WO2019111700A1 - Infrared transmitting film forming material, infrared transmitting film and method for forming same, protective plate for display devices, and display device - Google Patents

Abstract

The purpose of the present invention is to provide: an infrared transmitting film forming material which is capable of forming an infrared transmitting film that has excellent appearance and excellent adhesion to a frame part that contains an inorganic black pigment; an infrared transmitting film which has excellent appearance and excellent adhesion to a frame part that contains an inorganic black pigment; a method for forming this infrared transmitting film; a protective plate for display devices, which comprises this infrared transmitting film; and a display device which is provided with this protective plate for display devices. The present invention is an infrared transmitting film forming material for forming an infrared transmitting film that is provided on an opening for infrared communication, which is formed in a frame part of a protective plate for display devices, said frame part containing an inorganic black pigment. This infrared transmitting film forming material contains at least one of a resin and a first compound (excluding a compound that contains at least one element selected from among phosphorus, sulfur, aluminum, titanium and zirconium) that has two or more polymerizable groups in each molecule, and a second compound that contains at least one element selected from among phosphorus, sulfur, aluminum, titanium and zirconium.

Description

Infrared ray transmitting film forming material, infrared ray transmitting film and method for forming the same, protective plate for display device, and display device

The present invention relates to an infrared ray transmitting film forming material, an infrared ray transmitting film and a method for forming the same, a protective plate for a display device, and a display device.

It is general to adopt a structure in which a protective plate such as a cover glass is provided on the outermost surface of display devices such as mobile phones and portable information terminals (see Patent Document 1). The protective plate is provided with a frame portion (bezel) made of a material having a high light shielding property for hiding the wiring and the like in the peripheral portion. In addition, some devices such as mobile phones are equipped with an infrared communication unit for performing face authentication, communication with other mobile phones, etc. In such a case, infrared communication is performed in part of the frame portion. An infrared transmission window is provided to perform the

If the infrared transmitting window provided in the frame portion is noticeable, it may not be preferable from the aspect of the appearance. Therefore, it has been practiced to form an infrared transmitting film of the same color as that of the frame portion in a region (an opening for infrared communication in the frame portion) provided with an infrared transmitting window. By providing such an infrared ray transmitting film, it is supposed that it can be synchronized with the color of the peripheral frame portion while maintaining the infrared ray transmitting property. The formation of the infrared transmitting film is performed, for example, by vapor deposition. On the other hand, resin materials, such as a photosensitive resin composition, are also used for formation of the infrared rays permeable film used for a solid-state image sensor etc. (refer patent document 2).

JP, 2009-69321, A JP, 2015-68945, A

It is also conceivable to perform the formation of the infrared ray transmitting film on the opening provided in the frame portion using the above resin material from the viewpoint of productivity and the like. On the other hand, some frame parts have black, white and the like, but the black frame parts are often colored with an inorganic black pigment such as carbon black. However, the inventors have found that, when the frame portion contains the inorganic black pigment, the adhesion between the infrared ray transmitting film formed using the above-mentioned conventional resin material and the frame portion becomes insufficient. did. In addition, in films | membranes, such as an infrared rays permeable film, peeling arises from an edge part normally. For this reason, it can be said that it is important to improve the adhesion between the infrared ray transmitting film and the frame portion in order to make it difficult to cause peeling of the infrared ray transmitting film provided in the opening of the frame portion for a long time. Further, regarding the appearance of the protective plate for a display device, the difference in color with the black frame portion is not sufficiently eliminated in the infrared transmitting film formed of the resin material to which the coloring agent is simply added.

This invention is made based on the above situations, The objective is the infrared rays transmission which can form the infrared rays permeable film which is excellent in adhesiveness with the frame part containing an inorganic black pigment, and an external appearance. A film forming material, an infrared ray transmitting film excellent in adhesion to a frame portion containing an inorganic black pigment, and appearance, a method of forming such an infrared ray transmitting film, a protective plate for a display device having such an infrared ray transmitting film, It is providing a display provided with this protection plate for display.

Invention made in order to solve the above-mentioned subject forms infrared rays permeable film formation which forms an infrared rays permeable film provided in an opening for infrared rays communication formed in a frame part containing an inorganic black pigment with which a protection plate for display devices is provided. And at least one of a resin and a first compound having two or more polymerizable groups in one molecule (excluding a compound containing at least one element selected from phosphorus, sulfur, aluminum, titanium and zirconium), and phosphorus And a second compound containing at least one element selected from sulfur, aluminum, titanium and zirconium.

Another invention made in order to solve the above-mentioned subject is an infrared rays permeable film formed from the infrared rays permeable film formation material concerned.

Yet another invention made for solving the above problems is a step of applying the infrared ray transmitting film forming material to an opening for infrared communication formed in a frame portion containing an inorganic black pigment, and the above coating It is a formation method of the infrared rays permeable film provided with the process of exposing the coating film formed by a process process, and the process of heating the coating film after the said exposure process.

Another invention made in order to solve the above-mentioned subject is an infrared rays permeable film formed by the formation method of the infrared ray permeable film concerned.

Yet another invention made to solve the above problems comprises a transparent substrate and a frame portion disposed on the periphery of one surface of the transparent substrate and containing an inorganic black pigment, and the frame portion is provided A protective plate for a display device in which an opening for infrared communication is formed, comprising: an infrared transmitting film provided in a region on the one surface of the transparent substrate in which the opening is formed; It is a protective plate for a display comprising at least one element selected from the group consisting of phosphorus, sulfur, aluminum, titanium and zirconium.

Another invention made in order to solve the above-mentioned subject is a display provided with the protective plate for the display.

According to the present invention, adhesion to the frame portion containing the inorganic black pigment, and infrared ray transmitting film forming material capable of forming an infrared ray transmitting film excellent in appearance, adhesion to the frame portion containing the inorganic black pigment And an infrared transmitting film excellent in appearance, a method of forming such an infrared transmitting film, a protective plate for a display device having such an infrared transparent film, and a display device comprising the protective plate for the display .

It is a top view which shows the structure of the protection plate for display apparatuses which concerns on one Embodiment of this invention. It is sectional drawing in A-A 'of FIG.

<Protective plate for display device>
A protective plate for a display device according to an embodiment of the present invention comprises a transparent substrate and a frame portion disposed on the periphery of one surface of the transparent substrate and containing an inorganic black pigment, and the frame portion is provided It is a protective plate for a display device in which an opening for infrared communication is formed. The display device protective plate has an infrared ray transmitting film provided in a region where an opening is formed on one surface of the transparent substrate. The infrared ray transmitting film contains at least one element (hereinafter also referred to as "element (X)") selected from phosphorus, sulfur, aluminum, titanium and zirconium.

The protective plate for a display device of FIGS. 1 and 2 according to an embodiment of the present invention includes a transparent substrate 100, a frame portion 110 disposed on the periphery of one surface of the transparent substrate 100, and an infrared ray transmitting film And 120 are provided. The frame portion 110 is provided with an opening 130 for infrared communication (see FIG. 2). An infrared transmitting film 120 is provided in the opening 130. That is, the infrared transmitting film 120 is laminated on the surface of the transparent substrate 100 in which the opening 130 for transmitting the infrared light is formed. The infrared transmitting film 120 contains an element (X).

