CN107003451A

CN107003451A - Thermal isolation film and its manufacture method and use its insulator

Info

Publication number: CN107003451A
Application number: CN201580065429.1A
Authority: CN
Inventors: 久光聪史; 川浪明土
Original assignee: Konica Minolta Opto Inc
Current assignee: Konica Minolta Inc; Konica Minolta Opto Inc
Priority date: 2014-12-05
Filing date: 2015-12-03
Publication date: 2017-08-01
Also published as: JPWO2016088851A1; JP6673220B2; WO2016088851A1

Abstract

The present invention provides a kind of in the thermal isolation film with the hard conating containing tungsten oxide, improves the adaptation of hard conating, and can prevent the means of the discoloration of hard conating.The present invention is a kind of thermal isolation film, it has base material and hard conating, the hard conating is formed by hard conating with the solidfied material of coating fluid, and is configured at least one surface of the base material, and the hard conating coating fluid contains following (a)~(c)：(a) tungsten oxide, (b) (methyl) acrylic ester compound, it, which is included, must contain (methyl) acrylic ester compound with primary hydroxyl, (c) metal salt.

Description

Thermal isolation film and its manufacture method and use its insulator

Technical field

The present invention relates to a kind of thermal isolation film and its manufacture method and use its insulator.More specifically, it is of the invention Be related to it is a kind of in the thermal isolation film with the hard conating containing tungsten oxide, improve hard conating adaptation and prevent hard conating Discoloration technology.Also, the present invention relates to a kind of insulator containing described thermal isolation film.

Background technology

As a ring of strategy of Saving Energy, put on from reducing from the viewpoint of the load of air-conditioning equipment, to being installed on building The glass pane of thing or vehicle, the requirement of the thermal isolation film of the transmission of the hot line (infrared ray) of shielding sunshine grow to even greater heights.

Because thermal isolation film is attached at the glass pane of building or vehicle and uses, therefore, in addition to the transparency and thermal insulation, Be also required to traumatic resistance so that laminating when or clean when occur without damage.Therefore, it is however generally that, formed on film surface with table Hard conating for the purpose of the protection of face.

As this thermal isolation film, for example, propose a kind of near infrared shielding film, its on base material film a surface tool Have by comprising the hot radiation shielding metal oxide as infrared absorbing agents and specific active energy ray-curable compound The hard conating of hard conating formation material formation, has adhesive layer in another side.

Show excellent heat-insulated additionally, it is known that having and using tungsten oxide as the thermal isolation film of hot radiation shielding metal oxide Property.But, easily changed colour in the environment of washiness using the thermal isolation film for having tungsten oxide particle, stayed in terms of weatherability There is technical problem.

In order to solve this technical problem, disclose a kind of by having on base material by containing tungsten oxide and metal salt The formation of infrared shield particles of material sub- dispersion liquid layer infrared shielding film suppress insulative properties through when deterioration skill Art (referring for example to Japanese Unexamined Patent Publication 2009-197146 publications).

The content of the invention

But, the layer and base material of tungsten oxide are generated in the film disclosed in Japanese Unexamined Patent Publication 2009-197146 publications Adaptation it is low, the problem of layer with tungsten oxide is peeling-off, expect improve.In addition, preventing the insulative properties of thermal isolation film Through when deterioration (discoloration) effect it is also insufficient, further expect improve.

Therefore, can it is an object of the present invention to provide a kind of in the thermal isolation film with the hard conating containing tungsten oxide To improve the adaptation of hard conating, and the means of the discoloration of hard conating can be prevented.

The above-mentioned technical problem of the present invention is solved by following means.

A kind of thermal isolation film, it has base material and hard conating, and the hard conating is formed by hard conating with the solidfied material of coating fluid, And be configured at least one surface of the base material, the hard conating coating fluid contains following (a)~(c)：

(a) tungsten oxide,

(b) (methyl) esters of acrylic acid chemical combination of (methyl) acrylic ester compound with primary hydroxyl must be included Thing,

(c) metal salt.

Embodiment

Below, embodiments of the present invention are illustrated.But, the present invention is not limited to following mode.

It should be noted that " (methyl) acrylate " or " (methyl) acrylic acid " is acrylate and first in this specification The general name of base acrylate.Compound containing (methyl) such as (methyl) acrylic acid etc. is to have " first in title similarly The general name of the compound of base " and compound without " methyl ".

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

＜ thermal isolation films ＞

An embodiment of the invention is related to a kind of thermal isolation film, and it has base material and hard conating,

The hard conating is formed by hard conating with the solidfied material of coating fluid, and is configured at least one surface of the base material On, the hard conating coating fluid contains following (a)~(c)：

(a) tungsten oxide,

(c) metal salt.According to the film of an embodiment of the invention with this composition, hard conating can be improved Adaptation, and the discoloration of hard conating can be prevented.

The present inventor etc. are in order that with the hard conating containing the tungsten oxide as hot radiation shielding metal oxide In thermal isolation film, the adaptation of hard conating and preventing (weatherability) and further investigation being repeated for discoloration are had concurrently.And find： By using following hard conating coating fluids, the hard conating coating, which is added with, must include (methyl) third with primary hydroxyl (methyl) acrylic ester compound and metal salt of olefin(e) acid ester type compound, can have adaptation and the discoloration of hard conating concurrently The fact that prevent surprising as (weatherability), complete the present invention.

The present inventor etc. are close on the hard conating that is formed by the hard conating containing tungsten oxide and metal salt with coating fluid The reason for conjunction property is low, it is believed that be that metal salt works as free radical scavenger, hinders to form the ultraviolet hardening of hard conating The result that composition is solidified.

Here, improving the mechanism of adaptation, the present inventor as the hard conating by an embodiment of the invention Be Deng supposition because：(methyl) acrylic ester compound with primary hydroxyl keeps (methyl) acrylic acid shortlyer using hydrogen bond The mutual distance of reactive group of ester type compound, therefore, even if containing metal salt, is not easy to hinder (methyl) esters of acrylic acid The curing reaction of compound, can improve crosslink density.

In addition, preventing the mechanism of discoloration as the hard conating by an embodiment of the invention, the present inventor etc. pushes away Survey is：The hydroxyl of (methyl) acrylic ester compound or its solidfied material with primary hydroxyl is adsorbed in tungsten oxide.Here, It is believed that metal salt have suppress insulative properties through when deterioration function, the function of this metal salt is due to metal Salt catches the moisture or free radical in hard conating.Moreover, prevent discoloration the reasons why speculate be because：Tungsten oxide, metal salt and The solidification of (methyl) acrylic ester compound with primary hydroxyl or (methyl) acrylic ester compound with primary hydroxyl Thing is close and exists, and thus, the moisture for the reason for metal salt catches the deterioration as tungsten oxide or the effect of free radical are cooperateed with Ground is enhanced.In addition, being speculated as：In (methyl) acrylic ester compound with hydroxyl, (methyl) with primary hydroxyl Acrylic ester compound is compared with (methyl) acrylic ester compound with secondary hydroxyl and tert-hydroxyl, and three-dimensional upper volume is not Greatly, therefore, tungsten oxide ((a) composition) is easily adsorbed at, therefore, excellent effect is played.

It should be noted that above-mentioned mechanism is based on speculating, its skill of correct and mistake not to embodiments of the present invention The scope of art produces influence.In addition, on having a case that other layers arbitrarily set between hard conating and base material, it is believed that can To be applicable above-mentioned mechanism.

[base material]

There is base material support hard conating or other layers arbitrarily set (to be representative such as with dielectric multilayer film Functional layer) function.

Base material can use various resin films, preferably transparent.It is, for example, possible to use polyolefin film (polyethylene, polypropylene Deng), polyester film (polyethylene terephthalate, PEN etc.), polyvinyl chloride, cellulose triacetate, Polyimides, poly- butyral film, cyclo-olefin-polymer films, transparent cellulose nano-fibrous membrane etc..Wherein, polyester is preferably used Film.

In the polyester film, from viewpoints such as the transparency, mechanical strength, dimensional stabilitys, as the polyester for forming film, Preferably with the glycol such as the dicarboxylic acid components such as terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid, ethylene glycol or 1,4 cyclohexane dimethanol into It is divided into the polyester with film formative of main constituent.Wherein, as the polyester for forming film, more preferably with poly- to benzene two Formic acid glycol ester or PEN are for the polyester of main constituent or by terephthalic acid (TPA), 2,6- naphthalenes Dicarboxylic acids and ethylene glycol formation copolyester and using the mixture of more than two kinds of these polyester as main constituent Polyester.As base material, further preferably using polyethylene terephthalate film.

, can be with addition to the above-mentioned base material enumerated in addition, the base material of the thermal isolation film as an embodiment of the invention Using for dielectric multilayer film described later and with self-supporting base material.As the dielectric multilayer film with self-supporting, It is not particularly limited, can enumerates such as with coetrusion or the dielectric multilayer film of casting method making altogether.

Material and thickness that the material and thickness of base material are preferably set so that with the percent thermal shrinkage of thermal isolation film divided by base material Value obtained by percent thermal shrinkage is in the range of 1~3.

Wherein, the thickness of base material is preferably 30~200 μm.When the thickness of base material is more than 30 μm, it is not likely to produce in processing Gauffer, therefore preferably.On the other hand, when the thickness of base material is less than 200 μm, when thermal isolation film is fitted with matrix, for example The tracing ability of the matrix of curved surface is improved, gauffer is not likely to produce, therefore preferably.From the same viewpoint, the thickness of base material is more Preferably 30~150 μm, more preferably 35~125 μm, most preferably particularly preferably 40~80 μm, 40~60 μm.

Base material is particularly preferably double axial orientated polyester film, can also use non-stretched or at least carry out in one direction The polyester film of stretching.Improved from intensity, from the viewpoint of thermal expansion suppresses, preferably stretched film.Particularly for automobile During the laminated glass of front glass, more preferably stretched film.

[hard conating]

In an embodiment of the invention, " hard conating " is with JIS K 5600-5-4：Pencil on the basis of 1999 Hardness is more than H layer, preferably more than 2H layer.For the hardness of hard conating, in terms of traumatic resistance, applying bending Deng external stress when do not produce it is preferably hard in the range of the destruction or stripping etc. of layer.

The hard conating of an embodiment of the invention preferably by by hard conating coating solution on base material, so Irradiation ultraviolet radiation makes curing of coating and formed afterwards, and the hard conating coating fluid contains：(a) tungsten oxide, (b) must include tool There are (methyl) acrylic ester compound of (methyl) acrylic ester compound of primary hydroxyl, and (c) metal salt.That is, this hair The hard conating of a bright embodiment is formed by hard conating with the solidfied material of coating fluid, under the hard conating coating fluid contains State (a)~(c)：

(a) tungsten oxide,

(b) (methyl) acrylic ester compound, it must include (methyl) esters of acrylic acid chemical combination with primary hydroxyl Thing,

(c) metal salt.

Here, (a) tungsten oxide (is also referred to as hot radiation shielding metal oxide as described later with infrared absorbance For [infrared shield metal oxide]) a kind, therefore, the hard painting being made up of hard conating with the solidfied material of coating fluid Layer has the heat insulating function that the transmission to hot line (infrared ray) is shielded.

The thickness of hard conating is not particularly limited, preferably 1~10 μm.By the way that thickness is set into more than 1 μm, it can maintain The hardness of hard conating.On the other hand, by the way that thickness is set into less than 10 μm, the cracking of hard conating caused by stress can be prevented. From the same viewpoint, the thickness of hard conating is more preferably 1.5~8 μm, more preferably 2~7 μm.

(forming method of hard conating)

First, hard conating is illustrated with each composition contained in coating fluid.

(a) tungsten oxide

Tungsten oxide is a kind of the hot radiation shielding metal oxide with infrared absorbance.

The hard conating coating fluid of an embodiment of the invention, which must contain, is used as hot radiation shielding metallic compound Tungsten oxide (hereinafter also referred to (a) composition).

As tungsten oxide, formula is used：W_yO_zRepresent, can use and Japanese Unexamined Patent Publication 2013-64042 publications or Japan The same tungsten oxide of tungsten oxide described in JP 2010-215451 publications.In above-mentioned formula, W represents tungsten.O is represented Oxygen.Y and z is the composition (composition of the oxygen relative to tungsten, z/y) of tungsten and oxygen, it is however generally that, it is less than 3 (z/y ＜'s 3) using meeting The material of relation.In addition, more preferably the composition of tungsten and oxygen meets the relation more than 2 and less than 3 (2 ＜ z/y ＜ 3), it is further excellent Be full foot 2.2~2.999 (2.2≤z/y≤2.999) relation.If this z/y ratios, then as stabilization on materials chemistry, High infrared ray absorbing energy can be played, and the infrared ray absorbing material that the free electron of requirement is efficiently produced can be turned into Material.

