JP2015125168A - Dielectric multilayer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric multilayer film which is highly durable and can maintain good flexibility and adhesion.SOLUTION: A dielectric multilayer film of the present invention has dielectric multiple layers comprising at least one each of a low refractive index layer and high refractive index layer laminated together and an adhesive layer, where at least one of the high refractive index layer and low refractive index layer contains a water-soluble polymer and a photocatalytic compound. The adhesion layer has an initial light transmittance Tof 30% or less at a wavelength of 280-410 nm, and a rate of change from the initial light transmittance Tto a light transmittance Tat the wavelength of 280-410 nm, measured after being continuously irradiated for 2000 hours from the adhesive layer side with light from a carbon-arc lamp set at an irradiance of 255 W/min an environment with a temperature of 40°C and humidity of 50%RH, is no more than 5%.

Description

  The present invention relates to a dielectric multilayer film.

  It is theoretically supported that a laminated film in which a high refractive index layer and a low refractive index layer are alternately laminated by adjusting the respective optical film thicknesses selectively reflects light of a specific wavelength. Such a laminated film transmits visible light and can selectively reflect near infrared rays. Therefore, such a laminated film is used as a heat-ray shielding reflective film (heat-ray reflective film) used for building windows, vehicle members, and the like.

  An infrared (heat ray) shielding film in which a heat ray reflective film is formed on a film is used by being attached to a building window or a vehicle member. Such a dielectric multilayer film transmits visible light and selectively blocks near-infrared rays, but the reflection wavelength can be controlled only by adjusting the film thickness and refractive index of each layer. It is possible to reflect visible light.

  As a method for forming the heat ray reflective film, there is generally a method of laminating by a dry film forming method, but formation of a heat ray reflective film by a dry film forming method is not practical because it requires a lot of manufacturing costs. . As a practical method, a coating solution containing a mixture of a water-soluble resin and inorganic fine particles is applied by a wet coating method and laminated (for example, see Patent Document 1), or a method of laminating a resin film (for example, Patent Document 2).

International Publication No. 2012/014607 Special table 2008-528313

  According to the technique disclosed in Patent Document 1, a dielectric multilayer film having high heat shielding properties can be obtained. Such a dielectric multilayer film is a highly durable dielectric multilayer film that can maintain good flexibility and adhesion because it is used by being attached to a window or a vehicle member of a building. There is a need to be.

  However, the present inventors have found that the above-mentioned characteristics may not be sufficient depending on the configuration of the film disclosed in Patent Document 1.

  Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to provide a highly durable dielectric multilayer film that can maintain good flexibility and adhesion.

  In view of the above problems, the present inventors have intensively studied. As a result, it was found that the durability of the dielectric multilayer film may not be good particularly when the dielectric multilayer film contains titanium oxide as a refractive index adjusting agent.

  Therefore, the present inventors have further studied, and in the process, attempted to add an ultraviolet absorber to the adhesive layer. However, the film having such a structure has good flexibility and adhesion immediately after production, but when exposed to sunlight for a long time, the flexibility and adhesion deteriorate with time. Sometimes.

  As a result of further studies on the above problems, surprisingly, by combining a dielectric multilayer film containing titanium oxide or the like with an adhesive layer having specific light transmittance characteristics described in detail below, It has been found that a dielectric multilayer film having excellent durability and durability can be obtained even when exposed to a long period of time.

  About the above, the present inventors considered as follows.

  The dielectric multilayer film contains a resin in addition to titanium oxide, but when the resin (particularly water-soluble polymer) does not contain an ultraviolet absorber in the adhesive layer, sunlight (particularly ultraviolet light) irradiates titanium oxide. As a result, the dielectric multilayer film becomes brittle because it is degraded by the photocatalytic action of titanium oxide. As a result, it is considered that the dielectric multilayer film and further other layers constituting the film are peeled off, and the flexibility and adhesion are lowered.

  On the other hand, an adhesive layer having a transmittance at a specific wavelength equal to or lower than a specific value is provided, and a wavelength (280 to 410 nm) that promotes photocatalysis is absorbed in the adhesive layer, thereby being included in the dielectric multilayer film. The photocatalytic action of titanium oxide is suppressed.

Furthermore, the light transmittance after elapse of a predetermined time under a predetermined condition with respect to the initial light transmittance T _{1 (UV) at} a wavelength (280 to 410 nm, particularly 390 nm) that promotes the photocatalytic action of the compound contained in the dielectric multilayer film By setting the rate of change of T _{2 (UV)} within a specific range, it is presumed that a temporal decrease in the effect of suppressing the photocatalytic action can also be suppressed. As a result, a dielectric multilayer film having excellent flexibility and adhesion and excellent durability can be obtained. The present invention is not limited to the above mechanism.

  From the above mechanism, the present inventors have not only the case where the dielectric multilayer film contains titanium oxide but also the case where the dielectric multilayer film contains a compound exhibiting other photocatalytic action, the specific light transmittance and light transmittance. It is considered that a dielectric multilayer film having excellent durability can be obtained by providing an adhesive layer having a change rate, and the present invention has been completed.

  That is, the above object of the present invention is achieved by the following configuration.

1. A dielectric multilayer film in which at least one low refractive index layer and high refractive index layer are laminated;
A dielectric multilayer film having an adhesive layer,
At least one of the high refractive index layer and the low refractive index layer contains a water-soluble polymer and a compound having a photocatalytic action,
The adhesive layer is the initial light transmittance _{T 1 (UV)} is 30% or less at a wavelength 280～410Nm, the relative initial light transmittance _{T 1 (UV),} temperature 40 ° C., under an environment of a humidity of 50% RH The rate of change of the light transmittance T _{2 (UV)} at a wavelength of 280 to 410 nm after irradiating light from the adhesive layer side for 2000 hours continuously with a carbon arc lamp having an irradiance of 255 W / m ² is 5% or less. A dielectric multilayer film;
2. The adhesive layer is continuous for 2000 hours with a carbon arc lamp having an irradiance of 255 W / m ^{2 in} an environment of a temperature of 40 ° C. and a humidity of 50% RH with respect to an initial light transmittance T _{1 (390) at} a wavelength of 390 nm. 1. The change rate of the light transmittance T _{2 (390)} at a wavelength of 390 nm after light irradiation from the adhesive layer side is 5% or less. A dielectric multilayer film according to claim 1;
3. The pressure-sensitive adhesive layer has a thickness of 3 to 30 μm. Or 2. A dielectric multilayer film according to claim 1;
4). The adhesive layer is a group consisting of 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof. Including at least one compound selected from 1 above. ~ 3. The dielectric multilayer film according to any one of
5. The compound having a photocatalytic action includes titanium oxide as described above. ~ 4. The dielectric multilayer film according to any one of
6). The adhesive layer further has an outermost layer disposed on the opposite side through the dielectric multilayer film,
The outermost layer is composed of 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof. Including at least one compound selected from 1 above. ~ 5. The dielectric multilayer film according to any one of
7). 5. The outermost layer contains an ultraviolet curable urethane acrylate resin. A dielectric multilayer film according to claim 1;
8). 5. The outermost layer includes an infrared absorber. Or 7. The dielectric multilayer film described in 1.

  According to the present invention, it is possible to provide a highly durable dielectric multilayer film that can maintain good flexibility and adhesion.

One embodiment of the present invention includes a dielectric multilayer film in which at least one low refractive index layer and high refractive index layer are laminated, and
A dielectric multilayer film having an adhesive layer,
At least one of the high refractive index layer and the low refractive index layer contains a water-soluble polymer and a compound having a photocatalytic action,
The adhesive layer is the initial light transmittance _{T 1 (UV)} is 30% or less at a wavelength 280～410Nm, the relative initial light transmittance _{T 1 (UV),} temperature 40 ° C., under an environment of a humidity of 50% RH The rate of change of the light transmittance T _{2 (UV)} at a wavelength of 280 to 410 nm after irradiating light from the adhesive layer side for 2000 hours continuously with a carbon arc lamp having an irradiance of 255 W / m ² is 5% or less. It is a dielectric multilayer film.

  Hereinafter, embodiments according to the dielectric multilayer film of the present invention will be described.

  In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “weight%”, “mass%”, and “part by mass”. And “parts by mass” are treated as synonyms.

≪Dielectric multilayer film≫
The dielectric multilayer film of the present invention essentially has a dielectric multilayer film in which at least one low refractive index layer and high refractive index layer are laminated and an adhesive layer. Here, at least one of the high refractive index layer and the low refractive index layer contains a water-soluble polymer and a compound having a photocatalytic action. Moreover, you may have the outermost layer (hard-coat layer) arrange | positioned on the opposite side via a dielectric multilayer film with respect to the adhesion layer. That is, the dielectric multilayer film of the present invention may have a configuration in which the layers are formed in the order of the adhesive layer, the dielectric multilayer film, and the outermost layer. Furthermore, as long as the effects of the present invention are not impaired, other functional layers and base materials may be provided between the above layers.

  Hereinafter, each component of the dielectric multilayer film of the present invention will be described in detail.

[Adhesive layer]
First, the adhesive layer which is a characteristic element in the dielectric multilayer film of the present invention will be described.

The pressure-sensitive adhesive layer of the present invention contains a pressure-sensitive adhesive, and as described above, the initial light transmittance T _{1 (UV) at} a wavelength of 280 to 410 nm is 30% or less, and the initial light transmittance T _{1 (UV)} Change rate of light transmittance T _{2 (UV)} after continuous irradiation with a carbon arc lamp having an irradiance of 255 W / m ² under an environment of a temperature of 40 ° C. and a humidity of 50% RH for 2000 hours (this specification) In this document, it is a layer having a 5% or less (also referred to as “change rate of UV transmittance”). In the present specification, the rate of change of the UV transmittance is a value calculated by the following mathematical formula (1).

In addition, in the said Numerical formula (1), light transmittance T1 _(UV) and T2 _(UV) shall point out the value measured by the method as described in an Example.

  By making the rate of change of the UV transmittance at a specific wavelength in the adhesive layer within the above range, the photocatalytic action of the compound contained in the dielectric multilayer film described later can be effectively suppressed over a long period of time, and the dielectric multilayer Deterioration of each layer included in the membrane film can be suppressed. As a result, a dielectric multilayer film having excellent durability can be obtained. In the present invention, the transmittance change rate in the pressure-sensitive adhesive layer is preferably 3% or less, more preferably 1% or less, from the viewpoint of improving durability. On the other hand, the lower limit of the transmittance change rate is preferably as low as possible, and is not particularly limited. Therefore, the lower limit of the change rate of the transmittance is 0% (that is, no change).

At this time, the initial light transmittance T _{1 (UV) at} a wavelength of 280 to 410 nm in the adhesive layer is 30% or less. If the initial light transmittance T1 _(UV) is more than 30%, the adhesive layer cannot effectively absorb ultraviolet rays (particularly, a wavelength that promotes photocatalytic action), and the compound contained in the dielectric multilayer film Shows a photocatalytic action, and the resin constituting the dielectric multilayer film deteriorates. On the other hand, by setting the initial light transmittance T _{1 (UV)} to 30% or less, the photocatalytic action of the compound in the dielectric multilayer film can be effectively suppressed. Body multilayer film can be obtained. Furthermore, the initial light transmittance T _{1 (UV)} is more preferably 15% or less, even more preferably 5% or less, and particularly preferably 1% or less.

Furthermore, specifically, the light transmittance T _{2 (UV)} after the elapse of a predetermined time under the above-mentioned predetermined conditions is preferably 35% or less, more preferably 25% or less, and more preferably 10% or less. Even more preferably, it is particularly preferably 5% or less, and most preferably 2% or less. When the light transmittance T _{2 (UV)} is 35% or less, the effect of effectively suppressing the catalytic action of the compound contained in the dielectric multilayer film is sustained even when exposed to sunlight for a long time. A dielectric multilayer film having good durability can be obtained.

The light transmittances T _{1 (UV)} and T _{2 (UV)} are both preferably as small as possible, but the substantial lower limit is 0.00001%.

Therefore, from the above, the adhesive layer has a UV transmittance change rate of 5% or less, an initial light transmittance T1 _(UV) of 30% or less, and a light transmittance T2 _{( UV)} is preferably 35% or less.

Furthermore, the adhesive layer was continuously used for 2000 hours with a carbon arc lamp having an irradiance of 255 W / m ^{2 in} an environment of a temperature of 40 ° C. and a humidity of 50% RH with respect to the initial light transmittance T _{1 (390) at} a wavelength of 390 nm. It is preferable that the change rate of the light transmittance T _{2 (390)} after light irradiation (also simply referred to as “change rate of transmittance at 390 nm” in this specification) is 5% or less. In the present specification, the rate of change in transmittance at 390 nm is a value calculated by the following mathematical formula (2).

In addition, in the said Numerical formula (2), light transmittance T1 ₍₃₉₀₎ and T2 ₍₃₉₀₎ shall point out the value measured by the method as described in an Example.

  A compound having a photocatalytic action, such as titanium oxide or zirconium oxide, contained in the dielectric multilayer film absorbs ultraviolet light particularly around 390 nm and exhibits a catalytic action. Therefore, in particular, by setting the rate of change in transmittance at 390 nm within the above range, the adhesive layer absorbs light having a wavelength that promotes photocatalysis over a long period of time, so that the photocatalytic action can be suppressed for a longer period. As a result, the effect of suppressing deterioration of each layer included in the dielectric multilayer film is further improved.

  In the present invention, the transmittance change rate in the pressure-sensitive adhesive layer is preferably 3% or less, more preferably 1% or less, from the viewpoint of improving durability. On the other hand, the lower limit of the transmittance change rate is preferably as low as possible, and is not particularly limited, but is substantially 0.001%.

