JP2010115874A - Window pane outer coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a window pane outer coating film maintaining colorless transparency over a long period. <P>SOLUTION: A weather-proof layer 3 and a photocatalyst layer 4 are laminated on one face of a base material film 2 of the window pane outer coating film 1. The weather-proof layer 3 is formed to have 7 μm or more of film thickness. The window pane outer coating film is formed to make a difference between a refractive index of the photocatalyst layer 4 and a refractive index of the base material film 2 satisfy a relational expression : 0.0≤(refractive index of the base material film 2)-(refractive index of the photocatalyst layer 4)<0.2. The window pane outer coating film contains an aluminum compound in a hydrolyzed condensate of a titanium alkoxide forming the photocatalyst layer 4, and is formed to make the Al atom in the aluminum compound and the Ti atom in the hydrolyzed condensate of the titanium alkoxide satisfy a relation : 15≤äthe Al atom in the aluminum compound/[(the Al atom in the aluminum compound)+(the Ti atom in the hydrolyzed condensate of the titanium alkoxide)]}×100≤35. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a glass window covering film.

  Transparent inorganic glass building materials represented by soda lime glass are more transparent, weatherproof, abrasion resistant, chemical resistant, flame retardant, and antifouling than organic transparent materials such as polycarbonate and acrylic Therefore, it plays an extremely important function as a building material (display window) for visually recognizing indoor displays from outside.

  However, the transparent inorganic glass building material may be broken by a strong impact or repeated impact (fatigue). For this reason, from the viewpoint of preventing the destruction of the transparent inorganic glass building material and preventing the scattering, a glass window outer film that externally attaches a window film to the transparent inorganic glass building material has attracted attention.

  By the way, transparent inorganic glass building materials are excellent in antifouling property, and can reduce the frequency of complicated cleaning operations. However, since the window film to be bonded to the transparent inorganic glass building material is easily soiled, if it is externally attached to the transparent inorganic glass building material, the frequency of the cleaning operation is increased. For this reason, various proposals have been made to add an antifouling function to the outermost surface of the window film. For example, Patent Document 1 proposes a coating composition for a film and a coating film which are excellent in antifouling property, durability and transparency and have a photocatalytic function.

JP 2000-65558 A

  However, the titanium oxide used for the photocatalyst of the film coating composition of Patent Document 1 is not easy to apply to plastic due to its strong photocatalytic activity. For this reason, such a coating film has, for example, a haze (Hz) after exposure (according to 10 years) in an accelerated weathering test for 3000 hours (SWM 3000 hours) with a carbon arc sunshine weather meter (SWM) S300 in the visible light region. ) Value of less than 1.5% and total light transmittance of greater than 85%, it does not reach the performance required for a glass window covering film, and the film is yellowed or clouded. There is a case.

  In addition, since the glass window outer film is processed through a wet process, an interference fringe may occur due to an optical change that an inorganic film having a high refractive index shrinks with time. . Thus, it is difficult to provide a glass window outer film that can maintain a high degree of colorless transparency over a long period of time.

  In addition to the transparency in the visible light region, the glass window covering film is also required to have a UV cut function and a crime prevention function for the purpose of preventing fading of indoor design objects. Furthermore, as the Japanese knowledge of interiors deepens, the design and design of the glass window covering film may be required.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a glass window outer film capable of maintaining colorless transparency over a long period of time.
Another object of the present invention is to provide a glass window covering film capable of maintaining colorless transparency over a long period of time and having both a UV cut function and a crime prevention function.

（式中Ｒ^１はメチル基またはエチル基である。）
で表される繰り返し単位、

（式中Ｒ^２は炭素数２〜５のアルキレン基である。式（Ａ−２）で表される繰り返し単位において少なくとも一部のＲ^ａは単結合であり、残りが水素原子である。Ｒ^ａが単結合の場合はウレタン結合を介して、他の式（Ａ−２）で表される繰り返し単位と結合している。）
で表される繰り返し単位、

（但し、式中Ｙは水素原子またはメチル基であり、Ｒ^３は水素原子、炭素数２〜５のアルキル基、紫外線吸収残基からなる群より選ばれる少なくとも一種の基である。但し、Ｙがメチル基であり、かつＲ^３がメチル基またはエチル基である場合を除く。）で表される繰り返し単位からなる。 In order to achieve the above object, the glass window covering film of the present invention comprises:
On one side of the base film, a weather resistance layer, a photocatalyst layer, a slight adhesion layer, and a protective film are laminated, and on the other side, an adhesion layer and a separate film are laminated,
The base film is made of any one of a polyester resin, an acrylic resin, a polycarbonate resin, a polyvinyl chloride resin, or a polyolefin resin, and has a tensile strength of 50 N / 25 mm or more and an elongation of 60. %, And the thickness is 20 μm to 400 μm,
The weather resistant layer comprises a crosslinked acrylic copolymer comprising repeating units represented by the following formula (A-1), the following formula (A-2) and the following formula (A-3), a biuret type polyisocyanate compound precursor, If necessary, an organic tin compound and / or a quaternary ammonium salt compound as a curing catalyst is formed from an acrylic resin that is thermoset to a film thickness of 7 μm or more.
The photocatalyst layer is hydrophilized by light irradiation, and the hydrophilization speed when irradiated with light having a half-value width of 15 nm or less after being kept in a dark place is 2 (1 / deg / min / min) in the region where the wavelength of the irradiated light is 370 nm or more. 10 ⁵ ), and in at least a part of the region where the wavelength of the irradiation light is 300 nm to 360 nm, the photocatalyst particles of 2 (1 / deg / min / 10 ⁵ ) or more and the average particle size of 150 nm or less The metal compound fine particles other than the photo-semiconductor particles are present in the hydrolysis condensate of titanium alkoxide, and the titanium alkoxide is hydrolyzed and condensed with the organic polymer compound, so that the content rate is in the depth direction from the surface. A continuously changing complex,
The fine adhesive layer is composed of an organic adhesive, and the adhesive force to the photocatalyst layer is 0.2 N / 25 mm or more, the wavelength of irradiation light is 300 nm, and the half width is 15 nm or less. Hydrophilicity R1 when the photocatalyst layer is irradiated with ultraviolet light immediately after the protective film is peeled off and hydrophilicity when the photocatalyst layer is irradiated with the same ultraviolet light after being sufficiently hydrophilic and kept in the dark again. The relationship with the conversion rate R2 is R2 <10 × R1 or more,
The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive having an adhesive force to construction glass of 2 N / 25 mm or more,
The difference between the refractive index of the photocatalyst layer and the refractive index of the base film to be coated is
0.0 ≦ (refractive index of base film) − (refractive index of photocatalyst layer) <0.2
Adjusted to satisfy the relationship
An aluminum compound is contained in the hydrolysis condensate of the titanium alkoxide, and an Al atom in the aluminum compound and a Ti atom in the hydrolysis condensate of the titanium alkoxide,
15 ≦ {Al atom in aluminum compound / [Al atom in aluminum compound + Ti atom in hydrolysis condensate of titanium alkoxide]} × 100 ≦ 35
Satisfy the relationship
At least one layer of the base film, the weather-resistant layer, and the adhesive layer contains an ultraviolet absorber, and the ultraviolet light blocking rate of 380 nm or less in the laminated structure from the photocatalyst layer to the adhesive layer is 99% or more. Yes, in any of the initial physical properties and after 3000 hours of the sunshine weather meter, the total light transmittance is 85% or more, the yellowness is 5 or less, the turbidity is 2% or less, and in the range of 400 nm to 800 nm. The difference between the maximum value and the minimum value of the average value of the surface reflection spectrum in an arbitrary 10 nm range is 3% or less,
It is characterized by that.