In the display device protective plate, the infrared ray transmitting film 120 contains the specific element (X), so that the adhesion between the infrared ray transmitting film 120 and the frame portion 110 containing the inorganic black pigment is excellent. Moreover, the infrared permeable film 120 is also excellent in light resistance. Furthermore, the infrared transmitting film 120 has good adhesion to the transparent substrate 100.

[Transparent substrate]
The transparent substrate 100 is a substrate formed of a transparent material. Examples of the transparent substrate 100 include a glass substrate, a silicon wafer, a plastic substrate, and a substrate having various metals formed on the surface thereof. As a plastic substrate, for example, a substrate mainly composed of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide and the like can be mentioned. Among these, the transparent substrate 100 is preferably a glass substrate.

The average thickness of the transparent substrate 100 is, for example, 0.1 mm or more and 1.5 mm or less.

[Frame portion]
The frame portion 110 is disposed on the periphery of one surface of the transparent substrate 100. The frame portion 110 divides a display area of a predetermined shape.

The frame portion 110 contains an inorganic black pigment. The inorganic black pigment is not particularly limited, such as carbon black, titanium black, magnetite and the like. The inorganic black pigment is dispersed in the frame portion 110. Thus, the frame portion 110 containing the inorganic black pigment is black. The content ratio of the inorganic black pigment in the frame portion 110 is, for example, 1% by mass or more and 70% by mass or less, and may be 5% by mass or more and 30% by mass or less.

The frame portion 110 usually further contains a resin as a base material. Examples of the resin contained in the frame portion 110 include acrylic resin, cycloolefin resin, polyimide, polyether, polyester resin, polyurethane resin and the like.

The frame portion 110 can be formed, for example, by applying a resin composition containing a resin and an inorganic black pigment on the surface of the transparent substrate 100 and performing heating. Alternatively, a photosensitive resin composition containing an inorganic black pigment may be coated and formed through exposure and heating. In addition, the separately formed frame portion 110 may be laminated on the surface of the transparent substrate 100.

[Aperture]
The opening (infrared ray transmitting window) 130 is a through hole provided in the frame portion 110. The opening 130 is provided for infrared communication.

The opening 130 is provided at a position facing the infrared communication unit of the display device when the display device protective plate is disposed in the display device. Examples of the planar shape of the opening 130 include a circular shape, an elliptical shape, and a rectangular shape. The size of the opening 130 is preferably 1 mm to 10 mm, more preferably 1 mm to 5 mm, as the major axis in the case of an elliptical or circular shape and the longitudinal or lateral length in the case of a rectangular shape. Preferably, 2 mm or more and 4 mm or less is more preferable.

[Infrared ray permeable membrane]
Infrared ray transmitting film 120 is provided on the surface of transparent substrate 100 in the region where opening 130 is formed. The infrared transmitting film 120 is formed to fill the area of the opening 130. That is, the infrared ray transmitting film 120 covers the area in the surface of the transparent substrate 100 in which the opening 130 is provided. In other words, the back surface (the lower surface in FIG. 2) of the infrared transmitting film 120 is in contact with the front surface of the transparent substrate 100, and the side surface of the infrared transmitting film 120 is in contact with the side surface of the frame portion 110. . The infrared ray permeable film 120 is preferably substantially black.

The infrared permeable film 120 contains an element (X). Element (X) is contained in the infrared rays permeable film 120, for example as an element which comprises the [B] compound mentioned later. Usually, the infrared ray transmitting film 120 is formed of a composition containing a resin, at least one of a compound having two or more polymerizable groups in one molecule, and a colorant, a photosensitizer, etc. in addition to the above-mentioned [B] compound. Ru. As the infrared ray transmitting film 120, one formed of an infrared ray transmitting film forming material described below can be suitably used. Moreover, as the infrared rays permeable film 120, what was obtained by the formation method of the infrared rays permeable film mentioned later can be used suitably.

[Covering layer]
It is preferable that the said display apparatus protective plate further has a coating layer laminated | stacked on an infrared rays permeable film. This covering layer is laminated, for example, on the upper surface (the surface opposite to the transparent substrate 100) of the infrared ray transmitting film 120 in FIGS. The covering layer is usually a transparent resin layer.

The refractive index of the covering layer is preferably 1.4 or less. Such a coating layer having a refractive index (optical refractive index) of 1.4 or less functions as an antireflective layer, and can reduce performance deterioration due to infrared reflection. The lower limit of the light refractive index of the covering layer may be, for example, 1.1, 1.2 or 1.3. The optical film thickness (physical film thickness × refractive index) of this covering layer (antireflection layer) is preferably 1⁄4 of the wavelength of the infrared ray used.

<Infrared permeable film forming material>
An infrared transmitting film forming material according to an embodiment of the present invention is a resin (hereinafter, also referred to as “[A1] resin”) and a first compound having two or more polymerizable groups in one molecule (hereinafter, “A2 At least one selected from the group consisting of phosphorus, sulfur, aluminum, titanium and zirconium, and at least one of the following compounds (hereinafter also referred to as “[A1] resin and [A2] compound together as“ [A] component ”) And a second compound (hereinafter, also referred to as “[B] compound”) containing the element (element (X)) of It is preferable that the said infrared rays permeable film formation material contains a [C] coloring agent and / or a [D] photosensitizer as a suitable component, and in the range which does not impair the effect of this invention, it contains other arbitrary components. May be The said infrared rays permeable film formation material is a material which forms the infrared rays permeable film 120 provided in the opening part 130 for infrared rays communication formed in the frame part 110 containing the inorganic black pigment with which the protection plate for display apparatuses is equipped. Each component will be described below.

<[A] component>
[A] component is at least one of [A1] resin and [A2] compound.

[[A1] resin]
[A1] The resin is a transparent or opaque resin. [A1] The resin may have two or more polymerizable groups in one molecule. [A1] The weight average molecular weight (Mw) of the resin is preferably, for example, in the range of 3,000 or more and 500,000 or less. The glass transition temperature (Tg) of the resin [A1] so as to ensure the thermal stability and solvent resistance of the infrared ray permeable film, and to exhibit resistance in a heating production process of 100 ° C. or higher applied to a display device or the like. As a minimum, 110 ° C is preferred and 120 ° C is more preferred. As an upper limit of the above-mentioned Tg, 380 ° C is preferred, 370 ° C is more preferred, and 360 ° C is still more preferred.

[A1] As the resin, for example, cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin Polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester Examples thereof include system-curable resins, silsesquioxane-based UV-curable resins, polystyrene resins, and phenol resins. These resins can be used alone or in combination of two or more. [A1] As the resin, the following resins are preferable.

(Cyclic olefin resin)
As cyclic olefin resin, a resin obtained from at least one of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ), and further hydrogenating the resin The resin obtained by

In the above formula (X ₀ ), R ^x1 to R ^x4 are each independently an atom or a group selected from the following (i) to (viii). Each of k ^x , m ^x and p ^x is independently 0 or a positive integer.
(I) a hydrogen atom (ii) a halogen atom (iii) a trialkylsilyl group (iv) an oxygen atom, a sulfur atom, a nitrogen atom or a substituent containing a silicon atom or a substituted hydrocarbon having 1 to 30 carbon atoms Group (v) substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi) polar group (excluding (iv))
(Vii) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^x1 to R ^{x4 which} are not involved in the bond are each independently represented by the above (i) Represents an atom or a group selected from (vi).
(Viii) R ^x1 and R ^x2 or R ^x3 and R ^x4 each represent a monocyclic or polycyclic hydrocarbon ring or heterocycle formed by bonding to each other, and R ^x1 to R ^{x4 which} are not involved in the bonding are And each independently represents an atom or a group selected from the above (i) to (vi), or R ^x2 and R ^x3 are a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding to each other And R ^x1 to R ^x4 which do not participate in the bond respectively independently represent an atom or a group selected from the above (i) to (vi).