In addition, as tungsten oxide, compound tungsten oxide can be used.The composition of compound tungsten oxide is not limited especially System, from the viewpoint of stability, preferably formula：The oxide that MxWyOz is represented, can be used and Japanese Unexamined Patent Publication 2013- The same tungsten oxide of tungsten oxide described in No. 64042 publications or Japanese Unexamined Patent Publication 2010-215451 publications.Above-mentioned formula In, M represent selected from H, He, alkali metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、 More than a kind of element in Re, Be, Hf, Os, Bi, I.W represents tungsten.O represents oxygen.X, y and z are in general using the group of tungsten and M 2 are met into (compositions of the M relative to tungsten, x/y) composition (composition of the oxygen relative to tungsten, z/y) for meeting 0 ＜ x/y≤1, tungsten and oxygen X, y and z of ＜ z/y≤3.Additionally, it is preferred that tungsten and M composition (compositions of the M relative to tungsten, x/y) meet 0.001≤x/y≤1 The relation of composition (composition of the oxygen relative to tungsten, z/y) satisfaction 2.2≤z/y≤3 of relation, tungsten and oxygen, more preferably satisfaction 0.2≤ X/y≤0.5 and the relation of 2.45≤z/y≤3, further preferably meet the pass of 0.31≤x/y≤0.35 and 0.27≤z/y≤3 System.Here, alkali metal is the race's element of periodic table 1 outside dehydrogenation, it is lithium, sodium, potassium, rubidium, caesium, francium.Alkaline-earth metal is except beryllium, magnesium Outside the race's element of periodic table 2, be calcium, strontium, barium, radium.Rare earth element is Sc, Y and lanthanide series (from the lanthanum of No. 57 to No. 71 The element of lutetium).Particularly from the viewpoint of the optical characteristics as infrared absorbing material, weatherability improve effect, preferably M Element is more than a kind of material in Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, and particularly preferred M element is Cs's Cs_xW_yO_zWhat is represented is combined tungsten oxide containing caesium.

As the tungsten oxide that can be used in an embodiment of the invention, it is not particularly limited, example can be enumerated Such as Cs_0.33WO₃、Rb_0.33WO₃Deng.As tungsten oxide, particularly preferably use as the Cs that tungsten oxide is combined containing caesium_0.33WO₃。

In contrast, another embodiment of the invention is that (a) tungsten oxide is to be combined the heat-insulated of tungsten oxide containing caesium Film.

The shape of (compound) tungsten oxide is not particularly limited, can using particle shape, spherical, bar-shaped, Needles shapes, tabular, The arbitrary structure such as column, amorphous, flakey, fusiform, but preferably particle shape.In addition, the size such as tungsten oxide It is not particularly limited.But, in the case where tungsten oxide etc. is particle shape, the average grain diameter with regard to particles such as tungsten oxides is (flat Equal primary particle size, diameter) for, from the reflection of visible ray can be suppressed, and ensure hot line assimilation effect, do not produce in addition scattered The deterioration of mist degree caused by penetrating, it can be ensured that from the aspect of the transparency, preferably 5~150nm, more preferably 5~100nm enter One step is preferably 10~80nm, particularly preferably 30~60nm, most preferably 40~50nm.It should be noted that on above-mentioned Average grain diameter, in itself or appears in the section of index layer or the particle on surface with electron microscope observation particle, determines 1,000 The particle diameter of individual arbitrary particle, is obtained in the form of simple average value (number is average).Here, the particle diameter of each particle assumes The diameter of the bowlder equal with its projected area is represented.

In addition, as these specific trade names, being not particularly limited, it can enumerate for example as caesium doped tungsten oxide class CWO dispersion liquids (manufacture of YMF-02A Sumitomo Metal Mining Co., Ltd) etc..

Hard conating is not particularly limited with the content of the tungsten oxide in coating fluid, from by things such as hardness, film modulus of elasticity The property optical characteristics such as value or transmitance is adjusted to from the viewpoint of desired value, relative to molten except hard conating coating fluid The gross mass of composition outside agent, preferably 10~80 mass %, more preferably 20~60 mass %, more preferably 20~ 40 mass %, particularly preferably 20~30 mass %.

(b) (methyl) acrylic ester compound of (methyl) acrylic ester compound with primary hydroxyl must be included

It is used as (methyl) acrylate of the material of the hard conating coating fluid of the invention of an embodiment of the invention Class compound is the polymerizable compound solidified using ultraviolet.

It should be noted that in this specification, the term with (methyl) acrylic ester compound is not only to include monomer, And the concept of the oligomer or prepolymer by ultraviolet radiation curable can also be included.

The hard conating coating fluid of an embodiment of the invention must must be included with primary hydroxyl containing (b) (methyl) acrylic ester compound (hereinafter also referred to (b) composition) of (methyl) acrylic ester compound.

Using only the hard conating for having (methyl) acrylic ester compound without primary hydroxyl, its adaptation step-down, color Color change is big.This adaptation is low to think that reason is：As noted previously, as metal salt and hinder (methyl) esters of acrylic acid The curing reaction of compound.In addition, the change on color thinks that greatly reason is：As described above, nearby be not present tungsten oxide, Metal salt and (methyl) acrylic ester compound with primary hydroxyl or (methyl) esters of acrylic acid chemical combination with primary hydroxyl The solidfied material of thing, it is impossible to synergistically improved the moisture in layer and the effect of radical-scavenging effect.As making in the manner (methyl) acrylic ester compound, by the way that (methyl) acrylic ester compound with primary hydroxyl, solution must be included Certainly described problem.

In present specification, " primary hydroxyl " means hydroxyl of the oxygen atoms bond in primary carbon of itself.As with primary carbon Structure, can enumerate such as methylene.

As (methyl) acrylic ester compound with primary hydroxyl, it is not particularly limited, can enumerates for example：(methyl) Acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, 3- hydroxy propane -1, 2- diyls two (methyl) acrylate, glycerine list (methyl) acrylate, two glycerine list (methyl) acrylate, two glycerine three (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite list (methyl) acrylate, pentaerythrite Two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol two (methyl) acrylate, two seasons penta 4 Alcohol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, sorb Sugar alcohol two (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylate, sorbose Alcohol five (methyl) acrylate, D-sorbite list (methyl) acrylate two glycerine two (methyl) acrylate, isocyanuric acid EO Modified diacrylate etc..

In addition, the number for the primary hydroxyl having as (methyl) acrylic ester compound with primary hydroxyl in intramolecular Mesh, preferably 1~4 (embodiment：1).For less than 4 when, from the viewpoint of adaptation, more preferably.From same viewpoint Set out, more preferably 1~2, more preferably 1.

In addition, being used as (methyl) acrylic ester compound with primary hydroxyl, from the viewpoint of adaptation, preferred season Penta tetrol three (methyl) acrylate, more preferably dipentaerythritol five (methyl) acrylate, pentaerythritol triacrylate, two The acrylate of pentaerythrite five, further preferred pentaerythritol triacrylate.

There is (methyl) acrylic ester compound of primary hydroxyl can be used alone or combine two or more and make for these With.

(methyl) acrylic ester compound with primary hydroxyl relative to (methyl) acrylic ester compound ((b) into Point) the ratio of gross mass be preferably 10~100 mass %.From the viewpoint of adaptation, preferably more than 10 mass %.From From the viewpoint of same, more preferably 30~100 mass %, more preferably 50~100 mass %.

It is used as (methyl) acrylate with primary hydroxyl contained in (methyl) acrylic ester compound ((b) composition) (methyl) acrylic ester compound beyond class compound, as long as can be irradiated and be solidified by ultraviolet, does not have There is special limitation.It is used as (methyl) esters of acrylic acid chemical combination beyond (methyl) acrylic ester compound with primary hydroxyl Thing, can use such as (methyl) acrylic ester compound, polyurethane (methyl) acrylic ester compound, (methyl) propylene Sour epoxy ester series compound, polyalcohol (methyl) acrylic ester compound, polyester (methyl) acrylic ester compound, poly- silicon Oxygen alkane (methyl) acrylic ester compound etc..

Specifically, it can enumerate for example：Ethylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylic acid Ester, 1,6- hexane diols two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, (first of 1,10- decanediols two Base) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, (the first of polyethylene glycol two Base) acrylate, DPG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, (the first of polypropylene glycol two Base) acrylate, neopentyl glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, propoxylation Double [4- (2- (the first of Ethoxylated bisphenol A bis- (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylate, 9,9- Base) acryloyloxyethoxy) phenyl] fluorenes, propoxylated bisphenol two (methyl) acrylate, (the first of Tricyclodecane Dimethanol two Base) acrylate, ethoxylation isocyanuric acid three (methyl) acrylate, 6-caprolactone be modified three-(2- (methyl) propenyloxy group Ethyl) isocyanuric acid ester, ethoxylation tetramethylol methane tetraacrylate, trimethylolpropane tris (methyl) acrylate, season penta Tetrol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, polysiloxanes two (methyl) acrylate etc..Separately Outside, can be suitably using the EBECRYL (registration mark) 350 of such as Daicel-Allnex Co., Ltd. manufacture, the chemical work of SHIN-ETSU HANTOTAI X-22-2445, X-22-1602 of the manufacture of industry Co., Ltd. commercially available product.

Here, as (methyl) acrylic ester compound ((b) composition), can be suitably using such as East Asia synthesis strain formula The commercially available products such as ARONIX (registration mark) M-305, ARONIX M-402, ARONIX M-405 of commercial firm's manufacture.Need explanation It is that these are recorded in embodiment described later in detail.

The hydroxyl value of (methyl) acrylic ester compound ((b) composition) is preferably more than 10.It is hard to apply when hydroxyl value is more than 10 The adaptation improvement of layer and the variable color preventing effectiveness of hard conating are further improved.The reason is considered, by using hydrogen Key, keeps the mutual distance of reactive group of (methyl) acrylic ester compound shortlyer, even if containing metal salt, is not easy to resistance Hinder the curing reaction of (methyl) acrylic ester compound, can more play the effect for improving crosslink density.In addition, (methyl) The hydroxyl value of acrylic ester compound ((b) composition) is more preferably more than 40.When hydroxyl value is more than 40, the change of hard conating can be made Color prevents effect further good.Also, the hydroxyl value of (methyl) acrylic ester compound ((b) composition) is more preferably 80 More than.When hydroxyl value is more than 80, the adaptation improvement of hard conating is further improved.

In addition, the hydroxyl value of (methyl) acrylic ester compound ((b) composition) is preferably less than 200.Hydroxyl value is less than 200 When, the inhibition of the curling produced by moisture absorption more becomes big.

In contrast, another preferred embodiment of the invention must be included (methyl) with primary hydroxyl for (b) The hydroxyl value of (methyl) acrylic ester compound of acrylic ester compound is more than 10 thermal isolation film.

In addition, another embodiment of present invention further optimization, which is (b), must include (the first with primary hydroxyl Base) acrylic ester compound (methyl) acrylic ester compound hydroxyl value be more than 40 thermal isolation film.

It should be noted that the hydroxyl value of (methyl) acrylic ester compound ((b) composition) can be according to primary hydroxyl The species of (methyl) acrylic ester compound, (methyl) beyond (methyl) acrylic ester compound with primary hydroxyl The species of acrylic ester compound and these contents and be adjusted.

The hydroxyl value of (methyl) acrylic ester compound ((b) composition) can be measured according to JIS K0070 (1992). Specifically, when the hydroxyl value is defined as making sample 1g acetylations, the hydroxide required for the acetic acid being bonded for neutralization with hydroxyl The mg numbers of potassium.Specifically, accurate weighing sample Xg (the about 1g) in flask, wherein adding acetylation reagent exactly (in second The reagent that pyrido constant volume is 400mL is added in acid anhydrides 20mL) 20mL.Air cooled tube is installed on the mouth of flask, 95~ Enter heating in 100 DEG C of glycerol bath.After 30 minutes 1 hour, cooled down, Purified Water 1mL is added from air cooled tube, by second Acid anhydrides is decomposed into acetic acid.Then, titrated using potential difference titration outfit with 0.5mol/L potassium hydroxide-ethanol solutions, will To the flex point of titration curve be set to terminal.Also, as blank test, it is not put into sample and is titrated, obtains titration bent The flex point of line.Hydroxyl value is calculated using following formula.