At this time, the initial light transmittance T _{1 (390) at} a wavelength of 280 to 410 nm is specifically preferably 30% or less, more preferably 15% or less, and more preferably 5% or less. Even more preferred is 1% or less. When the initial light transmittance T _{1 (390)} is 30% or less, the adhesive layer can effectively absorb ultraviolet rays (particularly, a wavelength that promotes photocatalytic action), and the compound contained in the dielectric multilayer film The photocatalytic action can be effectively suppressed. As a result, a dielectric multilayer film having excellent durability can be obtained.

Furthermore, the light transmittance T _{2 (390)} after the elapse of a predetermined time under a predetermined condition is specifically preferably 35% or less, more preferably 25% or less, and 10% or less. Even more preferred is 2% or less. When the light transmittance T _{2 (390)} is 35% or less, the effect of effectively suppressing the catalytic action of the compound contained in the dielectric multilayer film is sustained even when exposed to sunlight for a long time. A dielectric multilayer film having good durability can be obtained.

The light transmittances T _{1 (390)} and T _{2 (390)} are both preferably as small as possible, but the substantial lower limit is 0.00001%.

Therefore the above, the adhesive layer, the rate of change of transmittance in its 390nm is not more than 5%, the initial light transmittance _{T 1 (390)} is 30% transmittance of light after a predetermined time _{T 2 (390)} is preferably 35% or less.

  In order to more effectively exhibit the above-described effect of suppressing photocatalysis, when the dielectric multilayer film of the present invention is installed on a window glass or the like, the adhesive layer is on the light (sunlight) incident side. Preferably provided. In other words, it is preferable that the adhesive layer and the dielectric multilayer film are disposed in this order from the light incident side in an in-applied configuration. The internal pasting configuration is a configuration in which a dielectric multilayer film is pasted indoors, for example, on a window glass or the like. With such a configuration, the absorption of ultraviolet rays by the adhesive layer can be increased, and the amount of ultraviolet rays incident on the dielectric multilayer film can be extremely reduced.

  The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive layer can satisfy the above characteristics. For example, acrylic pressure-sensitive adhesive, silicon-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, polyvinyl acetal-based pressure-sensitive adhesive Examples thereof include an ethylene-vinyl acetate pressure-sensitive adhesive.

  When the dielectric multilayer film of the present invention is bonded to a window glass, water is sprayed on the window, and the adhesive layer of the dielectric multilayer film is bonded to the wet glass surface, a so-called water bonding method is applied. It is preferably used from the viewpoints of correction and position correction. For this reason, an acrylic pressure-sensitive adhesive that has a weak adhesive force in the presence of water is preferably used.

  The acrylic pressure-sensitive adhesive used may be either solvent-based or emulsion-based, but is preferably a solvent-based pressure-sensitive adhesive because it is easy to increase the adhesive strength and the like, and among them, those obtained by solution polymerization are preferable. As a raw material when producing such a solvent-based acrylic pressure-sensitive adhesive by solution polymerization, for example, as a main monomer serving as a skeleton, an acrylic ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acryl acrylate, As a comonomer to improve cohesive strength, vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc., to further promote crosslinking, to give stable adhesive strength, and to maintain a certain level of adhesive strength even in the presence of water Examples of the functional group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, and glycidyl methacrylate. Since the adhesive layer of the laminated film requires a particularly high tack as the main polymer, those having a low glass transition temperature (Tg) such as butyl acrylate are particularly useful.

  As a commercial item of the said acrylic adhesive, Coponyl series (made by Nippon Synthetic Chemical Co., Ltd.) etc. are mentioned, for example.

  The pressure-sensitive adhesive layer preferably contains an ultraviolet absorber so that the change rate of the transmittance is 5% or less. The ultraviolet absorber used at this time is not limited as long as the change rate of the transmittance can be specified, and may be either inorganic or organic, but does not exhibit a photocatalytic action. Is preferable.

  Examples of the inorganic ultraviolet absorber include titanium oxide, zinc oxide, cerium oxide, iron oxide and the like. However, among these inorganic ultraviolet absorbers, when using those exhibiting a photocatalytic action, as the resin constituting the adhesive layer, a resin that is not affected by the photocatalytic action of the inorganic ultraviolet absorbent (for example, polysiloxane) Resin).

  Any compound can be used as the ultraviolet absorber contained in the adhesive layer as long as it has the above absorption characteristics. Among them, benzophenone, phenyl salicylate, triazine, hindered amine, benzoate and the like can be mentioned. Of these, triazines are preferred.

  Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazi 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine, [2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol] (Tinuvin 1577FF, trade name, Ciba Specialty Chemicals) Manufactured), [2- [4,6-bis (2,4dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol], 2,4,6-tris ( Biphenylyl) -1,3,5-triazine and the like. Commercially available products include “LA-46” manufactured by Adeka Corporation, “Tinubin 1577ED”, “Tinuvin 400”, “Tinubin 405”, “Tinubin 460”, “Tinubin 477”, “Tinubin 479”, “Tinubin 1159” manufactured by BASF Corporation. Or the like. The said ultraviolet absorber may be used individually by 1 type, and may be used together 2 or more types.

  Among the above triazine-based ultraviolet absorbers, 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and these It is preferable that it is at least one selected from the group consisting of derivatives.

  Hereinafter, “2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof” will be specifically described below. Explained.

  First, “2,4,6-tris (hydroxyphenyl) -1,3,5-triazine and a derivative thereof” is specifically a compound represented by the following general formula (1). In the present specification, these compounds are also simply referred to as “hydroxyphenyltriazine compounds”.

In the general formula _{(1), R 1, R} 3, R 5 are each independently a hydroxy group or a carbon atom number of 1 to 20 alkoxy _{groups, R 2, R 4, R} 6 are each Independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms Represents an alkynyl group, an amino group, a cyano group or a nitro group, k, m, and p are integers of 1 to 5, l, n, and q are integers of 0 to 5, and k + l = m + n = p + q = 5.

The alkoxy group having 1 to 20 carbon atoms of R ₁ , R ₃ , and R ₅ may be linear, branched, or cyclic. Examples of the alkoxy group of R _{1 to} R ₃ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, and a 2-ethylhexyloxy group. Among these, in order to improve solubility in a solvent, an alkoxy group having 1 to 8 carbon atoms is preferable, an alkoxy group having 1 to 5 carbon atoms is more preferable, and in particular, an n-propoxy group, an isopropoxy group, n -A butoxy group is preferred.

The halogen atoms of R ₂ , R ₄ , and R ₆ are not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be selected. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a fluorine atom.

The alkyl group having 1 to 20 carbon atoms of R ₂ , R ₄ and R ₆ may be linear or branched. Examples of the alkyl group represented by R _{1 to} R ₆ include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-octyl group, and a 2-ethylhexyl group. Groups. Among these, from a viewpoint of improving the solubility with respect to the solvent at the time of forming the adhesion layer by coating (coating method), an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, n- A propyl group and an isopropyl group are more preferable, and a methyl group and an ethyl group are more preferable.

Examples of the cycloalkyl group having 3 to 20 carbon atoms of R ₂ , R ₄ , and R ₆ include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among these, a cycloalkyl group having 4 to 8 carbon atoms is preferable from the viewpoint of improving the solubility in a solvent when the adhesive layer is formed by coating (coating method), and a cyclobutyl group, a cyclopentyl group, a cyclo A hexyl group and a cycloheptyl group are more preferable, and a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group are more preferable.

The alkenyl group having 2 to 20 carbon atoms of R ₂ , R ₄ and R ₆ may be linear, branched or cyclic as long as it has one or more double bonds. . For example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group and the like can be mentioned. Among these, in order to improve solubility in a solvent, an alkenyl group having 2 to 8 carbon atoms is preferable, an alkenyl group having 2 to 5 carbon atoms is more preferable, and a vinyl group and an allyl group are particularly preferable.

The alkynyl group having 2 to 20 carbon atoms of R ₂ , R ₄ and R ₆ may be linear, branched or cyclic as long as it has one or more triple bonds. For example, an ethynyl group, a propargyl group, etc. are mentioned. Among these, in order to improve the solubility in a solvent, an alkynyl group having 2 to 8 carbon atoms is preferable, an alkynyl group having 2 to 5 carbon atoms is more preferable, and an ethynyl group is particularly preferable.

R _{2, R} 4, an amino group of _{R 6 is} a group represented by -NH 2, -NHR 'or -NR' _2. R ′ may be different from each other, and each R ′ is selected from an alkyl group having 1 to 20 carbon atoms. R ′ is the same as the description of the alkyl group of R ₂ , R ₄ , and R ₆ above, and thus the description thereof is omitted. However, in order to improve solubility in a solvent, R ′ has 1 to 8 carbon atoms. Alkyl groups are preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are particularly preferable.

k, l, and m represent the numbers of R _{1 to} R ₃ groups bonded to the phenyl group, respectively, k, m, and p are integers of 1 to 5, and l, n, and q are 0 to 5 K + l = m + n = p + q = 5. In order to improve the solubility in a solvent, k, m, and p are preferably integers of 1 to 3, and more preferably 1 or 2. In particular, when k, m, and p are 2, it is preferable that the hydroxy group or alkoxy group of R ₁ , R ₃ , and R ₅ is substituted at the 2,4 position with respect to triazine.

  As a commercial item of the hydroxyphenyl triazine type compound represented by the general formula (1), for example, “Tinuvine 477” can be cited.

  Next, “2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof” will be specifically described below. In the present specification, the above compound is also simply referred to as “biphenylyltriazine compound”.

In the biphenylyl triazine-based compound, in the general formula (1), R ₁ , R ₃ , and R ₅ are each independently an aryl group having 6 to 30 carbon atoms, and R ₂ , R ₄ , R 5 ₆ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a carbon atom. Represents an alkynyl group having a number of 2 to 20, an amino group, a cyano group, or a nitro group, k, m, and p are integers of 1 to 5, l, n, and q are integers of 0 to 5, k + l = m + n = p + q = 5.

The aryl group having 6 to 30 carbon atoms of R ₁ , R ₃ , and R ₅ is not particularly limited, and examples thereof include non-condensed hydrocarbon groups such as a phenyl group and a biphenyl group; a pentarenyl group, an indenyl group, and a naphthyl group. A condensed polycyclic hydrocarbon group such as Can be mentioned. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable in consideration of the existence and durability of the maximum absorption wavelength in a specific wavelength region.

Further, R ₂ , R ₄ , R ₆ and k, m, p and l, n, q are the same as described above, and thus detailed description thereof is omitted, but k, m, p are 1 to 3 Is preferably an integer of 1, and more preferably 1 or 2. In particular, when k, m, and p are 1, the aryl group of R ₁ , R ₃ , and R ₅ is preferably substituted at the 4-position (p-position) with respect to triazine. Moreover, it is preferable that at least one of R ₂ , R ₄ , and R ₆ is a hydrogen atom.

  The compound represented by the general formula (1) may be used alone or in combination of two or more.

  The thickness of the adhesive layer is not particularly limited, but is preferably 3 μm to 30 μm, more preferably 5 to 25 μm, and particularly preferably 5 to 15 μm. If it is 3 micrometers or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is obtained. In addition, if the adhesive layer is too thin, the amount of the ultraviolet absorber contained will be small, and it will be difficult to obtain the above-mentioned predetermined ultraviolet absorption characteristics, but a sufficient amount of the ultraviolet absorber is set to 3 μm or more. Is contained in the pressure-sensitive adhesive layer, and the above-mentioned predetermined ultraviolet absorption characteristics can be sufficiently obtained. On the contrary, if the thickness is 30 μm or less, not only the transparency of the dielectric multilayer film is improved, but also when the dielectric multilayer film is pasted on the window glass and then peeled off, no cohesive failure occurs between the adhesive layers. There is a tendency for the adhesive residue on the surface to disappear. Furthermore, if the pressure-sensitive adhesive layer becomes too thick, the amount of the pressure-sensitive adhesive itself increases with respect to a certain amount of the UV absorber, and the pressure-sensitive adhesive itself is deteriorated by ultraviolet rays. There may not be. Therefore, the thickness of the adhesive layer is preferably 30 μm or less. In addition, in this specification, the value measured by observing a cross section with a scanning electron microscope (SEM) shall be employ | adopted for the thickness of each layer.

In this embodiment, the amount of the ultraviolet absorber contained in the adhesive layer is not particularly limited as long as the change rate of the transmittance can be within a specific range, and the extinction coefficient at 280 to 410 nm of the ultraviolet absorber. As a guide, the amount of the adhesive layer per unit area (1 m ² ) is preferably 155 mg / m ² or more, more preferably 160 mg / m ² or more, and 170 mg / m ² or more. Is particularly preferred. If it is 155 mg / m ² or more, light in the wavelength region that promotes the photocatalytic action of the compound contained in the dielectric multilayer film can be sufficiently absorbed. On the other hand, Tsukeryou is not particularly limited, preferable to be 2500 mg / ^{m 2} or less, more preferable to be 2000 mg / ^{m 2} or less, and particularly preferably 1000 mg / ^{m 2} or less. By setting it to 2500 mg / m ² or less, bleed-out (a phenomenon in which the additive emerges on the surface of the film (layer) over time) can be suppressed, and deterioration of haze (cloudiness) can be prevented.

In particular, 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof as UV absorbers Among these, when at least one kind is used, the amount of these compounds is preferably 165 mg / m ² or more, and more preferably 175 mg / ² or more. By setting the applied amount within the above range, it is possible to sufficiently secure the ultraviolet absorbing ability in the adhesive layer, and as a result, it is possible to effectively suppress the deterioration of the dielectric multilayer film.

  The adhesive layer may contain other additives such as stabilizers, surfactants, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion modifiers and the like. Good.