In the formula (Y 0), R y1 and R y2 are each independently represent an atom or a group selected from the above (i) ~ (vi), represents the following (ix), k y and p y Each independently represents 0 or a positive integer.
(Ix) R y1 and R y2 represent a monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring formed by bonding to each other.

(Aromatic polyether resin)
As the aromatic polyether resin, a resin having at least one of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) is preferable.

In the above formula (1), R ¹ to R ⁴ are each independently a monovalent organic group having 1 to 12 carbon atoms. Each of a to d is independently an integer of 0 to 4.

In the above formula (2), R ¹ to R ⁴ and a to d are each independently synonymous with R ¹ to R ⁴ and a to d of the above formula (1). Y is a single bond, -SO ₂ -or -CO-. R ⁷ and R ⁸ are each independently a halogen atom, a nitro group or a monovalent organic group having 1 to 12 carbon atoms. g and h each independently represent an integer of 0 to 4; m is 0 or 1; However, when m is 0, R ⁷ is not a cyano group. In the present specification, the organic group means a group containing a carbon atom.

The aromatic polyether resin preferably further has at least one of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In the above formula (3), R ⁵ and R ⁶ are each independently a monovalent organic group having 1 to 12 carbon atoms. Z is a single bond, -O-, -S-, -SO _2- , -CO-, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms. e and f are each independently an integer of 0 to 4. n is 0 or 1;

In the above formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h of the above formula (2) . R ⁵ , R ⁶ , Z, n, e and f each independently have the same meaning as R ⁵ , R ⁶ , Z, n, e and f in the above formula (3).

(Polyimide resin)
The polyimide resin is not particularly limited as long as it is a polymer compound having an imide bond in the repeating unit. The polyimide resin can be synthesized, for example, by the method described in JP-A-2006-199945, JP-A-2008-163107, and the like.

(Fluorene polycarbonate resin)
It will not specifically limit, if it is polycarbonate resin containing a fluorene site | part as fluorene polycarbonate-type resin. The fluorene polycarbonate resin can be synthesized, for example, by the method described in JP-A-2008-163194.

(Fluorene polyester resin)
The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. The fluorene polyester resin can be synthesized, for example, by the methods described in JP-A-2010-285505, JP-A-2011-197450, and the like.

(Fluorinated aromatic polymer resin)
The fluorinated aromatic polymer-based resin is a repeating unit containing an aromatic ring having at least one fluorine atom and at least one bond selected from an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond It is not particularly limited as long as it is a polymer having The fluorinated aromatic polymer resin can be synthesized, for example, by the method described in JP-A-2008-181121.

((Modified) acrylic resin)
(Modified) As an acrylic resin, it is an acrylic resin which is a polymer of one or two or more kinds of (meth) acrylic esters, and a copolymer of (meth) acrylic esters and other monomers A modified acrylic resin etc. can be mentioned. The modified acrylic resin may be a modified acrylic resin obtained by polymerization. The (modified) acrylic resin may have a polymerizable group such as an epoxy group, a vinyl group or a (meth) acryloyl group in the side chain. Examples of such (modified) acrylic resins include (modified) acrylic resins containing glycidyl (meth) acrylate as a monomer.

(Epoxy resin)
Examples of the epoxy resin include phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol epoxy resin, trisphenol epoxy resin, tetraphenol epoxy resin, phenol-xylylene epoxy resin, naphthol-xylylene epoxy resin, phenol And-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like.

(Commercial item)
[A1] As a commercial product of a resin, as a commercial product of cyclic olefin resin, for example, “ARTON” of JSR, “Zeonor” of Zeon Corporation, “APEL” of Mitsui Chemicals, and “TOPAS” of Polyplastics Etc. are mentioned. As a commercial item of polyether sulfone type resin, "Sumika excel PES" of Sumitomo Chemical, etc. are mentioned, for example. As a commercial item of polyimide system resin, "Neoprim L" of Mitsubishi Gas Chemical Company, etc. are mentioned, for example. As a commercial item of polycarbonate system resin, Teijin's "Pure ace" etc. are mentioned, for example. Examples of commercially available products of fluorene polycarbonate-based resins include “Iupizeta EP-5000” manufactured by Mitsubishi Gas Chemical Company. As a commercial item of fluorene polyester resin, "OKP4HT" of Osaka Gas Chemicals Co., Ltd. etc. are mentioned, for example. Examples of commercial products of (modified) acrylic resins include “Acryuvear” manufactured by Nippon Shokubai Co., Ltd., “Merproof G-0250SP” manufactured by NOF Corporation, and the like. As a commercial item of silsesquioxane type UV curing resin, "Silplus" of Nippon Steel Chemical Co., Ltd. etc. are mentioned, for example.

Among these, as the resin [A1], cyclic olefin resins and (modified) acrylic resins are preferable. Moreover, as [A1] resin, resin which has polymeric groups, such as a cyclic ether group, a vinyl group, a (meth) acryloyl group, is also preferable.

As a minimum of content of [A1] resin to a total of 100 mass parts of [A] ingredient and a [B] compound, 5 mass parts is preferred, 10 mass parts is more preferred, 20 mass parts is still more preferred, and 30 mass parts Is even more preferred. As a maximum of the above-mentioned content, 90 mass parts is preferred, 70 mass parts is more preferred, and 55 mass parts is still more preferred.

<[A2] Compound>
[A2] The compound is a compound having two or more polymerizable groups in one molecule (excluding a compound containing at least one element selected from phosphorus, sulfur, aluminum, titanium and zirconium). [A2] The compound may be a low molecular weight compound other than a resin. The upper limit of the molecular weight of the compound [A2] is, for example, preferably 3,000, more preferably 2,000, and particularly preferably 1,000. The lower limit of this molecular weight is, for example, 100, and may be 200.

Examples of the polymerizable group include a radical polymerizable group, a cation reactive group, and a group that undergoes a polyaddition reaction. As a radically polymerizable group, a (meth) acryloyl group, a vinyl group, a vinylphenyl group etc. are mentioned, for example. As a cation reactive group, a cyclic ether group, a vinyloxy group etc. are mentioned, for example. Examples of the polyaddition reaction group include a hydroxyl group and an isocyanate group. Examples of cyclic ether groups include oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl group and the like.

As a polymeric group, a radically polymerizable group and a cation reactive group are preferable. The polymerizable group is preferably at least one selected from a cyclic ether group, a (meth) acryloyl group, a vinyl group, a hydroxyl group and an isocyanate group.