Hydroxyl value={ (B-C) × f × 28.05/X }+D

(in formula, B represents the amount (mL) of the potassium hydroxide-ethanol solution of the 0.5mol/L for blank test, and C represents to be used for The amount (mL) of the 0.5mol/L of titration potassium hydroxide-ethanol solution, f represents the factor of 0.5mol/L potassium hydroxide-ethanol solutions, D represents acid number, 28.05 represent the 1mol amounts 56.11 of potassium hydroxide 1/2).

Hard conating is not particularly limited with the content of (methyl) acrylic ester compound ((b) composition) in coating fluid, Be adjusted to from by hardness or film modulus of elasticity from the viewpoint of desired value, relative to the solvent except hard conating coating fluid it The gross mass of outer composition, preferably 20~90 mass %, more preferably 20~80 mass %, more preferably 40~80 matter Measure %, most preferably particularly preferably 50~70 mass %, 60~70 mass %.

(c) metal salt

The hard conating coating fluid of an embodiment of the invention must containing metal salt (hereinafter also referred to (c) into Point).Here, metal salt have suppress function of the insulative properties through deteriorating after a while, but the function think due to Metal salt catches the moisture or free radical in hard conating.

As the metal for constituting metal salt, it is not particularly limited, can enumerates for example：Cs、Sr、Ba、Ti、Zr、Cr、Mo、W、 Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、In、Sn、Mg、Ni、Sc、Y、V、Al、Pb、Bi、 And it is above-mentioned it is cited beyond alkali metal, alkaline-earth metal etc..

Wherein, from the viewpoint of the effect for preventing discoloration, preferably Zn, Mg, Ni, In, Sn, more preferably Zn, Mg, Ni.

Can be acylate, inorganic acid salt as metal salt.Wherein, from the viewpoint of variable color preventing effectiveness, preferably It is more excellent for carboxylate, carbonyl complex salt, carbonate, phosphate, perchlorate, hypochlorite, chlorite, chlorate, hydrochloride Select perchlorate, carboxylate, further preferred carboxylate.

In contrast, another preferred embodiment of the invention is (c) metal salt for as the thermal isolation film of carboxylate.

As the carboxylic acid for constituting carboxylate, it is not particularly limited, can enumerates for example：Formic acid, acetic acid, propionic acid, butyric acid, penta Acid, caproic acid, 2 ethyl hexanoic acid, aphthenic acids, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, laurate, tetradecanoic acid, pentadecanoic acid, palm Acid, Heptadecanoic acide, stearic acid, oleic acid, linoleic acid, leukotrienes, arachidic acid, docosahexaenoic acid, eicosapentaenoic acid, grass Acid, malonic acid, butanedioic acid, benzoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), salicylic acid, gallic acid, benzene six Formic acid, cinnamic acid, pyruvic acid, lactic acid, malic acid, citric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, amino acid etc..Separately Outside, as the beta-diketon for constituting above-mentioned carbonyl complex salt, it can enumerate：Acetylacetone,2,4-pentanedione, benzoylacetone, benzoyl trifluoropropyl Ketone, hexafluoroacetylacetone, 2- thenyltrifluoroacetones etc..

Wherein, from the viewpoint of the effect for preventing discoloration, preferably acetic acid, 2 ethyl hexanoic acid, stearic acid.Wherein, especially Be from the compatibility with hard conating is good, mist degree inhibition it is excellent from the viewpoint of, further preferred 2 ethyl hexanoic acid.

As specific metal salt, it is not particularly limited, can enumerates and for example cross chloric acid Ni, stearic acid Mg, acetic acid Zn, double (2 ethyl hexanoic acid) Zn etc..

The content of metal salt is not particularly limited, relative to total matter of the composition in addition to the solvent of hard conating coating fluid Amount, preferably 0.005~10 mass %.When the content of metal salt is more than 0.005 mass %, the effect of the discoloration of hard conating is prevented Fruit is further improved.The reason is considered because obtaining the effect that metal salt catches moisture or free radical in hard conating well Really.In addition, when the content of metal salt is below 10 mass %, the adaptation improvement of hard conating is further improved.The reason It is considered because even if the metal salt containing the addition, being not easy to hinder the solidification of (methyl) acrylic ester compound Reaction, can more play the effect for improving crosslink density.From the same viewpoint, the content of metal salt is more preferably 0.01 ~1.0 mass %, more preferably 0.05~1.1 mass %, particularly preferably 0.05~1.0 mass %.

The hard conating of an embodiment of the invention in addition to above-mentioned essential component, can be contained molten with coating fluid Agent.Solvent is not particularly limited, can be from such as water, hydro carbons (toluene, dimethylbenzene), alcohols (methanol, ethanol, isopropanol, fourth Alcohol, cyclohexanol), ketone (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)), esters (methyl acetate, ethyl acetate, lactic acid first Ester), glycol ethers, suitably select in other organic solvent etc., or these material mixings are utilized.

Hard conating is not particularly limited with the content of the solvent in coating fluid, relative to the gross mass of coating fluid, is preferably 10~80 mass % or so, more preferably 20~80 mass %, more preferably 20~60 mass %, particularly preferably 40~ 60 mass %, most preferably 50~60 mass %.

Hard conating coating fluid can contain various additives as needed.As additive, it can enumerate for assigning light The surfactant of polymerization initiator, levelability, water proofing property, lubricity etc.；For improving curability caused by ultraviolet irradiation Dyestuff, pigment, sensitizer etc..

In addition, as the species of the Photoepolymerizationinitiater initiater, being not particularly limited, cationic photopolymerization initiation can be enumerated Agent, anionic property Photoepolymerizationinitiater initiater, free mafic Photoepolymerizationinitiater initiater, from the viewpoint of curability and productivity ratio, preferably Free mafic Photoepolymerizationinitiater initiater.

As free mafic Photoepolymerizationinitiater initiater, it is not particularly limited, such as acylphosphine oxide class, acetophenone can be used Class, Anthraquinones, thioxanthene ketone class, ketal class and benzophenone and azo-compound etc..As acylphosphine oxide class, without spy Do not limit, such as TMDPO, 2,4,6- trimethylbenzoyl phenyl second can be enumerated Epoxide phosphine oxide, double (2,6- Dimethoxybenzoyls) -2,4,4- trimethylpentylphosphine oxides, double (2,4,6- trimethylbenzenes Formoxyl) phenyl phosphine oxide etc..As acetophenones, it is not particularly limited, such as benzoin, benzoin methylether, benzene can be enumerated The benzoins such as benzoin ethyl ether, benzoin iso-propylether, benzylmethylketal and its alkyl ether；Acetophenone, 2,2- dimethoxys -2- Phenyl acetophenone, 1- hydroxycyclohexylphenylketones etc..As Anthraquinones, it is not particularly limited, such as tectoquinone, 2- can be enumerated EAQ, 2- amyl anthraquinones etc..As thioxanthene ketone class, it is not particularly limited, such as thioxanthones, 2,4- diethyl thiophenes can be enumerated Ton ketone, 2,4- diisopropylthioxanthones etc..As ketal class, be not particularly limited, can enumerate such as acetophenone dimethyl ketal, Benzyl dimethyl ketal etc..As benzophenone, it is not particularly limited, the double methylaminos two of benzophenone, 4,4- can be enumerated Benzophenone etc..

Wherein, preferably acylphosphine oxide class, more preferably double (2,4,6- trimethylbenzoyl) phenyl oxidations Phosphine.

Furthermore it is possible to the appropriate Irgacure (registration mark) 184 manufactured using such as BASF Japan Co., Ltd., The commercially available products such as Irgacure651, Irgacure1173, Irgacure819, LUCIRIN (registration mark) TPO.

These Photoepolymerizationinitiater initiaters can be used alone or combine two or more and use.These Photoepolymerizationinitiater initiaters make Consumption is relative to the mass parts of polymerizable component 100 based on (methyl) acrylate compounds ((b) composition), preferably 0.5 ~20 mass parts, more preferably 1~15 mass parts, more preferably 1~10 mass parts, particularly preferably 2~8 mass parts.

In addition, as the species of described surfactant, be not particularly limited, can use fluorine class surfactant, Acrylic surfaces activating agent, polysiloxane-based surfactant etc..Particularly in the levelability of coating fluid, water proofing property, lubrication Property viewpoint in terms of, preferably use fluorine class surfactant.As the example of fluorine class surfactant, such as DIC can be used MEGAFACE (registration mark) F series (F-430, F-477, F-552~F-559, F-561, F-562 of Co., Ltd.'s manufacture Deng), MEGAFACE (registration mark) RS serial (RS-76-E etc.), CHEMICAL plants of the AGCSEIMI of Dainippon Ink Chemicals's manufacture Surflon (registration mark) series of formula commercial firm manufacture, the POLYFOX series of OMNOVASOLUTIONS societies manufacture, Co., Ltd. T＆KTOKA ZX series, OPTOOL (registration mark) series of Daikin Industrial Co., Ltd manufacture, Co., Ltd. NEOS manufactures The commercially available product such as Ftergent (registration mark) serial (602A, 650A etc.).As acrylic surfaces activating agent, it can enumerate POLYFLOW series (Kyoeisha Chemical Co., Ltd.'s system), Newcol serial (Japanese emulsifying agent Co. Ltd. system), BYK (registrations Trade mark) -354 (BYK-CHEMIE JAPAN Co. Ltd. systems).As polysiloxane-based surfactant, BYK (registrations can be enumerated Trade mark) -345, BYK (registration mark) -347, BYK (registration mark) -348, (the BYK-CHEMIE of BYK (registration mark) -349 JAPAN Co. Ltd. systems).Surfactant can be used alone or two or more mixes and used.The content phase of surfactant For the gross mass of the composition in addition to the solvent of hard conating coating fluid, the mass % of preferably 0.01 mass %~1, more preferably For 0.01~0.5 mass %, more preferably 0.01~0.2 mass %.

The thermal isolation film of an embodiment of the invention is preferably manufactured by the manufacture method of following thermal isolation films, the side Method be included in base material at least one face side by hard conating coating solution after on base material, irradiation ultraviolet radiation makes film The process of solidification, the hard conating coating fluid contains following (a)~(c)：

(a) tungsten oxide,

(b) (methyl) acrylic ester compound, it must contain (methyl) esters of acrylic acid chemical combination with primary hydroxyl Thing,

(c) metal salt.

The film manufactured by described manufacture method for thermal isolation film a preferred embodiment, its have base material, And be configured at the hard conating at least one surface of base material, the hard conating by by hard conating coating solution in base material On, then, irradiation ultraviolet radiation makes curing of coating and formed, and the hard conating coating fluid contains the heat-insulated of following (a)~(c) Film：

(a) tungsten oxide,

(b) (methyl) acrylic ester compound must contain with primary hydroxyl (methyl) acrylic ester compound,

(c) metal salt, described film have base material and be configured at base material it is at least one side, by hard conating coating fluid The hard conating that constitutes of solidfied material, the hard conating coating fluid contains following (a)~(c)：

(a) tungsten oxide,

(b) (methyl) acrylic ester compound, (methyl) esters of acrylic acid chemical combination with primary hydroxyl must be contained Thing,

(c) metal salt.

Hard conating is prepared with coating fluid by being mixed to above-mentioned each composition.Order of addition, adding method do not have It is particularly limited to, can be while being stirred, one side is added each composition and mixed successively, can also be while being stirred, one side one Secondary property addition is mixed.

In addition, to (surface on the most top layer configured on the surface of base material or base material) coating hard conating painting on base material The method of cloth liquid is it is not also specifically limited, can be square such as the coating, spin coating, dip-coating using bar using known method Method.In addition, i.e. using molding coating machine (die coater), gravure coating machine (gravure coater), comma coating machine The continuous apparatus for coating such as (comma coater) can also be coated with.

As the drying condition after coating, it is not particularly limited, such as drying temperature is preferably 70~110 DEG C, when drying Between be preferably 30 seconds~5 minutes.