(In the formula, R ¹ is a methyl group or an ethyl group.)
A repeating unit represented by

(In the formula, R ² is an alkylene group having 2 to 5 carbon atoms. In the repeating unit represented by the formula (A-2), at least a part of ^Ra is a single bond, and the remainder is a hydrogen atom. ^{When a} is a single bond, it is bonded to a repeating unit represented by the other formula (A-2) via a urethane bond.)
A repeating unit represented by

(Wherein, Y is a hydrogen atom or a methyl group, and R ³ is at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 2 to 5 carbon atoms, and an ultraviolet absorbing residue. Is a methyl group, and R ³ is a methyl group or an ethyl group.).

For example, the photocatalyst particles are photo-semiconductor particles comprising crystalline titanium oxide having a crystal diameter in the range of 1 nm to 10 nm,
The content ratio of the optical semiconductor particles contained in the hydrolysis condensate of the titanium alkoxide is 3% or more.

  The refractive index of the photocatalyst layer is adjusted, for example, by adding silica-based fine particles. In this case, the silica-based fine particles include, for example, silica fine particles S1 having an average particle size of less than 40 nm and silica fine particles S2 having an average particle size of 40 nm or more and less than 80 nm, and the mixing ratio thereof is 80/20 ≦ S1 / S2 ≦ 50/50. It has been adjusted to be.

  The refractive index of the photocatalyst layer is adjusted, for example, by adding silica-based fine particles. In this case, the silica-based fine particles include, for example, silica fine particles S1 having an average particle size of less than 40 nm and silica fine particles S3 having an average particle size of 80 nm or more and less than 150 nm, and a mixing ratio of 95/5 ≦ S1 / S3 ≦ 65/35. It has been adjusted to be.

  At least a part of the base film on the pressure-sensitive adhesive layer side may be colored in advance with one or more colors by printing.

  According to the present invention, colorless transparency can be maintained over a long period of time.

  Hereinafter, the glass window covering film of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing an example of the configuration of the glass window covering film of the present invention.

  As shown in FIG. 1, the glass window covering film 1 is formed by laminating a weather resistant layer 3, a photocatalyst layer 4, a slightly adhesive layer 5, and a protective film 6 on one surface of a base film 2. An adhesive layer 7 and a separate film 8 are laminated on the other surface of 2.

  The base film 2 is formed of any one of a polyester resin, an acrylic resin, a polycarbonate resin, a polyvinyl chloride resin, or a polyolefin resin.

  Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polylactic acid, polycaprolactone, and the like. Among these, resistance to heat received during printing, mechanical strength, and direct bonding to a glass window are used. Therefore, it is most preferable to use polyethylene terephthalate in view of weather resistance prescription.

  Examples of the acrylic resin include a homopolymer of methyl methacrylate, and a copolymer obtained by copolymerizing other monomers having methyl methacrylate as a main component and other copolymerizability. Examples of other copolymerizable monomers include acrylic acid or a metal salt thereof; methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, acrylic acid 2 -Acrylic esters such as ethylhexyl; methacrylic acid or metal salts thereof; ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl; Vinyl acetate; Aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; Maleic anhydride; Maleimides such as N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide Compounds etc. It is below. When these are copolymerized with methyl methacrylate, one type may be used alone or two or more types may be used in combination.

  Examples of the polycarbonate-based resin include aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, and the like.

  Examples of the polyvinyl chloride resin include a homopolymer of vinyl chloride and a copolymer obtained by copolymerizing other monomers having vinyl chloride as a main component and other copolymerizability. Examples of other copolymerizable monomers include ethylene, propylene, vinyl acetate, vinyl bromide, vinylidene chloride, acrylonitrile, maleimide and the like.

  Examples of the polyolefin-based resin include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene obtained by homogenizing or copolymerizing ethylene, and polypropylene, polymethylpentene, and the like that are mono- or copolymerizing propylene.

  Moreover, the base film 2 is formed so that the thickness is 20 μm to 400 μm, the tensile strength is 50 N / 25 mm or more, and the elongation of the base film 2 is 60% or more. Here, when the tensile strength is 50 N / 25 mm or more and the elongation of the base film 2 is 60% or more, the tensile strength of the base film 2 is 50 N in the tensile strength and elongation test according to JIS A5759. / 25 mm or more and the elongation of the base film 2 is 60% or more. In general, glass is broken due to deformation of a sash generated during a disaster such as an earthquake or an impact caused by a human body collision, and the glass is scattered and dropped as a weapon. In order to prevent such scattering / dropping of glass, the adhesion of the glass scattering prevention film to the glass and the strength of the substrate are required. These strengths are the strength of the base material necessary to prevent the glass from scattering and falling, and the base film 2 satisfies these performances to satisfy the anti-scattering performance as a glass anti-scattering film. It becomes.

  The weather resistant layer 3 is formed from an acrylic resin. The acrylic resin comprises a crosslinked acrylic copolymer comprising repeating units represented by the following formula (A-1), the following formula (A-2) and the following formula (A-3), a biuret type polyisocyanate compound precursor, If necessary, it is formed by thermally curing a coating composition comprising a composition containing an organotin compound and / or a quaternary ammonium salt compound as a curing catalyst.

（式中Ｒ^１はメチル基またはエチル基である。）
で表される繰り返し単位、

(In the formula, R ¹ is a methyl group or an ethyl group.)
A repeating unit represented by

（式中Ｒ^２は炭素数２〜５のアルキレン基である。式（Ａ−２）で表される繰り返し単位において少なくとも一部のＲ^ａは単結合であり、残りが水素原子である。Ｒ^ａが単結合の場合はウレタン結合を介して、他の式（Ａ−２）で表される繰り返し単位と結合している。）
で表される繰り返し単位、

(In the formula, R ² is an alkylene group having 2 to 5 carbon atoms. In the repeating unit represented by the formula (A-2), at least a part of ^Ra is a single bond, and the remainder is a hydrogen atom. ^{When a} is a single bond, it is bonded to a repeating unit represented by the other formula (A-2) via a urethane bond.)
A repeating unit represented by

（但し、式中Ｙは水素原子またはメチル基であり、Ｒ^３は水素原子、炭素数２〜５のアルキル基、紫外線吸収残基からなる群より選ばれる少なくとも一種の基である。但し、Ｙがメチル基であり、かつＲ^３がメチル基またはエチル基である場合を除く。）で表される繰り返し単位からなる。

(Wherein, Y is a hydrogen atom or a methyl group, and R ³ is at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 2 to 5 carbon atoms, and an ultraviolet absorbing residue. Is a methyl group, and R ³ is a methyl group or an ethyl group.).

  The methacrylate monomer corresponding to the repeating unit represented by the above formula (A-1) is methyl methacrylate or ethyl methacrylate.

  Examples of the methacrylate monomer corresponding to the repeating unit represented by the formula (A-2) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. These can be used individually or in mixture of 2 or more types.

Specific examples of the alkyl group having 2 to 5 carbon atoms of R ^{3 in} the repeating unit represented by the formula (A-3) include, for example, an ethyl group, a propyl group, a butyl group, and a pentyl group.

Examples of the (meth) acrylate monomer in the case where R ³ in the repeating unit represented by the formula (A-3) is a C 2-5 alkyl group include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Examples include pentyl acrylate, propyl methacrylate, butyl methacrylate, and pentyl methacrylate, and these can be used alone or in admixture of two or more.