[A2] As a compound, a compound having two or more radical polymerizable groups (hereinafter also referred to as "radically polymerizable compound"), a compound having two or more cation reactive groups (hereinafter "cation reactive compound") Compounds having two or more groups undergoing polyaddition reaction (hereinafter also referred to as “addition reactive compounds”), and compounds having two or more thermally polymerizable groups (hereinafter also referred to as “thermally polymerizable compounds”) are preferable . The radically polymerizable compound crosslinks by a polymerization reaction by radicals generated by irradiation of ultraviolet light or the like in the presence of a photoradical generator. The cation reactive compound is crosslinked by a reaction by a cation generated by irradiation of ultraviolet light or the like in the presence of a photo cation generator. The addition reactive compound is crosslinked by an addition reaction with a base generated by irradiation of ultraviolet light or the like in the presence of a photobase generator. The radically polymerizable compound, the cationically reactive compound, the addition reactive compound, and the thermally polymerizable compound may be used alone or in combination of two or more.

The radically polymerizable compound has good polymerizability, so that the crosslink density of the infrared ray transmitting film can be increased, and an infrared ray transmitting film excellent in strength can be formed.

As a radically polymerizable compound, for example, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone modified with polyfunctional (meth) acrylate, an alkylene oxide modified with polyfunctional (meth) Acrylate, polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having hydroxyl group with polyfunctional isocyanate, carboxyl group obtained by reacting a polyfunctional (meth) acrylate having hydroxyl group with acid anhydride And polyfunctional (meth) acrylates and the like. In the present specification, “(meth) acrylic” is a description that means acrylic and / or methacrylic.

Specific examples of the radically polymerizable compound include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylates, polyethylene glycol di (meth) acrylates, bisphenol A bis (acryloyloxyethyl) ether, bisphenol A di (meth) acryloyloxymethyl ethyl ether, Phenol A di (meth) acryloyloxyethyl oxyethyl ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, propoxy modified bisphenol A di (meth) acrylate, ethoxy-propoxy modified bisphenol A Di (meth) acrylate, propoxy modified bisphenol F di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, tris (2) -Hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxy) Tokishifeniru] fluorene, the diglycidyl ether of bisphenol A (meth) difunctional acrylate epoxy (meth) acrylate obtained by addition of acrylic acid;
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) Acrylate, Ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol Hexahexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, dipentaerythritol penta (meth) acrylate and an acid Reactant with anhydride, Reactant of tripentaerythritol hepta (meth) acrylate and acid anhydride, propoxy modified pentaerythritol tetra (meth) acrylate, propoxy modified dipentaerythritol poly (meth) acrylate, butoxy modified pentaerythritol tetra (Meth) acrylate, butoxy modified dipentaerythritol poly (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone Modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified di Pentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol hepta (meth) Acrylate, caprolactone modified tripentaerythritol Kuta (meth) acrylate, reaction product of caprolactone modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride, caprolactone modified tripentaerythritol hepta ( Trifunctional or higher acrylates such as reaction products of (meth) acrylates with acid anhydrides;
Compounds obtained by reacting epoxy (meth) acrylate with carboxylic acids such as oxalic acid, malonic acid, succinic acid and hydrogenated phthalic acid, alcoholic compounds, phenolic compounds and the like can be mentioned.

As a cation reactive compound, for example, a compound having a methylolated amino group, a compound having an alkyl etherified amino group, a compound having an active methylene such as a methylol group-containing aromatic compound or an alkyl etherified aromatic compound; oxazoline compound Cyclic ether compounds such as ring-containing compounds, oxetane ring-containing compounds, cyclic thioether compounds, etc .; aldehyde group-containing phenol compounds; vinyl ether compounds; dipropenyl ether compounds and the like. Among these, from the viewpoint of further improving the adhesion of the infrared ray transmitting film, cyclic ether compounds are preferable, and oxirane ring-containing compounds and oxetane ring-containing compounds are more preferable.

Specific examples of the oxirane ring-containing compound include, for example, resorcinol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, ethylene / polyethylene glycol diglycidyl ether, propylene / polypropylene glycol diglycidyl ether 1,6-Hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, (3 ', 4'-epoxycyclohexane) methyl-3,4-epoxycyclohexylcarboxylate (as a commercial product, Daicel Corporation And the like, and the like. As a commercial item of the oxirane ring-containing compound, "EP-152" of Japan Epoxy Resins Co., Ltd. can be mentioned.

The oxetane ring-containing compound refers to a compound containing an oxetane ring (oxetanyl group) in the molecule. Specific examples of the oxetane ring-containing compound include, for example, 1,4-bis {[(3-ethyloxetan-3-yl) methoxy] methyl} benzene (as a commercial product, “OXT-121” manufactured by Toagosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane (commercially available is “OXT-221” manufactured by Toagosei Co., Ltd.), 4,4′-bis [(3- Ethyl-3-oxetanyl) methoxymethyl] biphenyl (as a commercial product, "ETERNACOLL OXBP" manufactured by Ube Industries, Ltd.), bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl) -3-oxetanylmethoxy) methyl-phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] sul , Bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [(3-ethyl-3-oxetanyl) Examples include methoxy) methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and oxetane oligomers (commercially available products are “Oligo-OXT” manufactured by Toagosei Co., Ltd.).

Examples of the addition reactive compound include compounds having a hydroxyl group and an isocyanate group in the molecule. As such a compound, the condensate etc. of a polyisocyanate compound and a polyol compound etc. are mentioned, for example. Further, a compound having a plurality of isocyanate groups (polyfunctional isocyanate) and a compound having a plurality of hydroxyl groups (polyol) can also be mentioned as an example of the addition reactive compound. As a commercial item of polyfunctional isocyanate, "VESTANAT T1890 / 100" of Evonik Japan Ltd. etc. can be mentioned. As the polyol, there can be mentioned "Duranol T5652" (polycarbonate diol) of Asahi Kasei Corp. and the like.

As the compound [A2], an aromatic compound may be preferable. The aromatic compound refers to a compound having an aromatic ring. By using the aromatic ring-containing [A2] compound, the adhesion to the frame portion containing the inorganic black pigment can be further enhanced. As the [A2] compound having an aromatic ring, a polyfunctional (meth) acrylate having an aromatic ring such as ethoxylated bisphenol A di (meth) acrylate or 9,9-bis [4- (2-acryloyloxyethoxyphenyl) fluorene And epoxy compounds having an aromatic ring.

As a minimum of content of a [A2] compound to a total of 100 mass parts of [A] ingredient and a [B] compound, 10 mass parts is preferred, 30 mass parts is more preferred, and 35 mass parts is still more preferred. [A2] By setting the content of the compound to the above lower limit or more, adhesion to the frame portion containing the inorganic black pigment can be further enhanced. As an upper limit of the said content, 90 mass parts is preferable, and 80 mass parts is more preferable.

It is preferable that the said infrared rays permeable film formation material contains both [A1] resin and an [A2] compound as a [A] component. By containing both [A1] resin and [A2] compound, the adhesion between the frame portion and the transparent substrate and the infrared ray transmitting film can be further improved. The content ratio of the [A1] resin and the [A2] compound is 20 parts by mass to 1000 parts by mass of the [A2] compound, preferably 50 parts by mass to 500 parts by mass, and more preferably 100 parts by mass of the [A1] resin. It is in the range of 100 parts by mass to 300 parts by mass.

As a minimum of content of [A] ingredient to a total of 100 mass parts of [A] ingredient and a [B] compound, 70 mass parts is preferred and 80 mass parts is more preferred. As an upper limit of the said content, 98 mass parts is preferable, and 95 mass parts is more preferable.

