CN107003450A - Stack membrane - Google Patents

Abstract

The present invention provides a kind of stack membrane, and it also suppresses the generation and discoloration of crackle in the stack membrane with the layer containing infrared absorbent under the high humidity environment that sunshine irradiates, and sulfidation-resistance is excellent.The present invention is a kind of stack membrane, it has base material and infrared ray-absorbing layer, the infrared ray-absorbing layer contains infrared absorbent, resin and antioxidant, and be configured on a surface of the base material, wherein, the infrared ray-absorbing layer is more than 6.5 with the film surface p H on the surface of base material opposite side.

Description

Stack membrane

Technical field

The present invention relates to a kind of stack membrane.

Background technology

In general, being proved in theory：High refractive index layer and the respective blooming of low-index layer are adjusted And the alternately stack membrane of lamination, the light of specific wavelength is optionally reflected, as transmission luminous ray, optionally The stack membrane of reflection near infrared ray is utilized.Such stack membrane is used as window or vehicle part thermal contours for building The reflectance coating of shielding.

But, in infrared (hot line) screened film obtained from this hot line reflectance coating is formed on film, it is considered to produce When property and optical characteristics, only stack membrane is difficult to fully shield region of ultra-red sometimes.For such problem points, by that will mix The layer for having the infrared absorbent with infrared ray absorption ability is arranged in film, can correct transmitted light.As described above Technology, a kind of infrared reflecting multilayer film is for example proposed in Japanese Unexamined Patent Application Publication 2008-528313 publications, its comprising first gather Compound layer and the second polymer layer alternately the infrared reflecting layer of lamination and are adjacent on the infrared reflecting layer and lamination Infrared Absorption nanoparticle layers.Here, infrared Absorption nanoparticle layers include the Sb doped oxygen as infrared absorbent Change tin (following, ATO), tin indium oxide (following, ITO) etc..

In addition, there is a kind of use to have the combined oxidation tungsten containing caesium disclosed in Japanese Unexamined Patent Publication 2008-200983 publications (CWO) as infrared absorbent, near-infrared shielding and the excellent near infrared shielding film of luminous ray transmittance.

The content of the invention

As Japanese Unexamined Patent Application Publication 2008-528313 publications, by setting the infrared Absorption containing infrared absorbent Nanoparticle layers shield the high multilayer film of ultrared effect there is provided a kind of.

But, the present inventor etc. has found：As Japanese Unexamined Patent Application Publication 2008-528313 publications, contain infrared absorbent Infrared Absorption nanoparticle layers it is long under high humidity during when being exposed to sunshine, produce asking for discoloration or crackle (cracking) Topic.In addition we know：When being exposed to acid rain during length, discoloration is produced.

In addition we know：When using CWO as Japanese Unexamined Patent Publication 2008-200983 publications, although hot radiation shielding performance is high, But, it can change colour when being exposed to sunshine during being grown under high humidity.In addition we know, when being exposed to acid rain during length, production Change color.

Therefore, the present invention is to complete in view of the foregoing, and its object is to there is provided a kind of stack membrane, it, which has, contains There is the layer of infrared absorbent, wherein, also suppress the generation and discoloration of crackle under the high humidity environment that sunshine irradiates, it is resistance to Cure is excellent.In addition, other purposes of the present invention are there is provided a kind of stack membrane, it, which has, contains infrared absorbent Layer, wherein, under the high humidity environment that sunshine irradiates, it can also keep infrared shielding effect.The present invention it is further its Its purpose is that there is provided a kind of stack membrane it has the layer containing infrared absorbent, wherein, irradiated even in sunshine Under high humidity environment, mist degree can also be reduced.

The problem of the present inventor etc. are in order to solve above-mentioned, has made intensive studies, and as a result distinguishes：By using following structures Into the achievable purpose of the present invention.

That is, above-mentioned problem of the invention is solved by following means.

1. a kind of stack membrane, it has base material and infrared ray-absorbing layer,

The infrared ray-absorbing layer contains infrared absorbent, resin and antioxidant, and is configured at the one of the base material On individual surface, wherein,

The infrared ray-absorbing layer is more than 6.5 with the film surface p H on the surface of base material opposite side.

2. the stack membrane as described in above-mentioned 1, wherein, the infrared absorbent is the combined oxidation tungsten containing caesium.

3. the stack membrane as described in above-mentioned 1 or 2, wherein, the antioxidant is selected from phenol antioxidant and hindered amine One or more of class antioxidant.

4. the stack membrane as any one of above-mentioned 1~3, wherein, the infrared ray-absorbing layer is made containing ultraviolet The composition of gel-type resin and Photoepolymerizationinitiater initiater carries out solidification.

5. the stack membrane as any one of above-mentioned 1~4, it further contains in 800~1300nm of wavelength region Dielectric multilayer film with least one reflection peak, the dielectric multilayer film is low-index layer and high refractive index layer alternating Ground lamination.

Embodiment

Below, embodiments of the present invention are illustrated.

According to the 1st aspect of the present invention there is provided a kind of stack membrane, it has base material and infrared ray-absorbing layer, described infrared Line absorption layer contains infrared absorbent, resin and antioxidant, and is configured on a surface of the base material, wherein, with The infrared ray-absorbing layer is more than 6.5 with the film surface p H on the surface of base material opposite side.

According to the present invention there is provided a kind of stack membrane, it has the layer containing infrared absorbent, wherein, even in the sun Under the high humidity environment of light irradiation, also suppress the generation and discoloration of crackle, sulfidation-resistance is excellent.

The stack membrane of the present invention has the infrared ray-absorbing layer containing infrared absorbent and resin.Here, distinguishing：As above Like that, make has the infrared ray absorbing containing infrared absorbent to the technology for the Japanese Unexamined Patent Application Publication 2008-528313 publications stated The stack membrane of layer, when the stack membrane is exposed into sunshine during length under high humidity, produces discoloration or crackle.

When infrared ray-absorbing layer containing infrared absorbent irradiates sunshine, infrared absorbent absorbs infrared ray and turned Change heat into.Now, the resin of the vicinity of infrared absorbent is high temperature and expansion, but resin outer nearby produces deterioration contraction, It is deformed in the inside of infrared ray-absorbing layer.It is speculated as：By repeating to produce expansion and shrinking, easily crack.

On the other hand, according to the present invention, by adding antioxidant, the free radical in resin can be caught and resin is prevented Deterioration.In addition, by the way that film surface p H is set into more than 6.5, make that the deterioration of antioxidant is slow, can improve prevents resin The effect of deterioration.As a result, thinking that the generation of crackle can be suppressed.

In addition we know：Infrared ray-absorbing layer containing infrared absorbent by exposure to sunshine expose under or high humidity Under environment, so that transmissivity changes.For example, infrared absorbent is in the sun as ATO or stibium-doped zinc oxide (AZO) The lower decrease in transmission (coloring) of light exposure.On the other hand, infrared absorbent as CWO sunshine exposure under transmissivity not It can change, but the transmissivity rise (decolouring) under high humidity environment.So, because infrared absorbent is exposed to sunshine Transmissivity change is produced under irradiation or high humidity, therefore the discoloration of stack membrane can be produced.

It is speculated as：Sunshine is exposed to during contained infrared absorbent is by length in infrared ray-absorbing layer, its electricity Sub- state changes, as a result, photo-absorption region changes, and causing the discoloration of infrared ray-absorbing layer, (infrared absorbent is When ATO or AZO, coloring).On the other hand, by adding antioxidant, the electronic state of infrared absorbent can be made The state in the early stage of stop, it is therefore contemplated that can effectively suppress the discoloration of infrared ray-absorbing layer, (infrared absorbent is ATO Or when AZO, coloring).Think, by the way that the film surface p H of infrared ray-absorbing layer further is adjusted into more than 6.5, to make to resist The deterioration of oxidant is slow, fully obtains the effect of antioxidant.

In addition, when irradiating sunshine to infrared ray-absorbing layer, free radical is produced in resin due to the influence of ultraviolet, Produce the deterioration of resin.Now, peroxide is produced by the participation of oxygen or moisture under high humidity environment, infrared ray-absorbing layer Easy acidification.In the case that infrared absorbent is the combined oxidation tungsten containing caesium, infrared absorbent particle periphery is acid Property when, because caesium occurs to depart from and decolourizes, but thinks by the way that film surface p H is set into more than 6.5, decolouring can be suppressed.Think logical The deterioration further added antioxidant and suppress resin is crossed, the change of color can be further reduced.

Hereinafter, to the inscape of stack membrane of the invention, it is described in detail.It should be noted that it is following, do not have In the case of being distinguished to low-index layer and high refractive index layer, it is referred to as " index layer " as the concept containing both.

In addition, in this specification, represent scope " X~Y " means " more than X below Y ".In addition, as long as no special theory Bright, operation transitivity etc. is determined to be measured under conditions of room temperature (20~25 DEG C)/40~50%RH of relative humidity.

[stack membrane]

The stack membrane of the present invention has base material and the infrared ray-absorbing layer being configured on a surface of the base material.Infrared ray Absorbed layer can be abutted and configured with base material, can also be between base material and infrared ray-absorbing layer across other layers (functional layer). In addition, for infrared ray-absorbing layer, the viewpoint such as other layers contained durability from stack membrane, preferred disposition is in light Incident surface.

One of feature of stack membrane of the present invention is, with infrared ray-absorbing layer, the base material with the infrared ray-absorbing layer The film surface p H on the surface of opposite side is more than 6.5.Hereinafter, infrared ray-absorbing layer is described in detail first.

[infrared ray-absorbing layer]

Because the stack membrane of the present invention has infrared ray-absorbing layer, infrared shielding effect is assigned, infrared shielding can be improved Effect.Infrared ray-absorbing layer is the layer of the absorbability of the light of the near infrared region with 800~2500nm of wavelength, and it is comprising red Ultraviolet absorbers, resin and antioxidant.In addition, in order to assign other functions or in order to improve various characteristics, infrared ray absorbing Layer can contain other additives.

In the stack membrane of the present invention, the film surface p H of infrared ray-absorbing layer is more than 6.5.Film surface p H is to be stacked on base The pH with the surface of base material opposite side of infrared ray-absorbing layer on material；Be relative to infrared ray-absorbing layer coating fluid Drying is coated, or carries out the pH on the film surface of infrared ray-absorbing layer formed by ultraviolet curing.It should be noted that this In specification, film surface p H specific assay method is carried out according to the method described in embodiment.

The film surface p H of infrared ray-absorbing layer higher limit is not particularly limited, if less than 11, then good operability, because This is preferred.In addition, the acidification of the resin with the infrared absorbent periphery to deteriorating and producing with resin suppresses, And the effect suppressed is coloured caused by light is excited to infrared absorbing material.

It is preferred that film surface p H depend on species, the desired performance of the infrared absorbent that uses or antioxidant, If such as film surface p H is more than 6.5, due to being neutrality~weakly alkaline environment, the deterioration of antioxidant can be made slow, Discoloration inhibition under the high humidity environment irradiated so as to sunshine is excellent.

In addition, the more preferably film surface p H of infrared ray-absorbing layer is 7.5~10.5.If film surface p H is 7.5~10.5, Then due to being alkaline atmosphere, by the combined oxidation tungsten containing caesium particle it is charge stabilized caused by discoloration inhibition it is special It is unexcellent.The film surface p H of further preferred infrared ray-absorbing layer is 8.5~9.5.

The present invention preferred embodiment in, infrared ray-absorbing layer contains the combined oxidation tungsten of caesium as infrared Light absorbers, the film surface p H of infrared ray-absorbing layer is 7.5~10.5.

It should be noted that infrared ray-absorbing layer forming method carry out it is aftermentioned, but infrared ray-absorbing layer can be to containing The coating fluid for having infrared absorbent, antioxidant and resin be coated formed by film；To containing infrared absorbent, Antioxidant, active energy ray-curable compound (ultraviolet curing resin etc.) and the coating fluid of Photoepolymerizationinitiater initiater enter Row coating, and any film in the film for being solidified to form it is irradiated by ultraviolet.Here, the film of infrared ray-absorbing layer Surface p H can be controlled by adjusting the pH of coating fluid.

The thickness of infrared ray-absorbing layer is preferably 1 μm~20 μm, more preferably 3~15 μm.If it is more than 1 μm, There is the tendency of infrared ray absorption ability raising, on the other hand, if it is less than 20 μm, the resistance to anti-thread breakage raising of film. In addition, by the way that thickness is adjusted into 1~20 μm, the reducing effect of mist degree can be obtained, the generation of crackle can be suppressed, entered simultaneously One step improves the inhibition of discoloration.