Thereafter, to film obtained from the coating hard conating coating fluid on base material, from the remote table of the base material from the film Surface side irradiation ultraviolet radiation, makes curing of coating.The condition of ultraviolet irradiation wavelength, illumination, light quantity now etc. is because of the purple used The species of outside line curability monomer or polymerization initiator and it is different, therefore, it can by the appropriate regularization condition of those skilled in the art. For example, in the case of using ultraviolet lamp, its illumination is preferably 50~1500mW/cm², irradiation energy preferably 50~1500mJ/ cm²。

[functional layer]

The thermal isolation film of an embodiment of the invention can have functional layer in addition to above-mentioned base material and hard conating. The species of functional layer is not particularly limited, below, and functional layer is that the situation of dielectric multilayer film (hereinafter also referred to as reflecting layer) is Example is enumerated, and is specifically illustrated.

(dielectric multilayer film)

Another preferred embodiment of the present invention is to be formed containing high refractive index layer and low-index layer alternative stacked Dielectric multilayer film thermal isolation film.

Dielectric multilayer film (reflecting layer) has the composition of low-index layer and high refractive index layer alternative stacked.It is described High refractive index layer and the low-index layer are thought as follows.

For example, constituting the composition (following, high index of refraction composition of layer) of high refractive index layer sometimes and constituting low-index layer Composition (following, low-refraction composition of layer) is mixed at the interface of two layers, is formed and is contained high index of refraction composition of layer and low folding Penetrate the layer (mixed layer) of rate composition of layer.In this case, in mixed layer, by the portion that high index of refraction composition of layer is more than 50 mass % The set of position is set to high refractive index layer, and the set at the position by low-refraction composition of layer more than 50 mass % is set to low-refraction Layer.Specifically, low-index layer for example contains the 1st metal oxide as low-refraction composition, high refractive index layer contains in addition In the case of having the 2nd metal oxide as high index of refraction composition, the metal of the film thickness direction in these stack membranes can be determined Oxide concentration is distributed, and according to its composition, regards high refractive index layer or low-index layer as.The metal oxide concentration wheel of stack membrane Exterior feature can use sputtering method to be etched from surface to depth direction, and using XPS surface analysis apparatus, outermost surfaces are set to 0nm, is sputtered with 0.5nm/min speed, is observed by determining atomic composition ratio.In addition, low-refraction into Point or high index of refraction composition in do not contain metal oxide particle, high refractive index layer or low-index layer a side only by water-soluble Property resin (organic bond) formation laminated body in, similarly operate, with water-soluble resin (organic bond) concentration point Cloth, for example, confirm that Mixed Zone is present by determining the concentration of carbon of film thickness direction, further determines its composition using EDX, by This can will regard high refractive index layer or low-index layer as by sputtering each layer etched.

As long as the reflecting layer is with more than at least one alternative stacked has the high index of refraction containing polymer on base material The number of plies (the index layer of the composition of the laminated body (unit) of layer and low-index layer, high refractive index layer and low-index layer Sum) be not particularly limited, preferably 6~2000 (i.e. Unit 3~1000), more preferably 10~1500 (i.e. 5~750 is single Member), more preferably 10~1000 (i.e. Unit 5~500), particularly preferably 10~30 (i.e. Unit 5~15).The number of plies exceedes When 2000, mist degree is easily produced, when it is less than 6, does not have difference on desired reflectivity sometimes.In addition, the one of the present invention As long as the thermal isolation film of individual embodiment has the composition of unit more than at least one on above-mentioned base material.

In dielectric multilayer film, high refractive index layer is preferably higher refractive index, and refractive index is preferably 1.70~2.50, More preferably 1.80~2.20, more preferably 1.90~2.20.In addition, low-index layer is preferably lower refractive index, Refractive index is preferably 1.10~1.60, more preferably 1.30~1.55, more preferably 1.30~1.50.

In dielectric multilayer film, from the viewpoint of infrared reflectivity can be improved with few number of plies, preferably by height folding Penetrate rate layer and low-index layer specific refractivity be designed as it is larger.In the unit being made up of high refractive index layer and low-index layer At least one in, the adjacent high refractive index layer and the refringence of low-index layer are preferably more than 0.1, more preferably 0.2 More than, more preferably more than 0.25.There is the unit of multiple low-index layers and high refractive index layer in dielectric multilayer film In the case of, the refringence of low-index layer and high refractive index layer in preferably all of unit is in above-mentioned preferred scope It is interior.But, can be the composition outside above-mentioned preferred scope on the most top layer of dielectric multilayer film or orlop.

The reflectivity of particular wavelength region is by the refringence of 2 layers (high refractive index layer and low-index layer) that abuts and folded The number of plies determines that refringence is bigger, more obtains identical reflectivity with few number of plies.On the refringence and the layer needed Number, can use commercially available optical design software to be calculated.For example, in order to obtain infrared reflectivity (infrared shielding rate) 90% More than, it is necessary to which lamination more than 100 layers, not only productivity ratio is reduced, and dissipating on laminate interface when refringence is less than 0.1 Penetrate change big, transparency reduction.From the viewpoint of the raising and the number of plies for reducing reflectivity, there is no the upper limit in refringence, but It is essentially 1.4 or so.

For above-mentioned refractive index, the refractive index of high refractive index layer, low-index layer is obtained according to following methods, as Both difference are obtained.That is, (as needed using base material) each index layer is made with individual layer, by the sample shear into 10cm × After 10cm, refractive index is obtained according to following methods.As spectrophotometer, U-4000 types (Co., Ltd. Hitachi's system is used Make manufactured), the surface (back side) of side opposite with the measure surface of each sample is subjected to roughened processing, then, with black Sprayer carries out light absorbs processing and prevents the reflection of the light at the back side, and visible region is determined under conditions of 5 degree of normal reflections 25 points of the reflectivity of (400nm~700nm), obtains average value, and mean refractive index is obtained by its measurement result.

Refractive index ratio of the reflection dependent on interlayer on adjacent bed boundary, therefore, the refractive index is than bigger, and reflectivity is got over It is high.In addition, make using monofilm observe when layer surface on reflected light and layer bottom in reflected light optical path difference as nd=ripples During the relation of long/4 expression, it can be controlled in the way of strengthening reflected light using position difference, reflectivity can be improved.Here, n is Refractive index, in addition, d is the physical film thickness of layer, nd is blooming.By using the optical path difference, reflection can be controlled.Utilize The relation controls the refractive index and film thickness of each layer, the reflection of control visible ray or near infrared light.I.e., it is possible in the refraction of each layer Rate, the thickness of each layer, the aspect of the lamination of each layer improve the reflectivity of particular wavelength region.

Dielectric multilayer film can make the particular wavelength region of reflectivity raising according to change and be set to visible light reflecting film Or near-infrared-ray reflection film.That is, if the particular wavelength region for improving reflectivity is set as into visible region, to be visible Light reflectance coating, if set near infrared region, then be near-infrared-ray reflection film.In addition, if will make what reflectivity was improved Particular wavelength region is set as UV light region, then is ultraviolet reflecting film.In the thermal isolation film of an embodiment of the invention In the case of middle use dielectric multilayer film, (near) infrared external reflection (shielding) film is set to.It is excellent in the case of infrared reflection film Select JISR3106：Transmitance under the 550nm of visible region shown in 1998 is more than 50%, more preferably more than 70%, More preferably more than 75%.Additionally, it is preferred that the transmitance under 1200nm is less than 35%, more preferably less than 25%, enter One step is preferably less than 20%.Decision design blooming and unit so that as this preferred scope.Additionally, it is preferred that Wavelength 900nm~1400nm region has the region more than reflectivity 50%.

[low-index layer and high refractive index layer]

In this specification, the term of " high refractive index layer " and " low-index layer " means：In 2 layers more adjacent of refraction In the case of rate difference, the high index layer of refractive index is set to high refractive index layer, low index layer is set to low-index layer. Therefore, the term of " high refractive index layer " and " low-index layer " is included：In each index layer for constituting dielectric multilayer film, Eye is all in addition to the form that each index layer has identical refractive index in the case of the index layer of adjacent 2 Form.

1 layer of the thickness (dried thickness) of index layer is preferably 20~1000nm, more preferably 50~500nm, Even more preferably it is 100~300nm, particularly preferably 100~200nm.1 layer of thickness of index layer can change die head Extrusion in film thickness direction width, and/or be adjusted according to stretching condition.It should be noted that to laminated body In the case of being stretched, above-mentioned thickness represents the thickness after stretching.

[polymeric material]

Low-index layer and high refractive index layer preferably comprise polymeric material.If form index layer is polymeric material Material, then can select the film build methods such as coating or spin coating.These methods are easy, and the heat resistance with base material is unrelated, therefore selection model Enclose wide, effective film build method is particularly can be described as to resin base material.For example if application type, then it can use roll-to-roll The mass production methods such as method, no matter in terms of cost, or in terms of the process time are all favourable.Further, since containing poly- The film of compound material is flexible high, therefore with being wound when being transported when production, is not easy to produce these defects, uses The excellent advantage of property.

Contained polymer is not particularly limited in index layer, as specific example, can enumerate：Poly terephthalic acid Glycol ester (PET), the copolymer (coPET) of polyethylene terephthalate, poly- (methyl methacrylate) (PMMA), poly- Copolymer (coPMMA), cyclohexanedimethanol (PETG), the copolymer of cyclohexanedimethanol of (methyl methacrylate) (coPETG), the copolymer (coPEN), poly- naphthalenedicarboxylic acid of PEN (PEN) PEN Glycol ester, the copolymer of PEN, poly- (methyl methacrylate) and poly- (methyl methacrylate) Copolymer etc., but it is not limited to these.In each high refractive index layer and low-index layer, a kind of these polymer or 2 can be used Plant the combination of the above.In addition, the example of the combination as preferred polymer, can enumerate U.S. Patent No. 6,352,761 and say Material described in bright book.Alternatively, it is also possible to use above-mentioned polymer, for example, by coetrusion or common curtain coating method etc., utilize Continuous planar film manufacturing line formation reflecting layer.

In addition, polymer contained in the high refractive index layer and the low-index layer is preferably to be acted as adhesive Water soluble polymer.Water soluble polymer is contained by high refractive index layer and low-index layer, organic solvent can be solved It is caused environmentally the problem of, alternatively, it is also possible to realize the flexibility of film, therefore preferably.It should be noted that high index of refraction Polymer contained by layer and low-index layer can be identical constituent, or different constituents, but excellent Choosing is different.As water soluble polymer, it can enumerate for example：Gelatin, thickening polysaccharide, polyvinyl alcohol, polyvinylpyrrolidone Ketone, polyacrylic acid, acrylic acid-acetonitrile copolymer, potassium acrylate-acetonitrile copolymer, vinyl acetate-acrylate copolymerization The acrylic resin such as thing or acrylic acid and acrylic ester copolymers, Styrene-acrylic copolymer, styrene-methyl propylene Acid copolymer, styrene-t-acrylate copolymer, styrene-α-methylstyrene-acrylic copolymer or The styrene acrylic resins such as styrene-α-methylstyrene-acrylic acid and acrylic ester copolymers, styrene-styrene sulfonic acid Sodium copolymer, styrene -2- hydroxyethylmethacry,ates copolymer, styrene -2- hydroxyethylmethacry,ates-styrene sulfonic acid Potassium copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, ethene Base naphthalene-maleic acid, vinyl acetate-maleate copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate Vinyl acetate lipin polymer such as ester-acrylic copolymer etc..Wherein, improved from crawling or film thickness uniformity (mist degree) etc. From the viewpoint of effect, preferred index layer contains as polyvinyl alcohol of polyvinyl alcohol or derivatives thereof as polymer. Polymer both can be used alone, can also two or more combination and use.In addition, polymer can both use composite, also may be used To use commercially available product.

Polymer is not particularly limited, International Publication No. 2012/128109, Japanese Unexamined Patent Publication 2013-121567 publications, Known polymer can be same used in Japanese Unexamined Patent Publication 2013-148849 publications etc., high refractive index layer and low-index layer Use sample.Specifically, as polyvinyl alcohol, common polyvinyl alcohol obtained from being hydrolyzed except polyvinyl acetate Outside, also comprising various modified polyvinylalcohols.

The average degree of polymerization of polyvinyl alcohol obtained from vinyl acetate is hydrolyzed is preferably 1, more than 000, more preferably Average degree of polymerization is 1,500~5,000.In addition, saponification degree is preferably 70~100 moles of %, more preferably 80~99.9 rub You are %, more preferably 85~99.9 moles %.

As modified polyvinylalcohol, it is not particularly limited, can enumerates for example：Cation-modified polyvinyl alcohol, anion change Property polyvinyl alcohol, nonionic modified polyvinyl alcohol, ethylene modified polyvinyl alcohol, vinyl alcohol polymer.