<[B] compound>
[B] The compound is a compound containing an element (X). [B] The compound may have one or more elements (X). The [B] compound may be of one type or of two or more types.

Although the optical principle is not clear, it was found that the difference between the frame part including the surrounding inorganic black pigment and the color becomes difficult to be clear when the infrared ray transmitting film contains a specific element (X) . There is a problem that the appearance is inferior because the joint becomes noticeable when the color of the infrared ray permeable film and the frame portion becomes clear. That is, according to the said infrared rays permeable film formation material, since the [B] compound containing element (X) is contained, the protective plate for display apparatuses which is excellent in an external appearance can be manufactured. Moreover, adhesion improvement with a frame part or a transparent substrate can also be aimed at by [B] compound containing element (X).

[B] The compound can improve the adhesion between the infrared ray transmitting film and the frame portion by interacting with other components in the infrared ray transmitting film and the organic components in the frame portion. As a functional group which can express such interaction, a hydroxyl group, a carboxy group, a carbonyl group, a hydrolysable group, a polymeric group etc. are mentioned. Among these functional groups, reactive groups such as hydrolyzable groups and polymerizable groups are particularly preferable as the functional group capable of forming a covalent bond. The [B] compound having such a reactive group can improve adhesion by reacting with other components of the infrared ray transmitting film forming material, [B] compounds, or components in the frame portion, etc. it can.

[B] The compound preferably has a hydrolyzable group containing an element (X). [B] The adhesion of the infrared ray transmitting film can be further improved by the compound having a hydrolyzable group containing the element (X). As such a hydrolysable group, an alkoxy borate group, an alkoxy aluminate group, an alkoxy titanate group, an alkoxy zirconate group etc. are mentioned, for example.

Examples of the phosphorus-containing [B] compound include phosphoric acid esters and the like. As a phosphoric acid ester, the compound etc. which are represented by following formula (P) are mentioned, for example.

In the above formula (P), R is a monovalent organic group having 1 to 30 carbon atoms. a is 1 or 2; When a is 2, two R may be the same or different.

In addition, you may mix and use multiple types as a compound represented by the said Formula (P). In this case, a in formula (P) may be represented by a decimal number between 1 and 2.

The organic group represented by R is, for example, a monovalent hydrocarbon group having 1 to 30 carbon atoms, a group (α) containing an oxygen atom, a carbonyl group or a combination thereof, between carbon and carbon of this hydrocarbon group The group etc. which substituted a part or all of the hydrogen atom which the said hydrocarbon group and group ((alpha)) have substituted by the hydroxyl group are mentioned.

The organic group represented by R preferably contains a polymerizable group. As a polymeric group, what was illustrated as a polymeric group which the said [A2] compound has, for example is mentioned. Among these, as the polymerizable group, a radical polymerizable group is preferable, and a (meth) acryloyl group is more preferable. [A2] By using such a compound as the compound, the adhesion of the infrared ray transmitting film obtained can be further enhanced.

The organic group represented by R is more preferably a group represented by the following formula.

In the above formulae, Ra is a hydrogen atom or a methyl group. n is an integer of 0 to 4;

N is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 0. When n is the above value, in addition to the adhesion of the formed infrared transmitting film, the light resistance is also enhanced. In addition, as the [B] compound containing phosphorus, a polymer of a compound in which R is represented by the above formula is also preferable.

Examples of sulfur-containing [B] compounds include thioether-based silane coupling agents and the like.

As a [B] compound containing aluminum, an aluminum-type coupling agent etc. are mentioned, for example.

Examples of titanium-containing [B] compounds include titanium-based coupling agents and the like.

Examples of the [B] compound containing zirconium include a zirconium-based coupling agent and the like.

Among these, the compound represented by the formula (P) is preferable as the compound [B]. By using the compound represented by the said Formula (P), the adhesiveness of the infrared rays permeable film obtained can be improved more. In particular, by using the compound represented by the above formula (P), in addition to the adhesion to the frame portion containing the inorganic black pigment, the adhesion to the transparent substrate can be further enhanced.

Moreover, as the [B] compound, a thioether based silane coupling agent, a ketimine based silane coupling agent, an aluminum based coupling agent, a titanium based coupling agent and a zirconium based coupling agent are also preferable.

As a minimum of content of a [B] compound to a total of 100 mass parts of a [A] ingredient and a [B] compound, 1 mass part is preferred, 5 mass parts is more preferred, and 10 mass parts is still more preferred. As a maximum of the above-mentioned content, 50 mass parts is preferred, 30 mass parts is more preferred, and 20 mass parts is still more preferred. By making content of a compound into the said range, the adhesiveness of an infrared rays permeable film can be improved more, and the color | collar with a frame part can also be match | combined more.

<[C] Colorant>
[C] The colorant is a substance that gives color by absorption or emission of visible light. [C] The coloring agent is a concept including both inorganic compounds and organic compounds, and includes any of dyes and pigments. It is preferable that the [C] coloring agent has low absorptivity to infrared rays.

[C] The colorant is preferably used in combination of two or more, in order to match the color tone with the black frame portion. In addition, by using two or more types of colorants, the solubility is improved by the interaction between the colorants, and the compatibility with the component (A) and the like is also enhanced. For this reason, adhesiveness can be improved more by using 2 or more types of coloring agents. [C] As a coloring agent, for example, a dye having an absorption maximum in a wavelength range of 400 nm to 580 nm (hereinafter, also referred to as "dye A"), a dye having an absorption maximum in a wavelength range of 580 nm to 700 nm (hereinafter, " And dyes (hereinafter, also referred to as “pigment C”) having an absorption maximum in a region of wavelengths of 700 nm to 800 nm. The infrared ray transmitting film forming material can achieve shielding of the visible region continuously, when it contains three kinds of dyes A to C as the [C] coloring agent. That is, when three kinds of dyes A to C are included as the [C] coloring agent, a suitable black coloring agent is obtained. The infrared ray transmitting film forming material may contain, as a [C] coloring agent, a coloring agent other than the dyes A to C.

Examples of the dye A include blue dyes and blue pigments.

Examples of blue dyes include xanthene dyes, triarylmethane dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, tetraazaporphyrin dyes, indigo dyes and the like. Among these, cyanine dyes are particularly preferable from the viewpoint of heat resistance. The cyanine dye is a dye containing, as a dye, only a compound having in its molecule a structure in which a conjugated double bond is formed by a plurality of methine groups between two heterocyclic rings. Specific examples of the cyanine dye include compounds represented by the following formulas (C1) and (C2) (hereinafter, also referred to as "compounds (C1) and (C2)") and the like.

In the above formula (C1), Z ¹ is an alkyl group having 1 to 12 carbon atoms or a phenyl group. Z ² is an alkyl group having 1 to 12 carbon atoms, a phenyl group or a naphthyl group. One or more hydrogen atoms of the phenyl group and the naphthyl group may be substituted with at least one of a halogen atom and an alkyl group having 1 to 12 carbon atoms.
In the above formula (C2), Z ³ and Z ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group. n is an integer of 1 to 12. X ^- is a counter anion.

X ^- is the counter anion represented by, for example, halide ions, ClO 4 _-, ^{OH -,} organic carboxylic acid anions, organic sulfonic acid anion, a Lewis acid anion, an organic metal complex anions, dyes derived anions, organic sulfonylimide acid Anions, organic sulfonyl methide acid anions and the like can be mentioned.