(infrared absorbent)

In the present invention, infrared ray-absorbing layer contains infrared absorbent.Here, " infrared absorbent " as long as with composition The resin material of stack membrane is excellent compared to infrared ray absorption ability, is not particularly limited, it is however generally that, addition can be used The infrared absorbent used in transparent resin.Here, as infrared absorbent, on relative to the mass of good solvent 100 Part dissolving, be dispersed with 1 mass parts compound solution, 800~2500nm near infrared ray wavelength region a part or Light transmittance is less than 50% in universe, further preferably turns into less than 30% compound.

Because infrared ray-absorbing layer contains infrared absorbent, infrared ray-absorbing layer absorbs infrared ray, now, and infrared ray is inhaled Receive agent to absorb infrared ray and generate heat (accumulation of heat) and the resin expansion near infrared absorbent particle, because away from infrared absorbent The resin in the region of particle carries out deterioration contraction and is deformed, and easily cracks.But, according to the present invention, pass through addition Antioxidant, further controls the film surface p H of infrared ray-absorbing layer more than 6.5, under the irradiation of sunshine, The generation of crackle can effectively be suppressed.

In addition, exposed to sunshine or when under high humidity during infrared absorbent length, its optical absorption characteristics can be sent out Changing, so that the reason for changing colour as film.But, by adding antioxidant, and by the film of infrared ray-absorbing layer Surface p H is controlled more than 6.5, can also suppress discoloration (coloring etc.).

As infrared absorbent contained in infrared ray-absorbing layer, it is not particularly limited, can be inhaled for inorganic infrared ray Receive agent, or organic infrared light absorbers.

As the inorganic infrared absorbent that can contain in infrared ray-absorbing layer, it can enumerate：Tin oxide, Sb doped oxygen Change tin (ATO), indium doping tin oxide (ITO), combined oxidation tungsten (caesium doped tungsten oxide (CWO)), lanthanum hexaboride containing caesium (LaB₆), zinc oxide, stibium-doped zinc oxide (AZO), indium doping zinc oxide (IZO), Ga-doped zinc oxide (GZO), aluminium doping oxygen Change zinc, nickel complex class compound.

In addition, as these specific business's product titles, can enumerate as the serial (Nissan Chemicals of Zinc-oxide-based CELNAX Industrial Co., Ltd manufactures), PAZET serial (manufacture of Hakusui Tech Co., Ltd.)；It is used as the ATO dispersion liquids of Sn system (manufacture of SR35M Advanced Nano Products Co., Ltd.), ITO dispersion liquids (Mitsubishi Materials electronization strains Formula commercial firm manufactures), KH serial (Sumitomo Metal Mining Co., Ltd's manufacture)；It is used as CWO points of the combined oxidation tungsten system containing caesium Dispersion liquid (manufacture of YMF-02A Sumitomo Metal Mining Co., Ltd)；It is used as the LaB of lanthanum hexaboride system₆Dispersion liquid (KHF-7AH Sumitomos Metal mine Co., Ltd. manufactures) etc..

Also, it is used as inorganic infrared absorbent, it is possible to use by Cd/Se, GaN, Y₂O₃, the composition such as Au, Ag material.

The average grain diameter of inorganic infrared absorbent is preferably 5~150nm, more preferably 10~120nm.By being adjusted to More than 5nm, makes dispersiveness or infrared ray-absorbable in resin remain well, by setting adjustment below 150nm, can press down The reduction of luminous ray transmissivity processed.It should be noted that for the measure of average grain diameter, utilizing transmission electron microscope Shot, randomly extract such as 50 particles and determine the particle diameter, be averaged.In addition, particle shape not In the case of being spherical, the value for being defined as measure major diameter and calculating.

As the organic infrared light absorbers that can contain in infrared ray-absorbing layer, it can enumerate：It is polyacetylene compound, poly- It is high to electric conductivity such as phenylene compounds, polyphenylene vinylene compound, polypyrrole, polythiophene compound, PEDOT-PSS Molecule；Ammonium compounds；Phthalocyanine compound；The electric conductivity carbons such as CNT, acetylene black, Ketjen black (registration mark), carbon black Material.

In addition, as these specific business's product titles, can enumerate：Denatoron P-502S、Denatoron P- 502RG, Denattron PT-432, Denattron NIR-IM1, Denattron NIR-AM1 (ChemteX plants of formulas of Nagase Commercial firm manufacture), Clevios CPP105D, Clevios CPP134.18D, Clevios CPP141D, Clevios CPG130.6 (BASF plants of (manufacture of Heraeus Co., Ltd.), SEPLEGYDA series (Shin-Etsu Polymer Co., Ltd's manufacture) Lumogen series Formula commercial firm manufactures) etc..

In above-mentioned, from viewpoints, infrared ray absorbing such as the dispersivenesses or infrared ray absorption ability in infrared ray-absorbing layer Agent is preferably selected from antimony-doped tin oxide, indium doping tin oxide, the combined oxidation tungsten containing caesium, lanthanum hexaboride, Sb doped oxidation It is one kind or two or more in zinc, indium doping zinc oxide, electroconductive polymer, electric conductivity carbon material.Particularly preferred infrared ray is inhaled Receipts agent is the combined oxidation tungsten containing caesium.Combined oxidation tungsten containing caesium it is excellent as the optical characteristics of infrared absorbent, And particularly if exposed to sunshine, coloring etc. is not easy to, is had excellent weather resistance.

The composition of combined oxidation tungsten containing caesium is not particularly limited, from the viewpoint of stability, preferred formula：Typically For Cs_xW_yO_zThe oxide of expression, can use Japanese Unexamined Patent Publication 2013-64042 publications or Japanese Unexamined Patent Publication 2010-215451 The same material of material described in publication.In above-mentioned formula, Cs is caesium, and W is tungsten, and O is oxygen.For x, y and z, preferred tungsten With the relation of Cs composition (composition, the x/y of the Cs relative to W) satisfaction 0.001≤x/y≤1, W and O composition are (relative to W's O composition, z/y) meet 2.2≤z/y≤3 relation.

The shape of combined oxidation tungsten containing caesium is not particularly limited, and can use particle shape, spherical, bar-shaped, needle-like, plate The arbitrary structure such as shape, column, indefinite shape, flakey, fusiform, but preferably particle shape.In addition, the composite oxygen containing caesium Change the size of tungsten particle it is not also specifically limited, in the case where the combined oxidation tungsten containing caesium is particle shape, average grain diameter is (flat Equal primary particle size, diameter) for, from the reflection of visible ray can be suppressed, and hot line assimilation effect is may insure, do not produced in addition The deterioration of mist degree caused by raw scattering, and from the aspect of ensuring the transparency, preferably 5~150nm, more preferably 5~100nm. For above-mentioned average grain diameter, with electron microscope observe appear in particle in itself or index layer section or the grain on surface Son, determines the particle diameter of 1,000 arbitrary particle, is obtained as its simple average value (number is average).Here, each particle Particle diameter is represented with the diameter for assuming the bowlder equal with its projected area.

It should be noted that above-mentioned infrared absorbent can be used alone or two or more is applied in combination.

The content of infrared absorbent in infrared ray-absorbing layer is not particularly limited, from by film-strength, film modulus of elasticity It is adjusted to Deng optical characteristics such as physics value or transmissivities from the viewpoint of desired value, relative to total matter of infrared ray-absorbing layer The gross mass of infrared ray-absorbing layer (is set to solid constituent conversion during 100 mass %) by amount, preferably 1~80 mass %, more Preferably 5~70 mass %.If content is more than 1 mass %, sufficient infrared absorption effect can be obtained, if its It for below 80 mass %, then can transmit the luminous ray sufficiently measured.

(resin)

In the present invention, infrared ray-absorbing layer contains resin simultaneously with above-mentioned infrared absorbent.It is water-soluble as the resin Property resin, organic solvent solubility resin can be used.

From the viewpoint of reduction carrying capacity of environment, process load, water-soluble resin is preferably comprised.As water-soluble resin, It is not particularly limited, polyvinyl alcohol resin, gelatin, cellulose family, thickening polysaccharide and with reactive functional groups can be enumerated Polymer.It should be noted that " water solubility " means in this specification：Under the original solution temperature of material, being dissolved in water 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 filtered off Within high molecular 50 mass % of the quality of insoluble matter for addition.

On the other hand, from the viewpoint of the humidity change dynamic effects of film diminish, organic solvent solubility tree is preferably comprised Fat.As organic solvent solubility resin, it is not particularly limited, can enumerates：Acrylic resin, polyurethane-modified acrylic acid tree Fat, polyurethane resin, polyester resin, melmac, polyvinyl acetate, cellulose acetate, makrolon, polyacetals, It is polybutyral, polyamide (nylon) resin, polystyrene resin, polyimide resin, ABS resin, polyvinylidene fluoride, ultraviolet Line gel-type resin.

As ultraviolet curing resin, (methyl) acrylate, urethane acrylate, polyester acrylic can be enumerated Ester, epoxy acrylate, epoxy resin, oxetane resin, these materials can as no-solvent type resin combination Use.

In the case of using above-mentioned ultraviolet curing resin, in order to promote solidification, 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) grade of-butanone 1 acetophenones, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, The benzoin class such as benzyl dimethyl ketal, benzophenone, 2,4 '-dichloro benzophenone, 4,4 '-dichloro benzophenone, to chlorine two The benzophenones such as Benzophenone, 2,4,6- trimethylbenzoyls diphenyl phosphine oxide, Anthraquinones, thioxanthene ketone class etc..These light gather Close initiator can be used alone, two or more can also be combined, or mixture.Particularly combined from curability Consider in terms of the stability or polymerisation reactivity of thing, preferably use acetophenones.

This Photoepolymerizationinitiater initiater can use commercially available product, can enumerate such as BASF Amada Co., Ltd.s manufacture IRGACURE (registration mark) 819, IRGACURE184, IRGACURE907, IRGACURE651 etc. are used as preferred illustration.

It should be noted that it is resistance to assign infrared ray-absorbing layer according to the species for the resin for constituting infrared ray-absorbing layer Nuzzling up property (hard painting propert), therefore, infrared ray-absorbing layer can have hard conating described later concurrently.For example, in the preferred reality of the present invention Apply in mode, infrared ray-absorbing layer makes the composition containing ultraviolet curing resin and Photoepolymerizationinitiater initiater be solidified and shape Into.By using above-mentioned ultraviolet curing resin, hard painting propert can be assigned to infrared ray-absorbing layer.Here, hard painting propert refers to Pencil hardness according to JIS K 5600-5-4 is more than H, preferably more than 2H.Just have the infrared ray of hard conating or hard conating concurrently For the hardness of absorbed layer, in terms of scratch resistance, the destruction or stripping of layer are not preferably produced when being applied with the external stresses such as bending It is harder from the range of grade.

(antioxidant)

In the present invention, infrared ray-absorbing layer contains antioxidant.Antioxidant is contained by infrared ray-absorbing layer, can be with Catch free radical and prevent the deterioration of resin.In addition, with the deterioration of resin, peroxide is produced by oxygen, the participation of water, The periphery of infrared absorbent particle can be avoided to carry out acidification and cause decolouring.

As the species of antioxidant, it is not particularly limited, known antioxidant can be used, as preferably anti-oxidant Agent, can be enumerated：Phenol antioxidant, thio-alcohol antioxidant, phosphite antioxidant, hindered amines antioxidant etc..

As phenol antioxidant, it can enumerate for example：1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, 2,2' methylene bis (4- ethyl -6- tert-butyl phenols), four-[methylene -3- (3', 5'- di-t-butyl -4'- hydroxy phenyls) Propionic ester] methane, 2,6- di-t-butyls-paracresol, 4,4'- thiobis (3 methy 6 tert butyl phenol), 4,4'- butanes Double (3 methy 6 tert butyl phenols), 1,3,5- tri- (3', 5'- di-t-butyl -4'- hydroxybenzyls)-guanamine, 4,6- Double [3- (the tertiary fourths of 3- of (1H, 3H, 5H) triketone, stearyl-β-(3,5- di-t-butyl -4- hydroxy phenyls) propionic ester, triethylene glycol Base -5- methyl -4- hydroxy phenyls) propionic ester], the double [1,1- dimethyl -2- [β-(3- tertiary butyl-4-hydroxy -5- methylbenzenes of 3,9- Base) propionyloxy] ethyl] -2,4,8,10- four oxaspiro [5,5] endecatylene, (the 3,5- bis- of 1,3,5- trimethyls -2,4,6- three Tertiary butyl-4-hydroxy benzyl) benzene, octadecyl 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester etc..Especially as phenol Class antioxidant, preferred molecular weight is more than 550 material.

As thio-alcohol antioxidant, it can enumerate for example：Distearyl -3,3'- thiodipropionates, pentaerythrite-four (β-lauryl-thiopropionate) etc..