  The pressure-sensitive adhesive layer can be produced by a conventionally known method, but it is preferable to use a method in which a pressure-sensitive adhesive layer forming composition (coating solution) is applied by wire bar coating, spin coating, or dip coating. The above composition (coating solution) can be applied and formed into a film by a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.

[Outermost layer (hard coat layer)]
In the dielectric multilayer film of the present invention, the outermost layer (hard coat layer) may be provided on the outermost surface of the base material on the dielectric multilayer film side as a surface protective layer for enhancing scratch resistance and the like. . The outermost layer according to the present invention may be formed only on one surface of the dielectric multilayer film of the present invention, or may be formed on both surfaces. The outermost layer is formed on the film surface opposite to the object to be attached in order to suppress physical damage from the outside and protect the dielectric multilayer film. Therefore, the outermost layer is disposed (laminated) on the side opposite to the adhesive layer through the dielectric multilayer film.

(UV absorber)
The structure of the outermost layer is not limited as long as it has a surface protection function, but the deterioration due to the irradiation of the dielectric multilayer film with ultraviolet rays is suppressed, and a more durable dielectric multilayer film is formed. In order to obtain it, it is preferable that the outermost layer also contains a UV absorber. Although the ultraviolet absorber contained in an outermost layer is not restrict | limited in particular, For example, it is preferable to use the same thing as the ultraviolet absorber contained in said adhesive layer. Among the above-mentioned ultraviolet absorbers, triazine-based ultraviolet absorbers are preferable because they have a higher effect of protecting the dielectric multilayer film and the effect lasts for a long time. Further, among these, 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof are included. It is preferable that at least one compound selected from the group is used as the ultraviolet absorber. The amount of the ultraviolet absorber contained in the outermost layer is not particularly limited as long as it can reduce the amount of ultraviolet rays incident on the dielectric multilayer film. As a guideline, the weight per unit area (1 m ² ) of the outermost layer of the UV absorber is preferably 80 mg / m ² or more, more preferably 100 mg / m ² or more, and 155 mg / m ² or more. Even more preferably, it is particularly preferably 160 mg / m ² or more, and most preferably 170 mg / m ² or more. If it is 80 mg / m ² or more, light in the wavelength region that promotes the photocatalytic action of the compound contained in the dielectric multilayer film can be sufficiently absorbed. On the other hand, Tsukeryou is not particularly limited, preferable to be 2500 mg / ^{m 2} or less, more preferable to be 2000 mg / ^{m 2} or less, still more preferable to be 1500 mg / ^{m 2} or less, 500 mg / ^{m 2} or less Is particularly preferred. By setting it to 2500 mg / m ² or less, bleed-out (a phenomenon in which the additive emerges on the surface of the film (layer) over time) can be suppressed, and deterioration of haze (cloudiness) can be prevented.

(Infrared absorber)
The outermost layer preferably contains an infrared absorber. In the present invention, the type of the infrared absorber used is not particularly limited as long as the characteristics of the film are satisfied. For example, it is preferable that inorganic nanoparticles are included. Here, the nano fine particles refer to particles having an average (primary) particle size of 1000 nm or less, more preferably those having an average particle size in the range of 1 to 500 nm, and even more preferably in the range of 1 to 100 nm. The particle diameter means the maximum distance among the distances between any two points on the outline of the particle (observation surface) observed using an observation means such as a transmission electron microscope. As the value of the average particle diameter, a value calculated as the number average value of the particle diameters of particles observed in several to several tens of fields using an observation means such as a transmission electron microscope is used.

When the inorganic particles are nano-particles, the visible light transmittance of the outermost layer is ensured. Such inorganic nanoparticles include zinc oxide, tin oxide, silicon oxide, alumina, zirconia, titanium oxide, lanthanum boride or cerium oxide, and these compounds doped with other metals, and mixtures thereof. It is done. In addition, Cd / Se, GaN, Y ₂ O ₃ , Au, Ag, and Cu nanoparticles can also be used. Suitable inorganic nanoparticles include those compounds doped with silicon oxide, zinc oxide, tin oxide, zirconia, lanthanum boride and other metals, more preferably doped with zinc oxide, other metals. Zinc oxide, tin oxide, tin oxide doped with other metals, zirconia, lanthanum boride and mixtures thereof. Among these, the inorganic nanoparticle is particularly preferably zinc oxide, zinc oxide doped with another metal, tin oxide, or tin oxide doped with another metal.

  The blending amount of the inorganic nanoparticles in the cured resin layer is preferably 30 to 80% by mass, and more preferably 50 to 70% by mass with respect to the outermost layer total amount (solid content conversion). When the content of the inorganic nanoparticles is in such a range, it becomes easy to achieve both the hard coat property of the outermost layer and the suppression of peeling or cracking of the film. In the present specification, a compound doped with another metal refers to both a state in which another metal is mixed in the compound or a state in which the compound and another metal (oxide) are bonded. . For example, zinc oxide doped with antimony means both a state in which antimony is mixed in zinc oxide or a state in which zinc oxide and antimony oxide are combined.

Examples of zinc oxide doped with other metals include antimony-doped zinc oxide, zinc antimonate (ZnO.Sb ₂ O ₅ ), indium-doped zinc oxide (indium zinc composite oxide: IZO), gallium-doped zinc oxide (gallium zinc Composite oxide: GZO) and aluminum doped zinc oxide (aluminum zinc composite oxide: AZO) are preferable, zinc antimonate (ZnO.Sb ₂ O ₅ ), gallium doped zinc oxide (gallium zinc composite oxide: GZO), aluminum Doped zinc oxide (aluminum zinc composite oxide: AZO) is more preferable.

  Examples of tin oxide doped with other metals include antimony-doped tin oxide (antimony tin composite oxide: ATO), indium-doped tin oxide (indium tin composite oxide: ITO), and gallium-doped tin oxide (gallium tin composite). Oxide: GTO) is preferable, and antimony-doped tin oxide (antimony tin composite oxide: ATO) and indium-doped tin oxide (indium tin composite oxide: ITO) are more preferable.

  The said inorganic nanoparticle may be used individually by 1 type, and may be used together 2 or more types.

  That is, in a preferred embodiment of the present invention, the outermost layer preferably comprises zinc oxide doped with zinc oxide and / or other metal (hereinafter also referred to as “zinc oxide-based particles”), and tin oxide and / or Alternatively, tin oxide doped with other metals (hereinafter also referred to as “tin oxide-based particles”) is included.

  Zinc oxide-based particles have a lower absorption capacity in the near-infrared region than tin oxide-based particles, and it is necessary to add about 1.3 times the weight of tin oxide-based particles. The content of the resin is reduced. As a result, since the resin component that causes the shrinkage stress is small, the shrinkage of the outermost layer is reduced, and a curl film smaller than the conventional one can be produced. Therefore, when zinc oxides are used in the outermost layer as an infrared absorber, a dielectric multilayer film with few cracks and peeling can be formed.

  In addition, since zinc oxide-based particles have a feature of higher ultraviolet absorption capacity than tin oxide-based particles, deterioration of the cured resin layer due to ultraviolet rays can be reduced, and reduction in scratch resistance due to long-term exposure can be prevented. Can do. At this time, when the film is used for the outer use rather than the inner use, the effect is more remarkably exhibited because it is more affected by the ultraviolet rays.

  Commercially available products dispersed in a solvent or water may be used as the zinc oxide-based particles and tin oxide-based particles. For example, as a zinc oxide particle system, Celnax (registered trademark) series (manufactured by Nissan Chemical Industries, Ltd.), passette series (manufactured by Hakusui Tech Co., Ltd.), as tin oxide particle system, an ATO dispersion, an ITO dispersion (above, Mitsubishi Materials Corporation), KH series (Sumitomo Metal Mining Co., Ltd.), and the like.

  In the present invention, the outermost layer may contain an infrared absorbent other than the inorganic nanoparticles. Such infrared absorbents are roughly classified into inorganic infrared absorbents other than inorganic nanoparticles and organic infrared absorbents. Examples of inorganic infrared absorbers include lanthanum boride and nickel complex compounds. Further, as the organic infrared absorber, an immonium-based, phthalocyanine-based, or aminium-based compound can be used.

  Examples of the organic commercial products include NIR-IM1, NIR-AM1 (manufactured by Nagase Chemitex Co., Ltd.), Lumogen (registered trademark) series (manufactured by BASF Corp.), and the like.

(Curable resin)
The configuration of the outermost layer is preferably a configuration including a resin that is cured by heat, ultraviolet rays, or the like (in the present specification, simply referred to as “curable resin”) in addition to the ultraviolet absorber and / or infrared absorber. .

Examples of the curable resin include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because of easy molding. Such curable resins can be used singly or in combination of two or more. As the curable resin, a commercially available product may be used, or a synthetic product may be used. -Thermosetting resin As a thermosetting resin, the inorganic type material represented by polysiloxane is mentioned.

  As the polysiloxane hard coat material applicable to the formation of the outermost layer according to the present invention, a compound represented by the following general formula (2) is preferable.

In the general formula (2), R and R ₁₀ each independently represent a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and a and b are a + b = 4 It is an integer that satisfies the relationship.

  Specific compounds include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, Examples include methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and hexyltrimethoxysilane. Further, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, N-β- (N-aminobenzylaminoethyl) -γ-aminopropylmethoxysilane, Mention may be made of hydrochloride and octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride. Those having a hydrolyzable group such as methoxy group or ethoxy group substituted with a hydroxy group are generally referred to as polyorganosiloxane hard coat materials.

  Specific examples of the polyorganosiloxane-based hard coat material include Surcoat Series, BP-16N (manufactured by Doken Co., Ltd.), SR2441 (Toray Dow Corning Co., Ltd.), Perma-New 6000 (California Hardcoating Company, Inc.) ) Etc. can be used.

Active energy ray curable resin Examples of the curable resin used in the outermost layer according to the present invention include a thermosetting resin and an active energy ray curable resin. Is preferred. Such curable resins can be used singly or in combination of two or more.

  The active energy ray resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray. The conductive resin layer, that is, the outermost layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet ray curable resin and an electron beam curable resin, but from the viewpoint of suppressing the complexity of the production process, the ultraviolet ray curable resin cured by ultraviolet ray irradiation. Resins are preferred.

  However, in the present invention, in order to suppress deterioration of the dielectric multilayer film, it is preferable to reduce the amount of ultraviolet rays incident on the dielectric multilayer film even during the production of the dielectric multilayer film. Therefore, when the outermost layer is formed using an ultraviolet curable resin in the sense that the deterioration due to ultraviolet rays is suppressed not only during the use of the film but also during production, the ultraviolet absorber is added to the outermost layer. It is good to be. With such a configuration, it is possible to reduce the amount of ultraviolet light incident on the dielectric multilayer film provided in the lowermost layer of the outermost layer and obtain a dielectric multilayer film excellent in durability.

  Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, an ultraviolet curable acrylic acrylate resin, and an ultraviolet curable epoxy resin. Etc. can be used. Among these, from the viewpoint of scratch resistance and flexibility, the outermost layer preferably contains an ultraviolet curable urethane acrylate resin.

  The UV curable urethane acrylate resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, 100 parts by mass of Unidic (registered trademark) 17-806 (manufactured by DIC Corporation) described in JP-A-59-151110 and 1 part by mass of Coronate (registered trademark) L (manufactured by Nippon Polyurethane Industry Co., Ltd.) A mixture of these is preferably used.

  The UV curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, JP-A No. 59-151112).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples thereof include those obtained by reacting monomers such as erythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and triethylene glycol diacrylate.

  In addition to the above, examples of commercially available products of active energy ray-curable resins used for forming the outermost layer include, for example, the Hitaroid (registered trademark) series (manufactured by Hitachi Chemical Co., Ltd.), the Shikko series (Nippon Synthetic Chemical Industry Co., Ltd.) Manufactured), a beam set series (Arakawa Chemical Industries, Ltd.), ETERMER 2382 (manufactured by ETERNAL CHEMICAL), and the like.

  The outermost layer can be prepared by a conventionally known method, but it is preferable to use a method of applying the outermost layer forming composition (coating solution) by wire bar coating, spin coating, or dip coating. The above composition (coating solution) can be applied and formed into a film by a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.

[Dielectric multilayer film]
The dielectric multilayer film is a laminate in which at least one low refractive index layer and at least one high refractive index layer are laminated. The dielectric multilayer film according to the present invention expresses a function of reflecting sunlight, infrared rays, visible rays, or ultraviolet rays, and at least one of the high refractive index layer and the low refractive index layer has a photocatalytic action. A compound having

  A preferred form of the dielectric multilayer film has a form of an alternating laminate in which low refractive index layers and high refractive index layers are alternately laminated. In the present specification, a refractive index layer having a higher refractive index than the other is referred to as a high refractive index layer, and a refractive index layer having a lower refractive index than the other is referred to as a low refractive index layer. In this specification, the terms “high refractive index layer” and “low refractive index layer” refer to a refractive index layer having a higher refractive index when comparing the refractive index difference between two adjacent layers. It means that the lower refractive index layer is a low refractive index layer. Therefore, the terms “high refractive index layer” and “low refractive index layer” mean that when each refractive index layer constituting the dielectric multilayer film is focused on two adjacent refractive index layers, All forms other than those having the same refractive index are included.

  The thickness per layer of the low refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 350 nm. On the other hand, the thickness per layer of the high refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 350 nm.

  Here, when measuring the thickness per layer, the high refractive index layer and the low refractive index layer may have a clear interface between them, or may have a structure in which the composition changes continuously. . When the composition is continuously changed from the interface, the maximum refractive index-minimum refractive index = Δn in the region where the layers are mixed and the refractive index continuously changes. A point of refractive index + Δn / 2 is regarded as a layer interface. The same applies to the layer thickness of the low refractive index layer described later.