Anion-modified polyvinyl alcohol can be enumerated：For example, there is the moon described in Japanese Unexamined Patent Publication 1-206088 publications The polyvinyl alcohol of ionic group, Japanese Unexamined Patent Application 61-237681 publications and with the ethene described in 63-307979 publications The copolymer of alcohol and vinyl compound with water soluble group, and the tool described in Japanese Unexamined Patent Publication 7-285265 publications There is modified polyvinylalcohol of water soluble group etc..

In addition, as nonionic modified polyvinyl alcohol, can enumerate：For example, will remember in Japanese Unexamined Patent Publication 7-9758 publications Polyvinyl alcohol derivative formed by a part of addition of the polyalkylene oxide base and vinyl alcohol of load, Japanese Unexamined Patent Publication 8-25795 The block copolymer of vinyl compound with hydrophobic group and vinyl alcohol described in publication, the silicon with silanol group Alkanol modified polyvinylalcohol, with acetoacetyl or carbonyl, the reactive group modified poly ethylene of carboxyl isoreactivity group Alcohol etc..

As cation-modified polyvinyl alcohol, it can enumerate：For example described in Japanese Unexamined Patent Application 61-10483 publications There is polyvinyl alcohol of primary~tertiary amino or quaternary ammonium group etc. in the main chain or side chain of above-mentioned polyvinyl alcohol.Described is cation-modified Polyvinyl alcohol by the copolymer of the ethylenically unsaturated monomer with cationic groups and vinyl acetate for example by carrying out soap Change and obtain.

As ethylene modified polyvinyl alcohol, for example, it can use Japanese Unexamined Patent Publication 2009-107324 publications, Japanese Unexamined Patent Publication Described in 2003-248123 publications, Japanese Unexamined Patent Publication 2003-342322 publications, Japanese Patent Application 2013-206813 publications etc. Ethylene modified polyvinyl alcohol etc..

As these polyvinyl alcohols, it is not particularly limited, can enumerates for example：It is used as ethylene modified polyvinyl alcohol EXCEVAL (registration mark) (trade name：Kuraray Co., Ltd. manufactures) or it is used as butylene glycol-EVOH Nichigo G polymer (registration mark) (trade name：The Nippon Synthetic Chemical Industry Co., Ltd manufactures), make aldehyde and polyvinyl alcohol (such as Sekisui Chemical Co., Ltd's system " S-LEC (registrars of polyvinyl polyvinyl butyral resin obtained from reaction Mark) "), the silanol-modified polyvinyl alcohol (such as Kuraray Co., Ltd.'s manufacture " R-1130 ") with silanol group, intramolecular (for example the Nippon Synthetic Chemical Industry Co., Ltd manufactures modified polyvinylalcohol resinoid with acetoacetyl " Gohsefimer (registration mark) Z/WR series ") etc..

In these polyvinyl alcohols, polyvinyl alcohol or ethylene modified polyvinyl alcohol are preferably used.

It should be noted that above-mentioned polyvinyl alcohol can be used alone, two or more can also be combined and used.Separately Outside, polyvinyl alcohol can both use composite, can also use commercially available product.

The weight average molecular weight of polyvinyl alcohol is preferably 1,000~1,000,000, more preferably 3,000~250,000, More preferably 60,000~250,000, particularly preferably 60,000~200,000.It should be noted that this specification In, the value of " weight average molecular weight " is used to be surveyed by static light scattering method, gel permeation chromatography (GPC), TOF MASS methods etc. Fixed value.The weight average molecular weight of water soluble polymer can carry out the coating in film by wet method, can make in above range Productivity ratio is improved, therefore preferably.

The content of water soluble polymer in index layer is 5~75 matter preferably with respect to the total solid content of index layer Measure %.When the content of water soluble polymer is more than 5 mass %, in the case of with film by wet method formation index layer, When film is dried obtained from coating, transparent deterioration caused by film surface disturbances can be prevented, therefore preferably.It is another Aspect, when the content of water soluble polymer is below 75 mass %, the situation containing metal oxide particle in index layer It is down preferred content, the refringence between low-index layer and high refractive index layer can be made to become big, therefore preferably.From same From the viewpoint of, the content of water soluble polymer is more preferably 10~70 mass %, more preferably 15~50 mass %, special You Xuanwei not the mass % of 20 mass %~30.It should be noted that in this specification, the content of water soluble polymer is dry by evaporation Gu the residual solid constituent of method is obtained.Specifically, thermal isolation film is impregnated in 95 DEG C of hot water 2 hours and removes the film of residual, Then, hot water is evaporated, the amount of obtained solid content is set to water soluble polymer amount.Now, in IR (infrared spectroscopy) spectrum In in 1700~1800cm^-1, 900~1000cm^-1And 800~900cm^-1Region when each 1 peak value can be seen respectively, its water Soluble macromolecular can be defined as polyvinyl alcohol.

[metal oxide particle]

At least one layer of low-index layer and high refractive index layer can contain metal oxide (particle).By containing gold Belong to oxide particle, the refringence between each index layer can be made to become big, reflection characteristic is improved.Pass through low-index layer and height Both index layers contain metal oxide particle, refringence can be made bigger., can by containing metal oxide particle To reduce lamination number, so as to which film is made.By reducing the number of plies, productivity ratio is improved, and can suppress to occur on laminate interface The reduction of the transparency caused by scattering.

As metal oxide particle, can use constitute metal oxide metal be selected from Li, Na, Mg, Al, Si, K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Rb、Sr、Y、Nb、Zr、Mo、Ag、Cd、In、Sn、Sb、Cs、Ba、La、 Ta, Hf, W, Ir, Tl, Pb, Bi and the one kind or two or more metal in rare earth metal metal oxide.

《Metal oxide particle in high refractive index layer》

As the metal oxide particle for high refractive index layer, it is not particularly limited, can enumerates for example：Titanium oxide, oxygen Change zirconium, zinc oxide, aluminum oxide, colloidal alumina, lead titanates, red lead, yellow lead, zinc yellow, chromium oxide, iron oxide, iron oxide black, oxidation Copper, magnesia, magnesium hydroxide, strontium titanates, yittrium oxide, hafnium oxide, niobium oxide, tantalum oxide, barium monoxide, indium oxide, europium oxide, oxygen Change lanthanum, zircon, tin oxide, lead oxide and as the lithium niobate for the composite oxides being made up of these oxides, potassium niobate, Lithium tantalate, aluminium-magnesium oxide (MgAl₂O₄) etc..

In addition, as metal oxide particle, rare earth oxide can also be used.It is used as the specific reality of rare earth oxide Example, can be enumerated：Scandium oxide, yittrium oxide, lanthana, cerium oxide, praseodymium oxide, neodymia, samarium oxide, europium oxide, gadolinium oxide, oxidation Terbium, dysprosia, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide, luteium oxide etc..

As the metal oxide particle for high refractive index layer, the metal oxide grain that preferred index is more than 1.90 Son, can be enumerated such as zirconium oxide, cerium oxide, titanium oxide, zinc oxide.Wherein, from that can be formed, transparent and refractive index is higher High refractive index layer from the aspect of, preferred titanium oxide, more preferably using rutile-type (square crystalline form) Titanium particles.For height The metal oxide particle of index layer can be independent a kind, and two or more can also be applied in combination.

The volume average particle size of the metal oxide particle used in high refractive index layer is preferably below 100nm, more preferably It is still more preferably 1~30nm for below 50nm, more preferably below 30nm, particularly preferably 1~20nm is optimal Elect 1~15nm as.If volume average particle size is above range, in the viewpoint side that mist degree is few and visible light transmission is excellent Face, preferably.

In the case of the metal oxide particle used in using Titanium particles as high refractive index layer, Titanium particles Preferably use to be made and the surface of titanium oxide sol is modified to be scattered in the oxidation of the states such as water or organic solvent Titanium particle.As the preparation method of aqueous titanium oxide sol, for example, it is referred to Japanese Unexamined Patent Application 63-17221 publications, day This Unexamined Patent 7-819 publications, Japanese Unexamined Patent Publication 9-165218 publications, Japanese Unexamined Patent Publication 11-43327 publications, Japan are special Open the item described in clear 63-17221 publications etc..

The average grain diameter of titanium oxide is preferably below 100nm, more preferably below 50nm, low and visible ray is saturating from haze value Cross rate it is excellent from the viewpoint of, more preferably 1~30nm, particularly preferably 1~20nm.It should be noted that here, flat Equal particle diameter refers to：By using laser diffraction and scattering method, the side of dynamic light scattering method or electron microscope observation particle in itself Method or the method for appearing in the section of index layer or the particle image on surface with electron microscope observation, determine 1,000 arbitrarily Particle particle diameter, be respectively present n1, n2 in the particle of particle diameter that there is d1, d2didk respectively In the group of the metal oxide of the particle shape of nink, in the case that the volume of 1 particle is set into vi, with averagely The volume average particle size that the volume that particle diameter mv={ Σ (vidi) }/{ Σ (vi) } is represented is weighted.

In addition, titanium oxide can be the form of the core shell particle coated with siliceous hydrous oxide.Core shell grain Son has the structure that the shell formed by siliceous hydrous oxide is coated with the surface as the Titanium particles of core.Pass through Contain this core shell particle in high refractive index layer, pass through the siliceous hydrous oxide and the phase interaction of water-soluble resin of shell With the interlayer that can suppress low-index layer and high refractive index layer is mixed.Here, " cladding " means on Titanium particles surface At least a portion is attached with the state of siliceous hydrous oxide.That is, it is used as the Titanium particles of metal oxide particle Surface can be coated with siliceous hydrous oxide completely, and the table of Titanium particles can also be coated with siliceous hydrous oxide The part in face.It is controlled from the refractive index for the Titanium particles being wrapped by according to the covering amount of siliceous hydrous oxide Viewpoint is set out, and the part on the surface of Titanium particles is preferably coated with siliceous hydrous oxide.Hereinafter, it is wrapped by this Titanium particles be also referred to as " silica attachment TiO 2 sol ".

The titanium oxide of the Titanium particles coated with siliceous hydrous oxide can be rutile-type, or rutile titania Ore deposit type, but more preferably rutile-type.Because, the Titanium particles of rutile-type and the Titanium particles phase of Detitanium-ore-type It is lower than photocatalyst activity, therefore, the weatherability rise of the low-index layer of high refractive index layer or adjoining, and refractive index liter It is high.

" siliceous hydrous oxide " in this specification can be hydrate, the organo-silicon compound of inorganic silicon compound Hydrolysate and/or condensation product it is any, but in order to obtain the effect of an embodiment of the invention, more preferably with silicon Silane alcohol base.

The covering amount of siliceous hydrous oxide is 3~30 mass % preferably with respect to metal oxide particle.This be because For when covering amount is below 30 mass %, the high index of refraction of high refractive index layer becomes easy, and covering amount is more than 3 mass % When, the particle by cladding can be stably formed.From the same viewpoint, the covering amount of siliceous hydrous oxide is more excellent Elect 3~10 mass %, more preferably 3~8 mass % as.

As the method that Titanium particles are coated with siliceous hydrous oxide, it can be made by known method Make, for example, be referred to Japanese Unexamined Patent Publication 10-158015 publications, Japanese Unexamined Patent Publication 2000-204301 publications, Japanese Unexamined Patent Publication Item described in 2007-246351 publications etc..

In general, Titanium particles with the suppression of the photocatalyst activity of particle surface or are improved in solvent etc. mostly Dispersiveness for the purpose of, implement surface treatment in the state of use, be used as surface treatment, preferably with silica, oxidation The one kind or two or more progress such as aluminium, aluminium hydroxide, zirconium oxide handles obtained particle.More specifically, it is known to：With by dioxy The clad cladding Titanium particles surface of SiClx formation and the negatively charged material of particle surface；Or be formed with by alumina The positively charged material in pH8~10 and surface of the clad of thing formation.

It is high from the viewpoint of irregular colour when film is used from the viewpoint of infrared shielding and the glass of reduction curve form The content of metal oxide particle in index layer preferably with respect to high refractive index layer the mass % of solid constituent 100 for 20~ 80 mass %, more preferably 30~75 mass %, more preferably 40~70 mass %, particularly preferably 60~70 matter Measure %.

《Metal oxide particle in low-index layer》

The average primary particle diameter of the metal oxide particle used in low-index layer is preferably below 100nm.