As phosphite antioxidant, it can enumerate for example：Three (2,4- di-tert-butyl-phenyls) phosphite esters, distearyl Base pentaerythritol diphosphites, two (2,6- di-tert-butyl-phenyls) pentaerythritol diphosphites, it is double-(2,6- di-t-butyls- 4- aminomethyl phenyls)-pentaerythritol diphosphites, four (2,4- di-tert-butyl-phenyls) 4,4'- diphenylenes-bisphosphonates, 2, 2'- di-2-ethylhexylphosphine oxides (4,6- di-tert-butyl-phenyls) octyl group phosphite ester, 2,2' methylene bis (4,6- di-tert-butyl-phenyls) 2- second Base hexyl phosphite ester etc..

As hindered amines antioxidant, it can enumerate for example：It is double (2,2,6,6- tetramethyl -4- piperidyls) decylates, double (1,2,2,6,6- pentamethyl -4- piperidyls) decylate, four (1,2,2,6,6- pentamethyl -4- piperidyls) -1,2,3,4- butane Tetrabasic ester, double (1,2,2,6,6- pentamethyl -4- piperidyls) -2- (3,5- di-tert-butyl-4-hydroxyl benzyls) -2- normal-butyls third Two acid esters, 1- methyl -8- (1,2,2,6,6- pentamethyl -4- piperidyls)-decylate, 1- [2- [3- (3,5- di-t-butyl -4- hydroxyls Base phenyl) propionyloxy] ethyl] -4- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionyloxy] -2,2,6,6- tetramethyls Piperidines, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, four (2,2,6,6- tetramethyl -4- piperidyls) -1,2,3,4- fourths Alkane-tetrabasic ester, triethylenediamine, 8- acetyl group -3- dodecyl -7,7,9,9- tetramethyl -1,3,8- thriazaspiro [4,5] last of the ten Heavenly stems Alkane -2,4- diketone etc..

Especially as hindered amines antioxidant, the preferred only light stabilizer of the hindered amines containing tertiary amine, it is specific and Speech, preferably double (1,2,2,6,6- pentamethyl -4- piperidyls)-decylates, double (1,2,2,6,6- pentamethyl -4- piperidyls) -2- (3,5- di-tert-butyl-4-hydroxyl benzyls) -2- n-butylmalonic acids ester, four (1,2,2,6,6- pentamethyl -4- piperidyls) -1,2, 3,4- butane tetracarboxylics acid esters or 1,2,2,6,6- pentamethyls -4- piperidine alcohols/tridecyl alcohol and 1,2,3,4- BTCAs Condensation product.

Wherein, phenol antioxidant or hindered amines antioxidant are particularly preferably used.Phenol antioxidant or hindered amine Class antioxidant has the effect caught to the free radical produced by autoxidation.By using these materials, i.e., Make also to can further improve the effect for suppressing discoloration in the case where sunshine exposes.

It should be noted that the antioxidant can be used alone or mix two or more and use.In addition, this is anti-oxidant Agent can use composite, can also use commercially available product.As the example of commercially available product, it can enumerate for example：No Crack (registrars Mark) 200, No Crack (registration mark) M-17, No Crack (registration mark) SP, No Crack (registration mark) SP-N, No Crack (registration mark) NS-5, No Crack (registration mark) NS-6, No Crack (registration mark) NS-30, No Crack (registration mark) 300, No Crack (registration mark) NS-7, No Crack (registration mark) DAH (more than, the emerging chemistry of imperial palace The manufacture of industrial Zhu Shihui Co., Ltd.), Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60、Adekastab AO-616、Adekastab AO-635、Adekastab AO-658、Adekastab AO-80、Adekastab AO-15、Adekastab AO-18、Adekastab 328、Adekastab AO-37、Adekastab LA-52、Adekastab LA-57、Adekastab LA-62、Adekastab LA-67、Adekastab LA-63、 Adekastab LA-68、Adekastab LA-82、Adekastab LA-87、Adekastab 2112、Adekastab HP- 10 (more than, ADEK Co., Ltd. manufacture), IRGANOX (registration mark) 245, IRGANOX (registration mark) 259, IRGANOX (registration mark) 565, IRGANOX (registration mark) 1010, IRGANOX (registration mark) 1024, IRGANOX (registration mark) 1035th, IRGANOX (registration mark) 1076, IRGANOX (registration mark) 1081, IRGANOX (registration mark) 1098, IRGANOX (registration mark) 1222, IRGANOX (registration mark) 1330, IRGANOX (registration mark) 1425WL, IRGAFOS (registration mark) 38, IRGAFOS (registration mark) 168, IRGAFOS (registration mark) P-EPQ, Tinuvin PA144, Tinuvin 765, Tinuvin660DF, Chimassorb2020 (manufacture of BASF Japanese strain Shi Hui commercial firms), Sumilizer (notes Volume trade mark) GM, Sumilizer (registration mark) GA-80 (more than, Sumitomo Chemical Co's manufacture) etc..

The content of antioxidant in infrared ray-absorbing layer is not particularly limited, relative to the gross mass of infrared ray-absorbing layer (gross mass of infrared ray-absorbing layer is set to solid constituent conversion during 100 mass %), preferably 0.01~10 mass %, more Preferably 0.05~3.0 mass %.If content is more than 0.01 mass %, excellent anti-oxidation function can be shown, such as Really it is below 10 mass %, then can obtain antioxidant effect corresponding with addition, and can obtain excellent optical characteristics.

(surfactant)

In infrared ray-absorbing layer, in addition to infrared absorbent, antioxidant and resin, preferably levelling is used as to play Under the purpose of the function such as agent or lubricant, surfactant is added.

As surfactant, it is not particularly limited, can enumerates：Amphion surfactant, cationic surface Activating agent, anionic surfactant, nonionic surfactant, fluorine class surfactant and silicon class surfactant. Wherein, from film coated surface from the viewpoint of uniformity, outward appearance, preferably acrylic surfaces activating agent, silicon class surfactant, Or fluorine class surfactant, particularly preferred fluorine class surfactant.As surfactant, the surface of chain alkyl is preferably comprised Activating agent, the surfactant of the alkyl more preferably with carbon number 6~20.

As amphion surfactant, it can enumerate：Alkyl betaine, alkyl amine oxide, cocamidopropyl propyl amide Glycine betaine, lauroylamidopropyl betaine, palm kernel fatty acid amido propyl betaine, sodium cocoamphoacetate, bay Acyl both sexes guanidine-acetic acid sodium, dodecanamide propyl hydroxyl sulfo betaine, dodecanamide propyl amine oxide, myristamide propylamine Oxide, hydroxy alkyl (C12-14) hydroxyethyl methyl amimoacetic acid.

As cationic surfactant, alkylamine salt, quaternary ammonium salt can be enumerated.

As anionic surfactant, it can enumerate：Alkyl sulfate salt, polyoxyethylene alkyl ether sulfuric acid, alkane Base benzene sulfonate, soap, ether phosphates, alkenyl succinic dipotassium.

As nonionic surfactant, it can enumerate：(for example Kao Corp manufactures polyoxyethylene alkyl ether Emulgen), polyoxyethylene sorbitan fatty acid ester (such as Kao Corp manufacture RHEODOL TW series), glycerine Fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine, alkyl chain triacontanol acid amides.

As fluorine class surfactant, it can enumerate：SURFLON S-211、SURFLON S-221、SURFLON S-231、 SURFLON S-241, SURFLON S-242, SURFLON S-243, SURFLON S-420 (Seimichemical plants of formulas of AGC Commercial firm manufacture), MEGAFACE F-114, MEGAFACE F-410, MEGAFACE F-477, MEGAFACE F-552, MEGAFACE F-553 (Dainippon Ink Chemicals's manufacture), MEGAFACE FC-430, MEGAFACE FC-4430, MEGAFACE FC- 4432 (manufactures of 3M Co., Ltd.).

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

It should be noted that above-mentioned surfactant can be used alone or two or more is applied in combination.

The content of surfactant in infrared ray-absorbing layer is not particularly limited, from fully obtaining as levelling agent or The purpose of the function of lubricant etc. is set out, when infrared ray-absorbing layer is set into 100 mass % with the gross mass of coating fluid, is preferably 0.001~0.30 mass % scope, more preferably 0.005~0.10 mass %.

In addition, the content of surfactant relative to infrared ray-absorbing layer gross mass (by total matter of infrared ray-absorbing layer Amount is when being set to 100 mass %), preferably 0.005~5 mass % scope, more preferably 0.01~3 mass %.

(other additives)

As described above, infrared ray-absorbing layer is in addition to infrared absorbent, resin and antioxidant, it can be lived containing surface Property agent, but as long as do not damage the present invention effect, can be further containing other additives beyond it.

For example, infrared ray-absorbing layer is as other additives, inorganic nano-particle can be contained.By containing organic/inorganic nano Particle, infrared ray-absorbing layer and base material are abutted and in the case of configuration, the adaptation relative to base material can be improved, and improve The marresistance of stack membrane.It should be noted that in this specification, " inorganic nano-particle " is meant by being surveyed using dynamic scattering method The particle that fixed average grain diameter is constituted for below 200nm inorganic compound (preferably inorganic oxide).

The specific composition of inorganic nano-particle is not particularly limited, can use can be as described below The SiO of metal oxide in dielectric multilayer film₂、Al₂O₃、ZrO₂、TiO₂、CeO₂Deng.

The content of inorganic nano-particle in infrared ray-absorbing layer is not particularly limited, from by case hardness, film springform The optical characteristics such as physics value or transmissivity such as amount are adjusted to from the viewpoint of desired value, preferably 10~80 mass %, more Preferably 20~65 mass %.

(forming method of infrared ray-absorbing layer)

To the forming method of infrared ray-absorbing layer, it is not particularly limited, as long as it is red for more than 6.5 to form film surface p H Outside line absorbed layer, but preferably use the previously prepared infrared ray suction for being used to form the infrared ray-absorbing layer with above-mentioned composition Layer coating fluid is received, and is coated with the method (damp process) of the coating fluid.

As the preparation method of infrared ray-absorbing layer coating fluid, as long as specific film surface p H can be obtained, do not have There is special limitation.Infrared ray-absorbing layer coating fluid can for example, by by infrared absorbent, resin, further as needed Other additives such as used surfactant make an addition to solvent, and are stirred mixing to prepare.Use ultraviolet curing In the case of type resin, Photoepolymerizationinitiater initiater is further added.Now, the order of addition of each composition is it is not also specifically limited, can To stir while adding each composition successively and being mixed, it can also stir while disposably adding and mixing.

For pH adjustment, as long as use arbitrary acid or alkalescence pH regulators, the feelings of such as aqueous solvent Condition, it is possible to using in infrared ray-absorbing layer coating fluid, add alkali and/or lemon as sodium carbonate or sodium hydroxide Sour method is carried out as acid, acetic acid or sulfuric acid.

As described above, being not particularly limited for the acid or alkaline pH regulators for adjusting film surface p H, using non-aqueous Organic solvent in the case of, using including the seasons such as the acid such as the aliphatic acid wherein dissolved, alkali metal salt, alkali salt, quaternary amine When there is polymer of quaternary ammonium salt etc. in the solution of ammonium salt, structure, desired pH scope is easily tailored as.

Further, it is possible to use the complex compound formation compound such as chelating reagent.

As the solvent for infrared ray-absorbing layer coating fluid, as long as can fully dispersion resin, infrared ray absorbing Agent and antioxidant, are not particularly limited, and can use various organic solvents or aqueous solvent.

As the organic solvent, it is not particularly limited, can enumerates for example：The alcohol such as methanol, ethanol, normal propyl alcohol, isopropanol The ethers such as the esters such as class, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, Anaesthetie Ether, propylene glycol monomethyl ether, two Ketones such as the amide-types such as NMF, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc..These organic solvents can be independent Using or mix two or more and use.In above-mentioned organic solvent, it is considered to resin, infrared absorbent and antioxidant it is scattered During property, esters, ethers, ketone are preferably used, further preferably using ketone.

As the aqueous solvent, it is not particularly limited, water or water and methanol, ethanol, normal propyl alcohol, isopropanol can be enumerated Or the mixed solvent of ethyl acetate etc..In above-mentioned aqueous solvent, it is considered to the dispersiveness of resin, infrared absorbent and antioxidant When, the mixed solvent of particularly preferred water and methanol, ethanol, normal propyl alcohol or isopropanol.

Using water and a small amount of organic solvent mixed solvent when, for the content of the mixed solvent reclaimed water, will mix Solvent entirety is set to 100 mass %, more preferably preferably 10~60 mass %, 20~50 mass %.

The concentration (using in the case of various kinds of resin, it amounts to concentration) of resin is preferred in infrared ray-absorbing layer coating fluid For 0.5~30 mass %.In addition, infrared ray-absorbing layer is preferably 0.1~50 with the concentration of the infrared absorbent in coating fluid Quality %.In addition, infrared ray-absorbing layer is preferably 0.01~10 mass % with the concentration of antioxidant in coating fluid.

In addition, infrared ray-absorbing layer is preferably 0.005~0.30 mass % with the concentration of surfactant in coating fluid.