  In the present invention, the profile of the refractive index adjusting agent of the dielectric multilayer film formed by laminating the high refractive index layer and the low refractive index layer is etched from the surface to the depth direction using the sputtering method, and the XPS surface Using an analyzer, the outermost surface can be set to 0 nm, sputtered at a rate of 0.5 nm / min, and the atomic composition ratio can be measured. It is also possible to confirm the cut surface by cutting the laminated film and measuring the atomic composition ratio with an XPS surface analyzer. In the mixed region, when the concentration of the refractive index adjusting agent changes discontinuously, the boundary can be confirmed by a tomographic photograph using an electron microscope (TEM).

  The XPS surface analyzer is not particularly limited, and any model can be used. For example, ESCALAB-200R manufactured by VG Scientific, Inc. can be used. Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

  In the dielectric multilayer film according to the present invention, from the viewpoint of productivity, the range of the total number of layers is preferably 6 to 50 layers, more preferably 8 to 40 layers, and further preferably 9 to 30 layers.

  In the dielectric multilayer film, it is preferable to design a large difference in refractive index between the low refractive index layer and the high refractive index layer from the viewpoint that the infrared reflectance can be increased with a small number of layers. In at least one of the laminates (units) composed of the low refractive index layer and the high refractive index layer, the difference in refractive index between the adjacent low refractive index layer and high refractive index layer is preferably 0.1 or more. More preferably, it is 0.3 or more, More preferably, it is 0.35 or more, Most preferably, it is more than 0.4. When the dielectric multilayer film has a plurality of laminates (units) of the high refractive index layer and the low refractive index layer, the refractive index difference between the high refractive index layer and the low refractive index layer in all the laminated bodies (units) is It is preferable that it exists in the said suitable range. However, the outermost layer and the lowermost layer of the dielectric multilayer film may have a configuration outside the above preferred range.

  The reflectance in the specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of stacked layers. The larger the difference in refractive index, the same reflectance can be obtained with a smaller number of layers. The refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain an infrared reflectance of 90% or more, if the difference in refractive index is less than 0.1, it is necessary to laminate 200 layers or more, which not only decreases productivity but also scattering at the interface of the layers. Becomes larger, the transparency is lowered, and it becomes very difficult to manufacture without failure. From the standpoint of improving reflectivity and reducing the number of layers, there is no upper limit to the difference in refractive index, but practically about 1.4 is the limit.

  Further, as the optical characteristics of the dielectric multilayer film, the transmittance in the visible light region shown in JIS R3106-1998 is preferably 50% or more, preferably 75% or more, more preferably 85% or more, It is preferable to have a region in which the reflectance exceeds 50% in a wavelength region of 900 nm to 1400 nm.

  The dielectric multilayer film only needs to have a configuration including at least one laminate (unit) including a high refractive index layer and a low refractive index layer on a base material. As the number of layers of the high refractive index layer and the low refractive index layer, from the above viewpoint, the range of the total number of layers is 100 layers or less, that is, 50 units or less, more preferably 40 layers (20 units) or less. More preferably, it is 20 layers (10 units) or less. In addition, the dielectric multilayer film may have a configuration in which at least one of the above units is laminated. For example, the dielectric multilayer film is a laminated film in which both the outermost layer and the lowermost layer of the laminated film are high refractive index layers or low refractive index layers. May be. When the dielectric multilayer film according to the present invention includes a base material, a layer configuration in which the lowermost layer adjacent to the base material is a low refractive index layer is preferable from the viewpoint of adhesion to the base material.

(Compound with photocatalytic activity)
In the present invention, at least one of the high refractive index layer and the low refractive index layer constituting the dielectric multilayer film contains a compound having a photocatalytic action. Here, “at least one of the high refractive index layer and the low refractive index layer” means that a compound having a photocatalytic action is contained in at least one of the high refractive index layer and the low refractive index layer constituting the dielectric multilayer film. Means that That is, the dielectric multilayer film of the present invention has a high refractive index layer that does not contain a photocatalytic compound as long as at least one of the high refractive index layer and the low refractive index layer contains a photocatalytic compound. And / or a low refractive index layer that does not contain a photocatalytic compound.

  From the viewpoint of the reflectance of the dielectric multilayer film, preferably, at least one of the high refractive index layers includes a compound having a photocatalytic action, and more preferably, all layers of the high refractive index layer are photocatalysts. It is a form containing a compound having an action.

  Furthermore, in the present invention, the “compound having a photocatalytic action” means a compound that exhibits a catalytic action when irradiated with light. The “photocatalytic action” specifically means an action of decomposing a water-soluble polymer contained in the dielectric multilayer film when irradiated with light.

  In the present invention, even with a dielectric multilayer film containing such a compound having a photocatalytic action, the adhesive layer can be adhered by adjusting the light transmittance of the adhesive layer and the rate of change of the light transmittance within a predetermined range. A highly durable derivative multilayer film excellent in flexibility and flexibility can be obtained.

  The compound having a photocatalytic action may be an inorganic compound or an organic compound. As an inorganic compound, the metal oxide particle etc. which are used as a 1st refractive index adjusting agent contained in the below-mentioned high refractive index layer and a 2nd refractive index adjusting agent contained in a low refractive index layer are mentioned, for example. Examples of organic compounds include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, n-butylamine, triethylamine, tri-n-butylphosphine, and the like. Examples thereof include, but are not limited to, sensitizers, and all substances that generate active substances such as radicals and cations by light irradiation are included.

(1) High Refractive Index Layer The configuration of the high refractive index layer according to the present invention is not particularly limited, but preferably includes a water-soluble polymer and a compound having a photocatalytic action. In this specification, “water-soluble polymer” means a G2 glass filter (maximum pore size) when dissolved in water at a concentration of 0.5 mass% at the temperature at which the water-soluble polymer is most dissolved. 40-50 μm) means that the mass of the insoluble matter filtered off is within 50% by mass of the added water-soluble polymer.

  As a more detailed constitution of the high refractive index layer, it contains a first water-soluble binder resin (water-soluble polymer) and a first refractive index adjusting agent, and the first refractive index adjusting agent has a photocatalytic action. It preferably contains a compound, and may further contain a curing agent, other binder resin, a surfactant, various additives, etc., if necessary.

  The refractive index of the high refractive index layer according to the present invention is preferably 1.80 to 2.50, more preferably 1.90 to 2.20.

(1-1) First water-soluble binder resin In the present invention, the first water-soluble binder resin (water-soluble polymer) preferably has a weight average molecular weight of 1,000 to 200,000, More preferably, it is 000-150,000.
In addition, in this specification, the value measured on the measurement conditions shown in following Table 1 using a gel permeation chromatography (GPC) is employ | adopted for a weight average molecular weight.

  The content of the first water-soluble binder resin in the high refractive index layer is preferably 5 to 50% by mass and 10 to 40% by mass with respect to 100% by mass of the solid content of the high refractive index layer. Is more preferable.

  The first water-soluble binder resin applied to the high refractive index layer is preferably polyvinyl alcohol. Moreover, it is preferable that the 2nd water-soluble binder resin (water-soluble polymer) which exists in the low-refractive-index layer mentioned later is also polyvinyl alcohol.

  Therefore, in the following, polyvinyl alcohol contained in the high refractive index layer and the low refractive index layer will be described together.

(1-1-1) Polyvinyl alcohol The high refractive index layer and the low refractive index layer according to the present invention preferably contain two or more kinds of polyvinyl alcohols having different saponification degrees. Here, in order to distinguish, polyvinyl alcohol (A) is used as the first water-soluble binder resin used in the high refractive index layer, and polyvinyl alcohol as the second water-soluble binder resin used in the low refractive index layer. Is referred to as polyvinyl alcohol (B). In addition, when each refractive index layer contains a plurality of polyvinyl alcohols having different saponification degrees and polymerization degrees, the polyvinyl alcohol having the highest content in each refractive index layer is changed to polyvinyl alcohol (A ), And polyvinyl alcohol (B) in the low refractive index layer.

  The “degree of saponification” as used in the present invention is the ratio of hydroxy groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxy groups in polyvinyl alcohol.

  In addition, when referring to “polyvinyl alcohol having the highest content in the refractive index layer” herein, the degree of polymerization is calculated assuming that the polyvinyl alcohol having a saponification degree difference of 3 mol% or less is the same polyvinyl alcohol. . However, a low polymerization degree polyvinyl alcohol having a polymerization degree of 1000 or less is a different polyvinyl alcohol (even if there is a polyvinyl alcohol having a saponification degree difference of 3 mol% or less, it is not regarded as the same polyvinyl alcohol). Specifically, when polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 mass%, 40 mass%, and 50 mass%, respectively. These three polyvinyl alcohols are the same polyvinyl alcohol, and these three mixtures are polyvinyl alcohol (A) or (B). In addition, the above-mentioned “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” suffices to be within 3 mol% when attention is paid to any polyvinyl alcohol. For example, 90 mol%, 91 mol%, 92 mol%, 94 mol % Of polyvinyl alcohol, when paying attention to 91 mol% of polyvinyl alcohol, the difference in saponification degree of any polyvinyl alcohol is within 3 mol%, so that the same polyvinyl alcohol is obtained.

  When polyvinyl alcohol having a saponification degree different by 3 mol% or more is contained in the same layer, it is regarded as a mixture of different polyvinyl alcohols, and the polymerization degree and the saponification degree are calculated for each. For example, PVA203: 5% by mass, PVA117: 25% by mass, PVA217: 10% by mass, PVA220: 10% by mass, PVA224: 10% by mass, PVA235: 20% by mass, PVA245: 20% by mass, most contained A large amount of PVA (polyvinyl alcohol) is a mixture of PVA 217 to 245 (the difference in the degree of saponification of PVA 217 to 245 is within 3 mol%, and thus is the same polyvinyl alcohol), and this mixture is polyvinyl alcohol (A) or ( B). Thus, in a mixture of PVA 217 to 245 (polyvinyl alcohol (A) or (B)), the degree of polymerization is (1700 × 0.1 + 2000 × 0.1 + 2400 × 0.1 + 3500 × 0.2 + 4500 × 0.7) / 0.7 = 3200, and the degree of saponification is 88 mol%.

  The difference in the absolute value of the degree of saponification between the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is preferably 3 mol% or more, and more preferably 5 mol% or more. If it is such a range, since the interlayer mixing state of a high refractive index layer and a low refractive index layer will become a preferable level, it is preferable. Moreover, although the difference of the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is so preferable that it is separated, it is 20 mol% or less from the viewpoint of the solubility to water of polyvinyl alcohol. It is preferable.

  Moreover, it is preferable that the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is 75 mol% or more from the viewpoint of solubility in water. Furthermore, between polyvinyl alcohol (A) and polyvinyl alcohol (B), one of them has a saponification degree of 90 mol% or more and the other is 90 mol% or less. Is preferable for achieving a preferable level. It is more preferable that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 95 mol% or more and the other is 90 mol% or less. In addition, although the upper limit of the saponification degree of polyvinyl alcohol is not specifically limited, Usually, it is less than 100 mol% and is about 99.9 mol% or less.

  In addition, the polymerization degree of two kinds of polyvinyl alcohols having different saponification degrees is preferably 1000 or more, particularly preferably those having a polymerization degree in the range of 1500 to 5000, and in the range of 2000 to 5000. Those are more preferably used. This is because when the polymerization degree of polyvinyl alcohol is 1000 or more, there is no cracking of the coating film, and when it is 5000 or less, the coating solution is stabilized. In the present specification, “the coating solution is stable” means that the coating solution is stable over time. When the degree of polymerization of at least one of polyvinyl alcohol (A) and polyvinyl alcohol (B) is in the range of 2000 to 5000, it is preferable because cracks in the coating film are reduced and the reflectance at a specific wavelength is improved. It is preferable that both the polyvinyl alcohol (A) and the polyvinyl alcohol (B) are 2000 to 5000 since the above effect can be more remarkably exhibited.

  The “degree of polymerization” as used in the present invention refers to the viscosity average degree of polymerization, and is measured according to JIS K6726 (1994). After re-saponification and purification of PVA, the intrinsic viscosity measured in water at 30 ° C. From [η] (dl / g), it is obtained by the following mathematical formula (3).

  The polyvinyl alcohol (B) contained in the low refractive index layer preferably has a saponification degree in the range of 75 to 90 mol% and a polymerization degree in the range of 2000 to 5000. When polyvinyl alcohol having such characteristics is contained in the low refractive index layer, it is preferable in that interfacial mixing is further suppressed. This is considered to be because there are few cracks of a coating film and set property improves.

  As the polyvinyl alcohol (A) and (B) used in the present invention, a synthetic product or a commercially available product may be used. As an example of the commercial item used as polyvinyl alcohol (A) and (B), for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA -203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04 , JF-05, JP-03, JP-04, JP-05, JP-45 (above, manufactured by Nippon Vinegar Poval Co., Ltd.) and the like.

  As long as the effects of the present invention are not impaired, the water-soluble binder resin according to the present invention may contain modified polyvinyl alcohol partially modified in addition to ordinary polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate. Good. When such a modified polyvinyl alcohol is included, the adhesion, water resistance, and flexibility of the film may be improved. Examples of such modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonionic-modified polyvinyl alcohol, and vinyl alcohol polymers.

  Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups, as described in JP-A No. 61-10383, in the main chain or side chain of the polyvinyl alcohol. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

  Examples of the ethylenically unsaturated monomer having a cationic group include those described in paragraph “0101” of JP2012-242644A.

  Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979. Examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.

  Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group as described in JP-A-7-9758 is added to a part of vinyl alcohol, and JP-A-8-25795. Block copolymer of vinyl compound having hydrophobic group and vinyl alcohol, silanol-modified polyvinyl alcohol having silanol group, reactive group modification having reactive group such as acetoacetyl group, carbonyl group and carboxy group Polyvinyl alcohol etc. are mentioned.

  It is also preferable to use a polyvinyl alcohol-based water-soluble polymer, such as EXEVAL (registered trademark, manufactured by Kuraray Co., Ltd.) or Nichigo G polymer (registered trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

  Two or more types of modified polyvinyl alcohol can be used in combination, such as the degree of polymerization and the type of modification.

  Although content of modified polyvinyl alcohol is not specifically limited, Preferably it is 1-30 mass% with respect to the total mass (solid content) of each refractive index layer. If it is such a range, the said effect will be exhibited more.

  In the present invention, it is preferable that two types of polyvinyl alcohol having different saponification degrees are used between layers having different refractive indexes.

(1-1-2) Other Binder Resins In the high refractive index layer according to the present invention, the first water-soluble binder resin (water-soluble polymer) other than polyvinyl alcohol contains a first refractive index adjuster. Any material can be used without limitation as long as the high refractive index layer can form a coating film. Also in the low refractive index layer described later, as the second water-soluble binder resin other than polyvinyl alcohol, the low refractive index layer containing the second refractive index adjusting agent forms a coating film as described above. Anything can be used without limitation. However, in view of environmental problems and flexibility of the coating film, water-soluble polymers (particularly gelatin, thickening polysaccharides, polymers having reactive functional groups) are preferable. These water-soluble polymers may be used alone or in combination of two or more.

  In the high refractive index layer, the content of other binder resin used together with polyvinyl alcohol preferably used as the first water-soluble binder resin is 5 to 50 mass with respect to 100 mass% of the solid content of the high refractive index layer. % Can also be used.

  In the present invention, it is not necessary to use an organic solvent and it is preferable from the viewpoint of environmental conservation. Therefore, the binder resin is composed of a water-soluble polymer. That is, in the present invention, a water-soluble polymer other than polyvinyl alcohol and modified polyvinyl alcohol may be used as the binder resin in addition to the polyvinyl alcohol and modified polyvinyl alcohol as long as the effect is not impaired. Among such water-soluble polymers, gelatin, celluloses, thickening polysaccharides, or polymers having reactive functional groups are particularly preferable. These water-soluble polymers may be used alone or in combination of two or more.

(1-2) First Refractive Index Adjusting Agent The first refractive index adjusting agent applicable to the high refractive index layer according to the present invention may be an inorganic material or an organic material. In general, inorganic materials are preferred because of their higher refractive index, and metal oxide particles having a refractive index of 2.0 or more and 3.0 or less are more preferred. In the case where metal oxide particles are used as the first refractive index adjusting agent, the metal oxide particles can be a compound having a photocatalytic action.

  More specifically, for example, titanium oxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, oxidized oxide Examples thereof include ferric iron, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. In addition, composite oxide particles composed of a plurality of metals, core / shell particles whose metal structure changes into a core / shell shape, and the like can also be used. In the organic system, a thiophene compound, a polyphenylene sulfide compound, a polyacetylene compound, a polyphenylene vinylene compound, a polypyrrole compound, or a polyaniline compound can be used.

  In order to form a transparent and higher refractive index layer having a higher refractive index, the high refractive index layer according to the present invention includes metal oxide particles having a high refractive index such as titanium and zirconium, that is, titanium oxide particles and It is preferable to contain zirconia oxide particles. Among these, from the viewpoint of the stability of the coating liquid for forming the high refractive index layer, the high refractive index layer more preferably contains titanium oxide particles. On the other hand, titanium oxide can be a compound having a photocatalytic action. Therefore, by including titanium oxide particles in the high refractive index layer, the refractive index difference between the high refractive index layer and the low refractive index layer can be increased, while the dielectric due to the photocatalytic action of the titanium oxide particles. Deterioration of the multilayer film can occur. However, according to the present invention, ultraviolet light having a wavelength that promotes photocatalytic action can be absorbed in the adhesive layer, so that the photocatalytic action of the titanium oxide particles can be suppressed. Therefore, according to the present invention, by using the titanium oxide particles, it is possible to bring out only the advantage relating to the refractive index difference that the refractive index difference between the high refractive index layer and the low refractive index layer can be increased. it can.

  Among titanium oxides, the rutile type (tetragonal type) has a lower catalytic activity than the anatase type, and the weather resistance of the high refractive index layer and adjacent layers is higher, and the refractive index is higher. Is more preferable.

  When core / shell particles are used as the first refractive index adjusting agent in the high refractive index layer according to the present invention, the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin Thus, from the effect of suppressing intermixing between the high refractive index layer and the adjacent layer, core / shell particles in which titanium oxide particles are coated (surface-treated) with a silicon-containing hydrated oxide are more preferable.

  The aqueous solution containing titanium oxide particles used for the core of the core-shell particles according to the present invention has a surface of an aqueous titanium oxide sol having a pH of 1.0 to 3.0 and a positive zeta potential of the titanium particles. It is preferable to use a hydrophobized and dispersible state in an organic solvent.

  When the content of the metal oxide particles used as the first refractive index adjuster according to the present invention is 15 to 80% by mass with respect to 100% by mass of the solid content of the high refractive index layer, the low refractive index layer and This is preferable from the viewpoint of providing a difference in refractive index. Furthermore, it is more preferable that it is 20-77 mass%, and it is further more preferable that it is 30-75 mass%. The content when the metal oxide particles other than the core / shell particles are contained in the high refractive index layer according to the present invention is particularly limited as long as the effects of the present invention can be obtained. It is not a thing.

  In the present invention, the volume average particle size of the metal oxide particles used as the first refractive index adjuster is preferably 50 nm or less, and more preferably in the range of 1 to 40 nm. A volume average particle size of 50 nm or less is preferable from the viewpoint of low visible light transmittance and low haze.

  In addition, the volume average particle diameter of the metal oxide particles used as the first refractive index adjusting agent according to the present invention refers to observing the particles themselves using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope. The particle diameter of 1,000 arbitrary particles was measured by the method and the method of observing the cross section and surface of the refractive index layer with an electron microscope, and d1, d2,. In a group of particulate metal oxides each having n1, n2,..., nk, particles having a particle size of dk, the volume average particle size when the volume per particle is vi. mv = average particle diameter weighted by a volume represented by {Σ (vi · di)} / {Σ (vi)}. More specifically, the volume average particle diameter of the metal oxide particles refers to a value measured by the method described in Examples.

(1-3) Curing Agent In the present invention, a curing agent can be used to cure the first water-soluble binder resin applied to the high refractive index layer. The curing agent that can be used together with the first water-soluble binder resin is not particularly limited as long as it causes a curing reaction with the first water-soluble binder resin. For example, when polyvinyl alcohol is used as the first water-soluble binder resin, boric acid and its salt are preferable as the curing agent. In addition to boric acid and its salts, known ones can be used, and in general, a compound having a group capable of reacting with polyvinyl alcohol or a compound that promotes the reaction between different groups possessed by polyvinyl alcohol. Select and use. Specific examples of the curing agent include, for example, epoxy curing agents (for example, diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, N, N-diglycidyl-4-glycidyloxyaniline, etc. ), Aldehyde curing agents (eg, formaldehyde, glyoxal, etc.), active halogen curing agents (eg, 2,4-dichloro-4-hydroxy-1,3,5, -s-triazine, etc.), active vinyl compounds (For example, 1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.

  Boric acid and its salts refer to oxygen acids and their salts having a boron atom as a central atom, specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid and octabored acid. Examples include acids and their salts.

(2) Low Refractive Index Layer The configuration of the low refractive index layer according to the present invention is not particularly limited, but includes a second water-soluble binder resin (water-soluble polymer) and a second refractive index adjuster. Further, if necessary, various additives such as a curing agent, a surface coating component, a particle surface protective agent, other binder resins, and a surfactant may be included.

  The refractive index of the low refractive index layer according to the present invention is preferably 1.10 to 1.60, more preferably 1.30 to 1.50.

(2-1) Second water-soluble binder resin (2-1-1) Polyvinyl alcohol As the second water-soluble binder resin applied to the low refractive index layer according to the present invention, polyvinyl alcohol is preferably used. Furthermore, it is more preferable that polyvinyl alcohol (B) different from the saponification degree of polyvinyl alcohol (A) present in the high refractive index layer is used in the low refractive index layer according to the present invention. In addition, description about polyvinyl alcohol (A) and polyvinyl alcohol (B), such as a preferable weight average molecular weight of 2nd water-soluble binder resin here, is 1st water-soluble binder resin of the said high refractive index layer. The explanation is omitted here, and the explanation is omitted here.

  The content of the second water-soluble binder resin in the low refractive index layer is preferably 10 to 99.9 mass% with respect to the solid content of 100 mass% of the low refractive index layer, and is 15 to 80 mass%. More preferably.

(2-1-2) Other water-soluble binder resins As the second water-soluble binder resin other than polyvinyl alcohol, which can be applied in the low refractive index layer according to the present invention, low refractive index containing a refractive index adjusting agent. Any material can be used without limitation as long as the rate layer can form a coating film. However, in view of environmental problems and flexibility of the coating film, water-soluble polymers (particularly gelatin, thickening polysaccharides, polymers having reactive functional groups) are preferable. These water-soluble polymers may be used alone or in combination of two or more.

  In the low refractive index layer, the content of other binder resin used together with polyvinyl alcohol preferably used as the second water-soluble binder resin is 0.1 to 0.1% by mass of the solid content of the low refractive index layer. It is preferable that it is 10 mass%.

  The low refractive index layer according to the present invention may contain water-soluble polymers such as celluloses, thickening polysaccharides, and polymers having reactive functional groups. These water-soluble polymers such as celluloses, thickening polysaccharides and polymers having reactive functional groups are the same as the water-soluble polymers described in the high refractive index layer described above. Is omitted.

(2-2) Second Refractive Index Adjusting Agent The second refractive index adjusting agent applied to the low refractive index layer according to the present invention may be an inorganic material or an organic material, Silica (silicon dioxide) is preferably used from the viewpoints of compatibility with the second water-soluble binder resin, liquid stability, cost, and the like, and specific examples include synthetic amorphous silica and colloidal silica. Of these, acidic colloidal silica sol is more preferably used, and colloidal silica sol dispersed in an organic solvent is more preferably used. Further, in order to further reduce the refractive index, hollow fine particles having pores inside the particles can be used as the second refractive index adjusting agent applied to the low refractive index layer, particularly silica (silicon dioxide). The hollow fine particles are preferred. When metal oxide particles are used as the second refractive index adjusting agent, the metal oxide particles can be a compound having a photocatalytic action.

  When the second refractive index adjusting agent applied to the low refractive index layer is metal oxide particles (preferably silicon dioxide), the average particle size is preferably 3 to 100 nm. The average particle diameter of primary particles of silicon dioxide dispersed in a primary particle state (particle diameter in a dispersion state before coating) is more preferably 3 to 50 nm, and further preferably 3 to 40 nm. 3 to 20 nm is particularly preferable, and 4 to 10 nm is most preferable. Moreover, as an average particle diameter of secondary particle | grains, it is preferable from a viewpoint with few hazes and excellent visible light transmittance | permeability that it is 30 nm or less.

  The average particle diameter of the metal oxide particles as the second refractive index adjusting agent applied to the low refractive index layer was determined by observing the particles themselves or the particles appearing on the cross section or surface of the refractive index layer with an electron microscope. The particle diameter of an arbitrary particle is measured and obtained as a simple average value (number average). Here, the particle size of each particle is represented by a diameter assuming a circle equal to the projected area.

  The colloidal silica used as the second refractive index adjusting agent is obtained by heating and aging a silica sol obtained by metathesis of sodium silicate with an acid or the like or passing through an ion exchange resin layer. -14091, JP-A-60-219083, JP-A-60-219084, JP-A-61-20792, JP-A-61-188183, JP-A-63-17807, JP-A-4-93284, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP 7-101142, JP-A-7-179029, JP-A-7-137431, and International Publication No. 94/26530 Are those mounting.

  Such colloidal silica may be a synthetic product or a commercially available product. The surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.

  Hollow particles can also be used as the second refractive index adjusting agent applied to the low refractive index layer. When using hollow particles, the average particle pore size is preferably 3 to 70 nm, more preferably 5 to 50 nm, and even more preferably 5 to 45 nm. The average particle pore diameter of the hollow particles is the average value of the inner diameters of the hollow particles. In the present invention, when the average particle pore diameter of the hollow particles is in the above range, the refractive index of the low refractive index layer is sufficiently lowered. The average particle diameter is 50 or more at random, which can be observed as a circle, an ellipse, or substantially a circle or an ellipse by electron microscope observation, and the number of holes is determined for each particle. Is obtained. The average particle hole diameter means the minimum distance among the distances between the outer edges of the hole diameter that can be observed as a circle, ellipse, substantially circle or ellipse, between two parallel lines.

  The second refractive index adjusting agent applied to the low refractive index layer may be surface-coated with a surface coating component.

  The content of the second refractive index adjusting agent in the low refractive index layer is preferably 0.1 to 85% by mass and 30 to 80% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferably, it is more preferably 45 to 75% by mass.

(2-3) Curing Agent In the low refractive index layer according to the present invention, a curing agent can be further contained in the same manner as the high refractive index layer. There is no particular limitation as long as it causes a curing reaction with the second water-soluble binder resin contained in the low refractive index layer. In particular, as the curing agent when polyvinyl alcohol is used as the second water-soluble binder resin applied to the low refractive index layer, boric acid, a salt thereof, and borax are preferable. In addition to boric acid and its salts, known ones can be used.

