiyaku Co., Ltd. manufacture), in addition, with embodiment 1 similarly operates, and prepares the low-index layer coating fluid 4 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 4 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 4

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 4 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 4.

(embodiment 5)

＜ contains the preparation ＞ of the low-index layer coating fluid 5 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by 3 mass Part the mass % aqueous solution of water dispersible polyurethane resin 6 (ADEKA BONTIGHTER HUX-830, average grain diameter=100nm, ADEKA Corp. manufactures) it is changed to the scattered mass % aqueous solution of acrylic resin 6 of moisture (AE-116, the average grain of 3 mass parts Footpath=80nm, E. TEC Co., Ltd's system), by the 5 mass % aqueous solution of the anionic surfactant of 1 mass parts (NoigenXL-40, Di-ichi Kogyo Seiyaku Co., Ltd.'s system) is changed to 5 matter of the anionic surfactant of 1 mass parts The % aqueous solution (HITENOL NF-08, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture) is measured, in addition, is grasped similarly to Example 1 Make, prepare the low-index layer coating fluid 5 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 5 containing water-dispersible hydrophobic resin is 1.50。

It should be noted that it is anionic resin to determine zeta potential and confirm that above-mentioned moisture dissipates acrylic resin.Specifically Assay method is same with the measure in above-mentioned water dispersible polyurethane resin.

The making ＞ of ＜ optical reflectance coatings 5

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 5 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 5.

(embodiment 6)

＜ contains the preparation ＞ of the low-index layer coating fluid 6 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by 3 mass The scattered mass % of acrylic resin 6 of moisture that the mass % aqueous solution of water dispersible polyurethane resin 6 of part is changed to 3 mass parts is water-soluble Liquid (AE-120A, average grain diameter=55nm, E. TEC Co., Ltd's manufacture), by the 5 of the anionic surfactant of 1 mass parts The quality % aqueous solution is changed to the 5 mass % aqueous solution (HITENOL NF-08, of the anionic surfactant of 1 mass parts One industrial pharmaceutical Co., Ltd. manufactures), in addition, operate similarly to Example 1, preparation contains water-dispersible hydrophobic tree The low-index layer coating fluid 6 of fat.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 6 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 6

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 6 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 6.

(embodiment 7)

＜ contains the preparation ＞ of the low-index layer coating fluid 7 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 6 mass % aqueous solution of state silica are set to 18 mass parts, and the 6 mass % aqueous solution of polyvinyl alcohol are set into 6 mass parts, will 3 mass parts the mass % aqueous solution of water dispersible polyurethane resin 6 (ADEKA BONTIGHTER HUX-830, average grain diameter= 100nm, ADEKA Corp.'s manufacture) it is changed to the scattered mass % aqueous solution (AE- of acrylic resin 6 of moisture of 47 mass parts 120A, average grain diameter=55nm, E. TEC Co., Ltd's manufacture), by 5 mass % of the anionic surfactant of 1 mass parts The aqueous solution (NoigenXL-40, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture) is changed to the anionic surfactant of 1 mass parts The 5 mass % aqueous solution (HITENOL NF-08, Di-ichi Kogyo Seiyaku Co., Ltd. manufacture), it is in addition, same with embodiment 1 Operate sample, prepare the low-index layer coating fluid 7 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 7 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 7

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 7 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 7.

(embodiment 8)

＜ contains the preparation ＞ of the low-index layer coating fluid 8 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 19 mass parts, and the 6 mass % aqueous solution of polyvinyl alcohol are set into 38 mass parts, By the mass % aqueous solution of water dispersible polyurethane resin 6 of 3 mass parts (ADEKA BONTIGHTER HUX-830, average grain diameter= 100nm, ADEKA Corp.'s manufacture) it is changed to the scattered mass % aqueous solution (AE- of acrylic resin 6 of moisture of 18 mass parts 120A, average grain diameter=55nm, E. TEC Co., Ltd's manufacture), by 5 mass % of the anionic surfactant of 1 mass parts The aqueous solution (NoigenXL-40, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture) is changed to the anionic surfactant of 1 mass parts The 5 mass % aqueous solution (HITENOL NF-08, Di-ichi Kogyo Seiyaku Co., Ltd. manufacture), it is in addition, same with embodiment 1 Operate sample, prepare the low-index layer coating fluid 8 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 8 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 8

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 8 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 8.