It is coated by the infrared ray-absorbing layer to preparation as described above with coating fluid, infrared ray suction can be formed Receive layer.Here, as coating method, be not particularly limited, the coating that can be carried out by, for example, bar, using spin coating, The damp process of the coating of dip-coating etc. is formed.Furthermore it is possible to dispensing coating machine, gravure coating machine, unfilled corner wheel coating machine etc. even Continuous apparatus for coating is coated, is film-made.

Coating, the drying condition of above-mentioned infrared ray-absorbing layer, can be with it is not also specifically limited, in order to promote to solidify, be crosslinked Using appropriate temperature, drying time.Particularly in the case where using ultraviolet curing resin as resin, in addition suitably Adjust illumination wavelength, illumination, the light quantity of ultraviolet light.

[base material]

The stack membrane of the present invention, which is included, to be used to support above-mentioned infrared ray-absorbing layer or other layers arbitrarily set (such as electric Amboceptor multilayer film etc.) base material.As the base material of stack membrane, various resin films can be used, polyolefin film (poly- second can be used Alkene, polypropylene etc.), polyester film (polyester terephthalate (PET), PEN etc.), polyvinyl chloride, 3 acetic acid Cellulose etc., preferably polyester film.As polyester film (hereinafter referred to as polyester), be not particularly limited, be preferably with dicarboxylic acids into Divide and diol component is main constituent and with film formative polyester.

Thickness for the base material of the present invention is preferably 10~300 μm, particularly preferably 20~150 μm.In addition, base material can The base material of overlapping 2 is thought, in this case, its species can be with identical or different.

The transmissivity of visible region shown in the JIS R3106-1998 of base material is preferably more than 85%, particularly preferably More than 90%.By base material be above-mentioned transmissivity more than, it is visible shown in the JIS R3106-1998 when making to be set to stack membrane The transmissivity in light region is more than the 50% (upper limit：100%) aspect be it is favourable, preferably.

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.

In addition, as the base material of the present invention, in addition to the base material enumerated in above-mentioned, dielectric multilayer described later can be used There is the base material of self-supporting in film.As the dielectric multilayer film with self-supporting, it is not particularly limited, can enumerates for example Dielectric multilayer film made of coetrusion or common casting method etc..

[dielectric multilayer film]

For the stack membrane of the present invention, in the case where the light (such as infrared light) with specific wavelength is injected, it is At least reflect a part for the light and play shield effectiveness (and being effect of heat insulation in the case of infrared light), preferably enter one Dielectric multilayer film of the step with low-index layer and high refractive index layer alternately lamination.It is preferred that the dielectric multilayer film There is at least one reflection peak in 800~1300nm of wavelength region.Here, dielectric multilayer film can be set across base material In the opposite side of infrared ray-absorbing layer, it can also be arranged at and infrared ray-absorbing layer phase the same side on base material.

In the manner, constitute dielectric multilayer film index layer be low-index layer or be high refractive index layer according to The contrast of the refractive index of adjacent index layer judges.Specifically, when some index layer being set into datum layer, if adjacent It is connected to the index layer of the datum layer refractive index compared with datum layer low, then judgment standard layer is that (adjoining course is high refractive index layer Low-index layer).On the other hand, if the refractive index of adjoining course is high compared with datum layer, judgment standard layer is low-refraction Layer (adjoining course is high refractive index layer).Therefore, index layer is high refractive index layer or is that low-index layer is basis and adjoining course The relation for the refractive index having and the relative layer determined, according to the relation with adjoining course, some index layer can be high folding Penetrate rate layer, or low-index layer.

As index layer, it is not particularly limited, preferably uses the known index layer used in the technical field. As known index layer, the index layer that method formation is for example film-made using dry type can be enumerated；Pass through the extrusion molding of resin The index layer formed；With index layer formed by use film by wet method.Wherein, from the viewpoint of manufacture efficiency, Preferably use film by wet method.

As described above, be low-index layer or be high refractive index layer be according to and the relation of adjacent index layer determine Relative layer, some index layer can turn into low-index layer, can also turn into high refractive index layer, below, in index layer, The composition of high refractive index layer and low-index layer to representative is illustrated.

(by carrying out the index layer that extrusion molding is formed to resin)

In the present invention, the resin that can be used in alternate high refractive index layer and low-index layer is not limited especially Fixed, preferably at least 1 layer is birefringence and is orientated.It is, for example, possible to use remembering in Japanese Unexamined Patent Application Publication 2008-528313 publications The resin of load or the appropriate resin modified.

As specific example, the copolymerization of polyethylene terephthalate, polyethylene terephthalate can be enumerated Thing, poly- (methyl methacrylate), the copolymer of poly- (methyl methacrylate), terephthalic acid (TPA)-cyclohexanedimethanol-second two Alcohol copolymer, PEN, copolymer of PEN etc., but it is not limited to these. 1 kind of these resins can be used in each high refractive index layer and low-index layer, or uses combination of more than two kinds.In addition, conduct It is preferred that resin combination example, the combination of the resin described in 6,352, No. 761 specifications of U.S. Patent No. can be enumerated.Can To use above-mentioned resin, for example, pass through continuous flat film manufacturing line formation dielectric multilayer film using coetrusion.

(index layer formed using film by wet method)

In wet type membrane formation, can by being coated successively to coating fluid, dry method；Coating fluid is weighed Layer coating, the method etc. dried and form index layer.The index layer of the stack membrane of the manner preferably passes through the film by wet Method and formed, more preferably by the way that coating fluid is carried out into double-layer coating, the method for drying is formed.

- high refractive index layer-

For high refractive index layer, from the viewpoint of the control of refractive index becomes easily, metal oxide is preferably comprised Particle, water-soluble resin, curing agent, surfactant, other additives can be contained as needed in addition.Need explanation It is that in facility, metal oxide particle and water-soluble resin contained in high refractive index layer are referred to as " the 1st metal individually below Oxide particle " and " the 1st water-soluble resin ".

(1) the 1st metal oxide particle

As the 1st metal oxide particle, it is not particularly limited, preferably refractive index is 2.0~3.0 metal oxide Particle.Specifically, it can enumerate：Titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, colloidal alumina, lead titanates, red lead, yellow lead, Zinc yellow, chromium oxide, iron oxide, iron oxide black, cupric oxide, magnesia, magnesium hydroxide, strontium titanates, yittrium oxide, niobium oxide, europium oxide, oxygen Change lanthanum, zircon, tin oxide etc..Wherein, for the 1st metal oxide particle, from transparent and high formation refractive index high refraction From the viewpoint of rate layer, preferably titanium oxide, zirconium oxide, from the viewpoint of weatherability raising, more preferably rutile-type is being (just Prismatic crystal shape) titanium oxide.

In addition, titanium oxide can be the form of the core shell particle coated with siliceous hydrous oxide.The core shell Particle has by the surface of Titanium particles on the titanium oxide as core, and the shell being made up of siliceous hydrous oxide is wrapped The structure covered.

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 state component 100 of high refractive index layer, more preferably preferably 15~85 mass %, 20~80 mass %, More preferably 30~77 mass %.

In addition, the 1st metal oxide particle is more preferably volume average particle size for 1~100nm, more preferably 3~ 50nm.When volume average particle size is below 100nm, mist degree is less and visible light transmission is excellent, therefore preferably.Need explanation It is that in this specification, the value of " volume average particle size " uses the value determined by following method.Specifically, electronics is used Microscope observation appears in the section of index layer or arbitrary 1000 particles on surface and determines particle diameter, has respectively The particle of d1, d2 ... di ... dk particle diameter is the presence of n1, n2 ... in the group of ni ... nk metal oxide particles, In the case where volume of every 1 by particle is set to vi, calculate with volume average particle size mv={ Σ (vidi) }/{ Σ (vi) } The average grain diameter that the volume of expression is weighted.

(2) the 1st water-soluble resins

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, polyvinyl alcohol resin is preferably used.

Polyvinyl alcohol resin

As the polyvinyl alcohol resin, common poly- second obtained from polyvinyl acetate is hydrolyzed can be enumerated Enol (unmodified polyethylene alcohol), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonionic modified polyethylene The modified polyvinylalcohols such as alcohol, vinyl alcohol polymer.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 use at present can be with widely used various bright in silver halide picture photosensitive Material Field Glue.It can enumerate and for example carry out the ferment treatment gelatin of ferment treatment and bright in the manufacturing process of acid treatment gelatin, alkali treated gelatin, gelatin Gum derivative etc., the gelatine derivative is used as the amino of functional group, imino group, hydroxyl, carboxyl, and apparatus to have in molecule The reagent for having the group that can be reacted is handled and is modified to.

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

Cellulose family

As cellulose family, it is preferable to use water miscible cellulose derivative.It can enumerate for example：Carboxy methylcellulose Plain (cellulose carboxyl methyl ether), methylcellulose, hydroxy-methyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose etc. Water-soluble cellulose derivative；Carboxy methyl cellulose (cellulose carboxyl methyl ether), carboxy ethyl cellulose etc. are containing carboxylic acid group's Cellulose family；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, is the material that intramolecular has many hydrogen bond bases.The thickening polysaccharide has root The larger characteristic of differences in viscosity when viscosity according to the difference of intermolecular hydrogen bond force caused by temperature during low temperature and high temperature.Separately Outside, when adding metal oxide microparticle in viscosifying polysaccharide, the hydrogen being considered in low temperature with its metal oxide microparticle is caused Viscosity rises caused by key.For its viscosity ascensional range, viscosity at 15 DEG C is usually more than 1.0mPas, is preferably More than 5.0mPas, more preferably more than 10.0mPas.

As workable thickening polysaccharide, be not particularly limited, it is however generally that, can enumerate known natural simple polysaccharide, Natural complex polysaccharide, the simple polysaccharide of synthesis, synthesis complex polysaccharide.On the detailed of these polysaccharide, " biochemistry word is referred to Allusion quotation (second edition), Tokyo 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, it can enumerate for example：PVP class, polyacrylic acid, AA-AN copolymerization thing, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylate copolymer, acrylic acid-the third The acrylic resins such as olefin(e) acid ester copolymer；Styrene-acrylic copolymer, Styrene-methyl Acrylic Acid Copolymer, benzene second Alkene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic copolymer, styrene-Alpha-Methyl benzene The styrene acrylic resins such as ethylene-acrylic acid-acrylate copolymer；Styrene-styrene sodium sulfonate copolymers, benzene second Alkene -2- hydroxyethylmethacry,ates copolymer, styrene -2- hydroxyethylmethacry,ates-styrene sulfonic acid potassium copolymer, benzene second Alkene-maleic acid, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid are common Polymers, vinyl acetate-maleate copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic copolymerization The vinyl acetate lipin polymer such as thing；And their salt.Wherein, PVP class and being total to containing it are preferably used Polymers.

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 determined by gel permeation chromatography (GPC).

For the content of the 1st water-soluble resin, relative to the solid constituent 100 mass % of high refractive index layer, preferably 5 ~50 mass %, more preferably 10~40 mass %.

(3) curing agent

Curing agent have with the 1st water-soluble resin (preferably polyvinyl alcohol resin) reaction contained in high refractive index layer and Form the function of the network of hydrogen bond.

As curing agent, as long as occurring curing reaction with the 1st water-soluble resin, it is not particularly limited, it is however generally that, The compound with the group that can be reacted from water-soluble resin can be enumerated or promote the different groups that have of water-soluble resin that Compound as this reaction.

As concrete example, in the case where using polyvinyl alcohol as the 1st water-soluble resin, boric acid and its salt are preferably used It is used 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 oxygen acid and its salt of the atom centered on boron atom.Specifically, may be used Enumerate：Adjacent boric acid, hypoboric acid, metaboric acid, tetraboric acid, five boric acid, eight boric acid and their salt.

For the content of curing agent, relative to the mass % of solid constituent 100 of high refractive index layer, preferably 1~10 matter Measure %, more preferably 2~6 mass %.

During especially with polyvinyl alcohol as 1 water-soluble resin, total usage amount of curing agent, 1g polyvinyl alcohol is preferred For 1~600mg, 1g polyvinyl alcohol is more preferably 100~600mg.

(4) surfactant

As the surfactant that can contain in high refractive index layer, it is not particularly limited, can uses with that can add In the same surfactant of the surfactant of above-mentioned infrared ray-absorbing layer, therefore, detail explanation is omitted.