As the metal oxide particle for being mainly used in low-index layer, silica is preferably used as metal oxide Particle, particularly preferably using colloidal silica.Contained metal oxide particle (preferably silica) in low-index layer Average grain diameter be preferably 3~100nm.The primary particle of the silica disperseed with the state of primary particle is averaged Particle diameter (with the particle diameter of the scattered liquid status before coating) is more preferably 3~50nm, more preferably 3~40nm, particularly preferably For 3~20nm, most preferably 4~10nm.In addition, as the average grain diameter of offspring, mist degree is few and visible light permeability In terms of excellent viewpoint, preferably below 30nm.For the average grain diameter of the metal oxide in low-index layer, electronics is used Microscope to appearing in particle in itself or the section of index layer or the particle on surface are observed, determine 1,000 it is arbitrary The particle diameter of particle, is obtained as its simple average value (number is average).Here, the particle diameter of each particle is equal to its throwing with hypothesis The diameter of the bowlder of shadow area is represented.

As the content of the metal oxide particle in low-index layer, relative to the solid constituent of low-index layer, from From the viewpoint of refractive index, preferably 5~80 mass %, more preferably 10~75 mass %, more preferably 50~75 matter Measure %, particularly preferably 65~75 mass %.

Colloidal silica is double decomposition to be carried out to acid as sodium metasilicate etc. or by obtained from amberlite lipid layer Obtained from silicon dioxide gel progress is heat aging, for example, it is recorded in Japanese Unexamined Patent Application 57-14091 publications, Japanese Unexamined Patent Publication Clear 60-219083 publications, Japanese Unexamined Patent Application 60-219084 publications, Japanese Unexamined Patent Application 61-20792 publications, Japanese Unexamined Patent Publication Clear 61-188183 publications, Japanese Unexamined Patent Application 63-17807 publications, Japanese Unexamined Patent Publication 4-93284 publications, Japanese Unexamined Patent Publication 5-278324 publications, Japanese Unexamined Patent Publication 6-92011 publications, Japanese Unexamined Patent Publication 6-183134 publications, Japanese Unexamined Patent Publication 6- No. 297830 publications, Japanese Unexamined Patent Publication 7-81214 publications, Japanese Unexamined Patent Publication 7-101142 publications, Japanese Unexamined Patent Publication 7- No. 179029 publications, Japanese Unexamined Patent Publication 7-137431 publications and International Publication No. 94/26530 etc..This colloidal silica Silicon can both use composite, can also use commercially available product.Colloidal silica can change for its surface has been carried out into cation The material of property, alternatively, it is also possible to the material to be handled with Al, Ca, Mg or Ba etc..

This colloidal silica can both use composite, can also use commercially available product.As commercially available product, can enumerate by SNOWTEX series (SNOWTEX (registration mark) OS, SNOWTEX OXS, SNOWTEX that Nissan Chemical Ind Ltd sells S、SNOWTEX OS、SNOWTEX 20、SNOWTEX 30、SNOWTEX 40、SNOWTEX O、SNOWTEX N、SNOWTEX C Deng).

(other additives)

Each index layer than that described above, for example, can contain Japanese Unexamined Patent Application 57-74193 publications, same to 57-87988 Number publication and with the ultra-violet absorber described in 62-261476 publications, Japanese Unexamined Patent Application 57-74192 publications, same to 57- No. 87989 publications, with 60-72785 publications, with 61-146591 publications, Japanese Unexamined Patent Publication 1-95091 publications and same 3- Anti-fading agent, Japanese Unexamined Patent Application 59-42993 publications described in No. 13376 publications etc., with 59-52689 publications, same to 62- No. 280069 publications, with the fluorescent whitening agent described in 61-242871 publications and Japanese Unexamined Patent Publication 4-219266 publications etc., The pH adjusting agents such as sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, defoamer, diethylene glycol etc. moisten Various additives known to lubrication prescription, preservative, antistatic agent, delustering agent etc..The content of these additives is preferably with respect to refraction The solid constituent of rate layer is 0.1~10 mass %.

Or, in the case where each index layer contains water soluble polymer, in order that water soluble polymer solidifies, also may be used To use curing agent.As curing agent, it can enumerate：Boric acid and its salt, ethylene glycol diglycidylether, 1,4- butanediols two shrink Glycerin ether, 1,6- 2-glycidyls butylcyclohexane, N, N- diglycidyl -4- glycidyloxyanilines, D-sorbite gather Glycidol ether, glycerine polyglycidyl ether etc.), aldehydes curing agent (formaldehyde, glyoxal etc.), reactive halogen class curing agent (2, Chloro-4-hydroxyl -1,3,5- s-triazine of 4- bis- etc.), reactive ethylene base class compound (1,3,5- triacryls-hexahydro-equal three Piperazine, bi-vinyl sulfonyl methyl ether etc.), al alum, borax etc..The content of curing agent in index layer is preferably with respect to refraction The solid constituent of rate layer is 1~10 mass %, more preferably 1~5 mass %.

Or, in order to adjust surface tension during coating, each index layer can contain surfactant.Here, conduct Surfactant, can use anionic based surfactants, nonionic class surfactant, amphoteric surfactant etc., more Preferably anionic based surfactants.As preferred compound, dredging containing carbon number 8~30 in 1 molecule can be enumerated The material of aqueous group and sulfonic group or its salt.The content of surfactant in each index layer is preferably with respect to index layer Solid constituent be 0.01~5 mass %, more preferably 0.01~1 mass %.

The manufacture method of dielectric multilayer film is not particularly limited, and can enumerate for example by making high refractive index layer coating fluid And low-index layer be coated with coating fluid, dry formed by method.

High refractive index layer is not particularly limited with coating fluid and low-index layer with the preparation method of coating fluid, can be enumerated and be added Addition polymerization compound, metal oxide particle, the other additives added as needed and solvent are stirred the side of mixing Method.Now, the order of addition of each composition is also not particularly limited, both can be while being stirred, and each composition is added on one side successively And mix, can also be while being stirred, one side is disposably added and mixed.Further it can also be adjusted as needed using solvent Whole is appropriate viscosity.

In addition, when preparing high refractive index layer coating fluid and low-index layer formation coating fluid, can be appropriate on one side Heating is carried out while preparing.

Here, not limited especially with the solvent of coating fluid with coating fluid and low-index layer for adjusting high refractive index layer System, preferably water, organic solvent or its mixed solvent.Additionally, it is contemplated that when in terms of environment caused by the dispersing of organic solvent, it is more excellent Select the mixed solvent of water or water and a small amount of organic solvent, particularly preferred water.As the organic solvent, it can enumerate for example：First Alcohols, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, the dihydroxypropane single-ethers such as alcohol, ethanol, 2- propyl alcohol, n-butyl alcohol The ethers such as the esters such as acetic acid esters, diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, dimethylformamide, N- crassitudes Ketones such as the amide-types such as ketone, acetone, methyl ethyl ketone, acetylacetone,2,4-pentanedione, cyclohexanone etc..These organic solvents can be used alone or Two or more mixes and used.Consider in terms of the environment, in terms of the simplicity of operation, as the solvent of coating fluid, particularly preferably The mixed solvent of water or water and methanol, ethanol or ethyl acetate, more preferably water.

Using water and a small amount of organic solvent mixed solvent when, will be mixed for the content of the water of the in the mixed solvent Bonding solvent is integrally set to 100 mass %, more preferably preferably 80~99.9 mass %, 90~99.5 mass %.Because, Here, by being set to more than 80 mass %, volume caused by the volatilization of solvent, which changes, to be reduced, operation is improved, in addition, passing through It is set to below 99.9 mass %, homogenieity increase when liquid is added, the liquid physical property that can be stablized.

Then, to the high refractive index layer coating fluid and low-index layer coating solution using above-mentioned middle preparation in base On material and dry it, the method for forming dielectric multilayer film is illustrated.

As the coating method, it is not particularly limited, can be for gradually rubbing method, while any side of double-layer coating Method, but be preferably double-layer coating simultaneously from viewpoints such as productivity ratio.

As coating method, such as coating method, U.S. Patent No. 2,761,419 are preferably used, with the 2nd, 761,791 Slip pearl coating method, extrusion coated method of use loading hopper described in number publication etc..

With regard to carry out simultaneously double-layer coating when high refractive index layer coating fluid and low-index layer coating fluid temperature and Speech, in the case of using pearl coating method is slided, the temperature of preferably 25~60 DEG C of temperature range, more preferably 30~45 DEG C Scope.In addition, in the case of using curtain coating mode, the temperature of preferably 25~60 DEG C of temperature range, more preferably 30~45 DEG C Spend scope.

The viscosity of high refractive index layer coating fluid and low-index layer coating fluid when carrying out double-layer coating simultaneously does not have Especially limitation.But, in the case of using pearl coating method is slided, in the range of the preferable temperature of above-mentioned coating fluid, Preferably 5~100mPas scope, more preferably 10~50mPas scope.In addition, in the situation using curtain coating mode Under, in the range of the preferable temperature of above-mentioned coating fluid, preferably 5~1200mPas scope, more preferably 25~ 500mPas scope.If the scope of this viscosity, then double-layer coating simultaneously can be effectively carried out.

In addition, being used as 15 DEG C of viscosity of coating fluid, more preferably preferably more than 100mPas, 100~30,000mPa S, more preferably 3,000~30,000mPas, most preferably 10,000~30,000mPas.

As coating and drying means, be not particularly limited, as with gradually rubbing method formation reflectance coating when it is specific Example, will warm up 25~60 DEG C, and the low-index layer coating fluid and high refractive index layer for being preferably heated to 30 DEG C~45 DEG C are used Any coating solution of coating fluid is on base material and being dried and forming layer, then, by another coating solution in this On layer and it is dried and forming layer.Repeat gradually to be coated with, be in order to required for showing desired reflecting properties The number of plies, so as to obtain reflectance coating precursor.When being dried, preferably the film of formation is dried more than 30 DEG C.For example, It is preferred that being dried in the range of 5~50 DEG C of wet-bulb temperature, 5~100 DEG C of film surface temperature (preferably 10~50 DEG C), for example, blow 40 ~85 DEG C of warm wind 1~5 second and be dried.As drying means, warm air drying, infra-red drying, microwave drying can be used.Separately Outside, compared with the drying in single technique, the drying of multistage technology is preferably carried out, the temperature ＜ of constant rate of drying portion is more preferably set to The temperature of falling rate of drying portion.The temperature range of constant rate of drying portion now is preferably set to 25~60 DEG C, the temperature of falling rate of drying portion Scope is set to 50~100 DEG C.

In addition, in the case of by the way that double-layer is coated with and to form reflecting layer simultaneously, preferably by low-index layer coating fluid and High refractive index layer is heated to 25~60 DEG C with coating fluid, and low-index layer coating fluid is carried out on base material and high refractive index layer is used Double-layer is coated with while coating fluid, then, the temperature of the film of formation is temporarily cooled into preferably 1~15 DEG C (fixation), thereafter It is dried more than 10 DEG C.More preferably drying condition is 5~50 DEG C of wet-bulb temperature, the bar of the scope of 10~50 DEG C of film surface temperature Part.For example, the warm wind that can blow 80 DEG C send and is dried for 1~5 second.In addition, as the type of cooling after firm coating, from carrying From the viewpoint of the uniformity for the film that height is formed, preferably carried out with horizontal fixed form.

Here, the fixation means：By cold wind etc. is blown to film and reduce temperature etc. means improve film combine The viscosity of thing, the process for carrying out reduction or the gelation of the mobility of each interlayer and the material in each layer.Cold wind is set to be blown from surface To coated film, the state that will not adhere to any material on finger when the surface of coated film presses finger is defined as fixation and terminated State.

From to blowing a cold wind over and fixing time (set time) of end being preferably within 6 minutes, more preferably at the time of coating Within 5 minutes, within more preferably 2 minutes.In addition, the time of lower limit is not particularly limited, it is preferred to use 10 seconds with On time, more preferably using the time of more than 45 seconds.By using the set time it is certain more than, the composition in layer can be abundant Ground is mixed.On the other hand, by the way that the set time short time will be set to, it can prevent the interlayer of metal oxide nanoparticles from expanding Dissipate, the refringence of high refractive index layer and low-index layer is set to desired layer.It should be noted that in high refractive index layer , can also even if being not provided with fixed work order in the case that boundary face between low-index layer promptly causes high resiliency Form preferred interface.

It should be noted that in addition to the concentration of change water-soluble resin or the concentration of metal oxide nanoparticles, Gu Fixing time can be various known solidifying by adding gelatin, pectin, agar, carragheen, gellan gum (gellan gum) etc. Other compositions such as gelatinizing agent and be adjusted.