Examples of the halide ion include Cl ⁻ , Br ⁻ , I ^{− and the} like.
Examples of the organic carboxylate anion include benzoate ion, alkanoate ion, trihaloalkanoate ion, and nicotinate ion.
Examples of the organic sulfonate anion include benzene sulfonate ion, naphthalene sulfonate ion, p-toluene sulfonate ion, alkane sulfonate ion and the like.
Examples of the Lewis acid anion include tetrafluoroborate ion, hexafluoroantimonate ion, tetrakis (pentafluorophenyl) boron anion and the like.

Specific examples of the compound (C1) include compounds represented by the following formula (C1-1) (hereinafter, also referred to as “compound (C1-1)”) and the like, and specific examples of the compound (C2) include Examples thereof include a compound represented by the following formula (C2-1) (hereinafter, also referred to as “compound (C2-1)”) and the like. The maximum absorption (λmax) of the compound (C1-1) is 466 nm, and the maximum absorption (λmax) of the compound (C2-1) is 549 nm.

In addition, as the blue pigment, the pigments described in [0072] of JP-A-2017-090780 and [0049] of JP-A-2016-07030 can be used. I. Pigment blue 15: 6, 16, and 79 are preferable.

Examples of the dye B include yellow and green dyes, yellow and green pigments, and the like. Examples of yellow and green dyes include squarylium dyes, triarylmethane dyes, cyanine dyes, phthalocyanine dyes and the like. Among these, triarylmethane dyes are particularly preferable from the viewpoint of heat resistance.

Examples of triarylmethane dyes include compounds represented by the following formula (C3) (hereinafter, also referred to as "compound (C3)") and the like.

In the formula (C3), ^{Z 5} are each independently a hydrogen atom, an alkyl group or a phenyl group having 1 to 12 carbon atoms. T is an aromatic group or heterocyclic group having 3 to 10 carbon atoms which may have a substituent. X ^- is a counter anion.

By X ^- as the counter anion represented, for example, a halide ion, a perchlorate ion, a hydroxide ion, an organic carboxylate anion, an organic sulfonic acid anion, a Lewis acid anion, an organic metal complex anions, dyes derived anions, organic A sulfonyl imide acid anion, an organic sulfonyl methide acid anion, etc. are mentioned.

Specific examples of the compound (C3) include, for example, a compound represented by the following formula (C3-1) (hereinafter, also referred to as “compound (C3-1)”) and the like. The maximum absorption (λmax) of the compound (C3-1) is 604 nm.

With regard to yellow and green pigments, examples of yellow pigments include [0040] of JP-A-2017-116767, [0013] of JP-A-2016-191047, and [0042] of JP-A-2016-038584. Pigments described in [0027] of 2015-045736, [0025] of JP-A-2014-215416, and the like can be used. I. Pigment Yellow 129, 138, 139, 150, 185 and 231 are preferable.
As a green pigment, for example, C.I. I. Pigment green 7, 36, 58, 59, 62, 63, etc., C.I. I. Pigment green 7, 36, 58, 59 are preferred.

Examples of the dye C include red dyes and red pigments. Examples of red dyes include squarylium dyes and phthalocyanine dyes.

Examples of squalilium dyes include compounds represented by the following formula (C4) (hereinafter, also referred to as "compound (C4)") and the like.

In the above formula (C4), X is each independently a methylene group which may be substituted by one or more hydrogen atoms with an alkyl group or alkoxyl group having 1 to 12 carbon atoms or an alkylene group having 2 to 12 carbon atoms is there. Z ⁶ , Z ⁷ and Z ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenyl group. Z ⁹ is an alkyl group of 1 to 12 carbon atoms or a fluorinated alkyl group of 1 to 12 carbon atoms.

Specific examples of the compound (C4) include, for example, compounds represented by the following formula (C4-1) (hereinafter, also referred to as “compound (C4-1)”) and the like. The maximum absorption (λmax) of the compound (C4-1) is 712 nm.

Examples of phthalocyanine dyes include compounds represented by the following formula (C5) (hereinafter, also referred to as “compound (C5)”) and the like.

In the above formula (C5), each Z ¹⁰ independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group. M is a metal atom or a metal oxide.

Examples of the metal atom include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe and the like. As a metal oxide, VO, TiO etc. are mentioned, for example.

Specific examples of the compound (C5) include, for example, compounds represented by the following formula (C5-1) (hereinafter, also referred to as “compound (C5-1)”) and the like. The maximum absorption (λmax) of the compound (C5-1) is 738 nm.

Further, as the red pigment, for example, [0020] of JP-A-2017-068159, [0020] of WO-2017 / 030155, [-0018] of JP-A-2016-177190, [0027] of JP-A-2016-164623, JP-A-2016- Pigments described in [0016] of 147977, [0009] of JP-A-2016-011419, and [0019] of WO 2015/182278 can be used. Among these, C.I. I. Pigment red 166, 177, 242, 254, 264, 269 are preferable.

The difference in absorption maximum wavelength between the dye A and the dye B is preferably 40 nm or more and 200 nm or less. As a difference of the absorption maximum wavelength of the above-mentioned pigment B and pigment C, 80 nm or more and 200 nm or less are preferable. By setting the difference between the absorption maximum wavelengths of the dye A, the dye B and the dye C in the above range, the visible region can be shielded continuously at a high level, and the transmittance in the near infrared region of the infrared ray transmitting film is further improved. Can.

When the said infrared rays permeable film formation material contains a [C] coloring agent, as a minimum of content of a [C] coloring agent, 0. 0 to a total of 100 mass parts of a [A] ingredient and a [B] compound. 1 part by mass is preferable, 1 part by mass is more preferable, and 2 parts by mass is more preferable. As a maximum of the above-mentioned content, 20 mass parts is preferred, 15 mass parts is more preferred, and 10 mass parts is still more preferred. [C] By setting the content of the coloring agent in the above range, the transmittance of the visible light region of the infrared ray transmitting film can be further lowered, and the transmittance of the near infrared light region can be further enhanced.

<[D] photosensitive agent>
[D] Photosensitizers include, for example, photoradical generators, photocationic acid generators, photobase generators and the like. The photoradical generator is a compound that generates radicals by irradiation of light and initiates radical polymerization of a radically polymerizable compound. The maximum absorption wavelength of the photoradical generator is preferably in the range of 150 nm or more and 380 nm or less from the viewpoint of performing exposure by ultraviolet light exposure. The photo cation generator is a compound which generates a cation by irradiation of light and which starts crosslinking of the cation reactive compound by the reaction with the cation. The photobase generator is a compound which generates a base by irradiation of light and which starts crosslinking of the addition-reactive compound by a reaction catalyzed by the base. The photo radical generator, the photo cation generator and the photo base generator may be used alone or in combination of two or more.

As the photo radical generator, for example, JP-A 2008-276194, JP-A 2003-241372, JP-A-2009-519991, JP-A-2009-531730, WO 2010/001691, WO 2010/146883, JP-A-2011-132215, JP-A 2008- And compounds described in JP-A-2009-519904 and the like.

Examples of the photoradical generator include biimidazole compounds, acyl phosphine oxide compounds, phenone compounds, oxime compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds and the like.