(5) other additives

High refractive index layer can also contain other additives.As other additives, amino acid, latex resin, lithium can be enumerated Compound etc..In addition, Japanese Unexamined Patent Application 57-74193 publications, Japanese Unexamined Patent Application 57-87988 publications, Japanese Unexamined Patent Application 62- Ultra-violet absorber described in No. 261476 publications；Japanese Unexamined Patent Application 57-74192 publications, Japanese Unexamined Patent Application 57-87989 Number publication, Japanese Unexamined Patent Application 60-72785 publications, Japanese Unexamined Patent Application 61-146591 publications, Japanese Unexamined Patent Publication 1-95091 Anti-fading agent described in publication, Japanese Unexamined Patent Publication 3-13376 publications etc.；Japanese Unexamined Patent Application 59-42993 publications, Japan JP 59-52689 publications, Japanese Unexamined Patent Application 62-280069 publications, Japanese Unexamined Patent Application 61-242871 publications, Japan Fluorescent whitening agent described in Unexamined Patent 4-219266 publications etc.；Sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, hydrogen-oxygen Change the pH regulators such as potassium, potassium carbonate；Defoamer；The lubricants such as diethylene glycol；Preservative；Mould inhibitor；Antistatic agent；Delustering agent； Heat stabilizer；Antioxidant；Fire retardant；Nucleator；Inorganic particulate；Organic filler；Viscosity reductant；Lubricant；Infrared absorbent； Pigment；Various additives etc. known to pigment etc. can be used as other additives.

- low-index layer-

From the viewpoint of the control of refractive index becomes easily, low-index layer also preferably comprises metal oxide grain in addition Son.In addition water-soluble resin, curing agent, surfactant, other additives can be contained as needed.It should be noted that In convenient profit, metal oxide particle and water-soluble resin contained in low-index layer are referred to as " the 2nd metal oxygen individually below Compound particle " and " the 2nd water-soluble resin ".

(1) the 2nd water-soluble resin

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

Now, high refractive index layer and low-index layer are poly- as the 1st water-soluble resin and the use of the 2nd water-soluble resin In the case of vinyl alcohol resin, the different polyvinyl alcohol resins of saponification degree are preferably used respectively.Thus, interface is suppressed Mixing, infrared reflectivity (infrared shielding rate) becomes better, and mist degree can be with step-down.It should be noted that " soap in this specification Change degree " means that hydroxyl is total relative to the acetyl group epoxide (material for being derived from the vinyl acetate of raw material) and hydroxyl in polyvinyl alcohol Several ratios.

(2) the 2nd metal oxide particles

As the 2nd metal oxide particle, it is not particularly limited, preferably uses synthesis non-crystalline silica, colloidal state two The silica such as silica (silica), more preferably using acid colloidal silica sol.In addition, being reduced from further From the viewpoint of refractive index, as the 2nd metal oxide particle, the inside of particle can be used to have cuniculate hollow minute particle, Particularly preferably using the hollow minute particle of silica (silica).

Colloidal silica can for its surface has been carried out it is cation-modified obtain material, alternatively, it is also possible to being use Material obtained from Al, Ca, Mg or Ba etc. are handled.

In addition, the 2nd metal oxide particle can carry out surface coating using Surface coating composition.

For the 2nd metal oxide particle (preferably silica) contained in the low-index layer of the present invention, it is put down (number is average for equal particle diameter；Diameter) it is preferably 3~100nm, more preferably 3~50nm.It should be noted that in this specification, With regard to metal oxide microparticle " (number is average for average grain diameter；Diameter) " for, appear in particle sheet with electron microscope observation The particle in the section or surface of body or index layer, determines the particle diameter of 1,000 arbitrary particle, is used as its simple average value (number is average) is obtained.Here, the particle diameter of each particle is represented with the diameter for assuming the bowlder equal with its projected area.

For the content of the 2nd metal oxide particle in low-index layer, relative to the total solid of low-index layer The mass % of composition 100, preferably 0.1~85 mass %, more preferably 30~80 mass %, more preferably 45~75 matter Measure %.

From viewpoints such as adjustment refractive indexes, the 2nd above-mentioned metal oxide can be used alone, and can also combine 2 kinds Use above.

(3) curing agent, surfactant, other additives

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

The dielectric of the such high refractive index layer constituted and low-index layer is more more than alternately lamination has In tunic, at least one layer of high refractive index layer and low-index layer is preferably the index layer formed using film by wet method, Both high refractive index layer and low-index layer are more preferably the index layer formed using film by wet method.Also, height refraction At least one layer of rate layer and low-index layer preferably comprises metal oxide particle.That is, stack membrane of the invention is also containing friendship The alternately dielectric multilayer film of lamination low-index layer and high refractive index layer, preferably low-index layer or high refractive index layer contains There is metal oxide particle.

Also, more preferably both high refractive index layer and low-index layer contain metal oxide particle.

From the viewpoint of infrared reflectivity can be improved with few number of plies, preferably significantly it is related to the stack membrane of the present invention Low-index layer and high refractive index layer between specific refractivity.In the manner, by low-index layer and high refractive index layer In at least one of the laminated body of composition, adjacent low-index layer and the refringence of high refractive index layer are preferably more than 0.1, More preferably more than 0.3.In the case of the laminated body with multiple high refractive index layers and low-index layer, whole laminated bodies In high refractive index layer and low-index layer refringence preferably in above-mentioned preferred scope.But, in this case, close Can be the composition outside above-mentioned preferred scope in the superiors or undermost index layer that constitute dielectric multilayer film.

It is used as the optical characteristics of the stack membrane of the manner, the transmissivity of the visible region shown in JIS R 3106-1998 Preferably more than 50%, 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%.

In addition, in general, infrared shield film the sun go directly light incident light spectrum in infrared domain and indoor temperature Rising has relation, by being shielded, can suppress the rising of indoor temperature.With JIS JIS R3106-1998 institutes Based on the weight coefficient of record, observing will be infrared complete from infrared minimal wave length (760nm) to most long wavelength (3200nm) When the gross energy in domain is set to 100, during from 760nm to the cumlative energy of each wavelength, the energy from 760nm to 1300nm, which is amounted to, accounts for red About the 75% of foreign lands entirety.Therefore, shield the wavelength region be summer energy-saving effect caused by hot radiation shielding efficiency it is best.This The infrared shielding film of invention makes as the blooming and unit of dielectric multilayer film, particularly preferably design dielectric multilayer film The near-infrared wavelength region obtained in 800~1300nm has the reflection peak (maximum) more than reflectivity 50%, more preferably designs Dielectric multilayer film so that there is the reflection peak that maximum reflectivity is about more than 80% in the region.

As the number of plies (total number of plies of high refractive index layer and low-index layer) of the index layer of dielectric multilayer film, from upper From the viewpoint of stating, preferably 6~50 layers, more preferably 8~40 layers, more preferably 9~31 layers, particularly preferably 11~ 30 layers.The number of plies of the index layer of dielectric multilayer film is in above range, achievable excellent heat-proof quality and the transparency, film Suppression peeled off or chapped etc., therefore preferably.It should be noted that dielectric multilayer film have multiple high refractive index layers and/ Or in the case of low-index layer, each high refractive index layer and/or each low-index layer can be identical layer respectively, or Different layers.

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

Here, in the case of the thickness of 1 layer of measure, without clear and definite in the border of high refractive index layer and low-index layer Interface, constitute and continuously change sometimes.The interface zone that continuously changes is constituted this, is set to largest refractive index-most In the case of little refraction rate=Δ n, regard the minimum refractive index of 2 interlayers+Δ n/2 place 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 uses sputtering method from table It is etched towards depth direction, most surface can be set to, with 0.5nm/min by 0nm by using XPS surface analysis apparatus Speed sputtering, determine atomic composition ratio and observe.Alternatively, it is also possible to by the way that stack membrane is cut off, use section XPS surfaces Analytical equipment determines atomic composition ratio to confirm.

XPS surface analysis apparatus is not particularly limited, and any machine can be used.As the XPS surface analysis apparatus, The ESCALAB-200R that can for example use VGscientific companies to manufacture.X-ray anode uses Mg, with power output 600W (accelerating potential 15kV, emitter current 40mA) is measured.

[adhesive layer]

The stack membrane of the present invention can further have adhesive layer.The adhesive layer generally across base material be arranged at it is infrared The surface of line absorption layer opposite side, can also further set known peeling paper (barrier film).As the composition of adhesive layer, do not have There is special limitation, can be used such as dry laminating agent, wet laminating agent, adhesive, sealant, hot solvent.As adhesive, It can be used such as polyester resin, polyurethane based resin, polyvinyl acetate esters resin, acrylic resin, nitrile rubber.

The thickness of adhesive layer is preferably 1~100 μm, more preferably 3~50 μm.If it is more than 1 μm, there is bonding Property improve tendency, can obtain sufficient bonding force.On the contrary, if it is less than 100 μm, not only the transparency of stack membrane is carried Height, and stack membrane is attached at after glass pane, do not cause aggegation to destroy in bonding interlayer when peeling off, there is adhesive not The tendency remained in glass surface.

As the forming method of adhesive layer, it is not particularly limited, preferably the base material with being formed with above-mentioned infrared ray-absorbing layer Differently, adhesive layer is coated with coating fluid on peeling paper (barrier film) and dries and form adhesive layer, then, to bonding The method that layer and dielectric multilayer film or base material are fitted.

[hard conating]

The present invention stack membrane as the sealer for improving resistance to nuzzling up property, can base material with bonding The superiors of the opposite side in layer side, are folded to the hard conating containing the resin solidified due to heat or ultraviolet etc. Layer.In the case that special infrared ray-absorbing layer does not have the function as hard conating concurrently, further preferably with hard conating.

As the solidified resin used in hard conating, thermohardening type resin or ultraviolet curing resin can be enumerated, from From the aspect of being easily formed, preferred ultraviolet curing resin, wherein, more preferably pencil hardness is at least 2H solidified resin. Such gel-type resin can be used alone or two or more is applied in combination.

It should be noted that as this ultraviolet curing resin, can use and can be used as above-mentioned [infrared ray suction Receive layer] item in the same ultraviolet curing resin of the ultraviolet curing resin of resin that illustrates, therefore, it is specifically It is bright to omit.

From the viewpoint of the raising of hard painting propert and the transparent raising of stack membrane, 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 can enumerate the hard conating painting for example prepared containing above-mentioned each composition Cloth liquid, then, is coated using bar etc. to coating fluid, and coating fluid is solidified using heat and/or UV, forms the side of hard conating Method etc..

[other functional layers]

The stack membrane of the present invention can have the layer (other functional layers) beyond above-mentioned layer.For example, as other layers, Intermediate layer can be set." intermediate layer " means the layer or base material and dielectric multilayer between base material and infrared ray-absorbing layer herein Layer between film.

As the constituent material in intermediate layer, polyester resin can be enumerated, polyvinyl alcohol resin, vinylite, poly- Vinyl acetal resin, acrylic resin, polyurethane resin etc., preferably use the low material of the compatibility of additive, Tg.

[manufacture method of stack membrane]

On the manufacture method of stack membrane, it is not particularly limited, as long as containing infrared absorbent, resin and anti-oxidant Agent, and film surface p H can be formed for more than 6.5 infrared ray-absorbing layers, then it can use any means.Here, on infrared ray Absorbed layer, dielectric multilayer film, adhesive layer, the forming method of hard conating itself have been carried out above-mentioned, therefore, omit herein each The detailed description of the manufacture method of layer (multilayer film).

As the method for manufacture stack membrane, for example following method can be enumerated.It can enumerate：(1) on a surface of base material Dielectric multilayer film is formed on (with configuration barrier film and the surface of the surface opposite side of adhesive layer), on the dielectric multilayer film Infrared ray-absorbing layer is formed, thereafter, the method for forming hard conating on the infrared ray-absorbing layer as needed；(2) in base material Dielectric multilayer film is formed on one surface (surface of configuration barrier film and adhesive layer), thereafter, on another surface of base material Infrared ray-absorbing layer is formed, also, forms method of hard conating etc. on the infrared ray-absorbing layer as needed.In above-mentioned manufacture In method (1) and any means of (2), when infrared ray-absorbing layer is the composition for having hard conating concurrently, hard painting is formed that can omit In terms of the process of layer preferably.

[application of stack membrane]

The stack membrane of the present invention can apply to the field of broadness.For example, being used as window or automotive window outside building room Fitted Deng long-time in the equipment of sunshine, and assign the windows such as the hot line reflectance coating of hot line reflecting effect patch use Film or agricultural vinyl house film etc., are used with the purpose for mainly improving weatherability.In addition, being used as automobile is sandwiched in The automobile stack membrane between glass and glass such as laminated glass it is also preferred that being used.

Embodiment

Below, embodiment is enumerated, the present invention is specifically described, but the present invention is not limited to these.It should be noted that In embodiment, the expression of " part " or " % " is used sometimes, but as long as without specified otherwise, then it represents that " mass parts " or " matter Measure % ".