More specifically, in fixed work order, the temperature of used cold wind is preferably 0~25 DEG C, more preferably 5~10 ℃.In addition, film also depends on the travelling speed of film, preferably 10~360 seconds, more preferably 10 exposed to the time of cold wind ~300 seconds, more preferably 10~120 seconds.

It is coated, making the coating thickness of high refractive index layer coating fluid and low-index layer coating fluid turns into above-mentioned institute Show it is preferred dry when thickness.

More than, enumerated in case of functional layer is dielectric multilayer film, its composition is specifically described, even if function Layer is the various functions layer beyond dielectric multilayer film, can also be applicable the present invention.It is used as the dielectric multilayer film of functional layer Functional layer in addition, can be enumerated such as antistatic backing, closely sealed imparting intermediate layer, color material layer, on these specific compositions, Can be suitably with reference to known opinion.

[adhesive layer]

In addition, the thermal isolation film of an embodiment of the invention can have adhesive layer.The adhesive layer be generally arranged at The most surface of the opposite side of hard conating in the base material of thermal isolation film, and known peeling paper can be further set.It is used as bonding The composition of layer, is not particularly limited, and can be used such as dry laminating agent, wet laminating agent, adhesive, heat sealing agent, hot solvent.Make For adhesive, such as polyester resin, polyurethane based resin, polyvinyl acetate esters resin, acrylic resin, nitrile can be used Rubber etc..

It should be noted that adhesive layer can be properly added cooperation ultra-violet absorber, antioxidant, antistatic agent, heat Stabilizer, lubricant, filler, coloring, bonding regulator etc..

(purposes)

The thermal isolation film of the manner can apply to the field of broadness.For example, as the window outside the room for fitting in building or Automotive window isometric period exposed to sunshine equipment and assign the window patch of heat insulating function with film, agricultural with vinyl house film Deng being used with the purpose for mainly improving weatherability.

[insulator]

The thermal isolation film of a particularly embodiment of the manner can be used preferably as insulator.Insulator refers to： Thermal isolation film directly or via adhesive linkage or in the case where thermal isolation film has adhesive layer via adhesive layer is fitted in into glass or glass Glass substitutes the part of the matrixes such as resin.

The material for forming matrix is not particularly limited, and as concrete example, can enumerate for example：It is glass, polycarbonate resin, poly- Sulphone resin, acrylic resin, vistanex, polyether resin, polyester resin, polyamide, polysulfide ether resin, unsaturation are poly- Ester resin, epoxy resin, melmac, phenolic resin, diallyl phthalate resin, polyimide resin, The various resins such as polyurethane resin, vinylite, polyvinyl alcohol resin, styrene resin, vinyl chloride resin, metal Plate, ceramics etc..For the species for the resin for forming matrix, thermoplastic resin, heat-curing resin, ionizing radiation are solid The property changed resin can be used.Furthermore it is possible to combine two or more different types of resin and use.Go out from the viewpoint of practicality Hair, the material for forming matrix is particularly preferably glass.Matrix can by extrusion molding, calendaring molding, injection molded, it is hollow into Method known to shape, compression molding etc. is manufactured.The thickness of matrix is not particularly limited, preferably 0.1mm~5cm.

Matrix can be plane, or curved surface.For the method for the thermoforming fitted with the matrix with curved surface It is not particularly limited, it is however generally that, a surface maying be used at the matrix with curved surface, the hard conating for making thermal isolation film are interior Side, i.e., deform it, thereafter, in the matrix with curved surface towards in the state of matrix side relative to base material along the shape of matrix It is outside in the hard conating of thermal isolation film, i.e., with base in the state of being tossed about relative to base material court with matrix phase on the surface of opposite side Show consideration for the method closed.

Therefore, other preferably one embodiments of the invention are the insulator that thermal isolation film is fitted in matrix.

As described above, the thermal isolation film of an embodiment of the invention can fit across adhesive linkage with matrix.Form viscous The bonding agent or adhesive for connecing layer are not particularly limited, and can enumerate for example using the resin of photo-curable or Thermocurable as principal component Bonding agent or adhesive.As bonding agent or adhesive, there is bonding agent or the bonding of durability preferably with respect to ultraviolet Agent.As bonding agent or adhesive, specifically, preferably acrylic adhesives or polysiloxane-based adhesive are special from bonding From the viewpoint of property or cost, further preferred acrylic adhesives.It is particularly strong from peeling off as acrylic adhesives From the aspect of the control of degree is easy, preferred solvent class.The feelings of acrylic acid solvent adhesive are used as using polymerisation in solution polymer Under condition, as monomer, known material can be used.In addition, as bonding agent or adhesive, polyvinyl fourth can be used Acetal-based resin or vinyl-vinyl acetate copolymer resinoid.It is used as polyvinyl butyral resinoid or ethylene-acetate second The concrete example of enoate copolymer resinoid, can be enumerated for example：Plasticity polyvinyl butyral (Sekisui Chemical Co., Ltd Manufacture, Mitsubishi Monsanto be melted into Co., Ltd. manufacture etc.), vinyl-vinyl acetate copolymer (E.I.Du Pont Company manufacture, Wu Tian Pharmaceutical industries Co., Ltd. manufacture, Duramin), ethene improved-vinyl acetate copolymer (TOSOH Co., Ltd manufacture, Mersen G (registration mark)) etc..

It should be noted that can be properly added in adhesive linkage cooperation ultra-violet absorber, antioxidant, antistatic agent, Heat stabilizer, lubricant, filler, coloring, bonding regulator etc..

[heat-proof quality]

Thermal isolation film or the heat-proof quality of insulator, sunshine heat shielding performance in general can be by with JIS R3209： 1998 (compound glasses), JIS R3106：1998 (the examinations of the hot pick-up rate of transmitance, reflectivity, emissivity, sunshine of glass sheet class Proved recipe method), JIS R3107：On the basis of 1998 (method is determined in the calculation of the coefficient of heat conduction in the thermal resistance and building of glass sheet class) Method obtain.

Embodiment

Hereinafter, embodiment is enumerated, the present invention is specifically described, but the present invention is not limited to these embodiments.Following In embodiment and comparative example, make the thermal isolation film with base material and the hard conating containing tungsten oxide and carry out various evaluate.

《The making of thermal isolation film》

The preparation ＞ of ＜ coating fluids

The coating fluid used in the making of embodiment and the thermal isolation film of comparative example is prepared as described below.

(hard conating coating fluid HC1 preparation)

Will as (methyl) acrylic ester compound ((b) composition) ARONIX (registration mark) M-405 (two seasons penta 4 The acrylate of alcohol five:Dipentaerythritol acrylate=10~20:The mixture of 90~80 (mass ratioes), East Asia synthesis strain formula Commercial firm manufactures) 390 mass parts and (silicone diacrylate, Daicel-Allnex plant formulas of EBECRYL (registration mark) 350 Commercial firm manufactures) 0.4 mass parts are mixed, add as be combined tungsten oxide caesium doped tungsten oxide dispersion liquid (YMF-02A, The mass % of total solid content concentration 28 (the mass % of caesium doped tungsten oxide ((a) composition) concentration 18.5), composition：Cs_0.33WO₃, it is average Particle diameter 50nm, Sumitomo Metal Mining Co., Ltd manufacture) 650 mass parts, as metal salt ((c) composition) cross chloric acid nickel (Ni) Hexahydrate (Kanto Kagaku K. K.'s manufacture) 3 mass parts, the mass parts of methyl ethyl ketone 300 as solvent.Also, addition As polymerization initiator Irgacure (registration mark) 819 (double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides, BASF Amada Co., Ltd.s system) 20 mass parts, fluorine class surfactant (Ftergent (registration mark) 650A, Co., Ltd. NEOS is manufactured) 0.5 mass parts, prepare hard conating coating fluid HC1.

(hard conating coating fluid HC2 preparation)

Chloric acid nickel (Ni) hexahydrate of crossing as metal salt is changed to magnesium stearate (Mg) (Kanto Kagaku K. K. Manufacture), in addition, operated with hard conating in the same manner as coating fluid HC1, prepare hard conating coating fluid HC2.

(hard conating coating fluid HC3 preparation)

Chloric acid nickel (Ni) hexahydrate of crossing as metal salt is changed to zinc acetate (Zn) (anhydrous) (Northeast chemistry strain formula Commercial firm manufactures), in addition, operated with hard conating in the same manner as coating fluid HC1, prepare hard conating coating fluid HC3.

(hard conating coating fluid HC4 preparation)

Chloric acid nickel (Ni) hexahydrate of crossing as metal salt is changed to double (2 ethyl hexanoic acid) zinc (Zn) (solid constituents The Mineral spirits solution of concentration 80%, Wako Pure Chemical Industries, Ltd.'s manufacture) 3.8 mass parts, in addition, it is coated with hard conating Liquid HC1 is similarly operated, and prepares hard conating coating fluid HC4.

(hard conating coating fluid HC5 preparation)

By ARONIX (registration mark) M-405 (two seasons penta 4 of (methyl) acrylic ester compound (being used as (b) composition) The acrylate of alcohol five:Dipentaerythritol acrylate=10~20:The mixture of 90~80 (mass ratioes), East Asia synthesis strain formula Commercial firm manufactures) it is changed to ARONIX (registration mark) M-402 (Dipentaerythritol Pentaacrylates:The acrylic acid of dipentaerythritol six Ester=30~40:The mixture of 70~60 (mass ratioes), Toagosei Co., Ltd's manufacture), and double (2- of metal salt will be used as Thylhexoic acid) addition of zinc (Zn) is changed to 0.076 mass parts, in addition, grasped with hard conating in the same manner as coating fluid HC4 Make, prepare hard conating coating fluid HC5.

(hard conating coating fluid HC6 preparation)

The addition of double (2 ethyl hexanoic acid) zinc (Zn) as metal salt is changed to 0.38 mass parts, in addition, Operated with hard conating in the same manner as coating fluid HC5, adjustment hard conating coating fluid HC6.

(hard conating coating fluid HC7 preparation)

The addition of double (2 ethyl hexanoic acid) zinc (Zn) as metal salt is changed to 3.8 mass parts, in addition, with Hard conating is similarly operated with coating fluid HC5, adjustment hard conating coating fluid HC7.

(hard conating coating fluid HC8 preparation)

The addition of double (2 ethyl hexanoic acid) zinc (Zn) as metal salt is changed to 7.6 mass parts, in addition, with Hard conating is similarly operated with coating fluid HC5, adjustment hard conating coating fluid HC8.

(hard conating coating fluid HC9 preparation)

The addition of double (2 ethyl hexanoic acid) zinc (Zn) as metal salt is changed to 38 mass parts, in addition, with Hard conating is similarly operated with coating fluid HC5, adjustment hard conating coating fluid HC9.

(hard conating coating fluid HC10 preparation)

By ARONIX (registration mark) M-405 (two seasons penta 4 of (methyl) acrylic ester compound (being used as (b) composition) The acrylate of alcohol five:Dipentaerythritol acrylate=10~20:The mixture of 90~80 (mass ratioes), East Asia synthesis strain formula Commercial firm manufactures) it is changed to ARONIX (registration mark) M-305 (pentaerythritol triacrylates:Tetramethylol methane tetraacrylate= 55~63:The mixture of 45~37 (mass ratioes), Toagosei Co., Ltd's manufacture), in addition, with hard conating coating fluid HC4 is similarly operated, and prepares hard conating coating fluid HC10.

(hard conating coating fluid HC11 preparation)

Will as (methyl) acrylic ester compound ARONIX (registration mark) M-405 (propylene of dipentaerythritol five Acid esters:Dipentaerythritol acrylate=10~20:The mixture of 90~80 (mass ratioes), Toagosei Co., Ltd's system Make) KAYARAD (registration mark) TMTPA (trimethylolpropane trimethacrylate, Nippon Kayaku K. K's manufacture) is changed to, In addition, operated with hard conating in the same manner as coating fluid HC2, prepare hard conating coating fluid HC11.