  A biuret type polyisocyanate compound precursor refers to a precursor of a biuret type polyisocyanate compound obtained by reacting various diisocyanate compounds with water. Examples of the diisocyanate compound include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, hexamer. Examples include methylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

  Examples of the organic tin compound include monobutyltin tris (2-ethylhexanoate), dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethylhydroxytin oleate, and dibutyltin bis (2-ethylhexanoate). Acid), bis (2-ethylhexanoate) tin, monobutyltin triacetate, dibutyltin diacetate, tributyltin monoacetate, dibutyltin methyl maleate, monobutyltin tri (methyl glycolate), monobutyltin tri (methyl) Propionate), monobutyltin trilaurate, dibutyltin dilaurate, tributyltin monolaurate, dibutyltin di (n-butyl maleate), monobutyltin tri (butyl glycolate), monobutyltin tri (butyl propiate) Nate), monohexyltin trioctate, dihexyltin dioctoate, trihexyltin monooctate, dihexyltin di (n-octylmalate), monohexyltintri (octylglycolate), monohexyltintri (methylmalate), Monooctyltin triacetate, dioctyltin diacetate, trioctyltin monoacetate, dioctyltin di (methyl malate), monooctyltin tri (methyl glycolate), monooctyltin tri (methylpropionate), monooctyltin tripropionate, dioctyl Tindipropionate, trioctyltin monopropionate, dioctyltindi (n-propylmalate), monooctyltintri (propylglycolate), monooctyltinto (Propyl propionate), monooctyltin trioctate, dioctyltin dioctoate, trioctyltin monooctate, dioctyltin di (n-octylmalate), monooctyltin tri (octylglycolate), monooctyltin tri (Octylpropionate) monooctyltin trilaurate, dioctyltin dilaurate, trioctyltin monolaurate, dioctyltin di (n-lauryl malate), monooctyltin tri (lauryl glycolate), monooctyltin tri (lauryl) Propionate), n-butyltin hydroxide and the like.

  Examples of the quaternary ammonium salt compound include 2-hydroxyethyl, tri-n-butylammonium, 2,2-dimethylpropionate, 2-hydroxyethyl, tri-n-butylammonium, 2,2-dimethylbutanoate, 2-hydroxypropyl tri-n-butylammonium 2,2-dimethylpropionate, 2-hydroxypropyl tri-n-butylammonium 2,2-dimethylbutanoate, 2-hydroxypropyl tri-n-butylammonium 2,2-dimethylpentanoate, 2-hydroxypropyl tri-n-butylammonium 2-ethyl-2-methylpropionate, 2-hydroxypropyl tri-n-butylammonium 2-ethyl-2-methylbutanoate 2-hydroxypropyl tri-n-butyl Ammonium 2-ethyl-2-methylpentanoate, 2-hydroxypropyl tri-n-octylammonium 2,2-dimethylpropionate, 2-hydroxypropyl tri-n-octylammonium 2,2-dimethylbuta Noate, 2-hydroxypropyl · triamylammonium · 2,2-dimethylbutanoate, 2-hydroxypropyl · triamylammonium · 2,2-dimethylpentanoate and the like. These may be used alone or in combination of two or more.

  As a method of forming the weather resistant layer 3, the acrylic copolymer, a biuret type polyisocyanate compound precursor as a crosslinking agent, and an organic tin compound and / or a quaternary ammonium salt compound as a curing catalyst, if necessary, etc. Is dissolved in a solvent, and this coating composition is applied to one surface of the substrate film 2, and then the solvent is removed by heating or the like, followed by further heating and thermosetting (crosslinking).

  Examples of solvents used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane, and esters such as ethyl acetate and ethoxyethyl acetate. Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-methoxy-2-propanol , Alcohols such as 2-butoxyethanol, hydrocarbons such as n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, light oil, kerosene, acetonitrile, nitromethane, water, etc. Even if used in It may be used as a mixture of two or more stone.

  As a method of applying to one surface of the base film 2, the shape of the base film 2 to be applied, such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, a roller coating method, etc. It can be appropriately selected depending on the case.

  The weather resistant layer 3 is formed so that its thickness is 7 μm or more. In order to use the glass window covering film 1 for windowing, the initial stage and after the accelerated weathering test 3000 hours (SWM 3000 hours) by the carbon arc type sunshine weather meter (SWM) S300 according to JIS K7350 (equivalent to 10 years) It is necessary that the yellowness (YI) is smaller than 5.

  FIG. 2 shows the relationship between the film thickness of the weathering layer 3 and the yellowness (YI). Since SWM3000 time corresponds to approximately 50 MWM cycles, the yellowness (YI) value after 70 cycles of MWM was evaluated in consideration of safety. As shown in FIG. 2, it is understood that the thickness of the weathering layer 3 should be 7.5 μm or more in order to make YI smaller than 5. However, in this test, in consideration of safety, the value of YI after 70 cycles of MWM is evaluated, so in practice, if the thickness of the weathering layer 3 is 7 μm or more, the YI after exposure for 3000 hours of SWM is used. It can be smaller than 5. Therefore, the thickness of the weathering layer 3 should just be formed so that it may become 7 micrometers or more.

  In addition, when the base film 2 to be used is formed from a polyvinyl chloride resin, a polyolefin resin, or the like, the additive contained in the resin rarely bleeds out to the surface over time and contaminates the photocatalyst surface. In addition, the desired antifouling property may be impaired. However, if the thickness of the weather resistant layer 3 is 2 μm or more, it is possible to suppress bleeding out of the surface of these additives to the surface, which is preferable.

  Moreover, in order to further improve the adhesiveness between these coating films and the substrate film 2, a surface treatment can be performed by an oxidation method, an unevenness method, or the like, if desired. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet process), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, etc., and examples of the unevenness method include a sand blast method and a solvent treatment. Law. These surface treatment methods are appropriately selected according to the type of the substrate, provided that the transparency is not impaired.

  The photocatalyst layer 4 is a layer that becomes hydrophilic by light irradiation. The photocatalyst layer 4 constitutes a composite having a component gradient structure in which the hydrolysis condensate of titanium alkoxide undergoes hydrolytic condensation with an organic polymer compound, and the content thereof continuously changes from the surface toward the depth direction. ing.

  The hydrolyzed condensate of titanium alkoxide is obtained by hydrolytic condensation of titanium alkoxides hydrolyzed by adding an aqueous solution containing an acid catalyst such as nitric acid to titanium alkoxide.

  Among such titanium alkoxides, titanium tetraalkoxide is preferable. Examples of the titanium tetraalkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetraalkoxide. Preferred examples include -n-butoxide, titanium tetraisobutoxide, titanium tetra-sec-butoxide, and titanium tetra-tert-butoxide. These may be used individually by 1 type and may be used in combination of 2 or more type.

  As the solvent used for the hydrolysis condensation, alcohols are preferable, and alcohols having an etheric oxygen having 3 or more carbon atoms are more preferable from the viewpoint of controlling the hydrolysis-condensation reaction and stabilizing the condensate. Examples of alcohols having ether oxygen having 3 or more carbon atoms include solvents having an interaction with titanium alkoxide, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like. And cellosolve solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. . Among these, cellosolve solvents are particularly preferable. These solvents may be used singly or in combination of two or more.

In the hydrolyzed condensate of titanium alkoxide, the hydrophilization rate when irradiated with light having a half-value width of 15 nm or less after maintaining in a dark place is 2 (1 / deg / min / min) in the region where the wavelength of irradiated light is 370 nm or more. 10 ⁵ ), and in at least a part of the region where the wavelength of the irradiation light is 300 nm to 360 nm, the photocatalyst particles of 2 (1 / deg / min / 10 ⁵ ) or more and the average particle size of 150 nm or less There are metal compound-based fine particles other than the optical semiconductor particles.

As the photocatalyst particles, titanium oxide particles mainly composed of anatase type crystals can be used.
Titanium oxide fine particles (anatase crystal titanium oxide particles) mainly composed of the anatase type crystal are photocatalyst particles, and a small amount of rutile type crystal may be mixed. Visible light-responsive photocatalyst particles that are partially contained can also be used. The average particle diameter of the anatase crystalline titanium oxide particles is preferably in the range of 1 nm to 500 nm, more preferably in the range of 1 nm to 100 nm, and most preferably in the range of 1 nm to 50 nm because of having an excellent photocatalytic function. This average particle diameter can be measured by a scattering method using laser light.