《The making of stack membrane》

The ＞ of ＜ embodiments 1

(preparation of infrared ray-absorbing layer coating fluid 1)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 1.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Co., Ltd. manufactures) 633 mass parts

YMF-02A (combined oxidation tungsten (the Cs containing caesium_0.33WO₃), the mass % of solid constituent 28.7, the matter of particle concentration 18.5 Measure %, average grain diameter 15nm, refractive index 1.66：Sumitomo Metal Mining Co., Ltd manufactures) 294 mass parts

Adekastab AO-80 (phenol antioxidant：ADEKA Corp. manufactures) 3.9 mass parts

Acrit 1SX-1065 (quaternary antistatic polymer：Great achievement fine chemical Co., Ltd. manufactures) 6.4 Mass parts

The mass parts of methyl ethyl ketone 62.

(preparation of adhesive layer coating fluid 1)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares adhesive layer coating fluid 1.

COPONYL N-2147 (acrylic adhesives：The manufacture of synthesis KCC of Japan) 638 mass parts

(the hydroxyphenyltriazinuv class ultra-violet absorbers of Tinuvin 477：BASF Amada Co., Ltd.s manufacture) 20 mass parts

CORONATE HX (crosslinking agents：Japanese Polyurethane Industrial Co., Ltd manufacture) 0.7 mass parts

The mass parts of ethyl acetate 341.

(making of stack membrane 1)

50 μm of the thickness as base material polyethylene terephthalate (PET) film (Japan spin Co., Ltd. manufacture A4300 on), the infrared ray-absorbing layer coating fluid 1 of above-mentioned middle preparation is coated with using gravure coating machine, silicon carbide is being dried Dried 1 minute at 100 DEG C and form infrared ray-absorbing layer.

Also, using dispensing coating machine in barrier film (NS-23MA：Middle PAX Co., Ltd. manufacture) to above-mentioned middle preparation Adhesive layer coating fluid 1 is coated, and after being dried 1 minute at 80 DEG C, lamination is had to the infrared ray-absorbing layer of above-mentioned middle making Film pet sheet face and bonding layer surface laminating, make stack membrane 1.The thickness of the infrared ray-absorbing layer of stack membrane 1 is 5 μm, is glued The thickness for closing layer is 10 μm.

(film surface p H measure)

It is provided with using on METTLER TOLEDO Co., Ltd. manufacture Five Easy FE20 (equal performance equipment) The pH meter of Surface electrodes, after pure water 0.6ml is added dropwise in infrared ray absorbing layer surface, is determined with the pH meter after 60s The pH of water droplet.

The film surface p H of the infrared ray-absorbing layer of stack membrane 1 is 6.5.

The ＞ of ＜ embodiments 2

(preparation of infrared ray-absorbing layer coating fluid 2)

The infrared ray-absorbing layer of 6.4 mass parts with the 1SX-1065 of coating fluid 1 is changed to Chelest MZ-8 (organic molten Agent soluble type chelating agent, pH7.6：Chelest Co., Ltd. manufactures) 2.8 mass parts, in addition, with same step system Standby infrared ray-absorbing layer coating fluid 2.

(making of stack membrane 2)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 2 using infrared ray-absorbing layer, in addition, with stack membrane 1 Similarly make stack membrane 2.

The film surface p H of the infrared ray-absorbing layer of stack membrane 2 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 3

(preparation of infrared ray-absorbing layer coating fluid 3)

The infrared ray-absorbing layer of 6.4 mass parts is changed to TBAB-100A (tetrabutyl bromines with the 1SX-1065 of coating fluid 1 Change ammonium：Lion Co., Ltd. manufactures) 2.8 mass parts, in addition, infrared ray-absorbing layer coating fluid is prepared with same step 3。

(making of stack membrane 3)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 3 using infrared ray-absorbing layer, in addition, with stack membrane 1 Similarly make stack membrane 3.

The film surface p H of the infrared ray-absorbing layer of stack membrane 3 is determined as described above, and as a result film surface p H is 9.0.

The ＞ of ＜ embodiments 4

(preparation of infrared ray-absorbing layer coating fluid 4)

The infrared ray-absorbing layer of 6.4 mass parts is changed to Chelest400 (EDTA with the 1SX-1065 of coating fluid 1 4Na·4H₂O、pH11.2：Chelest Zhu Shihui Co., Ltd. manufactures) 2.8 mass parts, in addition, with same step system Standby infrared ray-absorbing layer coating fluid 4.

(making of stack membrane 4)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 4 using infrared ray-absorbing layer, in addition, with stack membrane 1 Similarly make stack membrane 4.

The film surface p H of the infrared ray-absorbing layer of stack membrane 4 is determined as described above, and as a result film surface p H is 11.0.

The ＞ of ＜ comparative examples 1

(preparation of infrared ray-absorbing layer coating fluid 5)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 5.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Zhu Shihui Co., Ltd. Manufacture) 656 mass parts

YMF-02A (combined oxidation tungsten (the Cs containing caesium_0.33WO₃), the mass % of solid constituent 28.7, the matter of particle concentration 18.5 Measure %, average grain diameter 15nm, refractive index 1.66：Sumitomo Metal Mining Co., Ltd manufactures) 294 mass parts

The mass parts of methyl ethyl ketone 50.

(making of stack membrane 5)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 5 using infrared ray-absorbing layer, in addition, with stack membrane 1 Similarly make stack membrane 5.

The film surface p H of the infrared ray-absorbing layer of stack membrane 5 is determined as described above, and as a result film surface p H is 5.5.

The ＞ of ＜ comparative examples 2

(preparation of infrared ray-absorbing layer coating fluid 6)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 6.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Zhu Shihui Co., Ltd. Manufacture) 643 mass parts

YMF-02A (combined oxidation tungsten (the Cs containing caesium_0.33WO₃), the mass % of solid constituent 28.7, the matter of particle concentration 18.5 Measure %, average grain diameter 15nm, refractive index 1.66：Mine Zhu Shihui Co., Ltd. of Sumitomo Metal Industries manufactures) 294 mass parts

Adekastab AO-80 (phenol antioxidants：ADEKA Corp.'s system) 3.9 mass parts

The mass parts of methyl ethyl ketone 59.

(making of stack membrane 6)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 6 using infrared ray-absorbing layer, in addition, with stack membrane 1 Similarly make stack membrane 6.

The film surface p H of the infrared ray-absorbing layer of stack membrane 6 is determined as described above, and as a result film surface p H is 5.5.

The ＞ of ＜ comparative examples 3

(preparation of infrared ray-absorbing layer coating fluid 7)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 7.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Zhu Shihui Co., Ltd. Manufacture) 646 mass parts

YMF-02A (combined oxidation tungsten (the Cs containing caesium_0.33WO₃), the mass % of solid constituent 28.7, the matter of particle concentration 18.5 Measure %, average grain diameter 15nm, refractive index 1.66：Sumitomo Metal Mining Co., Ltd manufactures) 294 mass parts

Chelest MZ-8 (organic solvent soluble type chelating agent, pH7.6：Chelest Zhu Shihui Co., Ltd. manufactures) 2.8 mass parts

The mass parts of methyl ethyl ketone 56.

(making of stack membrane 7)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 7 using infrared ray-absorbing layer, in addition, with stack membrane 1 Similarly make stack membrane 7.

The film surface p H of the infrared ray-absorbing layer of stack membrane 7 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ comparative examples 4

(preparation of infrared ray-absorbing layer coating fluid 8)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 8.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Co., Ltd. manufactures) 911 mass parts

Adekastab AO-80 (phenol antioxidant：ADEKA Corp. manufactures) 3.9 mass parts

Chelest MZ-8 (organic solvent soluble type chelating agent, pH7.6：Chelest Co., Ltd. manufactures) 2.8 mass Part

The mass parts of methyl ethyl ketone 82.

(making of stack membrane 8)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 8 using infrared ray-absorbing layer, in addition, with stack membrane 1 Similarly make stack membrane 8.

The film surface p H of the infrared ray-absorbing layer of stack membrane 8 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 5

(preparation of infrared ray-absorbing layer coating fluid 9)

Infrared ray-absorbing layer is changed into Adekastab AO-50 with the Adekastab AO-80 of coating fluid 2, and (phenols resists Oxidant：ADEKA Corp. manufactures), in addition, infrared ray-absorbing layer coating fluid 9 is prepared with same step.

(making of stack membrane 9)

Infrared ray-absorbing layer coating fluid 2 is replaced with coating fluid 9 using infrared ray-absorbing layer, in addition, with stack membrane 2 Similarly make stack membrane 9.

The film surface p H of the infrared ray-absorbing layer of stack membrane 9 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 6

(preparation of infrared ray-absorbing layer coating fluid 10)

Infrared ray-absorbing layer is changed to Tinuvin PA144 (hindered amines with the Adekastab AO-80 of coating fluid 2 Antioxidant：BASF Amada Co., Ltd.s manufacture), in addition, infrared ray-absorbing layer coating fluid is prepared with same step 10。

(making of stack membrane 10)

Infrared ray-absorbing layer coating fluid 2 is replaced with coating fluid 10 using infrared ray-absorbing layer, in addition, with stack membrane 2 similarly make stack membrane 10.

The film surface p H of the infrared ray-absorbing layer of stack membrane 10 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 7

(preparation of infrared ray-absorbing layer coating fluid 11)

Infrared ray-absorbing layer is changed into Tinuvin 765 with the Adekastab AO-80 of coating fluid 2, and (hindered amines resists Oxidant：BASF Amada Co., Ltd.s manufacture), in addition, infrared ray-absorbing layer coating fluid 11 is prepared with same step.

(making of stack membrane 11)

Infrared ray-absorbing layer coating fluid 2 is replaced with coating fluid 11 using infrared ray-absorbing layer, in addition, with stack membrane 2 similarly make stack membrane 11.

The film surface p H of the infrared ray-absorbing layer of stack membrane 11 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 8

(preparation of infrared ray-absorbing layer coating fluid 12)

Infrared ray-absorbing layer is changed to Tinuvin 660DF (hindered amines with the Adekastab AO-80 of coating fluid 2 Antioxidant：BASF Japanese strain Shi Hui Co., Ltd. manufactures), in addition, infrared ray-absorbing layer use is prepared with same step Coating fluid 12.

(making of stack membrane 12)

Infrared ray-absorbing layer coating fluid 2 is replaced with coating fluid 12 using infrared ray-absorbing layer, in addition, with stack membrane 2 similarly make stack membrane 12.

The film surface p H of the infrared ray-absorbing layer of stack membrane 12 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 9

(preparation of infrared ray-absorbing layer coating fluid 13)

Infrared ray-absorbing layer is changed into Chimassorb2020FDL with the Adekastab AO-80 of coating fluid 2 (to be obstructed Amine antioxidants：BASF Amada Co., Ltd.s manufacture), in addition, infrared ray-absorbing layer painting is prepared with same step Cloth liquid 13.

(making of stack membrane 13)

Infrared ray-absorbing layer coating fluid 2 is replaced with coating fluid 13 using infrared ray-absorbing layer, in addition, with stack membrane 2 similarly make stack membrane 13.

The film surface p H of the infrared ray-absorbing layer of stack membrane 13 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 10

(preparation of infrared ray-absorbing layer coating fluid 14)

Infrared ray-absorbing layer is changed to the (phosphite esters of Adekastab 2112 with the Adekastab AO-80 of coating fluid 2 Class antioxidant：ADEKA Corp. manufactures), in addition, infrared ray-absorbing layer coating fluid is prepared with same step 24。

(making of stack membrane 14)

Infrared ray-absorbing layer coating fluid 2 is replaced with coating fluid 14 using infrared ray-absorbing layer, in addition, with stack membrane 2 similarly make stack membrane 14.

The film surface p H of the infrared ray-absorbing layer of stack membrane 14 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 11

(preparation of infrared ray-absorbing layer coating fluid 15)

Infrared ray-absorbing layer is changed to Adekastab HP-10 (phosphorous acid with the Adekastab AO-80 of coating fluid 2 Esters antioxidant：ADEKA Corp. manufactures), in addition, infrared ray-absorbing layer coating fluid is prepared with same step 15。

(making of stack membrane 15)

Infrared ray-absorbing layer coating fluid 2 is replaced with coating fluid 15 using infrared ray-absorbing layer, in addition, with stack membrane 2 similarly make stack membrane 15.

The film surface p H of the infrared ray-absorbing layer of stack membrane 15 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 12

(making of stack membrane 16)

Ultraviolet hardening hard conating is formed on the infrared ray-absorbing layer of the stack membrane 9 of above-mentioned middle making, lamination is made Film 16.

On hard conating, using hard masking liquid UV-3701 (Toagosei Co., Ltd's manufacture), it is coated with gravure coating machine, After being dried at 90 DEG C of drying temperature, using high-pressure mercury-vapor lamp, accumulated light 300mJ/cm is adjusted to²Solidify coating layer, shape Into hard conating, it is 2 μm to make dry film thickness.