  The content of the curing agent in the low refractive index layer is preferably 1 to 15% by mass and more preferably 2 to 10% by mass with respect to 100% by mass of the solid content of the low refractive index layer.

  In particular, the total amount of the curing agent used when polyvinyl alcohol is used as the second water-soluble binder resin is preferably 1 to 800 mg per 1 g of polyvinyl alcohol, and more preferably 100 to 700 mg per 1 g of polyvinyl alcohol.

  Moreover, since the specific example of a hardening | curing agent is the same as that of the content demonstrated by the term of the high refractive index layer mentioned above, it is the same, and description is abbreviate | omitted here.

(3) Additive of Refractive Index Layer The high refractive index layer and the low refractive index layer according to the present invention can contain various additives as necessary. Moreover, it is preferable that content of the additive in a high refractive index layer is 0.0001-20 mass% with respect to 100 mass% of solid content of a high refractive index layer. Examples of such additives are described below.

(3-1) Surfactant In the present invention, at least one of the high refractive index layer and the low refractive index layer may further contain a surfactant. As the surfactant, any of zwitterionic, cationic, anionic, and nonionic types can be used. More preferably, a betaine zwitterionic surfactant, a quaternary ammonium salt cationic surfactant, a dialkylsulfosuccinate anionic surfactant, an acetylene glycol nonionic surfactant, or a fluorine cationic interface An activator is preferred.

  The addition amount of the surfactant according to the present invention is in the range of 0.0001 to 0.30 mass% when the total mass of the coating liquid for high refractive index layer or the coating liquid for low refractive index layer is 100 mass%. It is preferable that it is 0.0005-0.10 mass%.

(3-2) Other Additives The high refractive index layer or the low refractive index layer according to the present invention can contain an amino acid, an emulsion resin, a lithium compound, and the like as appropriate as other additives. Further, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, JP-A-57- No. 878989, JP-A-60-72785, JP-A-61-146591, JP-A-1-95091, JP-A-3-13376, etc. Fluorescence enhancement described in JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266 Whitening agent, sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate and other pH adjusters, antifoaming agents, diethylene glycol and other lubricants, preservatives, Known additives such as additives, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared absorbers, dyes, pigments, etc. Etc.

(4) Dielectric Multilayer Film Forming Method The dielectric multilayer film forming method according to the present invention is not particularly limited, but the first water-soluble binder resin and the first refraction are formed on the substrate (transparent resin film). A production method including a step of applying a coating solution for a high refractive index layer containing a refractive index adjusting agent and a coating solution for a low refractive index layer containing a second water-soluble binder resin and a second refractive index adjusting agent is preferable.

  The coating method is not particularly limited as long as it is a wet coating method. For example, a roller coating method, a rod bar coating method, an air knife coating method, a spray coating method, a slide curtain coating method, or US Pat. No. 2,761,419. Examples thereof include a slide hopper coating method and an extrusion coating method described in the specification and US Pat. No. 2,761,791. In addition, as a method of applying a plurality of layers in multiple layers, sequential multilayer application or simultaneous multilayer application may be used.

  Hereinafter, the simultaneous multilayer coating by the slide hopper coating method, which is a preferred production method (coating method) of the present invention, will be described in detail.

(4-1) Solvent The solvent for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited, but water, an organic solvent or a mixed solvent thereof is preferable.

  Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether and propylene. Examples include ethers such as glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more.

  From the viewpoint of environment and simplicity of operation, the solvent for the coating solution is particularly preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate.

(4-2) Concentration of coating solution The concentration of the first water-soluble binder resin in the coating solution for the high refractive index layer is preferably in the range of 1 to 10% by mass. Moreover, it is preferable that the density | concentration of the 1st refractive index regulator (metal oxide particle) in the coating liquid for high refractive index layers exists in the range of 1-50 mass%.

  The concentration of the second water-soluble binder resin in the coating solution for the low refractive index layer is preferably in the range of 1 to 10% by mass. Moreover, it is preferable that the density | concentration of the 2nd refractive index regulator (metal oxide particle) in the coating liquid for low refractive index layers exists in the range of 1-50 mass%.

(4-3) Preparation Method of Coating Liquid The preparation method of the coating liquid for the high refractive index layer and the coating liquid for the low refractive index layer is not particularly limited. For example, the water-soluble binder resin, the refractive index adjusting agent, and the necessity There may be mentioned a method in which other additives added in accordance with the above are added and mixed by stirring. At this time, the order of addition of the water-soluble binder resin, the refractive index adjuster, and other additives used as necessary is not particularly limited, and each component may be added and mixed sequentially while stirring. However, they may be added and mixed at once. If necessary, it is further adjusted to an appropriate viscosity using a solvent.

  In the present invention, it is preferable to form a high refractive index layer using an aqueous coating solution for high refractive index layer prepared by adding and dispersing core / shell particles. At this time, the core / shell particles are prepared by adding to the coating solution for the high refractive index layer as a sol having a pH in the range of 5.0 to 7.5 and a negative zeta potential of the particles. It is preferable.

(4-4) Viscosity of coating liquid The viscosity at 40 to 45 ° C. of the coating liquid for the high refractive index layer and the coating liquid for the low refractive index layer when performing simultaneous multilayer coating by the slide hopper coating method is 5 to 300 mPa · s. 10 to 250 mPa · s is more preferable. Further, the viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer when performing simultaneous multilayer coating by the slide curtain coating method is preferably 5 to 1200 mPa · s, and 25 to 500 mPa · s. -S is more preferable.

  Further, the viscosity at 15 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably 10 mPa · s or more, more preferably 15 to 30000 mPa · s, further preferably 20 to 20000 mPa · s, ˜18000 mPa · s is particularly preferable.

(4-5) Coating and drying method The coating and drying method is not particularly limited, but the coating liquid for high refractive index layer and the coating liquid for low refractive index layer are heated to 30 ° C. or higher to form a base material (transparent resin After the simultaneous multilayer coating of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer on the film), the temperature of the formed coating film is preferably cooled to 1 to 15 ° C. (set), and then It is preferable to dry at 10 ° C. or higher. More preferable drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. Moreover, as a cooling method immediately after application | coating, it is preferable to carry out by a horizontal set system from a viewpoint of the uniformity improvement of the formed coating film.

  What is necessary is just to apply | coat so that the coating thickness of the coating liquid for high refractive index layers and the coating liquid for low refractive index layers may become the preferable thickness at the time of drying as shown above.

  Here, the set means a step of increasing the viscosity of the coating composition and reducing the fluidity of the substances in each layer and in each layer by means such as applying cold air to the coating film to lower the temperature. To do. A state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.

  It is preferable that the time (setting time) from application of cold air to completion of setting after application is within 5 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. If the set time is too short, mixing of the components in the layer may be insufficient. On the other hand, if the set time is too long, the interlayer diffusion of the refractive index adjusting agent proceeds and there is a risk that the refractive index difference between the high refractive index layer and the low refractive index layer will be insufficient. In addition, if the high elasticity between the high refractive index layer and the low refractive index layer occurs quickly, the step of setting may not be provided.

  The set time is adjusted by adjusting the concentration of the water-soluble binder resin and the refractive index adjusting agent (compound with photocatalytic action), and various other known gelling agents such as gelatin, pectin, agar, carrageenan, gellan gum, etc. It can adjust by adding the component of.

  The temperature of the cold air is preferably 0 to 25 ° C, and more preferably 5 to 10 ° C. Moreover, although the time for which a coating film is exposed to cold wind also depends on the conveyance speed of a coating film, it is preferable that it is 10 to 120 seconds.

  If at least one of the high refractive index layer and the low refractive index layer contains a compound having a photocatalytic action, the dielectric multilayer film of the present invention includes a high refractive index layer not containing a compound having a photocatalytic action, and / or Alternatively, a low refractive index layer not containing a compound having a photocatalytic action may be included. An example of the refractive index layer that does not contain such a compound having a photocatalytic action is a refractive index layer formed by extrusion molding of a resin.

  Examples of a method for forming a refractive index layer formed by resin extrusion include a method in which a molten resin obtained by melting a resin is extruded onto a casting drum from a multilayer extrusion die and then rapidly cooled. At this time, after extruding and cooling the molten resin, the resin sheet may be stretched. The stretching ratio of the resin can be appropriately selected according to the resin, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

  The resin is not particularly limited as long as it is a thermoplastic resin, and examples thereof include polyalkylene resins, polyester resins, polycarbonate resins, (meth) acrylic resins, amide resins, silicone resins, and fluorine resins.

  Examples of the polyalkylene resin include polyethylene (PE) and polypropylene (PP).

  Examples of the polyester resin include polyester resins having a dicarboxylic acid component and a diol component as main components. At this time, the dicarboxylic acid component includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexane. And dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-butanediol, cyclohexanedimethanol, cyclohexanediol, and the like. Among these, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene naphthalate (PEN) are preferable.

  Examples of the polycarbonate resin include a reaction product of bisphenol A or its derivative bisphenol and phosgene or phenyl dicarbonate.

  Examples of the (meth) acrylic resin include acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2- Examples include homopolymers and copolymers such as ethylhexyl, cyclohexyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide.

  Examples of the amide resin include aliphatic amide resins such as 6,6-nylon, 6-nylon, 4,6-nylon, 6,10-nylon, and 6,12-nylon; aromatic diamines such as phenylenediamine and chloride. An aromatic polyamide made of an aromatic dicarboxylic acid such as terephthaloyl or isophthaloyl chloride or a derivative thereof can be used.

  Examples of the silicone resin include resins containing a siloxane bond having an organic group such as an alkyl group or an aromatic group as a structural unit. The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iobutyl group, a sec-butyl group, and a tert-butyl group. The aromatic group is not particularly limited, and examples thereof include a phenyl group and a tolyl group. Among these, those having a methyl group and / or a phenyl group are preferable, and dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and modified products thereof are more preferable.

  Examples of the fluororesin include homopolymers or copolymers such as tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and vinylidene fluoride.

  The above-described resins may be used alone or in combination of two or more.

  In the refractive index layer formed by extrusion molding of resin, a preferable material combination of a high refractive index layer and a low refractive index layer includes PET-PEN and the like.

  As other components of the dielectric multilayer film of the present invention, conventionally known components can be appropriately used. Other components will be described in detail below.

[Base material (support)]
As the substrate (film support) used in the present invention, various resin films can be used, polyolefin films (polyethylene, polypropylene, etc.), polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, A cellulose acetate etc. can be used, Preferably it is a polyester film. Although it does not specifically limit as a polyester film (henceforth polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components. The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like. Among the polyesters having these as main constituent components, from the viewpoint of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred. Among these, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.

  The thickness of the film support used in the present invention is preferably 10 to 300 μm, particularly 20 to 150 μm. The film support of the present invention may be a laminate of two sheets. In this case, the type may be the same or different.

  The substrate can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the substrate, it is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

[Anchor layer]
When the adhesion to the lower layer of the outermost layer is not obtained, an anchor layer (primer layer) may be formed before the outermost layer is laminated. The thickness of the anchor layer is not particularly limited, but is about 0.1 to 10 μm. Preferable examples of the resin constituting the anchor layer include a polyvinyl acetal resin and an acrylic resin. Examples are shown below.

(Polyvinyl acetal resin)
The polyvinyl acetal-based resin is, for example, a resin obtained by acetalizing polyvinyl alcohol by reaction with at least one suitable aldehyde, and specifically, polyvinyl acetal, polyvinyl formal, polyvinyl butyral or partially formalized. Examples thereof include copolymer acetals such as polyvinyl butyral and polyvinyl butyral acetal containing a part. These polyvinyl acetal resins can be obtained as commercial products described in paragraph “0098” of JP 2012-242500 A, for example. Further, these polyvinyl acetal resins may contain other repeating units.

(acrylic resin)
As an acrylic resin, resin which uses the monomer described in Paragraph "0069" of Unexamined-Japanese-Patent No. 2012-139948 as a polymer structural component is mentioned, for example. These monomers can be used alone or in combination of two or more. Preferable examples include methyl methacrylate-ethyl acrylate-ammonium acrylate-acrylamide copolymer, methacrylamide-butyl acrylate-sodium acrylate-methyl methacrylate-N-methylolacrylamide copolymer, and the like. The acrylic resin can be produced and obtained as an acrylic emulsion, an acrylic aqueous solution, an acrylic dispersion, or the like.

  These resins can be used as one kind or a mixture of two or more kinds. Further, isocyanate can be used as a crosslinking agent, and organic diisocyanate compounds include aromatic diesters such as xylylene diisocyanate, isophorone diisocyanate and alicyclic diisocyanates, tolylene diisocyanate and 4,4-diphenylmethane diisocyanate. Aliphatic diisocyanates such as aromatic diisocyanates and hexamethylene diisocyanate are preferred. When used in an aqueous system, blocked isocyanate can be used, for example, product number 214 manufactured by Baxenden.

[Other functional layers]
The dielectric multilayer film of the present invention has a conductive layer, an antistatic layer, a gas barrier layer, an easy adhesion layer (adhesive layer), an antifouling layer, a deodorizing layer, a droplet layer, an easy layer for the purpose of adding further functions. Sliding layer, abrasion-resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrared absorbing layer, printing layer, fluorescent light emitting layer, hologram layer, release layer, adhesive layer, adhesive layer, high refractive index of the present invention It has one or more functional layers such as an infrared cut layer (metal layer, liquid crystal layer), colored layer (visible light absorption layer), and an intermediate film layer used for laminated glass other than the layer and the low refractive index layer. Also good.