  Further, inside and / or on the surface of the titanium oxide particles, as metal compound-based fine particles other than optical semiconductor particles, V, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Pt and Au At least one metal and / or metal compound selected from the group consisting of: By containing these, since it has a still higher photocatalytic function, it is preferable. Examples of the metal compound include metal oxides, hydroxides, oxyhydroxides, sulfates, halides, nitrates, and metal ions. The content of the metal compound-based fine particles is appropriately selected according to the type of the substance, but the content ratio of the optical semiconductor particles contained in the hydrolysis condensate of titanium alkoxide is preferably 3% or more.

  This anatase crystalline titanium oxide particle can be produced by a known method, but it is advantageous to use it in the form of a titanium oxide sol in order to disperse it uniformly in the coating solution. In order to produce the titanium oxide sol, for example, powdered anatase crystalline titanium oxide may be dissolved in the presence of acid or alkali, or the particle diameter may be controlled by pulverization. In addition, the hydrous or neutralized decomposition of titanium sulfate or titanium chloride may be used to control the crystallite size and particle size by physical and chemical methods. Furthermore, a dispersion stabilizer can be used to impart dispersion stability in the sol solution.

The hydrolysis condensate of titanium alkoxide contains an aluminum compound, for example, aluminum nitrate. The amount of aluminum compound (aluminum nitrate) added is such that Al atoms in the aluminum compound and Ti atoms in the hydrolysis condensate of titanium alkoxide are:
15 ≦ {Al atom in aluminum compound / [Al atom in aluminum compound + Ti atom in hydrolysis condensate of titanium alkoxide]} × 100 ≦ 35
Included to satisfy the relationship. If the addition amount of aluminum nitrate is less than 15 (%), there is a possibility that a sufficient anti-shrinkage effect may not be obtained. On the other hand, if the addition amount of aluminum nitrate is more than 35 (%), it is difficult to obtain a uniform thin film. Moreover, it is because it is difficult to crystallize. By making it within such a range, clouding can be prevented.

  Examples of the organic polymer compound include an organic polymer obtained by copolymerizing an ethylenically unsaturated monomer containing no metal and an ethylenically unsaturated monomer having a coupling silicon-containing group. Preferred examples include compounds.

  Examples of the ethylenically unsaturated monomer containing no metal include, for example, an ethylenically unsaturated monomer represented by the general formula (III),

（式中、Ｒ^４は水素原子又はメチル基、Ｘは一価の有機基である。）
好ましくは一般式（III−ａ）

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and X is a monovalent organic group.)
Preferably general formula (III-a)

（式中、Ｒ^４は水素原子又はメチル基、Ｒ^５は一価の炭化水素基又はエポキシ基、ハロゲン原子若しくはエーテル結合を有する炭化水素基を示す。）
で表されるエチレン性不飽和単量体を一種又は二種以上混合して使用してもよい。

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a monovalent hydrocarbon group, an epoxy group, a halogen atom or a hydrocarbon group having an ether bond.)
One or a mixture of two or more ethylenically unsaturated monomers represented by

In the ethylenically unsaturated monomer represented by the general formula (III-a), as the hydrocarbon group represented by R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms, carbon number Preferable examples include 3 to 10 cycloalkyl groups, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups, pentyl groups, hexyl groups, octyl groups, and decyl groups. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclooctyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group having 7 to 10 carbon atoms such as a group, a naphthyl group, and a methylnaphthyl group include a benzyl group, a methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

  Examples of the hydrocarbon group having an epoxy group, a halogen atom or an ether bond include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms having an atom or a bond. Preferred examples include an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms. A chlorine atom etc. are mentioned as a halogen atom of the said substituent.

  Examples of the ethylenically unsaturated monomer represented by the general formula (III-a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, 2- ( 3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  In addition to these, the ethylenically unsaturated monomer represented by the general formula (III) includes styrene, α-methylstyrene, α-acetoxystyrene, m-, o- or p-bromostyrene, m -, O- or p-chlorostyrene, m-, o- or p-vinylphenol, 1- or 2-vinylnaphthalene and the like, and further stabilizers for polymerizable polymers having an ethylenically unsaturated group, for example, ethylenic An antioxidant, an ultraviolet absorber, a light stabilizer and the like having an unsaturated group can also be used. These may be used alone or in combination of two or more.

  On the other hand, as the ethylenically unsaturated monomer having a coupling silicon-containing group, for example, the general formula (IV)

（式中、Ｒ^６は水素原子又はメチル基、Ａは炭素数１〜４のアルキレン基、Ｒ^７はメチル基又はエチル基を示す。）
で表される化合物を好ましく挙げることができる。一般式（IV）において、３つのＲ^７は互いに同一でも異なっていてもよい。

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, A represents an alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a methyl group or an ethyl group.)
Preferred examples include compounds represented by: In the general formula (IV), three R ⁷ may be the same or different from each other.

Examples of the ethylenically unsaturated monomer represented by the general formula (IV) include 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, γ- (meta ) Acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and the like.
These ethylenically unsaturated monomers having a coupling silicon-containing group may be used alone or in combination of two or more.

  Coupling silicon is obtained by radical polymerization of this metal-free ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a coupling silicon-containing group in the presence of a radical polymerization initiator. A compound having a self-gradient composed of an organic polymer compound having a containing group is obtained.

  A solution obtained by dissolving the organic polymer compound having a coupling silicon-containing group thus obtained in an appropriate solvent such as alcohol, ketone, ether, a hydrolyzed / condensed product of titanium alkoxide, and other than titanium By mixing a metal compound alone and / or a solution containing a reaction liquid containing the metal compound diluted as necessary, the coupling silicon-containing group in the organic polymer compound is hydrolyzed, and the hydrolysis condensate of titanium alkoxide and It reacts selectively and the coating composition for the photocatalyst layer 4 which has a component inclination structure is obtained.

The photocatalyst layer 4 has a difference between the refractive index and the refractive index of the base film 2 to be coated.
0.0 ≦ (refractive index of base film 2) − (refractive index of photocatalyst layer 4) <0.2
It is adjusted to satisfy the relational expression of The refractive index of the photocatalyst layer 4 is adjusted, for example, by adding silica-based fine particles to the photocatalyst layer 4.

  As the silica-based fine particles, for example, colloidal silica in which silica fine particles are colloidally dispersed in water or an organic solvent is used. Colloidal silica can be used in either a water-dispersed type or an organic solvent-dispersed type, but in order to increase the hydrophilicity of the surface, it is preferable to use a water-dispersed type in which a large number of hydroxyl groups are present on the surface of silica fine particles. Moreover, in order to lengthen the pot life of a coating composition, since many hydroxyl groups may cause aggregation, it is preferable to use an organic solvent dispersion type.

  The water-dispersed colloidal silica is further divided into an acidic aqueous dispersion type and a basic aqueous dispersion type. The water-dispersed colloidal silica can be used in either an acidic aqueous dispersion type or a basic aqueous dispersion type. However, from the viewpoint of diversity of curing catalyst selection, appropriate hydrolysis of titanium alkoxide, and realization of a condensed state, an aqueous acidic dispersion type colloidal silica. Silica is preferably used.

  As such colloidal silica, specifically, as a product dispersed in an acidic aqueous solution, as a product dispersed in a basic aqueous solution, Snowtex O of Nissan Chemical Industry Co., Ltd., Cataloid SN of Catalytic Chemical Industry Co., Ltd. Nissan Chemical Industries, Ltd. Snowtex 30, Snowtex 40, Catalytic Chemical Industry Co., Ltd. Cataloid S30, Cataloid S40, Nissan Chemical Industries, Ltd. MA-ST, IPA-ST , IPA-ST-L, IPA-ST-ZL, NBA-ST, IBA-ST, EG-ST, XBA-ST, NPC-ST, DMAC-ST, Catalytic Chemical Industries, Ltd. OSCAL1132, OSCAL1232, OSCAL1332, OSCAL1432, OSCAL1532, OSCAL1632, OSCAL1732, etc. It is.