The ＞ of ＜ embodiments 13

(making of stack membrane 17)

On the polyester terephthalate film (Japan spins Co., Ltd. A4300) of 23 μm of thickness, gravure coating machine is used Above-mentioned hard masking liquid UV-3701 is coated with, after being dried at 90 DEG C of drying temperature, using high-pressure mercury-vapor lamp, accumulated light is adjusted to 300mJ/cm²Solidify coating layer, form hard conating, it is 2 μm to make dry film thickness.In the table with the hard conating opposite side of the film The adhesive layer coating fluid 1 of above-mentioned middle preparation is further coated with face using dispensing coating machine, dries 1 minute, obtains at 80 DEG C To adhesive layer (10 μm of dry film thickness).Thereafter, the surface of infrared ray-absorbing layer of the stack membrane 9 of above-mentioned middle making is made with being formed with The surface of the adhesive layer of the film of the hard conating of above-mentioned middle making is fitted, and makes stack membrane 17.

The ＞ of ＜ comparative examples 5

(preparation of infrared ray-absorbing layer coating fluid 18)

Materials described below is carried out to be mixed and stirred for 30 minutes, infrared ray-absorbing layer coating fluid 18 is prepared.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Co., Ltd. manufactures) 638 mass parts

(Advanced Nano Products companies manufacture ATO dispersions：35 mass %MIBK dispersions) 238 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp. manufactures) 3.9 mass parts

Chelest400(EDTA·4Na·4H₂O、pH11.2：Chelest Co., Ltd. manufactures) 1.4 mass parts

The mass parts of methyl ethyl ketone 115.

(making of stack membrane 18)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 18 using infrared ray-absorbing layer, in addition, with stack membrane 1 similarly makes stack membrane 18.

The film surface p H of the infrared ray-absorbing layer of stack membrane 18 is determined as described above, as a result film surface p H is 5.5.

The ＞ of ＜ embodiments 14

(preparation of infrared ray-absorbing layer coating fluid 19)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 19.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Zhu Shihui Co., Ltd. Manufacture) 633 mass parts

(Advanced Nano Products companies manufacture ATO dispersions：35 mass %MIBK dispersions) 238 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp. manufactures) 3.9 mass parts

Chelest400(EDTA·4Na·4H₂O、pH11.2：Chelest Zhu Shihui Co., Ltd. manufactures) 2.8 mass parts

The mass parts of methyl ethyl ketone 115.

(making of stack membrane 19)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 19 using infrared ray-absorbing layer, in addition, with stack membrane 1 similarly makes stack membrane 19.

The film surface p H of the infrared ray-absorbing layer of stack membrane 19 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 15

(preparation of infrared ray-absorbing layer coating fluid 20)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 20.

Acrit 8UA-301 (polyurethane-modified acrylic acid polymer：Great achievement fine chemical Zhu Shihui Co., Ltd. Manufacture) 633 mass parts

(Advanced Nano Products companies manufacture ATO dispersions：35 mass %MIBK dispersions) 238 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp. manufactures) 3.9 mass parts

Chelest400(EDTA·4Na·4H₂O、pH11.2：Chelest Co., Ltd. manufactures) 5.6 mass parts

The mass parts of methyl ethyl ketone 115.

(making of stack membrane 20)

Infrared ray-absorbing layer coating fluid 1 is replaced with coating fluid 20 using infrared ray-absorbing layer, in addition, with stack membrane 1 similarly makes stack membrane 20.

The film surface p H of the infrared ray-absorbing layer of stack membrane 20 is determined as described above, and as a result film surface p H is 10.0.

The ＞ of ＜ embodiments 16

(preparation of infrared ray-absorbing layer coating fluid 21)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 21.

ARONIX M-305 (pentaerythritol triacrylates/tetramethylol methane tetraacrylate：Toagosei Co., Ltd's system Make) 149 mass parts

Purple light UV-7600B (urethane acrylate class UV curable resins：The manufacture of synthesis KCC of Japan) 70 Mass parts

YMF-02A (combined oxidation tungsten (the Cs containing caesium_0.33WO₃), the mass % of solid constituent 28.7, the matter of particle concentration 18.5 Measure %, average grain diameter 15nm, refractive index 1.66：Sumitomo Metal Mining Co., Ltd manufactures) 368 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp. manufactures) 4.9 mass parts

ChelestMZ-8 (organic solvent soluble type chelating agent, pH7.6：Chelest Co., Ltd. manufactures) 7.0 mass Part

IRGACURE819 (Photoepolymerizationinitiater initiaters：BASF Amada Co., Ltd.s manufacture) 15 mass parts

Ftergent 650A (fluorine class surfactants：NEOS Co., Ltd. manufactures) 0.1 mass parts

The mass parts of 4-methyl-2 pentanone 386.

(making of stack membrane 21)

Using gravure coating machine, in the polyethylene terephthalate film of 50 μm of thickness, (Japan spins Co., Ltd. A4300 on), the infrared ray-absorbing layer coating fluid 21 of above-mentioned middle preparation is coated with, 1 point is dried in the case where drying 100 DEG C of silicon carbide Zhong Hou, using high-pressure mercury-vapor lamp, with accumulated light 300mJ/cm²Coating layer is set to be solidified to form infrared ray-absorbing layer.

Also, using dispensing coating machine in barrier film (NS-23MA：The manufacture of middle PAX Co., Ltd.) on be coated with above-mentioned middle system Standby adhesive layer coating fluid 1, dries 1 minute at 80 DEG C and forms adhesive layer.Thereafter, to being formed with the red of above-mentioned middle making The surface of the polyester terephthalate of the film of outside line absorbed layer is fitted with the surface of adhesive layer, makes stack membrane 21.It is infrared The thickness of line absorption layer is 5 μm, and the thickness of adhesive layer is 10 μm.

The film surface p H of the infrared ray-absorbing layer of stack membrane 21 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 17

(preparation of infrared ray-absorbing layer coating fluid 22)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 22.

ARONIX M-305 (pentaerythritol triacrylates/tetramethylol methane tetraacrylate：Toagosei Co., Ltd's system Make) 150 mass parts

Purple light UV-7600B (urethane acrylate class UV curable resins：Synthesis chemistry Zhu Shihui Co., Ltd. of Japan Manufacture) 70 mass parts

YMF-02A (combined oxidation tungsten (the Cs containing caesium_0.33WO₃), the mass % of solid state component 28.7, the matter of particle concentration 18.5 Measure %, average grain diameter 15nm, refractive index 1.66：Sumitomo Metal Mining Co., Ltd manufactures) 368 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp. manufactures) 4.9 mass parts

TBAB-100A (TBABs：Lion Co., Ltd. manufactures) 5.3 mass parts

IRGACURE819 (Photoepolymerizationinitiater initiaters：BASF JAPAN Co., Ltd. manufactures) 15 mass parts

Ftergent 650A (fluorine class surfactants：NEOS Co., Ltd. manufactures) 0.1 mass parts

The mass parts of 4-methyl-2 pentanone 386.

(making of stack membrane 22)

Infrared ray-absorbing layer coating fluid 21 is replaced with coating fluid 22 using infrared ray-absorbing layer, in addition, with lamination Film 21 similarly makes stack membrane 22.

The film surface p H of the infrared ray-absorbing layer of stack membrane 22 is determined as described above, and as a result film surface p H is 9.0.

The ＞ of ＜ comparative examples 6

(preparation of infrared ray-absorbing layer coating fluid 23)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 23.

ARONIX M-305 (pentaerythritol triacrylates/tetramethylol methane tetraacrylate：Toagosei Co., Ltd's system Make) 20 mass parts

Purple light UV-7600B (urethane acrylate class UV curable resins：Synthesis KCC of Japan manufacture) 105 mass parts

CELNAXCX-Z410BK (AZO dispersion liquids solid component concentration 40%, 80~120nm of particle diameter：Nissan Chemical Industries Co., Ltd. manufactures) 507 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp.'s system) 4.9 mass parts

Chelest400(EDTA·4Na·4H₂O、pH11.2：Chelest Co., Ltd. manufactures) 1.8 mass parts

IRGACURE819 (Photoepolymerizationinitiater initiaters：BASF Japanese strain Shi Hui Co., Ltd. manufactures) 15 mass parts

Ftergent 650A (fluorine class surfactants：NEOS Co., Ltd. manufactures) 0.1 mass parts

The mass parts of 4-methyl-2 pentanone 346.

(making of stack membrane 23)

Infrared ray-absorbing layer coating fluid 21 is replaced with coating fluid 23 using infrared ray-absorbing layer, in addition, with lamination Film 21 similarly makes stack membrane 23.

The film surface p H of the infrared ray-absorbing layer of stack membrane 23 is determined as described above, and as a result film surface p H is 6.2.

The ＞ of ＜ embodiments 18

(preparation of infrared ray-absorbing layer coating fluid 24)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 24.

ARONIX M-305 (pentaerythritol triacrylates/tetramethylol methane tetraacrylate：Toagosei Co., Ltd's system Make) 15 mass parts

Purple light UV-7600B (urethane acrylate class UV curable resins：Synthesis KCC of Japan manufacture) 105 mass parts

CELNAXCX-Z410BK (AZO dispersion liquids solid component concentration 40%, 80~120nm of particle diameter：Nissan Chemical Industries Co., Ltd. manufactures) 507 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp.'s system) 4.9 mass parts

ChelestMZ-8 (organic solvent soluble type chelating agent, pH7.6：Chelest Co., Ltd. manufactures) 7.0 mass Part

IRGACURE819 (Photoepolymerizationinitiater initiaters：BASF Amada Co., Ltd.s manufacture) 15 mass parts

Ftergent 650A (fluorine class surfactants：NEOS Co., Ltd. manufactures) 0.1 mass parts

The mass parts of 4-methyl-2 pentanone 346.

(making of stack membrane 24)

Infrared ray-absorbing layer coating fluid 21 is replaced with coating fluid 24 using infrared ray-absorbing layer, in addition, with lamination Film 21 similarly makes stack membrane 24.

The film surface p H of the infrared ray-absorbing layer of stack membrane 24 is determined as described above, and as a result film surface p H is 7.0.

The ＞ of ＜ embodiments 19

(preparation of infrared ray-absorbing layer coating fluid 25)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 25.

ARONIX M-305 (pentaerythritol triacrylates/tetramethylol methane tetraacrylate：Toagosei Co., Ltd's system Make) 15 mass parts

Purple light UV-7600B (urethane acrylate class UV curable resins：Synthesis KCC of Japan manufacture) 105 mass parts

CELNAXCX-Z410BK (AZO dispersion liquids solid component concentration 40%, 80~120nm of particle diameter：Nissan Chemical Industries Co., Ltd. manufactures) 507 mass parts

Adekastab AO-50 (phenol antioxidant：ADEKA Corp. manufactures) 4.9 mass parts

Chelest400(EDTA·4Na·4H₂O、pH11.2：Chelest Co., Ltd. manufactures) 7.0 mass parts

IRGACURE819 (Photoepolymerizationinitiater initiaters：BASF Amada Co., Ltd.s manufacture) 15 mass parts

Ftergent 650A (fluorine system surfactants：NEOS Co., Ltd. manufactures) 0.1 mass parts

The mass parts of 4-methyl-2 pentanone 346.

(making of stack membrane 25)

Infrared ray-absorbing layer coating fluid 21 is replaced with coating fluid 25 using infrared ray-absorbing layer, in addition, with lamination Film 21 similarly makes stack membrane 25.

The film surface p H of the infrared ray-absorbing layer of stack membrane 25 is determined as described above, and as a result film surface p H is 10.5.

The ＞ of ＜ embodiments 20

(low-index layer coating fluid L1 preparation)

Add the 10 mass % aqueous solution (SNOWTEX OXS, Nissan Chemical social workers of colloidal silica successively at 45 DEG C Industry Co., Ltd. manufacture) 430 mass parts, the mass parts of the 3 mass % aqueous solution of boric acid 150, the mass parts of water 85, polyvinyl alcohol (JP- 45th, the manufacture of JAPAN VAM＆POVAL Co., Ltd., the degree of polymerization 4500, saponification degree 88mol%) the 4 mass % aqueous solution, 300 mass Part and the mass % aqueous solution of surfactant 5 (Softazoline LSB-R, river grind the manufacture of fine chemical Co., Ltd.) 3 mass parts, 1000 mass parts are diluted to pure water, prepare low-index layer coating fluid L1.

(high refractive index layer coating fluid H1 preparation)

Waterborne suspension (the TiO obtained from making titanium dioxide hydrates be suspended in water₂Concentration 100g/L) 10L (liter) In, add sodium hydrate aqueous solution (10 moles/L of concentration) 30L under agitation, be warming up to 90 DEG C, it is ripe 5 hours after, use hydrochloric acid Neutralized, filtered, washed, thus obtain alkali process titanium compound.It should be noted that in above-mentioned reaction (processing), two Titanium oxide hydrate uses material obtained from carrying out pyrohydrolysis to titanium sulfate aqueous solution according to known methods.