(embodiment 9)

＜ contains the preparation ＞ of the low-index layer coating fluid 9 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 19 mass parts, and the 6 mass % aqueous solution of polyvinyl alcohol are set into 38 mass parts, By the mass % aqueous solution of water dispersible polyurethane resin 6 of 3 mass parts (ADEKA BONTIGHTER HUX-830, average grain diameter= 100nm, ADEKA Corp.'s manufacture) it is changed to the scattered mass % aqueous solution liquid (AE- of acrylic resin 6 of moisture of 18 mass parts 120A, average grain diameter=55nm, E. TEC Co., Ltd's manufacture), in addition, operate similarly to Example 1, preparation contains The low-index layer coating fluid 9 of water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 9 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 9

In above-described embodiment 1 (making of optical reflectance coating 1), by the low-refraction containing water-dispersible hydrophobic resin Layer coating fluid 1 is changed to the low-index layer coating fluid 9 containing water-dispersible hydrophobic resin prepared as described above, except this Outside, operate similarly to Example 1, make optical reflectance coating 9.

(embodiment 10)

The making ＞ of ＜ optical reflectance coatings 10

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture from the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Property hydrophobic resin low-index layer coating fluid 8, also, replace from substrate side 11th layer, will be the 19th layer from substrate side The low-index layer containing water-dispersible hydrophobic resin is set to, in addition, is operated similarly to Example 1, makes optics Reflectance coating 10.

(embodiment 11)

＜ contains the preparation ＞ of the low-index layer coating fluid 10 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 19 mass parts, and water-soluble resin is changed to 6 mass % water of polyvinyl alcohol Solution (JC-40, average degree of polymerization：4000th, saponification degree：99 moles of %, the manufacture of JAPAN VAM＆POVAL Co., Ltd.) 38 mass Part, by water dispersible polyurethane resin 6 mass the % aqueous solution (ADEKA BONTIGHTER HUX-830, the average grain diameter of 3 mass parts =100nm, ADEKA Corp.'s system) it is changed to the scattered mass % aqueous solution (AE- of acrylic resin 6 of moisture of 18 mass parts 120A, average grain diameter=55nm, E. TEC Co., Ltd's manufacture), by 5 mass % of the anionic surfactant of 1 mass parts The aqueous solution (NoigenXL-40, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture) is changed to the anionic surfactant of 1 mass parts The 5 mass % aqueous solution (HITENOL NF-08, Di-ichi Kogyo Seiyaku Co., Ltd. manufacture), it is in addition, same with embodiment 1 Operate sample, prepare the low-index layer coating fluid 10 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 10 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 11

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to above-mentioned making by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Low-index layer coating fluid 10 containing water-dispersible hydrophobic resin, also, the 11th layer from substrate side is replaced, will be from base material Side plays the 19th layer and is set to the low-index layer containing water-dispersible hydrophobic resin, in addition, grasps similarly to Example 1 Make, make optical reflectance coating 11.

(embodiment 12)

＜ contains the preparation ＞ of the low-index layer coating fluid 11 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 19 mass parts, and water-soluble resin is changed to 6 mass % water of polyvinyl alcohol Solution (JP-45, average degree of polymerization：4500th, saponification degree：99 moles of %, the manufacture of JAPAN VAM＆POVAL Co., Ltd.) 38 mass Part, by water dispersible polyurethane resin 6 mass the % aqueous solution (ADEKA BONTIGHTER HUX-830, the average grain diameter of 3 mass parts =100nm, ADEKA Corp.'s manufacture) it is changed to the scattered mass % aqueous solution (AE- of acrylic resin 6 of moisture of 18 mass parts 120A, average grain diameter=55nm, E. TEC Co., Ltd's manufacture), by 5 mass % of the anionic surfactant of 1 mass parts The aqueous solution (NoigenXL-40, Di-ichi Kogyo Seiyaku Co., Ltd.'s system) is set to the 5 of the anionic surfactant of 1 mass parts The quality % aqueous solution (HITENOL NF-08, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture), in addition, similarly to Example 1 Operation, prepares the low-index layer coating fluid 11 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 11 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 12