  For example, by adjusting the silica fine particles S1 having an average particle size of less than 40 nm and the silica fine particles S2 having an average particle size of 40 nm or more and less than 80 nm so that the mixing ratio is 80/20 ≦ S1 / S2 ≦ 50/50. The difference between the refractive index of the photocatalyst layer 4 and the refractive index of the base film 2 is made less than 0.2.

  For example, the silica fine particles S1 having an average particle size of less than 40 nm and the silica fine particles S3 having an average particle size of 80 nm or more and less than 150 nm are adjusted so that the mixing ratio is 95/5 ≦ S1 / S3 ≦ 65/35. Accordingly, the difference between the refractive index of the photocatalyst layer 4 and the refractive index of the base film 2 may be less than 0.2.

  The slightly adhesive layer 5 is formed of an adhesive made of an organic adhesive that can have an adhesive strength to the photocatalyst layer 4 of 0.2 N / 25 mm or more in an adhesive strength test according to JIS A5759.

Further, the slightly adhesive layer 5 was sufficiently hydrophilized with the hydrophilization rate R1 when the photocatalyst layer 4 was irradiated with ultraviolet light having a wavelength of irradiation light of 300 nm and a half width of 15 nm or less immediately after the protective film 6 was peeled off. The relationship with the hydrophilization speed R2 when the photocatalyst layer 4 is irradiated with the same ultraviolet light after being kept in the dark again later is
R2 <10 × R1
It is formed from such an adhesive. As such an adhesive, for example, an acrylic, urethane, silicone rubber, or rubber adhesive that is generally used conventionally can be appropriately used.

  The protective film 6 may be any film that can protect the photocatalyst layer 4, and various films can be used. The reason why the protective film 6 is provided is to protect the photocatalyst layer 4 that is weak against abrasion and abrasion until the photocatalytic activity is exhibited and the use is started. In addition, in the printing process, the printing film can be conveyed by a single sheet without causing an overlap feeding phenomenon in which a plurality of sheets are conveyed in a printing machine. For this reason, the sheet surface of the protective film 6 may be subjected to an uneven treatment or various treatments.

  The pressure-sensitive adhesive layer 7 is formed of a pressure-sensitive adhesive whose adhesive force to construction glass can be 2 N / 25 mm or more in a pressure-sensitive adhesive test according to JIS A5759. By forming from an adhesive that can have such an adhesive force, it is possible to exhibit glass scattering prevention and penetration prevention functions.

  The separate film 8 may be any film as long as it protects the adhesive layer 7 and the base film 2 and has peelability from the adhesive layer 7, and uses various films according to the type of adhesive of the adhesive layer 7. Can do.

  Moreover, the ultraviolet absorber is contained in at least 1 layer of the base film 2, the weather-resistant layer 3, and the adhesion layer 7. FIG. The ultraviolet absorber is not particularly limited as long as it is a substance that absorbs ultraviolet light of 380 nm or less, but the following compounds are preferably exemplified.

  As an example of the ultraviolet absorber, specifically, 2 (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzo Triazole, 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2 (2′-hydroxy-3′-tert-butyl-5′-methylphenyl)- 5-chlorobenzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2 (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2 (2 Benzotriazoles such as' -hydroxy-5'-t-octylphenyl) benzotriazole; 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate Cyanoacrylates such as benzoates and ethyl-2-cyano-3,5-diphenylacrylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 '-Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-o-octoxybenzophenone, 2-hydroxy-4-i-octoxybenzophenone, 2- Hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-disulfobenzophenone-di-sodium salt, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2, -Hydroxy Benzophenones such as -4-octadecyloxybenzophenone; salicylic acid esters such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, 2-cyano-3,3-diphenylacrylic acid Examples thereof include substituted acrylonitriles such as ethyl and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. These ultraviolet absorbers may be used alone or in combination of two or more.

  Furthermore, you may contain 1 type of ultraviolet scattering agents, a hindered amine light stabilizer (HALS), an excitation energy absorber, a radical scavenger, etc., or these in combination as appropriate.

  Examples of light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6, succinate. 6-tetramethylpiperidine polycondensate, poly [6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6 6-tetra-methyl-4-piperidyl) imino] hexamethylene [2,2,6,6-tetramethyl-4-piperidylimide], tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, N, N '-Bis (3-amino (Lopyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6, -tetramethyl-4-piperidyl) imino] propionamide, TINUVIN 770, 123, 144, 622 (above, Ciba Geigy), SANOL LS-770, 765, 292, 2626 (above, product name of Sankyo Co., Ltd.), ADK STAB LA-52, 57, 62 (above, Asahi Denka Co., Ltd.), etc. Hindered amines can be used. These light stabilizers may be used alone, in combination of two or more kinds, and may be used in combination with an ultraviolet absorber.

  Examples of UV scattering agents include inorganic materials such as metal oxide powders. Powders made from fine particles of titanium dioxide, zinc oxide, cerium oxide, etc., or titanium dioxide fine particles are compounded with iron oxide. Examples thereof include a hybrid inorganic powder obtained by treatment, and a hybrid inorganic powder obtained by coating the surface of cerium oxide fine particles with amorphous silica. An ultraviolet scattering agent is a material that provides an ultraviolet shielding effect by scattering ultraviolet rays. However, since the ultraviolet scattering effect is greatly influenced by the particle size, the average particle size is preferably 5 μm or less, particularly in the range of 10 nm to 2 μm. Is preferred. In the case where the ultraviolet scattering agent has photocatalytic activity, it is preferable to use a material in which the surface of the particles is thinly coated with water glass or the like to eliminate photocatalytic activity.

  The blocking rate of 380 nm or less of ultraviolet light in the laminated structure (photocatalyst layer 4, weather resistant layer 3, substrate film 2, and adhesive layer 7) from the photocatalyst layer 4 to the adhesive layer 7 is 99% or more. This is to prevent the dye from being decomposed and faded by ultraviolet rays of 380 nm or less as much as possible. The ultraviolet blocking rate can be easily measured from the UV-Viss spectrum.

  In addition, in the initial stage in the laminated structure from the photocatalyst layer 4 to the adhesive layer 7 and in any state after 3000 hours of accelerated weathering test using a sunshine weather meter, the total light transmittance is from the viewpoint of weather resistance and discoloration resistance. It is set to be 85% or more, yellowness is 5 or less, and turbidity is 2% or less.

  Furthermore, in the laminated structure from the photocatalyst layer 4 to the adhesive layer 7, the difference between the maximum value and the minimum value of the average value of the surface reflection spectrum in an arbitrary 10 nm range in the range of 400 nm to 800 nm is 3% or less.

  In addition, this invention is not restricted to said embodiment, A various deformation | transformation and application are possible. For example, before forming the adhesive layer 7 on the base film 2, a film in which the ground surface side of the base film 2 is colored in advance by printing and then the adhesive layer 7 is laminated on the colored side, At least a part of these may be colored with one or more colors.

  Next, an Example and a comparative example are given and this invention is demonstrated in more detail. The following examples show suitable examples of the present invention, and the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of Titanium Alkoxide Hydrolysis Condensate To 149 g of ethyl cellosolve, 76 g of titanium tetraisopropoxide (“trade name: A-1” manufactured by Nippon Soda Co., Ltd.) was added dropwise with stirring to obtain a solution (A ) To this solution (A), a mixed solution of 58 g of ethyl cellosolve, 4.6 g of distilled water and 13 g of 60 wt% concentrated nitric acid was added dropwise with stirring to obtain a solution (B). Thereafter, the solution (B) was stirred at 30 ° C. for 4 hours to obtain a hydrolytic condensation liquid (C) of titanium alkoxide.