Alkali process titanium compound is suspended in pure water, and makes TiO₂Concentration is 20g/L, relative to TiO under stirring₂Amount is added 0.4 mole of % citric acid simultaneously heats up.When fluid temperature reaches 95 DEG C, concentrated hydrochloric acid is added, it is 30g/L to make concentration of hydrochloric acid, while dimension Fluid temperature is held, while stirring 3 hours.

The pH and zeta potential of obtained titanium oxide sol water class dispersion liquid are determined, as a result pH is 1.4, zeta potential is+40mV.And And, the Zetasizer Nano manufactured using Malvern companies carry out particle size determination, and as a result volume average particle size is 35nm, single Decentralization is 16%.

It is aqueous in 20.0 mass % titanium oxide sols of the Titanium Dioxide Rutile Top grade particle containing volume average particle size 35nm Pure water 1kg is added in dispersion liquid 1kg.

Pure water 2kg is added in the 10.0 mass % titanium oxide sol aqueous liquid dispersions 0.5kg obtained in above-mentioned, then, It is heated to 90 DEG C.Thereafter, SiO is slowly added₂Concentration is 2.0 mass % silicate aqueous solution 1.3kg, then, by what is obtained Dispersion liquid carries out heating for 18 hours in autoclave at 175 DEG C, is further concentrated, with rutile-type knot The titanium oxide of structure obtains clad for SiO₂20.0 mass % silica modified Titanium particles colloidal sol aqueous dispersions.

Then, 20.0 mass % colloidal sol aqueous dispersions of silica modified Titanium particles are added successively at 45 DEG C 320 mass parts, the mass parts of the 1.92 mass % aqueous solution 120 of citric acid, the mass parts (PVA- of 10 mass % poly-vinyl alcohol solutions 20 103rd, the degree of polymerization 300, saponification degree 99mol%, KURARAY Co., Ltd. manufacture), the mass of the 3 mass % aqueous solution 100 of boric acid Part, 4 mass % solution 350 mass parts (manufacture of KURARAY Co., Ltd., PVA-124, the degree of polymerization 2400, the saponification of polyvinyl alcohol Spend 88mol%) and the mass parts of 5 mass % solution 1 of surfactant (fine is ground in Softazoline LSB-R, river Chemical Co., Ltd. manufactures), 1000 mass parts are diluted to pure water, high refractive index layer coating fluid H1 is prepared.

(making of stack membrane 26)

Using the sliding hopper apparatus for coating that 9 layers of double-layer are coated with can be carried out, while the low-index layer obtained in will be above-mentioned With coating fluid L1 and high refractive index layer coating fluid H1 insulations at 45 DEG C, while being heated to the poly- to benzene of 45 DEG C of 50 μm of thickness On naphthalate film (Japan spins A4300), orlop and the superiors are set to low-index layer, it is handed over respectively in addition Double-layer is coated with while alternately carrying out amounting to 9 layers so that the low-index layer of thickness when drying is each layer 150nm, height refraction Each layer of rate layer is 130nm.It should be noted that the confirmation of the Mixed Zone (mixed layer) of interlayer and the measure (confirmation) of thickness can To determine high index of refraction with XPS surface analysis apparatus to section by the way that stack membrane (dielectric multilayer film film sample) is cut off Material (TiO₂) and low-index material (SiO₂) amount confirm to ensure the thickness of above-mentioned each layer.

Just after coating, blowing 5 DEG C of cold wind fixes it.Now, to i.e. using will not on finger touch-surface, finger The time (set time) for having any attachment is 5 minutes.

Fix after terminating, blowing 80 DEG C of warm wind dries it, make by the 9 layers of dielectric constituted multilayer film unit.Such as The refractive index of the above-mentioned high refractive index layer formed like that is 1.95, and the refractive index of low-index layer is 1.45.

Then, the infrared ray-absorbing layer coating fluid 9 of above-mentioned middle preparation is coated on poly- to benzene using gravure coating machine On the surface of the dielectric multilayer film unit opposite side of dicarboxylic acid esters film, dry 1 minute and formed at 100 DEG C of drying temperature Infrared ray-absorbing layer.

Also, the adhesive layer coating fluid 1 of above-mentioned middle preparation is coated on barrier film (NS-23MA using dispensing coating machine：In This PAX Co., Ltd. manufactures), dried 1 minute at 80 DEG C, form adhesive layer.Thereafter, the infrared of above-mentioned middle making will be formed with The surface of the dielectric multilayer film unit of the film of line absorption layer is fitted with the surface of adhesive layer, makes stack membrane 26.Lamination The thickness of the infrared ray-absorbing layer of film 26 is 5 μm, and the thickness of adhesive layer is 10 μm.

The film surface p H of the infrared ray-absorbing layer of stack membrane 26 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ embodiments 21

(making of stack membrane 27)

Infrared ray-absorbing layer coating fluid 9 is replaced with coating fluid 2 using infrared ray-absorbing layer, in addition, is carried out with folding The same operation of making of tunic 26, makes stack membrane 27.

The film surface p H of the infrared ray-absorbing layer of stack membrane 27 is determined as described above, and as a result film surface p H is 7.5.

The ＞ of ＜ comparative examples 7

(preparation of infrared ray-absorbing layer coating fluid 28)

Materials described below is mixed, is stirred at room temperature 30 minutes, prepares infrared ray-absorbing layer coating fluid 28.

Sartomer SR399E (manufacture of Sartomer JAPAN Co., Ltd.) 100 mass parts

YMF-01 (combined oxidation tungsten (the Cs containing caesium_0.33WO₃)：Sumitomo Metal Mining Co., Ltd manufactures) 500 mass parts

IRGACURE127 (Photoepolymerizationinitiater initiaters：BASF Amada Co., Ltd.s manufacture) 5 mass parts

The mass parts of toluene 100

(making of stack membrane 28)

Using gravure coating machine, in 25 μm of polyester terephthalate film (Mitsubishi Chemical's polyester film Co. Ltd. system of thickness Make, trade name " PET25T600EW07 ") one side on, be coated with the infrared ray-absorbing layer coating fluid 28 of above-mentioned middle preparation, make Coating layer is dried 1 minute in the case where drying interval temperature 70 C.Thereafter, using high-pressure mercury-vapor lamp, with accumulated light 125mJ/cm²Make Coating layer is solidified to form infrared ray-absorbing layer.

Also, using dispensing coating machine in barrier film (NS-23MA：The manufacture of middle PAX Co., Ltd.) on be coated with above-mentioned middle system Standby adhesive layer coating fluid 1, dries 1 minute at 80 DEG C and forms adhesive layer.

Then, the pet sheet face of the film to being formed with infrared ray-absorbing layer is fitted with bonding layer surface, makes stack membrane 28.The thickness of the infrared ray-absorbing layer of the stack membrane 28 is 4 μm, and the thickness of adhesive layer is 10 μm.

The film surface p H of the infrared ray-absorbing layer of stack membrane 28 is determined as described above, and as a result film surface p H is 6.0.

《The evaluation of stack membrane》

To the stack membrane of above-mentioned making, following evaluation is carried out.Show the result in following tables 1,2.

The evaluation ＞ of ＜ weatherabilities

As weathering tester is promoted, using the xenon weatherometer for having used xenon lamp, in illumination 180mW/cm², temperature 40 DEG C of degree, under humidity 50%RH, irradiated at 120 minutes in repeat water injection in 18 minutes, thereafter, irradiation 2000 hours is (resistance to Time property experiment).Thereafter, the observation of the presence or absence of the measure that is changed colour with following method, crackle and the measure of mist degree.

(measure of discoloration)

To the spectrophotometric determination of stack membrane sample Hitachi's U-4100 equal performances after above-mentioned atmospheric exposure test Transmissivity, calculates L^*a^*b^*L in color space^*、a^*、b^*, calculate (after atmospheric exposure test)-(before atmospheric exposure test (just Phase)) color space on changes delta E.Δ E is less than 3.5, preferably shorter than 3, especially preferably less than 2.

(observation for having flawless)

Stack membrane sample 15cm × 5cm (75cm are observed by visual observation²) infrared ray-absorbing layer side most surface layer, it is right The quantity of crackle is counted, and based on the stack membrane sample average value of 10, is evaluated according to following benchmark.

◎：0,

○：1~5,

○△：6~10,

△：11~25,

×：More than 26.

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

(measure of mist degree)

According to ISO 14782, with haze meter (electricity Se Industrial Co., Ltd of Japan system makes NDH-7000) to stack membrane sample 15cm×5cm(75cm²) average value that determines at 5 is set to mist degree measured value.It is used as the haze value for hiding hotting mask, preferably 1.5% Below.

The evaluation ＞ of ＜ thermal insulations

Using spectrophotometer, (integrating sphere is used, Hitachi Ltd. manufactures, product title：U-4000 types) it is right The transmissivity and 5 ° of reflectivity (%) for determining sample are measured.Then, the survey is carried out according to the method described in JIS R3106 The calculation of definite value and sunshine reflection weight coefficient handles and obtains sunshine reflectivity, sunshine transmissivity, further obtains sunshine heat Acquirement rate (Tts).

For Tts, numerical value is smaller, more shows good thermal insulation.

For the rate of change of thermal insulation, the Tts carried out after above-mentioned atmospheric exposure test is obtained, (weatherability examination is obtained The Tts before Tts- atmospheric exposure tests after testing)/(Tts before atmospheric exposure test) × 100 (%) value.

＜ acid rain patience ＞

The stack membrane of above-mentioned making is impregnated in the liquid of 30 DEG C of 5% ammonium sulfate solution 7 days.Thereafter, by lamination Film is attached at glass-film, with the spectrophotometric determination transmissivity of Hitachi's U-4100 equal performances, calculates L^*a^*b^*Color space In L^*、a^*、b^*, calculate the changes delta E on the color space of (after ammonium sulfate solution dipping)-(before dipping).

○：Less than Δ E1,

○△：Δ E1 less than 2,

△：Δ E2 less than 3,

×：More than Δ E3.

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

Evaluation result by more than is shown in table 1,2.

Table 2

Shown by above-mentioned table 1 and table 2：Contain infrared absorbent and antioxidant in infrared ray-absorbing layer, by film table When face pH is adjusted to more than 6.5, infrared shield excellent performance, and it is not easy to change, the generation of crackle is few, can be passed through Suppression changes colour and suppressed the increased stack membrane of mist degree.By the way that film surface p H further is set into more than 6.5, acidity is being contacted with The part of rain produces the acidification of film, can suppress infrared ray-absorbing layer and go bad, therefore can suppress discoloration.

On the other hand, as stack membrane 5, stack membrane 6, stack membrane 18, stack membrane 23, stack membrane 28, infrared ray absorbing The film surface p H of layer is less than in the case of 6.5, easily changes colour under high humidity, sunshine exposure, also easily cracks.In addition may be used Know：Infrared shield performance is reduced.Also, produce discoloration after ammonium sulfate solution dipping.

When infrared absorbent is CWO, infrared shield excellent performance, the effect for suppressing discoloration is high.Particularly film surface PH is in the case that 7.5~10.5, infrared absorbent is CWO, significantly more to obtain The effect of invention.

In addition, when being compared to the result of stack membrane 9~15, it is known that：Made using phenols or hindered amines antioxidant During for antioxidant, suppress high humidity, the excellent effect of the lower discoloration of sunshine exposure.

In addition, as stack membrane 26, stack membrane 27, it is known that：Dielectric multilayer film is further equipped with by stack membrane, can Further improve shield effectiveness.

In stack membrane 21, stack membrane 22, stack membrane 24, stack membrane 25 provided with the infrared ray-absorbing layer with hard painting propert, The scratch resistance on surface is further improved.

It should be noted that the application is based on apllied Japanese patent application 2014-245412 on December 3rd, 2014 Number, the disclosure of which is cited by referring to as overall.

Claims (5)

1. a kind of stack membrane, it has base material and infrared ray-absorbing layer,

The infrared ray-absorbing layer contains infrared absorbent, resin and antioxidant, and is configured at a table of the base material On face, wherein,

The infrared ray-absorbing layer is more than 6.5 with the film surface p H on the surface of base material opposite side.

2. stack membrane as claimed in claim 1, wherein,

The infrared absorbent is the combined oxidation tungsten containing caesium.

3. stack membrane as claimed in claim 1 or 2, wherein,

The antioxidant is selected from one or more of phenol antioxidant and hindered amines antioxidant.

4. such as stack membrane according to any one of claims 1 to 3, wherein,

The infrared ray-absorbing layer be make the composition containing ultraviolet curing resin and Photoepolymerizationinitiater initiater solidified and Into.

5. such as stack membrane according to any one of claims 1 to 4, it further contains in 800~1300nm of wavelength region Dielectric multilayer film with least one reflection peak, the dielectric multilayer film is low-index layer and high refractive index layer alternating Ground lamination.