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to above-mentioned making by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Low-index layer coating fluid 11 containing water-dispersible hydrophobic resin, also, will from substrate side the 19th layer be set to containing moisture The low-index layer of property hydrophobic resin is dissipated, in addition, is operated similarly to Example 1, makes optical reflectance coating 12.

(embodiment 13)

The making ＞ of ＜ optical reflectance coatings 13

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin The low-index layer coating fluid 10 of property hydrophobic resin, also, from substrate side the 1st layer and the 19th layer be set to dredge containing water dispersible The low-index layer of water-base resin, in addition, operate similarly to Example 1, make optical reflectance coating 13.

(embodiment 14)

The making ＞ of ＜ optical reflectance coatings 14

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin The low-index layer coating fluid 11 of property hydrophobic resin, also, from substrate side the 1st layer and the 19th layer be set to containing water dispersible The low-index layer of hydrophobic resin, in addition, operate similarly to Example 1, make optical reflectance coating 14.

(embodiment 15)

The making ＞ of ＜ optical reflectance coatings 15

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Property hydrophobic resin low-index layer coating fluid 11, also, by whole low-index layer be set to containing water-dispersible hydrophobic Property resin low-index layer, in addition, operate similarly to Example 1, make optical reflectance coating 15.

(comparative example 1)

＜ contains the preparation ＞ of the low-index layer coating fluid 12 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 31 mass parts, and the 6 mass % aqueous solution of polyvinyl alcohol are set into 38 mass parts, The mass % aqueous solution of water dispersible polyurethane resin 6 is set to 1 mass parts, in addition, with containing water-dispersible hydrophobic resin Low-index layer coating fluid 1 similarly operate, prepare the low-index layer coating fluid 12 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 12 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 16

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Property hydrophobic resin low-index layer coating fluid 12, in addition, operate similarly to Example 1, make optical reflectance coating 16。

(comparative example 2)

＜ contains the preparation ＞ of the low-index layer coating fluid 13 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), water solubility tree Fat is changed to the 6 mass % aqueous solution (trade names of polyvinyl alcohol：PVA-210, average degree of polymerization：1000th, saponification degree：88 rub That %, Kuraray Co., Ltd.'s manufacture) 38 mass parts, the 10 mass % aqueous solution of acidic colloidal silica are set to 31 mass Part, the mass % aqueous solution of water dispersible polyurethane resin 6 is set to 1 mass parts, in addition, with containing water-dispersible hydrophobic tree The low-index layer coating fluid 1 of fat similarly operates, and prepares the low-index layer coating fluid containing water-dispersible hydrophobic resin 13。

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 13 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 17

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Property hydrophobic resin low-index layer coating fluid 13, also, replace from substrate side 11th layer, will be from the 19th layer of substrate side The low-index layer containing water-dispersible hydrophobic resin is set to, in addition, is operated similarly to Example 1, makes optics Reflectance coating 17.