Synthesis Example 2 Synthesis of Organic Component Solution Under a nitrogen atmosphere, 700 g of methyl isobutyl ketone, 337 g of methyl methacrylate, and 43 g of methacryloxypropyltrimethoxysilane were added to a 2 L separable flask, and the temperature was raised to 60 ° C. To this mixed solution, 117 g of methyl isobutyl ketone in which 3.3 g of azobisisobutyronitrile was dissolved was dropped to start the polymerization reaction, and stirred for 30 hours to obtain an organic component solution (D).

Example 1
(1) Preparation of a weather resistant primer-added PET film A hindered amine light stabilizer (HALS) on one side of a polyethylene terephthalate (PET) film ("HB3" manufactured by Teijin DuPont Films Ltd., thickness 50 μm) kneaded with an ultraviolet absorber UV-absorbing coating agent (Nippon Shokubai Co., Ltd. “UV-G301”) and isocyanate curing agent (Sumitomo Bayer Urethane Co., Ltd. “Desmodur N3200”) mixed at a ratio of 12 parts by mass. The obtained ethyl acetate solution was applied with a Mayer bar so that the dry film had a thickness of 9 μm, and then thermally crosslinked to prepare a PET film (E) with a weather resistant primer.

(2) Coating film of titanium alkoxide hydrolyzate mixed with colloidal silica and aluminum nitrate and organic component 29 g of ethyl cellosolve and aluminum nitrate nonahydrate (purity 99%, manufactured by Wako Pure Chemical Industries, Ltd.) 2 g was dissolved, and then 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2, 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the solution (G), and colloidal silica (product name: Snowtex manufactured by Nissan Chemical Industries, Ltd.) IPA-ST "(average particle size 20 nm)) 13.9 g in this order, and then stirred for 24 hours in a 32 ° C. warm bath and mixed with colloidal silica and aluminum nitrate mixed titanium alkoxide hydrolyzate and organic components A coating liquid (H) was prepared. The amount of aluminum nitrate added is 15%.

  The coating liquid (H) was applied on a PET film (E) with a weathering primer with a wet thickness of about 10 μm, and was applied using a Mayer bar so that the dry thickness was 100 nm.

  Table 1 shows the characteristics of the sample. Table 1 shows initial transparency and weather resistance after exposure to an accelerated weathering test 3000 hours (SWM 3000 hours) using a carbon arc type sunshine weather meter (SWM) (S300, manufactured by Suga Test Instruments Co.) according to JIS K7350. In addition, about the following Examples 2-9 and Comparative Examples 1-7, the characteristic of a sample, initial transparency, and the weather resistance after exposure to SWM3000 hours are shown in Table 1 similarly.

  As shown in Table 1, the value of haze (Hz) after exposure for 3000 hours at SWM is 1.3% and the value of yellowness (YI) is 3.5, which is highly transparent regardless of long-term exposure. Indicated. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, no occurrence of interference fringes with coloring over time was observed.

  Moreover, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited-field diffraction image, it was confirmed that the crystal diameter of the crystalline titanium oxide present in the film did not exceed 10 nm. Further, it was confirmed that crystalline titanium oxide was dispersed in amorphous titanium oxide.

(Example 2)
When creating a PET film with a weather-resistant primer, a hindered amine light stabilizer (HALS) is hybridized on one side of a polyethylene terephthalate (PET) film kneaded with an ultraviolet absorber (“HB3” manufactured by Teijin DuPont Films Ltd., thickness 50 μm). Acetic acid prepared by mixing 100 parts by mass of the UV-absorbing coating agent (“UV-G301” manufactured by Nippon Shokubai Co., Ltd.) and 12 parts by mass of an isocyanate curing agent (“Desmodur N3200” manufactured by Sumitomo Bayer Urethane Co., Ltd.) A sample was prepared in the same manner as in Example 1 except that the ethyl solution was applied with a Meyer bar so that the dry film thickness was 14 μm and then thermally crosslinked to prepare a weather resistant primer-attached PET film (E). .

  As shown in Table 1, the sample showed a high transparency of 1.4% and YI of 3.3 after SWM 3000 hours exposure, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, no occurrence of interference fringes with coloring over time was observed.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is non- It was confirmed that it was dispersed in the crystalline titanium oxide.

  Further, in the production of a PET film with a weathering primer, the same method as in Example 1 was used, except that a PET film (E) with a weathering primer was prepared so that the dry film had a thickness of 7 μm using the same solution. When the same measurement was performed on the prepared sample, it was confirmed that the results were almost the same as those of Examples 1 and 2.

(Example 3)
In preparation of titanium alkoxide hydrolyzate mixed with colloidal silica and aluminum nitrate, 7.7 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 54 g of ethyl cellosolve, followed by In the same manner as in Example 1 except that 43 g of the titanium alkoxide hydrolysis-condensation liquid (C) prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G) (amount of added aluminum nitrate 35%). A sample was created.

  As shown in Table 1, the sample showed high transparency regardless of long-term exposure, with the value of Hz after SWM 3000 hours exposure being 1.2% and the value of YI being 3.5. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, no occurrence of interference fringes with coloring over time was observed.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

Example 4
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the solution (G), and 11.1 g of colloidal silica a (Nissan Chemical Industries “trade name: Snowtex IPA-ST (average particle size 20 nm)”), colloidal silica b (“trade name: Snowtex IPA-ST-L (average particle size 50 nm)” manufactured by Nissan Chemical Industries, Ltd.) except that the coating liquid (H) of the hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate and the organic component was prepared by mixing in the order of g and then stirring in a warm bath at 32 ° C. for 24 hours. Samples were prepared in the same manner as in Example 1. Colloidal silica b / colloidal silica a in the coating liquid (H) = 20/80 wt%.

  As shown in Table 1, the sample showed a high transparency of 1.5% after exposure to SWM for 3000 hours and a YI value of 3.5, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, generation of interference fringes with time was not observed with coloring. Further, the hydrophilization speed was improved 2.1 times compared with Example 1.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Example 5)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the above-described solution (G), and colloidal silica a (“trade name: Snowtex IPA-ST (average particle size 20 nm)” manufactured by Nissan Chemical Industries, Ltd.) 7.0 g, Colloidal silica b (product name: Snowtex IPA-ST-L (average particle size 50 nm) manufactured by Nissan Chemical Industries, Ltd.) 7.0 g in this order, and then stirred for 24 hours in a 32 ° C. warm bath to produce a coating liquid (H) of a titanium alkoxide hydrolyzate mixed with colloidal silica and aluminum nitrate and an organic component Prepared a sample in the same manner as in Example 1. Colloidal silica b / colloidal silica a in the coating liquid (H) was 50/50 wt%.

  As shown in Table 1, the sample showed a high transparency of 1.5% after exposure to SWM for 3000 hours and a YI value of 3.5, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, generation of interference fringes with time was not observed with coloring. Further, the hydrophilization rate was improved by 2.0 times compared with Example 1.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Example 6)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the solution (G) described above, and colloidal silica a (manufactured by Nissan Chemical Industries, Ltd., “trade name: Snowtex IPA-ST (average particle size 20 nm)”) 3.5 g, Colloidal silica b (product name: Snowtex IPA-ST-L (average particle size 50 nm) manufactured by Nissan Chemical Industries, Ltd.) 10.4 g of the mixture was mixed in the order, and then stirred for 24 hours in a 32 ° C. warm bath to prepare a coating liquid (H) of a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate and an organic component. Prepared a sample in the same manner as in Example 1. Colloidal silica b / colloidal silica a in the coating liquid (H) was 75/25 wt%.