As a biimidazole compound, for example, 2,2′-bis (2,4-dichlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dimethylphenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis (2-methylphenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-diphenyl-4,5,4', 5'- Examples include tetraphenyl-1,2'-biimidazole and the like.

Examples of the acyl phosphine oxide compound include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide and the like.

Examples of phenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2 -Methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 1-hydroxy-4-methoxyphenyl-phenyl- Ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 -(3-Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone etc. Be

As the oxime compound, for example, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl Ethan-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O- Nzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl -6- (2-Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl -4- (2,2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 5-p-toluenesulfonyloxyimino-5H- Thiophene-2-ylidene)-(2-methylphenyl) acetonitrile and the like can be mentioned.

Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-bis (diethylamino) benzophenone, and 4,4'. And -tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

As a thioxanthone compound, for example, thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2 , 4-diisopropylthioxanthone and the like.

Among these, an acyl phosphine oxide compound, an oxime compound and a phenone compound are preferable as the photo radical generator.

As a photo cation generator, an onium salt compound, a halogen containing compound, a sulfone compound, a sulfonic acid compound, a sulfone imide compound, a diazomethane compound etc. are mentioned, for example.

Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like. As onium salt compounds, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p- Toluene sulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothio Phenium trifluoromethanesul , 4,7-di-n-butoxynaphthyl tetrahydrothiophenium nonafluorobutanesulfonate, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate and 4- (phenylthio) phenyldiphenylsulfonium hexafluorophos Fert is preferred.

As a halogen containing compound, a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound etc. are mentioned, for example. Examples of the haloalkyl group-containing hydrocarbon compound include 1,10-dibromo-n-decane and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane. Examples of the haloalkyl group-containing heterocyclic compound include phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, Naphthyl-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis- (trichloromethyl) -1,3,5-triazine, 2 And s-triazine derivatives such as-[2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine.

Examples of sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, α-diazo compounds of these compounds, and the like. As the sulfone compound, 4-trisphenacyl sulfone, mesityl phenacyl sulfone and bis (phenacylsulfonyl) methane are preferable.

Examples of the sulfonic acid compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates and the like. As a sulfonic acid compound, benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate and o-nitrobenzyl p-toluenesulfonate are preferable.

Examples of sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (trifluoromethylsulfonyloxy) -1,8-naphthalene di And the like.

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and the like.

Among these, a sulfone imide compound, an onium salt compound and a halogen-containing compound are preferable as the photocation generator from the viewpoint of further improving the strength of the infrared ray transmitting film.

Examples of the photo base generator include [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, 2-nitrobenzyl cyclohexyl carbamate, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, bis [[(2- Nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholino Benzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, hexaamminecobalt (III) tris (triphenylmethyl borate), 2-dimethyl amino 2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, and the like.

When the said infrared rays permeable film formation material contains a [D] photosensitive agent, as a minimum of content of a [D] photosensitive agent, it is 0. 0 with respect to a total of 100 mass parts of a [A] component and a [B] compound. 1 mass part is preferable, 0.5 mass part is more preferable, and 1 mass part is further more preferable. The upper limit of the content is preferably 30 parts by mass, more preferably 15 parts by mass, still more preferably 10 parts by mass, even more preferably 8 parts by mass, and even more preferably 5 parts by mass. [D] By setting the content of the photosensitizer in the above range, the strength, adhesion and the like of the infrared ray transmitting film can be further improved. Moreover, the light resistance of the infrared rays permeable film obtained can be improved by making content of a [D] photosensitizer below the said upper limit.

<Other optional components>
The infrared ray transmitting film forming material can contain other optional components other than the [A] to [D] components. Other optional components include, for example, color correction dyes, leveling agents, antistatic agents, heat stabilizers, light stabilizers, antioxidants, transparent nanoparticles, surfactants, solvents, flame retardants, lubricants, plasticizers, etc. Can be mentioned. As the other optional components, any one may be used alone, or two or more may be mixed and used.

Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, sulfur compounds, amine compounds and the like. Among these, hindered phenol compounds are preferable from the viewpoint of infrared ray permeability. The hindered phenolic compound is a compound having a substituent at both the 2- and 6-positions relative to the phenolic hydroxyl group. As a substituent, a methyl group and a t-butyl group are preferable. The hindered phenol compound may be any of monophenols, bisphenols and polyphenols.

As a light stabilizer, a hindered amine compound etc. are mentioned, for example. As the hindered amine compound, a 2,2 ', 6,6'-tetraalkylpiperidine derivative is preferable. As a substituent on the nitrogen atom, a hydrogen atom, an alkyl group and an alkoxy group are preferable. Further, as the 2- and 6-position substituents, an alkyl group and a phenyl group are preferable.

Transparent nanoparticles are nanoparticles of inorganic oxide materials that are transparent in the infrared wavelength range. The transparent nanoparticles are used for the purpose of adjusting the refractive index of the infrared ray transmitting film or increasing the hardness of the infrared ray transmitting film. As transparent nanoparticles, for example, nanoparticles of Al ₂ O ₃ , SiO ₂ , GeO ₂ , Y ₂ O ₃ , La ₂ O ₃ , Ce ₂ , CeO ₂ , TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O _{5 and the} like Etc.

The surfactant can improve the appearance of the infrared ray transmitting film, in particular, a dent due to the adhesion of a void due to a fine bubble, a foreign substance and the like, and can also improve the repelling in the drying step. As surfactant, well-known things, such as a cation type, an anion type, nonionic type, are mentioned, for example.

The solvent is not particularly limited as long as it is a liquid that can dissolve or disperse the component [A], the compound [B] and each component blended as needed. As used herein, the term "solvent" is used in the concept including both the dispersion medium and the solvent. As the solvent, for example, alcohols such as isopropyl alcohol, n-butyl alcohol, ethyl cellosolve, methyl cellosolve; glycols such as ethylene glycol, diethylene glycol and propylene glycol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; ethylene glycol monomethyl ether, ethylene glycol monoethylene ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol butyl ether, ethylene glycol monomethyl ether acetate And ethers such as ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate; esters such as methyl acetate, ethyl acetate and butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; n-hexane, n- Aliphatic hydrocarbons such as heptane; fluorine-based solvents such as tetrafluoropropyl alcohol and pentafluoropropyl alcohol; tetrahydrofuran; water and the like. These solvents may be used alone or in combination of two or more.

When the said infrared rays permeable film formation material contains a solvent, as a minimum of content of a solvent, 10 mass parts is preferable with respect to a total of 100 mass parts of [A] component and a [B] compound, and 30 mass parts More preferable. As a maximum of the above-mentioned content, 5,000 mass parts is preferred, and 2,000 mass parts is more preferred.

The lower limit of the viscosity at 25 ° C. of the infrared ray transmitting film forming material is preferably 100 mPa · sec, more preferably 200 mPa · sec, and even more preferably 550 mPa · sec. The upper limit of the viscosity is preferably 1,000 mPa · s, more preferably 850 mPa · s. By making the viscosity of the said infrared rays permeable film formation material into the said range, the printability at the time of screen-printing can be improved, for example, and the external appearance of the infrared rays permeable film obtained can be improved. In addition, by setting the viscosity of the infrared ray transmitting film forming material to the above range, the storage stability of the infrared ray transmitting film forming material, and the coatability and fillability to the opening can be compatible at a high level.