(comparative example 3)

＜ contains the preparation ＞ of the low-index layer coating fluid 14 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 10 mass parts, and the 6 mass % aqueous solution of polyvinyl alcohol are set into 4 mass parts, The mass % aqueous solution of water dispersible polyurethane resin 6 is set to 65 mass parts, in addition, with containing water-dispersible hydrophobic resin Low-index layer coating fluid 1 similarly operate, prepare the low-index layer coating fluid 14 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 14 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 18

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Property hydrophobic resin low-index layer coating fluid 14, in addition, operate similarly to Example 1, make optical reflectance coating 18。

(comparative example 4)

＜ contains the preparation ＞ of the low-index layer coating fluid 15 of water-dispersible hydrophobic resin

In above-described embodiment 1 (preparation of the low-index layer coating fluid 1 containing dispersed hydrophobic resin), by Aci-Jel The 10 mass % aqueous solution of state silica are set to 9 mass parts, and the 6 mass % that water-soluble resin is changed to polyvinyl alcohol are water-soluble Liquid (trade name：JM-23, average degree of polymerization：2300th, saponification degree：97 moles of %, the manufacture of JAPAN VAM＆POVAL societies) 4 mass Part, the moisture that the mass % aqueous solution of water dispersible polyurethane resin 6 is changed to 65 mass parts dissipates the mass % water of acrylic resin 6 Solution (AE-120A, average grain diameter=55nm, E. TEC Co., Ltd's manufacture), without using anionic surfactant, except this Outside, operate similarly to Example 1, prepare the low-index layer coating fluid 15 containing water-dispersible hydrophobic resin.

The refractive index for being coated with the film of the above-mentioned low-index layer coating fluid 15 containing water-dispersible hydrophobic resin is 1.50。

The making ＞ of ＜ optical reflectance coatings 19

In above-described embodiment 1 (making of optical reflectance coating 1), water-dispersible hydrophobic resin will be contained for forming The coating fluid of low-index layer is changed to dissipate containing moisture by the low-index layer coating fluid 1 containing water-dispersible hydrophobic resin Property hydrophobic resin low-index layer coating fluid 15, in addition, operate similarly to Example 1, make optical reflectance coating 19。

《Evaluation》

(measure of mist degree)

On the optical reflectance coating sample manufactured in above-described embodiment and comparative example, haze meter (the electric color industry of Japan is used The NDH2000 types of society's manufacture) measure mist degree (%), calculate the average value that optical reflectance coating sample 10 is opened.It should be noted that make For the haze value of optical reflectance coating, as long as being less than 2.5%, preferably less than 1.5%.

(observation for whetheing there is film failure)

The optical reflectance coating sample manufactured in above-described embodiment and comparative example is observed by visual observation, to more than diameter 2mm Sum (individual/1000m of film failure (splashing, condensation product)²) counted, calculate that optical reflectance coating sample 10 opens is averaged Value, is evaluated according to following metewand.

○：10/1000m²Hereinafter,

○△：More than 10/1000m², and 100/1000m²Hereinafter,

△：More than 100/1000m², and 500/1000m²Hereinafter,

×：More than 500/1000m²。

It should be noted that used with can having no problem in zero, zero △, △ practicalities.

(atmospheric exposure test)

Attach the light manufactured in above-described embodiment and comparative example via adhesive layer on thickness 3mm blue tinted glass respectively Learn reflectance coating.

Specifically, the barrier film following adhesive layers formation coating fluid manufactured relative to middle packs Co., Ltd. NS23MA polysiloxanes stripping surface, it is coated with unfilled corner wheel coating machine so that dry film thickness turns into 10 μm, is done at 90 DEG C Dry 1 minute and form adhesive layer.Be bonded on the adhesive layer it is above-mentioned in the film formed with dielectric substance multilayer film, in dielectric substance multilayer Adhesive layer is formed on film.

Adhesive layer forms the preparation of coating fluid

Relative to COPONYL (registration mark) N-6941M (the Nippon Synthetic Chemical Industry Co., Ltd's systems as adhesive Make), CoronateL-55E (Japanese polyurethane Industrial Co., Ltd manufacture) 3 mass % as curing agent are added, are entered One step adds Tinuvin477 (manufacture of BASFJapan Co., Ltd.) 5 mass % as ultra-violet absorber, is used as solvent Ethyl acetate be diluted so that solid constituent turns into 10 mass %, prepare adhesive layer formed coating fluid.