  As shown in Table 1, the sample showed a high transparency of 1.4% and YI of 3.5 after SWM 3000 hours exposure, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, generation of interference fringes with time was not observed with coloring. Further, the hydrophilization rate was not much different from Example 1.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Example 7)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the above solution (G), and colloidal silica a (“trade name: Snowtex IPA-ST (average particle size 20 nm)” manufactured by Nissan Chemical Industries, Ltd.) 13.2 g, Colloidal silica c (manufactured by Nissan Chemical Industries, Ltd., “trade name: Snowtex IPA-ST-ZL (average particle size 100 n ) ") Mix in order of 0.7 g, and then stir in a warm bath at 32 ° C. for 24 hours to prepare a coating liquid (H) of a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate and an organic component. A sample was prepared in the same manner as in Example 1 except that the sample was prepared. Colloidal silica c / colloidal silica a in the coating liquid (H) was 5/95 wt%.

  As shown in Table 1, the sample showed a high transparency of 1.4% and YI of 3.5 after SWM 3000 hours exposure, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, generation of interference fringes with time was not observed with coloring. Further, the hydrophilization rate was improved by 2.5 times compared with Example 1.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Example 8)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the solution (G) described above, and colloidal silica a (“trade name: Snowtex IPA-ST (average particle size 20 nm)” manufactured by Nissan Chemical Industries, Ltd.) 9.0 g, Colloidal silica c (manufactured by Nissan Chemical Industries, Ltd. “trade name: Snowtex IPA-ST-ZL (average particle size 100 nm )) 4.9 g in order, then stirred in a warm bath at 32 ° C. for 24 hours to prepare a coating liquid (H) of a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate and an organic component. A sample was prepared in the same manner as in Example 1 except that. Colloidal silica c / colloidal silica a in the coating liquid (H) was 35/65 wt%.

  As shown in Table 1, the sample showed a high transparency of 1.5% after exposure to SWM for 3000 hours and a YI value of 3.5, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 4,000 nm to 900 nm, generation of interference fringes with time was not observed with coloring. Further, the hydrophilization speed was improved 2.1 times compared with Example 1.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

Example 9
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the solution (G) described above, and colloidal silica a (“Nissan Chemical Industries, Ltd.“ trade name: Snowtex IPA-ST (average particle size 20 nm) ”) 7.6 g, Colloidal silica c (manufactured by Nissan Chemical Industries, Ltd. “trade name: Snowtex IPA-ST-ZL (average particle size 100 nm ) Mixing in the order of 6.3 g, and then stirring in a warm bath at 32 ° C. for 24 hours to prepare a coating liquid (H) of a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate and an organic component. A sample was prepared in the same manner as in Example 1 except that. Colloidal silica c / colloidal silica a in the coating liquid (H) was 45/55 wt%.

  As shown in Table 1, the sample showed a high transparency of 1.5% after exposure to SWM for 3000 hours and a YI value of 3.5, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, generation of interference fringes with time was not observed with coloring.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Comparative Example 1)
When creating a PET film with a weather-resistant primer, a hindered amine light stabilizer (HALS) is hybridized on one side of a polyethylene terephthalate (PET) film kneaded with an ultraviolet absorber (“HB3” manufactured by Teijin DuPont Films Ltd., thickness 50 μm). Acetic acid prepared by mixing 100 parts by mass of the UV-absorbing coating agent (“UV-G301” manufactured by Nippon Shokubai Co., Ltd.) and 12 parts by mass of an isocyanate curing agent (“Desmodur N3200” manufactured by Sumitomo Bayer Urethane Co., Ltd.) A sample was prepared in the same manner as in Example 1 except that an ethyl solution was applied with a Meyer bar so that the dry film thickness was 6 μm, and then thermally crosslinked to prepare a PET film (E) with a weather resistant primer. .

  As shown in Table 1, although the Hz value after SWM 3000 hours exposure of the sample was 1.2%, the YI value was 6.5, and high transparency could not be maintained by long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, no occurrence of interference fringes with coloring over time was observed.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited-field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Comparative Example 2)
While mixing and stirring 35 g of ethyl cellosolve and 51 g of 1-propanol, 4.2 g of the hydrolysis condensation liquid (C) of titanium alkoxide described above was added. Next, a solution obtained by mixing 0.35 g of nitric acid and 6.7 g of water was slowly added to this solution. Subsequently, 0.48 g of titanium oxide slurry (“PC201” manufactured by Sumitomo Chemical Co., Ltd.) was slowly added dropwise while stirring this solution. Then, colloidal silica a (“trade name: IPA-ST” manufactured by Nissan Chemical Industries, Ltd., average particle size 20 nm) (2.2 g) was added dropwise with stirring, and the mixture was stirred in a warm bath at about 30 ° C. for 4 hours. A coating liquid (I) was prepared.

  Next, the photocatalyst topcoat solution (I) was applied on the coating film of the coating solution of the titanium alkoxide hydrolyzate obtained by mixing colloidal silica and aluminum nitrate and the organic component, which was prepared by the same method as in Example 1. It apply | coated with the wet thickness of 10 micrometers, and it apply | coated using the Mayer bar so that dry thickness might be set to 50 nm.

  As shown in Table 1, the transparency of the sample after SWM 3000 hours exposure was 2.1% and the YI value was 3.5, and high transparency could not be maintained slightly due to long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, generation of interference fringes with coloring over time was recognized.

(Comparative Example 3)
In the preparation of a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 3.0 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 21 g of ethyl cellosolve. A sample was prepared in the same manner as in Example 1 except that 80 g of the titanium alkoxide hydrolysis-condensation liquid (C) prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G).

  As shown in Table 1, although the value of the initial Hz of the sample was 0.4%, the value of Hz after SWM 3000 hours exposure was 2.8%, the value of YI was 3.5, and long-term exposure. Therefore, high transparency could not be maintained. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, no occurrence of interference fringes with coloring over time was observed.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Comparative Example 4)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 8.3 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 58 g of ethyl cellosolve, followed by The same method as in Example 1 except that 38 g of the titanium alkoxide hydrolysis-condensation liquid (C) prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G) (amount of aluminum nitrate added 40%). A sample was created.

  As shown in Table 1, the initial Hz value of the sample was 2.7%, and high transparency could not be ensured immediately after coating.

(Comparative Example 5)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by Then, 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. Instead of 229 g of methyl isobutyl ketone, 132 g of ethyl cellosolve, 104 g of the solution (G) described above, and colloidal silica a (“trade name: Snowtex IPA-ST” manufactured by Nissan Chemical Industries, Ltd., average particle size 20 nm) Titanium oxide (product name: RTIPA-15wt% -G2 manufactured by CI Kasei Co., Ltd.), rugby ball shape: long (Average 80 nm / minor axis average 30 nm) In the order of 27.8 g, the mixture was stirred in a warm bath at 32 ° C. for 24 hours, and the hydrolyzate of titanium alkoxide mixed with rutile titanium oxide and aluminum nitrate and the organic component A sample was prepared in the same manner as in Example 1 except that the coating liquid (H) was prepared.

  As shown in Table 1, the initial Hz value of the sample was 0.5%, but because the refractive index difference with the weather resistant primer was 0.3, an interference fringe occurred immediately after coating, Transparency could not be secured.

(Comparative Example 6)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by Then, 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the solution (G) described above, and colloidal silica a (“trade name: Snowtex IPA-ST” manufactured by Nissan Chemical Industries, Ltd., average particle size 20 nm) 2.4 g, Colloidal silica b (manufactured by Nissan Chemical Industries, Ltd., “trade name: Snowtex IPA-ST-L” average particle size 50 nm) 1 The mixture was mixed in the order of 0.5 g and then stirred in a warm bath at 32 ° C. for 24 hours to prepare a coating liquid (H) of a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate and an organic component. A sample was prepared in the same manner as in Example 1. Colloidal silica b / colloidal silica a in the coating liquid (H) was 17/83 wt%.