(preparation of low-index layer coating fluid)

Add colloidal silica (the mass %, SNOWTEX (registrar of concentration 10 of 380 mass parts successively at 45 DEG C Mark) OXS, 4~6nm of average grain diameter of 1 particle, Nissan Chemical Ind Ltd's manufacture), the boric acid aqueous solution of 50 mass parts Polyvinyl alcohol (the mass % of concentration 4, JP-45, the degree of polymerization of (the mass % of concentration 3), 300 mass parts：4500th, saponification degree： 88mol%, JAPAN VAM＆POVAL Co., Ltd. manufacture), the aqueous surfactant solutions of 3 mass parts (the mass % of concentration 5, SOFTAZLINE (registration mark) LSB-R, river grind the manufacture of Fine Chemicals Co., Ltd.).1000 are refined to pure water Mass parts, prepare low-index layer coating fluid.

(preparation of high refractive index layer coating fluid)

(silica adheres to the preparation of TiO 2 sol)

In TiO 2 sol (the mass % of concentration 15.0, SRD-W, volume average particle size：5nm, rutile titanium dioxide Particle, Sakai Chemical Industry Co., Ltd.'s manufacture) add after the mass parts of pure water 2 in 0.5 mass parts, it is heated to 90 DEG C.Then, delay Slowly add 0.5 mass parts silicate aqueous solution and (dilute (silicic acid soda 4, Nippon Chemical Ind's system with pure water Make), and cause SiO₂Concentration is 0.5 mass % solution), then, carry out heating for 18 hours in autoclave, at 175 DEG C Processing, after cooling, concentrated with ultrafiltration membrane, single solid component concentration be 20 mass %, surface attachment have SiO₂Two Titanium oxide sol (also referred to as " silica attachment TiO 2 sol ") (volume average particle size：9nm).

(preparation of coating fluid)

Adhere to TiO 2 sol (the mass % of solid constituent 20) 113 mass parts relative to the silica so obtained, Aqueous citric acid solution (the mass % of concentration 1.92) 48 mass parts are added, the ethylene modified polyvinyl alcohol (matter of concentration 8 is further added Measure %, EXCEVAL (registration mark) RS-2117, ethylene modified degree 3.0mol%, saponification degree：97.5~99 moles of %, degree of polymerization 1700th, Kuraray Co., Ltd. manufactures) 113 mass parts, and be stirred, it is eventually adding the mass % of concentration 5 of surfactant The aqueous solution (SOFTAZLINE (registration mark) LSB-R, river grind the manufacture of Fine Chemicals Co., Ltd.) 0.4 mass parts, system Standby high refractive index layer coating fluid.

(the making of thermal isolation film sample 1：Embodiment 1)

In base material (the polyethylene terephthalate film that 50 μm of thickness, COSMOSHINE (registration mark) A4300, east Paj Co., Ltd. manufactures) on, hard conating coating fluid is coated with conditions of using dry film thickness as 5 μm with gravure coating machine HC1, is dried 1 minute at 90 DEG C.Then, using ultraviolet lamp, in illumination 100mW/cm², exposure 0.5J/cm²Under conditions of From the face side irradiation ultraviolet radiation from base material farther out of film, thus make curing of coating and form hard conating, make thermal isolation film examination Sample 1.

(the making of thermal isolation film sample 2~10,12：Embodiment 2~10, comparative example 1)

Hard conating is changed to hard conating coating fluid HC2~11 with coating fluid HC1 respectively, in addition, with thermal isolation film Sample 1 is similarly operated, and makes thermal isolation film sample 2~10,12.

(the making of thermal isolation film sample 11：Embodiment 11)

Using slide hopper apparatus for coating, while low-index layer is protected with coating fluid and high refractive index layer with coating fluid Temperature is at 45 DEG C, while being heated to 45 DEG C of base material (the polyethylene terephthalate film that 50 μm of thickness, COSMOSHINE (registration mark) A4300, Japan spin Co., Ltd. manufacture) on carry out 11 layers simultaneously double-layer coating (total film thicknesses；1.5μm).Now, Set, orlop and the superiors is set to low-index layer, and make low-index layer and high refractive index layer point beyond it Other alternative stacked.Coating weight is adjusted so that in thickness when drying, each layer of low-index layer is 150nm, height refraction Each layer of rate layer is 120nm.After coating, 5 DEG C of cold wind is blown after 5 minutes, the warm wind for blowing 80 DEG C is dried, make by 11 layers The dielectric multilayer film of formation.

Then, with the surface of the surface opposite side for forming dielectric multilayer film side of base material, using gravure coating Machine is coated with hard conating coating fluid HC10 under conditions of using dry film thickness as 5 μm, is dried 1 minute at 90 DEG C.Then, use Ultraviolet lamp, in illumination 100mW/cm², exposure 0.5J/cm²Under conditions of from face side irradiation of the film from base material farther out Ultraviolet, thus makes curing of coating and forms hard conating, makes thermal isolation film sample 11.

These thermal isolation film samples 1~12 are shown in detail in table 1.

《The measure of the hydroxyl value of (methyl) acrylic ester compound ((b) composition)》

The hydroxyl value of (methyl) acrylic ester compound ((b) composition) is measured according to JISK0070 (1992).

Specifically, in flask the gross mass Xg (1g) that accurate weighing prepares sample, it is hard actually to make an addition to The mass ratio of coating coating fluid includes each composition contained in (b) composition, wherein adding acetylation reagent exactly (in acetic acid The solution that pyrido constant volume is 400mL is added in acid anhydride 20mL) 20mL.Then, air cooled tube is installed on the mouth of flask, 95 Heated in~100 DEG C of glycerol bath.After 30 minutes 1 hour, cooled down, Purified Water 1mL is added from air cooled tube, will Acetic anhydride is decomposed into acetic acid.Then titrated using potential difference titration outfit with 0.5mol/L potassium hydroxide-ethanol solutions, will The flex point of obtained titration curve is set to terminal.Also, as blank test, it is not put into sample and is titrated, obtains titration Point of inflexion on a curve.Hydroxyl value is calculated using following formula.

Hydroxyl value={ (B-C) × f × 28.05/X }+D

(in formula, B represents the amount (mL) of the potassium hydroxide-ethanol solution of the 0.5mol/L for blank test, and C represents to be used for The amount (mL) of the 0.5mol/L of titration potassium hydroxide-ethanol solution, f represents the factor of 0.5mol/L potassium hydroxide-ethanol solutions, D represents acid number, 28.05 represent the 1mol amounts 56.11 of potassium hydroxide 1/2)

Evaluation result by more than is shown in table 1.

《The evaluation of thermal isolation film》

The adaptation ＞ of ＜ hard conatings

Using the 1506 bent spindle testing machines (manufacture of Elcometer companies) for the heart axle for being provided with diameter 10mm, to every Hotting mask sample 1~12, by hard conating be configured at outside and bend after, according to JIS-K5600-5-6:1999 cross-hatching, Be configured at outside face most surface by the sword of the razor of single-blade using relative to face for 90 ° angle with 2mm intervals draw lattice, making The gridiron pattern of 10mm square.The cellophane tape No.29 of Nitto Denko Corp's manufacture is attached, peeling paper band studies the stripping of film From state.

The number of the square of intersection is set to n, by the number of the square of residual film is set to n1 on supporter after paper tape is peeled off When, calculate F=n1/n × 100 (%), based on the thermal isolation film sample average value of 10, evaluated according to following benchmark.

◎：F >=90%

○：90% ＞ F >=80%

△：80% ＞ F >=70%

×：70% ＞ F

It should be noted that in actual use, if F is more than 70%, it may be said that ensuring interlayer adaptation.

＜ tone variations (discoloration) ＞

The thermal isolation film sample 1~12 of above-mentioned making is attached at glass, (Suga is tested using super xenon test apparatus Machine Co., Ltd. SX75), in activity 180W/m², rainfall 18 minutes/60 minutes cycling condition under carry out 1000 hours photographs Penetrate (weather resistance test).Determine saturating using spectrophotometer (integrating sphere use, Hitachi Co., Ltd's manufacture, U-4000 types) Spectrum is crossed, the aberration (Δ E) before and after weather resistance test is calculated.Following grades are charged to the test specimen average value of 6.

◎：Δ E is less than 1.5

○：Δ E be more than 1.5~be less than 2.0

△：Δ E be more than 2.0~be less than 2.5

×：Δ E is more than 2.5.

It should be noted that in actual use, if Δ E is less than 2.5, it may be said that ensuring to change colour (weatherability).

＜ mist degrees ＞

To each thermal isolation film, measure is made using haze meter (NDH2000 types, electricity Se Industrial Co., Ltd of Japan system) respectively heat-insulated The mist degree that film sample is 10, then calculates the average value of 10, thermal isolation film sample, the value is set into haze value.

Evaluation result by more than is shown in table 2.

[table 2]

Shown by the result of table 2：The thermal isolation film (embodiment 1~11) of an embodiment of the invention, hard conating it is close Conjunction property is good, suppresses the discoloration of hard conating.

In addition, the comparison by the thermal isolation film 4,7 and 10 of embodiment 4,7 and 10 confirms：By by (methyl) acrylic compounds The hydroxyl value of compound ((b) composition) is set to more than 40, and the discoloration inhibition of hard conating is further improved.Confirm in addition：By inciting somebody to action The hydroxyl value of (methyl) acrylic compounds ((b) composition) is set to more than 80, and the adaptation improvement of hard conating is further carried It is high.

Also, the comparison of the thermal isolation film 1~4 by embodiment 1~4 confirms：As metal salt, by using magnesium stearate (Mz), zinc acetate (Zn) and the carboxylate of double (2 ethyl hexanoic acid) zinc (Zn), can further suppress the discoloration of hard conating.Separately Outside, mist degree can further be reduced as the carboxylic acid for constituting metal salt by using 2 ethyl hexanoic acid.

In addition, the comparison by the thermal isolation film 5~9 of embodiment 5~9 confirms：By the way that the addition of metal salt is set into relative In hard removing coating coating fluid the composition gone out outside solvent gross mass be 0.01~5.0 mass %, the adaptation of hard conating And discoloration inhibition becomes good.Confirm in addition：It is hard to apply by the way that the addition of metal salt is set into 0.01~1.0 mass % The adaptation of layer is further improved, and can further realize low haze.And confirm：By the way that the addition of metal salt is set For 0.05~0.5 mass %, it can further suppress the discoloration of hard conating.

《The making and evaluation of insulator》

Insulator 1~11 is made using above-mentioned thermal isolation film sample 1~11.In thickness 5mm, 20cm × 20cm transparent propene Thermal isolation film sample 1~11 is bonded with acrylic adhesive on acid resin plate, insulator 1~11 is made respectively.

For the insulator 1~11 of above-mentioned making, the adaptation and discoloration that can confirm that hard conating suppress good.Separately Outside, although size is big, but can be easily with can confirm that excellent heat-proof quality.In addition, using with dielectric In the case of the thermal isolation film sample 11 of multilayer film, especially excellent heat-proof quality can confirm that.

The application is based on apllied Japanese patent application No. 2014-247437 on December 5th, 2014, the disclosure of which It is introduced into by referring to as overall.

Claims

1. a kind of thermal isolation film, it has base material and hard conating,

The hard conating is formed by hard conating with the solidfied material of coating fluid, and is configured at least one surface of the base material, The hard conating coating fluid contains following (a)~(c)：

(a) tungsten oxide,

(b) (methyl) acrylic ester compound of (methyl) acrylic ester compound with primary hydroxyl must be included,

(c) metal salt.

2. thermal isolation film as claimed in claim 1, wherein, (a) tungsten oxide is to be combined tungsten oxide containing caesium.

3. thermal isolation film as claimed in claim 1 or 2, wherein, (c) metal salt is carboxylate.

4. such as thermal isolation film according to any one of claims 1 to 3, wherein, (b) must include (the first with primary hydroxyl Base) acrylic ester compound (methyl) acrylic ester compound hydroxyl value be more than 10.

5. thermal isolation film as claimed in claim 4, wherein, (b) must include (methyl) acrylate with primary hydroxyl The hydroxyl value of (methyl) acrylic ester compound of class compound is more than 40.

6. such as thermal isolation film according to any one of claims 1 to 5, it includes high refractive index layer and low-index layer alternative stacked Dielectric multilayer film.

7. a kind of insulator, thermal isolation film according to any one of claims 1 to 6 is fitted in matrix and formed by it.

8. a kind of manufacture method of thermal isolation film, it includes：In at least one face side of base material, by hard conating coating solution In on base material, then, the process that irradiation ultraviolet radiation makes curing of coating, the hard conating coating fluid contains following (a)~(c)：

(a) tungsten oxide,

(b) (methyl) acrylic ester compound of (methyl) acrylic ester compound with primary hydroxyl must be contained,

(c) metal salt.