≪Infrared shield≫
The dielectric multilayer film of the present invention can be applied to a wide range of fields. For example, as a film for window pasting such as heat ray reflective film that gives heat ray reflection effect, film for agricultural greenhouses, etc. It is mainly used for the purpose of improving weather resistance. Moreover, it is used suitably also as a dielectric multilayer film film for motor vehicles sandwiched between glass and glass, such as laminated glass for motor vehicles. In this case, the dielectric multilayer film can be sealed from the outside gas, which is preferable from the viewpoint of durability.

  In particular, the dielectric multilayer film according to the present invention is suitably used for a member that is bonded to a substrate such as glass or a glass substitute resin directly or via an adhesive.

  Preferred examples of the substrate include a plastic substrate, a metal substrate, a ceramic substrate, and a cloth substrate, and the dielectric multilayer film of the present invention can be applied to a substrate in various forms such as a film, a plate, a sphere, a cube, and a cuboid. Can be provided. Among these, a plate-shaped ceramic substrate is preferable, and an infrared shielding body in which the dielectric multilayer film of the present invention is provided on a glass plate is more preferable. As an example of a glass plate, the float plate glass described in JISR3202: 1996 and polished plate glass are mentioned, for example, As glass thickness, 0.01-20 mm is preferable.

  As a method for providing the dielectric multilayer film of the present invention on the substrate, a method in which an adhesive layer is applied to the dielectric multilayer film as described above, and is attached to the substrate via the adhesive layer is preferably used. As a pasting method, a dry pasting method in which a film is pasted on a substrate as it is, and a water pasting method as described above can be applied, but in order to prevent air from entering between the substrate and the dielectric multilayer film. Moreover, it is more preferable to bond by the water bonding method from the viewpoint of ease of construction such as positioning of the dielectric multilayer film on the substrate.

  The infrared shield is an embodiment in which the dielectric multilayer film of the present invention is provided on at least one surface of the substrate, but the embodiment in which the dielectric multilayer film is provided on a plurality of surfaces of the substrate or the dielectric multilayer film of the present invention is provided. An aspect in which a plurality of bases are provided may be used. For example, an embodiment in which the dielectric multilayer film of the present invention is provided on both sides of the above-mentioned plate glass, an adhesive layer is coated on both sides of the dielectric multilayer film of the present invention, and the above-mentioned plate glass is provided on both sides of the dielectric multilayer film. A laminated glass-like embodiment may be used.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

<< Production of dielectric multilayer film >>
(Preparation of coating liquid L1 for low refractive index layer)
430 parts of a 10% by weight aqueous solution of colloidal silica (Snowtex OXS, manufactured by Nissan Chemical Co., Ltd.), 150 parts of a 3% by weight aqueous solution of boric acid, 85 parts of water, polyvinyl alcohol (JP-45, manufactured by Nihon Vinegar Poval, degree of polymerization 4500) , Saponification degree 88 mol%) 4 parts by weight aqueous solution 300 parts and surfactant 5% by weight aqueous solution (Softazoline LSB-R, manufactured by Kawaken Fine Chemical Co., Ltd.) 3 parts in order at 45 ° C., and finished with pure water to 1000 parts A coating solution L1 for a low refractive index layer was prepared.

(Preparation of coating liquid H1 for high refractive index layer)
30 L of an aqueous sodium hydroxide solution (concentration 10 mol / L) was added with stirring to 10 L (liter) of an aqueous suspension (TiO ₂ concentration 100 g / L) in which titanium dioxide hydrate was suspended in water. The mixture was heated to 0 ° C. and aged for 5 hours, and then neutralized with hydrochloric acid, filtered, and washed with water. In the above reaction (treatment), titanium dioxide hydrate was obtained by thermal hydrolysis of an aqueous titanium sulfate solution according to a known method.

The base-treated titanium compound was suspended in pure water to a TiO ₂ concentration of 20 g / L, and 0.4 mol% of citric acid was added to the amount of TiO ₂ with stirring to raise the temperature. When the liquid temperature reached 95 ° C., concentrated hydrochloric acid was added to a hydrochloric acid concentration of 30 g / L, and the mixture was stirred for 3 hours while maintaining the liquid temperature.

  When the pH and zeta potential of the obtained titanium oxide sol aqueous dispersion were measured, the pH was 1.4 and the zeta potential was +40 mV. Furthermore, when the particle size was measured by Zetasizer Nano manufactured by Malvern, the volume average particle size was 35 nm, and the monodispersity was 16%.

  1 kg of pure water was added to 1 kg of a 20.0 mass% titanium oxide sol aqueous dispersion containing rutile-type titanium oxide particles having a volume average particle diameter of 35 nm.

2 kg of pure water was added to 0.5 kg of the 10.0 mass% titanium oxide sol aqueous dispersion described above, and then heated to 90 ° C. Thereafter, 1.3 kg of an aqueous silicic acid solution having a SiO ₂ concentration of 2.0% by mass was gradually added, and then the obtained dispersion was subjected to heat treatment at 175 ° C. for 18 hours in an autoclave, and further concentrated. A sol aqueous dispersion of 20% by mass of silica-modified titanium oxide particles having a rutile structure and a coating layer of SiO ₂ was obtained.

  Subsequently, 320 parts of a 20.0% by mass sol aqueous dispersion of silica-modified titanium oxide particles, 120 parts of a 1.92% by mass aqueous solution of citric acid and 20 parts of a 10% by mass polyvinyl alcohol solution (PVA103, polymerization degree 300, saponification degree 99 mol) %, Manufactured by Kuraray Co., Ltd.), 100 parts of a 3% by weight aqueous solution of boric acid, 350 parts of a 4% by weight polyvinyl alcohol solution (manufactured by Kuraray Co., Ltd., PVA-124, polymerization degree 2400, saponification degree 88 mol%), and surfactant 1 part of a 5% by mass solution (SOFTAZOLINE LSB-R, manufactured by Kawaken Fine Chemical Co., Ltd.) was sequentially added at 45 ° C., and finished with 1000 parts of pure water to prepare a coating solution H1 for a high refractive index layer.

(Preparation of hard coat layer coating solution 1)
ZnO.Sb ₂ O ₅ (Sernax (registered trademark) CX-Z410K, zinc antimonate, manufactured by Nissan Chemical Co., Ltd.) 55 mass% as an infrared absorber, purple light UV-7600B (Nippon Gosei Co., Ltd.) as an ultraviolet curable resin Chemical Co., Ltd., UV curable urethane acrylate resin) 12.1% by mass and Beam Set (registered trademark) 575 (Arakawa Chemical Industries, Ltd., urethane acrylate) 5.2% by mass, 4-methyl-2 as a solvent -26.9% by weight of pentanone was added. Furthermore, 0.1% by mass of a fluorosurfactant (Furgent 650A, manufactured by Neos Co., Ltd.) and 0.7% by mass of a photopolymerization initiator (Irgacure 184, manufactured by BASF Japan Ltd.) are added and stirred for 30 minutes. Then, a hard coat layer coating solution 1 was prepared.

(Preparation of hard coat layer coating solution 2)
In the preparation of the coating liquid 1 for hard coat, 2,4,6-tris (biphenylyl) -1,3,5-triazine as an ultraviolet absorber (in the general formula (1), R ₁ , R ₃ , R ₅ is a phenyl group, R ₂ , R ₄ and R ₆ are each a hydrogen atom, k = m = p = 1, l = n = q = 4, R ₁ , R ₃ , A compound in which the phenyl group of R ₅ is substituted at the 4-position with respect to triazine) In the same manner as in the hard coat coating solution 1, except that 0.1% by mass was added. 2 was prepared.

(Preparation of coating solution 3 for hard coat layer)
In the preparation of the coating liquid 1 for hard coat, the hard coat described above was added except that 0.1% by mass of an ultraviolet absorber (Tinubin 477, manufactured by BASF Japan Ltd., hydroxyphenyltriazine-based ultraviolet absorber) was further added. Hard coating solution 3 was prepared in the same manner as coating solution 1.
(Preparation of coating solution 4 for hard coat layer)
In the preparation of the hard coat coating solution 1, except for addition of 0.1% by mass of an ultraviolet absorber (Tinubin 234, manufactured by BASF Japan Ltd., benzotriazole ultraviolet absorber), In the same manner as the coating solution 1, a coating solution 4 for hard coat was prepared.

(Preparation of hard coat layer coating solution 5)
A hard coat coating solution 5 was prepared in the same manner as the hard coat coating solution 3 except that no infrared absorber was added in the preparation of the hard coat coating solution 3.

(Preparation of hard coat layer coating solution 6)
In the preparation of the coating liquid 1 for hard coat, an ultraviolet curable resin was used as a polyol acrylate resin (dipentaerythritol hexaacrylate 45% by mass, trimethylolpropane triacrylate 35% by mass, lauryl acrylate 5% by mass, triethylene glycol diacrylate. A hard coat coating solution 5 was prepared in the same manner as in the hard coat coating solution 1 except that the polymerization rate was changed to 15% by mass.

(Preparation of coating solution 1 for adhesive layer)
Adhesive (Cooponyl N-2147, manufactured by Nippon Synthetic Chemical Co., Ltd.) 100% by mass, curing agent (Coronate L-55E, manufactured by Nippon Polyurethane Industry Co., Ltd.) 5% by mass, UV absorber (Tinubin 477, manufactured by BASF Japan Ltd.) Hydroxyphenyltriazine UV absorber) 3.2% by mass and 121.7% by mass of ethyl acetate as a solvent were added and stirred for 30 minutes to prepare a coating solution 1 for an adhesive layer.

(Preparation of coating solution 2 for adhesive layer)
In the preparation of the coating liquid 1 for the adhesive layer, the ultraviolet absorber was changed, and except that tinuvin 1159 (manufactured by BASF Japan Ltd., hydroxyphenyltriazine ultraviolet absorber) was added instead of tinuvin 477, An adhesive layer coating solution 2 was prepared in the same manner as the adhesive layer coating solution 1.

(Preparation of coating solution 3 for adhesive layer)
In the preparation of the coating solution 1 for the adhesive layer, the ultraviolet absorber was changed, and 2.8% by mass of 2,4,6-tris (biphenylyl) -1,3,5-triazine was added instead of tinuvin 477. In the same manner as in the adhesive layer coating solution 1, an adhesive layer coating solution 3 was prepared.

(Preparation of coating solution 4 for adhesive layer)
In the preparation of the coating solution 1 for the adhesive layer, the adhesive was changed except that the ultraviolet absorber was changed and tinuvin 326 (manufactured by BASF Japan Ltd., benzotriazole ultraviolet absorber) was added instead of tinuvin 477. In the same manner as the layer coating solution 1, an adhesive layer coating solution 4 was prepared.

(Preparation of coating solution 5 for adhesive layer)
In the preparation of the coating liquid 1 for the adhesive layer, the ultraviolet absorber was changed, except that Sumisorb (registered trademark) 130 (manufactured by Sumitomo Chemical Co., Ltd., benzophenone-based ultraviolet absorber) was added instead of Tinuvin 477. In the same manner as in the pressure-sensitive adhesive layer coating solution 1, a pressure-sensitive adhesive layer coating solution 5 was prepared.

Example 1
Thickness heated to 45 ° C. while maintaining the low refractive index layer coating solution L1 and the high refractive index layer coating solution H1 obtained above at 45 ° C. On top of a 50 μm polyethylene terephthalate film (Toyobo A4300: double-sided easy-adhesion layer, length 200 m × width 210 mm, refractive index: 1.58), the lowermost layer and the uppermost layer are low-refractive index layers; Furthermore, a total of nine layers were simultaneously applied so that the low refractive index layer had a thickness of 150 nm and the high refractive index layer had a thickness of 130 nm. In addition, the confirmation of the mixed region (mixed layer) between the layers and the measurement (confirmation) of the film thickness are performed by cutting the laminated film (dielectric multilayer film sample) and cutting the cut surface with an XPS surface analyzer. ₂ ) and the abundance of the low refractive index material (SiO ₂ ) were measured, and it was confirmed that the film thickness of each layer described above was secured.

  Immediately after application, 5 ° C. cold air was blown and set. At this time, even if the surface was touched with a finger, the time until the finger was lost (set time) was 5 minutes.

  After completion of the setting, warm air of 80 ° C. was blown and dried to prepare a dielectric multilayer unit consisting of nine layers. The refractive index of the high refractive index layer formed as described above was 1.95, and the refractive index of the low refractive index layer was 1.45.

Next, using a gravure coater, the hard coat layer coating solution 1 prepared above is applied to the opposite surface of the dielectric multilayer film unit, dried at a drying section temperature of 90 ° C., and then irradiated with an ultraviolet lamp. Was 1000 mW / cm ² , the irradiation amount was 0.3 J / cm ² , the coating layer was cured, and the outermost layer (hard coat layer) was formed so that the dry film thickness was 6 μm.

Further, the adhesive layer coating solution 1 prepared above was applied to a separator (NS-23MA: manufactured by Nakamoto Pax Co., Ltd.) using a die coater, dried at 80 ° C., and then adhered to the dielectric multilayer film unit surface. The layer surfaces were bonded to each other to produce a dielectric multilayer film 1 having an in-applied configuration (that is, a configuration applied to the indoor side of a window glass or the like). The thickness of the adhesive layer of the dielectric multilayer film 1 was 10 μm. At this time, the amount of tinuvin 477 which is an ultraviolet absorber in the adhesive layer was 600 mg / m ² .

(Example 2)
A dielectric multilayer film 2 was produced in the same manner as in Example 1 except that in Example 1 above, the thickness of the adhesive layer was changed to 35 μm. At this time, the amount of tinuvin 477 which is an ultraviolet absorber in the adhesive layer was 2100 mg / m ² .

(Example 3)
A dielectric multilayer film 3 was produced in the same manner as in Example 1 except that the film thickness of the adhesive layer was changed to 25 μm in Example 1. At this time, the amount of tinuvin 477, which is an ultraviolet absorber in the adhesive layer, was 1500 mg / m ² .