By the sample, using xenon lamp weather instrument, (SUGA testing machines society manufactures under conditions of 50 DEG C of 70%RH；Send very It is similar to the light of sunshine) to 180W/m²Intensity xenon light repeat the water injection of 18 minutes and 22 minutes dry carry out it is sudden and violent Dew.Thereafter, it was confirmed whether to produce film cracking in film after exposure by visual observation every 10 hours, according to following metewand Evaluated.

A：Film cracking is not produced,

B：Film cracking is somewhat produced,

C：Sufficient film cracking is produced by visual observation,

D：Film cracking is significantly produced on the whole in film.

Evaluation more than is set to crack generation time as more than C point.Evaluation result is shown in following tables 1。

Learnt by the result of above-mentioned table 1：The optical reflectance coating of embodiment 1~15：Containing with water-soluble resin and moisture The layer containing water-dispersible hydrophobic resin of property hydrophobic resin is dissipated, and contains water-dispersible hydrophobic tree relative to above-mentioned Solid constituent quality in the layer of fat, it is anti-with the optics of comparative example 1~4 containing the mass % of water-dispersible hydrophobic resin 5~55 Penetrate film to compare, have excellent weather resistance.Learn in addition：Film failure is also reduced.

Also, using anionic emulsion resin as water-dispersible hydrophobic resin, contain anionic surface activity The embodiment 5~8 of agent, compared with embodiment 1~4,9, film failure is further improved.

In addition, being used in the superiors has the water-soluble tree that anionic emulsion resin and average degree of polymerization are 4000~6000 The embodiment 11~15 of fat, weatherability further improves, while mist degree is also improved.Particularly learn：Orlop is also set to Embodiment 13, the embodiment 14 of the layer containing water-dispersible hydrophobic resin containing anionic emulsion resin, or will bag It is set to contain water-dispersible hydrophobic containing anionic emulsion resin containing the superiors and undermost whole low-index layer Property resin layer embodiment 15, weatherability improve effect it is higher.

It should be noted that the application is based on apllied Japanese patent application 2015-111712 on June 1st, 2015 Number, the disclosure of which is cited by referring to as overall.

Claims (7)

1. a kind of optical reflectance coating, it has base material and dielectric substance multilayer film,

The dielectric substance multilayer film is configured on a surface of the base material, and is replaced by low-index layer and high refractive index layer Lamination forms,

At least 1 layer in the low-index layer and the high refractive index layer is the layer containing water-dispersible hydrophobic resin, institute The layer containing water-dispersible hydrophobic resin is stated to dissipate containing water-soluble resin and relative to the moisture that gross mass is 5~55 mass % Property hydrophobic resin.

2. optical reflectance coating as claimed in claim 1, wherein,

The layer containing water-dispersible hydrophobic resin also contains anionic surfactant, the water-dispersible hydrophobic Resin is anionic emulsion resin.

3. optical reflectance coating as claimed in claim 1 or 2, wherein,

In the dielectric substance multilayer film, moisture is contained to be described in the superiors of the opposite side in side with contacting the base material Dissipate the layer of property hydrophobic resin.

4. such as optical reflectance coating according to any one of claims 1 to 3, wherein,

In the dielectric substance multilayer film, the orlop being in contact with the base material contains water-dispersible hydrophobic resin to be described Layer.

5. such as optical reflectance coating according to any one of claims 1 to 4, wherein,

The superiors of the dielectric substance multilayer film and orlop are low-index layer, and whole low-index layers is described contains The layer of water-dispersible hydrophobic resin.

6. such as optical reflectance coating according to any one of claims 1 to 5, wherein,

The average degree of polymerization of the water-soluble resin in the layer containing water-dispersible hydrophobic resin is 4000~6000.

7. the manufacture method of the optical reflectance coating described in claim 2, it includes：

Water-soluble resin, anionic surfactant and anionic emulsion resin is set to be dissolved or dispersed in aqueous solvent To prepare the stage of coating fluid；

The stage of the layer containing water-dispersible hydrophobic resin is formed by being coated with the coating fluid.