  As shown in Table 1, the sample showed a high transparency of 1.5% after exposure to SWM for 3000 hours and a YI value of 3.5, regardless of long-term exposure. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, no occurrence of interference fringes with coloring over time was observed. However, the hydrophilization rate was reduced by 0.7 times compared to Example 1.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited-field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

(Comparative Example 7)
In preparing a hydrolyzate of titanium alkoxide mixed with colloidal silica and aluminum nitrate, 4.2 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was dissolved in 29 g of ethyl cellosolve, followed by Then, 71 g of the hydrolytic condensate (C) of titanium alkoxide prepared in Synthesis Example 1 was added and stirred well to obtain a solution (G). Subsequently, 7.3 g of the organic component solution (D) prepared in Synthesis Example 2 was obtained. 236 g of methyl isobutyl ketone, 139 g of ethyl cellosolve, 104 g of the solution (G) described above, and colloidal silica a (“trade name: Snowtex IPA-ST” manufactured by Nissan Chemical Industries, Ltd., average particle size 20 nm) 7.0 g, Colloidal silica c (trade name: Snowtex IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd.) average particle diameter 100 nm 7.0 g in this order, and then stirred for 24 hours in a 32 ° C. warm bath to produce a coating liquid (H) of a titanium alkoxide hydrolyzate mixed with colloidal silica and aluminum nitrate and an organic component Prepared a sample in the same manner as in Example 1. Colloidal silica c / colloidal silica a in the coating liquid (H) was 50/50 wt%.

  As shown in Table 1, the sample exhibited a high transparency regardless of long-term exposure, with the value of Hz after SWM 3000 hours exposure being 1.6% and the value of YI being 3.5. Further, as a result of measuring the reflectance in the range of 400 nm to 900 nm, no occurrence of interference fringes with coloring over time was observed. However, the hydrophilization rate was reduced by 0.7 times compared to Example 1.

  Further, from the transmission electron micrograph after exposure for SWM 3000 hours and the results of the limited-field diffraction image, the crystal diameter of the crystalline titanium oxide present in the film does not exceed 10 nm, and the crystalline titanium oxide is amorphous. It was confirmed that it was dispersed in the quality titanium oxide.

It is a figure which shows the structure of the glass window covering film of this invention. It is a figure which shows the relationship between the film thickness of a weather resistant layer, and yellowness (YI).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass window covering film 2 Base film 3 Weatherproof layer 4 Photocatalyst layer 5 Slight adhesion layer 6 Protective film 7 Adhesion layer 8 Separate film

Claims (5)

On one side of the base film, a weather resistance layer, a photocatalyst layer, a slight adhesion layer, and a protective film are laminated, and on the other side, an adhesion layer and a separate film are laminated,
The base film is made of any one of a polyester resin, an acrylic resin, a polycarbonate resin, a polyvinyl chloride resin, or a polyolefin resin, and has a tensile strength of 50 N / 25 mm or more and an elongation of 60. %, And the thickness is 20 μm to 400 μm,
The weather resistant layer comprises a crosslinked acrylic copolymer comprising repeating units represented by the following formula (A-1), the following formula (A-2) and the following formula (A-3), a biuret type polyisocyanate compound precursor, If necessary, an organic tin compound and / or a quaternary ammonium salt compound as a curing catalyst is formed from an acrylic resin that is thermoset to a film thickness of 7 μm or more.
The photocatalyst layer is hydrophilized by light irradiation, and the hydrophilization rate when irradiated with light having a half-value width of 15 nm or less after holding in a dark place is 2 (1 / deg / min / 10 ⁵ ), and in at least a part of the region where the wavelength of the irradiation light is 300 nm to 360 nm, the photocatalyst particles of 2 (1 / deg / min / 10 ⁵ ) or more and the average particle size of 150 nm or less The metal compound fine particles other than the photo-semiconductor particles are present in the hydrolysis condensate of titanium alkoxide, and the titanium alkoxide is hydrolyzed and condensed with the organic polymer compound, so that the content rate is in the depth direction from the surface. A continuously changing complex,
The fine adhesive layer is composed of an organic adhesive, and the adhesive force to the photocatalyst layer is 0.2 N / 25 mm or more, the wavelength of irradiation light is 300 nm, and the half width is 15 nm or less. Hydrophilicity R1 when the photocatalyst layer is irradiated with ultraviolet light immediately after the protective film is peeled off and hydrophilicity when the photocatalyst layer is irradiated with the same ultraviolet light after being sufficiently hydrophilic and kept in the dark again. The relationship with the conversion rate R2 is R2 <10 × R1 or more,
The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive having an adhesive force to construction glass of 2 N / 25 mm or more,
The difference between the refractive index of the photocatalyst layer and the refractive index of the base film to be coated is
0.0 ≦ (refractive index of base film) − (refractive index of photocatalyst layer) <0.2
Adjusted to satisfy the relationship
An aluminum compound is contained in the hydrolysis condensate of the titanium alkoxide, and an Al atom in the aluminum compound and a Ti atom in the hydrolysis condensate of the titanium alkoxide,
15 ≦ {Al atom in aluminum compound / [Al atom in aluminum compound + Ti atom in hydrolysis condensate of titanium alkoxide]} × 100 ≦ 35
Satisfy the relationship
At least one layer of the base film, the weather-resistant layer, and the adhesive layer contains an ultraviolet absorber, and the ultraviolet light blocking rate of 380 nm or less in the laminated structure from the photocatalyst layer to the adhesive layer is 99% or more. Yes, in any of the initial physical properties and after 3000 hours of the sunshine weather meter, the total light transmittance is 85% or more, the yellowness is 5 or less, the turbidity is 2% or less, and in the range of 400 nm to 800 nm. The difference between the maximum value and the minimum value of the average value of the surface reflection spectrum in an arbitrary 10 nm range is 3% or less,
A glass window covering film characterized by that.

(In the formula, R ¹ is a methyl group or an ethyl group.)
A repeating unit represented by

(In the formula, R ² is an alkylene group having 2 to 5 carbon atoms. In the repeating unit represented by the formula (A-2), at least a part of ^Ra is a single bond, and the remainder is a hydrogen atom. ^{When a} is a single bond, it is bonded to a repeating unit represented by the other formula (A-2) via a urethane bond.)
A repeating unit represented by

(Wherein, Y is a hydrogen atom or a methyl group, and R ³ is at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 2 to 5 carbon atoms, and an ultraviolet absorbing residue. Is a methyl group, and R ³ is a methyl group or an ethyl group.). The photocatalyst particles are photo-semiconductor particles comprising crystalline titanium oxide having a crystal diameter in the range of 1 nm to 10 nm,
The glass window covering film according to claim 1, wherein the content ratio of the optical semiconductor particles contained in the hydrolysis condensate of the titanium alkoxide is 3% or more. The refractive index of the photocatalyst layer is adjusted by adding silica-based fine particles,
The silica-based fine particles are adjusted such that the mixing ratio of silica fine particles S1 having an average particle size of less than 40 nm and silica fine particles S2 having an average particle size of 40 nm or more and less than 80 nm is 80/20 ≦ S1 / S2 ≦ 50/50. The glass window covering film according to claim 1 or 2, wherein The refractive index of the photocatalyst layer is adjusted by adding silica-based fine particles,
The silica-based fine particles are adjusted so that the mixing ratio of silica fine particles S1 having an average particle size of less than 40 nm and silica fine particles S3 having an average particle size of 80 nm or more and less than 150 nm is 95/5 ≦ S1 / S3 ≦ 65/35. The glass window covering film according to claim 1 or 2, wherein   The glass window covering according to any one of claims 1 to 4, wherein at least a part of the base film on the adhesive layer side is colored in advance by one or more colors by printing. the film.

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