Example 4
A dielectric multilayer film 4 was produced in the same manner as in Example 1 except that in Example 1 above, the thickness of the adhesive layer was changed to 3 μm. At this time, the amount of tinuvin 477 which is an ultraviolet absorber in the adhesive layer was 180 mg / m ² .

(Comparative Example 1)
A comparative dielectric multilayer film 1 was produced in the same manner as in Example 1 except that in Example 1 above, the thickness of the adhesive layer was changed to 1 μm. At this time, the amount of tinuvin 477 which is an ultraviolet absorber in the adhesive layer was 60 mg / m ² .

(Example 5)
In Example 1 above, when forming the adhesive layer, Example 1 was used except that the adhesive layer coating liquid 2 was used instead of the adhesive layer coating liquid 1 and the thickness of the adhesive layer was changed to 10 μm. In the same manner, a dielectric multilayer film 5 was produced. At this time, the amount of tinuvin 1159 which is an ultraviolet absorber in the adhesive layer was 750 mg / m ² .

(Example 6)
In Example 1 above, when forming the adhesive layer, Example 1 was used except that the adhesive layer coating solution 3 was used instead of the adhesive layer coating solution 1 and the thickness of the adhesive layer was changed to 10 μm. In the same manner, a dielectric multilayer film 6 was produced. At this time, the amount of biphenylyltriazine, which is an ultraviolet absorber in the adhesive layer, was 654 mg / m ² .

(Comparative Example 2)
In Example 1 above, when forming the adhesive layer, Example 1 was used except that the adhesive layer coating liquid 4 was used instead of the adhesive layer coating liquid 1 and the thickness of the adhesive layer was changed to 10 μm. Comparative dielectric multilayer film 2 was prepared in the same manner as described above. At this time, the amount of tinuvin 326 which is an ultraviolet absorber in the adhesive layer was 654 mg / m ² .

(Comparative Example 3)
In Example 1 above, when forming the adhesive layer, Example 1 was used except that the adhesive layer coating solution 5 was used instead of the adhesive layer coating solution 1 and the thickness of the adhesive layer was changed to 10 μm. Comparative dielectric multilayer film 3 was prepared in the same manner as described above. At this time, the amount of Sumisorb 130 as an ultraviolet absorber in the adhesive layer was 654 mg / m ² .

(Example 7)
In Example 1, the outermost layer (hard coat layer) was formed in the same manner as in Example 1 except that the hard coat layer coating solution 2 was used instead of the hard coat layer coating solution 1. Thus, a dielectric multilayer film 7 was produced. At this time, the amount of tinuvin 477, which is an ultraviolet absorber in the adhesive layer, was the same as in Example 1. Further, the amount of biphenylyltriazine, which is an ultraviolet absorber in the hard coat layer, was 230 mg / m ² .

(Example 8)
In Example 1, the outermost layer (hard coat layer) was formed in the same manner as in Example 1 except that the hard coat layer coating solution 3 was used instead of the hard coat layer coating solution 1. Thus, a dielectric multilayer film 8 was produced. At this time, the amount of tinuvin 477, which is an ultraviolet absorber in the adhesive layer, was the same as in Example 1. The amount of tinuvin 477, which is an ultraviolet absorber in the hard coat layer, was 200 mg / m ² .

Example 9
In Example 1, the outermost layer (hard coat layer) was formed in the same manner as in Example 1 except that the hard coat layer coating solution 4 was used instead of the hard coat layer coating solution 1. Thus, a dielectric multilayer film 9 was produced. At this time, the amount of tinuvin 477, which is an ultraviolet absorber in the adhesive layer, was the same as in Example 1. The amount of tinuvin 234, which is an ultraviolet absorber in the hard coat layer, was 230 mg / m ² .

(Example 10)
In Example 1 above, when forming the outermost layer (hard coat layer), the hard coat layer coating solution 5 was used instead of the hard coat layer coating solution 1, and the thickness of the outermost layer was changed to 3 μm. Thus, a dielectric multilayer film 10 was produced in the same manner as in Example 1 above. At this time, the amount of tinuvin 477, which is an ultraviolet absorber in the adhesive layer, was the same as in Example 1. The amount of tinuvin 477, which is an ultraviolet absorber in the hard coat layer, was 100 mg / m ² .

(Example 11)
In Example 1, the outermost layer (hard coat layer) was formed in the same manner as in Example 1 except that the hard coat layer coating solution 6 was used instead of the hard coat layer coating solution 1. Thus, a dielectric multilayer film 14 was produced. At this time, the amount of tinuvin 477, which is an ultraviolet absorber in the adhesive layer, was the same as in Example 1. The amount of tinuvin 477, which is an ultraviolet absorber in the hard coat layer, was 230 mg / m ² .

  The structures of the dielectric multilayer films according to the above examples and comparative examples are shown in Tables 2 and 3 below.

≪Evaluation≫
Unless otherwise specified, the following physical properties were measured at a temperature of 23 ° C. ± 2 ° C. and a relative humidity (50 ± 5)%.

(Measurement of transmittance)
The transmittance of the adhesive layer of the dielectric multilayer film according to each example and comparative example was measured as follows. In addition, the value measured by the following method is employ | adopted for the value of the transmittance | permeability T1 _(UV) , T2 _(UV) , T1 _(390), and T2 ₍₃₉₀₎ of the adhesion layer in this specification. Shall.

  An adhesive layer is applied to the separator in the same manner as in the production of the dielectric multilayer film, and the surface of the adhesive layer is attached to a 3 mm-thick float glass, and the temperature is 23 ° C. and the humidity is 50% RH. After leaving for a minute, the separator was removed to obtain a test piece.

In accordance with JIS A5759: 2008, using a spectrophotometer “U-4100” manufactured by Shimadzu Corporation, the transmittance of the test piece was measured from 280 nm to 410 nm and multiplied by the solar weight coefficient. _Was calculated as the initial ultraviolet transmittance T _{1 (UV)} (%). Moreover, the transmittance | permeability in 390 nm was set to T1 ₍₃₉₀₎ (%) about the said test piece.

Next, using a sunshine weather meter (S80HB, manufactured by Suga Test Instruments Co., Ltd.), light having an irradiance of 255 W / m ² from the glass surface side (sunshine carbon arc (ie, , Carbon arc lamp) and a wavelength of 300 to 700 nm) were continuously irradiated for 2000 hours to perform accelerated deterioration treatment. After the accelerated deterioration treatment, the transmittance was measured in the same manner as described above, and the ultraviolet transmittance T _{2 (UV)} (%) was measured. Moreover, the transmittance | permeability in 390 nm was set to T2 ₍₃₉₀₎ (%) about the said test piece.

From the above-obtained T _{1 (UV)} , T _{1 (390)} , T _{2 (UV)} , and T _{2 (390)} , using the above equations (1) and (2), the respective rates of change are calculated. Calculated.

  The calculated values are shown in Table 2 and Table 3, respectively.

(Flexibility evaluation 1)
The dielectric multilayer film according to each of the examples and comparative examples was cut into a 50 mm width × 150 mm length and subjected to the following accelerated deterioration treatment. The accelerated deterioration treatment uses a sunshine weather meter (S80HB, manufactured by Suga Test Instruments Co., Ltd.), and the irradiance is 255 W / m ² from the separator side (that is, the adhesive layer side) in an environment of temperature 40 ° C. and humidity 50% RH. No. 1 (Sunshine carbon arc (i.e., carbon arc lamp), 300 to 700 nm) was continuously irradiated for 2000 hours. After the accelerated deterioration treatment, both ends of the film are fixed to the plate surfaces facing each other with a vertical distance of 20 mm using a jig, and the upper surface (upper plate surface) is translated by 50 mm in width and reciprocated 1000 times. The film appearance was evaluated. The film appearance was evaluated according to the following criteria. The evaluation results are shown in Table 2 and Table 3, respectively.

A: No change B: Almost no cracks are visually observed in the film (1-5)
○ Δ: Slight cracks can be visually confirmed on the film (6 to 10)
(Triangle | delta): A crack can be visually confirmed in a film (11-30 pieces).
X: Many cracks can be visually confirmed in the film (more than 30).

(Flexibility evaluation 2)
In the above flexibility evaluation 1, evaluation was performed in the same manner as in the above flexibility evaluation 1 except that light irradiation from the sunshine weather meter was performed not from the separator side but from the outermost layer (hard coat layer) side. Note that the evaluation criteria are the same as in the flexibility evaluation 1.

(Adhesion evaluation 1)
The film was subjected to accelerated deterioration treatment under the same conditions as in Flexibility Evaluation 1, and the adhesion was evaluated as follows for the film subjected to the treatment.

  The evaluation of the adhesion of each dielectric multilayer film unit was performed according to the cross-cut test method described in 5.6 (2004 edition) of JIS K 5600.

  The separator of the dielectric multilayer film was peeled off, and 100 grid cuts of 1 mm square reaching the substrate with a cutter knife were applied to the adhesive layer using a cutter guide with an interval of 1 mm. A cellophane adhesive tape ("CT405AP-18" manufactured by Nichiban Co., Ltd .; 18mm width) is attached to the cut surface, rubbed with an eraser from the top to completely adhere the tape, and then peeled off in the vertical direction to form a dielectric multilayer film How many film constituent layers remained on the substrate surface was measured for 100 grids. In addition, it evaluated by the following references | standards about the number of the parts (cells) which peeled. The evaluation results are shown in Table 2 and Table 3, respectively.

10: 0 peeled cells 8: 1 or more and less than 5 cells 6: 5 or more but less than 15 cells 4 4: 15 or more cells but less than 25 cells 2 The peeled squares are 25 or more and less than 45 0: The peeled squares are 45 or more and 100 or less.

(Adhesion evaluation 2)
In the adhesion evaluation 1, evaluation was performed in the same manner as in the adhesion evaluation 1 except that the light irradiation from the sunshine weather meter was performed not from the separator side but from the outermost layer (hard coat layer) side. Note that the evaluation criteria are the same as in the adhesion evaluation 1.

  As is clear from the evaluation results shown in the table, it can be seen that the various characteristics of the examples according to the present invention are superior to the comparative examples. And when the ultraviolet transmittance change of 280-410 nm in an adhesion layer is 5% or less, it was shown that dielectric multilayer film film adhesiveness and flexibility are improved remarkably. Furthermore, the ultraviolet absorber contained in the adhesive layer is preferably a hydroxyphenyl triazine compound and a biphenylyl compound, but in comparison with Examples 1 and 6, a biphenylyl triazine compound was used (Examples). 6) gave better results.

  On the other hand, with the ultraviolet absorbers conventionally included in the adhesive layer, the predetermined ultraviolet transmittance and the rate of change of the transmittance cannot be obtained, and the adhesion and flexibility after the accelerated deterioration treatment are reduced. Obtained.

  Furthermore, when it has the outermost layer containing a specific ultraviolet absorber, the dielectric multilayer film exhibited good flexibility and adhesion even after accelerated deterioration treatment in which light irradiation was performed from the outermost layer side. Therefore, a dielectric multilayer film having a dielectric multilayer film containing a compound having a photocatalytic action is a catalyst of a compound having a photocatalytic action particularly when the adhesive layer and the outermost layer contain a specific ultraviolet absorber. It is considered that the effect of suppressing the action is high and the adhesion and flexibility of the film are improved.

  Furthermore, it is considered that by further including an infrared absorber in the outermost layer, it is possible to obtain a dielectric multilayer film that is further suppressed in deterioration of the dielectric multilayer film and is excellent in adhesion and flexibility.

Claims (8)

A dielectric multilayer film in which at least one low refractive index layer and high refractive index layer are laminated;
A dielectric multilayer film having an adhesive layer,
At least one of the high refractive index layer and the low refractive index layer contains a water-soluble polymer and a compound having a photocatalytic action,
The adhesive layer is the initial light transmittance _{T 1 (UV)} is 30% or less at a wavelength 280～410Nm, the relative initial light transmittance _{T 1 (UV),} temperature 40 ° C., under an environment of a humidity of 50% RH The rate of change of the light transmittance T _{2 (UV)} at a wavelength of 280 to 410 nm after irradiating light from the adhesive layer side for 2000 hours continuously with a carbon arc lamp having an irradiance of 255 W / m ² is 5% or less. A dielectric multilayer film. The adhesive layer is continuous for 2000 hours with a carbon arc lamp having an irradiance of 255 W / m ^{2 in} an environment of a temperature of 40 ° C. and a humidity of 50% RH with respect to an initial light transmittance T _{1 (390) at} a wavelength of 390 nm. The dielectric multilayer film according to claim 1, wherein a change rate of light transmittance T2 ₍₃₉₀₎ at a wavelength of 390 nm after being irradiated with light from the adhesive layer side is 5% or less.   The dielectric multilayer film according to claim 1 or 2, wherein the adhesive layer has a thickness of 3 to 30 µm.   The adhesive layer is a group consisting of 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof. The dielectric multilayer film according to any one of claims 1 to 3, comprising at least one compound selected from the group consisting of:   The dielectric multilayer film according to claim 1, wherein the compound having a photocatalytic action includes titanium oxide. The adhesive layer further has an outermost layer disposed on the opposite side through the dielectric multilayer film,
The outermost layer is composed of 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine, 2,4,6-tris (biphenylyl) -1,3,5-triazine and derivatives thereof. The dielectric multilayer film according to any one of claims 1 to 5, comprising at least one compound selected from the group consisting of:   The dielectric multilayer film according to claim 6, wherein the outermost layer includes an ultraviolet curable urethane acrylate resin.   The dielectric multilayer film according to claim 6 or 7, wherein the outermost layer includes an infrared absorber.