<Infrared permeable membrane>
The said infrared rays permeable film is formed from the said said infrared rays permeable film forming material. The infrared ray transmitting film is usually a flat film formed in an opening for infrared communication. The said infrared rays permeable film can be formed by the formation method of the infrared rays permeable film shown below, etc., for example. Since the said infrared rays permeable film is formed from the said infrared rays permeable film forming material mentioned above, it is excellent in adhesiveness with a frame part. Furthermore, the infrared ray transmitting film has good appearance and light resistance, and also has good adhesion to a transparent substrate.

<Method of forming infrared permeable film>
The method of forming the infrared ray transmitting film is a step of applying the infrared ray transmitting film forming material to the opening for infrared ray communication formed in the frame portion containing the inorganic black pigment (hereinafter also referred to as “coating step” ), A step of exposing the coating film formed in the coating step (hereinafter also referred to as “exposure step”), and a step of heating the coating after the exposure step (hereinafter also referred to as “heating step”) And

According to the formation method of the said infrared rays permeable film, the infrared rays permeable film which is excellent in adhesiveness with the frame part containing the above-mentioned inorganic black pigment can be formed easily and reliably. Each step will be described below.

[Coating process]
At this process, the said infrared rays permeable film formation material is coated in the opening part formed in the frame part. Specifically, the infrared ray transmitting film-forming material is applied to a region of the transparent substrate on which the opening is formed, and the solvent is removed by prebaking as necessary. Form As a coating method, suitable methods, such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet method, a screen printing method, can be adopted, for example. Among these, the screen printing method is preferable. The conditions for pre-baking may vary depending on the type, content, etc. of the components of the infrared ray transmitting film forming material, but can be, for example, a temperature of 60 ° C. to 100 ° C., a time of 30 seconds to 10 minutes or so .

[Exposure process]
At this process, the coating film formed by the said filling process is exposed. By this exposure, radicals, cations, bases and the like are generated from the [D] photosensitizer, and crosslinking by the radically polymerizable compound of the [A2] compound, the cation reactive compound, the addition reactive compound and the like proceeds.

Examples of radiation used for exposure include ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

Examples of the ultraviolet light include g-ray (wavelength 436 nm) and i-ray (wavelength 365 nm). As far ultraviolet rays, for example, a KrF excimer laser etc. may be mentioned. Examples of X-rays include synchrotron radiation and the like. As a charged particle beam, an electron beam etc. can be mentioned, for example. Of these, ultraviolet radiation is preferred as radiation, and radiation including g-line and i-line is particularly preferred. The exposure dose can be, for example, 100 J / m ² or more and 10,000 J / m ² or less.

[Heating process]
At this process, the coating film after the said exposure process is heated. By this heating, curing of the coating further proceeds to form an infrared ray transmitting film.

As a method of heating, a method using a heating device such as a hot plate or an oven may, for example, be mentioned.

As a minimum of the temperature of heating, 120 ° C is preferred. As a maximum of the above-mentioned temperature, 200 ° C is preferred, 180 ° C is more preferred, and 150 ° C is still more preferred. The heating time varies depending on the type of heating device, but for example, 5 minutes or more and 40 minutes or less when heat treatment is performed on a hot plate, and 30 minutes or more and 80 minutes or less when heat treatment is performed in an oven. can do. The heating time is preferably 30 minutes or less when heat treatment is performed on a hot plate, and 60 minutes or less when heat treatment is performed in an oven.

In addition, the formation method of the said infrared rays permeable film is not limited to the said method. For example, it is not necessary to have an exposure process, such as when an infrared rays permeable film formation material does not contain [D] photosensitizer. Even with such a method, it is possible to obtain an infrared ray transmitting film having high adhesion by heating.

[Method of forming covering layer]
Below, it describes about the formation method of a coating layer. First, for example, a coating solution for forming a covering layer is applied on the formed infrared ray transmitting film. As this coating solution, a commercially available coating solution for an antireflective layer such as Arakawa Chemical Opstar TU 2359 or TU 2361 can be used.

As a coating method, a known wet coating method (spin coating method, spray coating method, dip coating method, die coating method, curtain coating method, screen coating method, ink jet method, flow coating method, gravure coating method, bar coating method, flexo method Coating methods, slit coating methods, roll coating methods, and the like can be mentioned, but the invention is not limited thereto. Among these, the inkjet method is preferable as the coating method. At this time, the ink droplets are emitted at, for example, 2 to 16 pl. After drying of the coating film, the coating film can be cured by exposure (irradiation with actinic rays) to form a coating layer. The drying temperature is preferably room temperature to 200 ° C., and more preferably room temperature to 150 ° C. Further, as the exposure conditions, for example, the illuminance of ultraviolet light can be 0.1 W / cm ² and the irradiation amount can be 200 mJ / cm ² .

<Display device>
A display device according to an embodiment of the present invention is a display device provided with the display device protective plate. In the protective plate for a display device, the frame portion is black including the inorganic black pigment, and the opening for infrared communication formed in the frame portion is filled or covered with the black infrared transmitting film. For this reason, the opening (infrared ray transmitting window) is inconspicuous, and the appearance (design) is excellent. Moreover, since the said infrared rays permeable film is excellent in adhesiveness with the frame part etc. which contain an inorganic black pigment, and since light resistance is also favorable, the outstanding designability is maintained for a long time.

The said display apparatus has a display apparatus main body and the said protection plate for display apparatuses. Usually, the display device protection plate is provided on the outermost surface so as to cover the display device body.

The display device preferably includes an infrared communication unit. The infrared communication unit is provided at a position facing the opening for infrared communication formed in the frame portion of the display device protection plate. The configuration of the display device other than the display device protective plate can be the same as that of a conventionally known display device.

Specific examples of the display device include a mobile phone including a smartphone, a portable information terminal, a tablet, a personal computer and its monitor, a television, a portable game machine, and the like.

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In addition, "part" in a description means a "mass part" unless there is particular notice. Moreover, the measuring method of each physical-property value is as follows.

[Viscosity of infrared ray permeable film forming material]
The viscosity of the infrared permeable film forming material was measured at 25 ° C. using an E-type viscometer (“VISCONIC ELD. R” manufactured by Toki Sangyo Co., Ltd.).

<Preparation of an infrared permeable film forming material>
The component (A), the compound (B), the colorant (C) and the photosensitive agent (D) used for the preparation of the infrared ray transmitting film forming material are shown below.

[[A] component]
A1-1: copolymer of glycidyl methacrylate and tricyclodecyl methacrylate (monomer ratio = 50/50, PGMEA solution)
A1-2: NOF Corporation's “Merproof G-0250SP” (an acrylic resin having an epoxy group in the side chain, powder)
A1-3: JSR's "ARTON" (cyclic olefin resin)
A1-4: “EP-152” (epoxy oligomer represented by the following formula (A1-4), epoxy equivalent 172 to 178) represented by Japan Epoxy Resins Co.

([A2] compound)
A2-1: "KAYARAD DPHA" (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) from Nippon Kayaku Co., Ltd.
A2-2: “A-BPEF” (9, 9-bis [4- (2-acryloyloxyethoxyphenyl) fluorene, a compound represented by the following formula (A2-2)) of Shin-Nakamura Chemical Co., Ltd.
A2-3: Tricyclodecanedimethanol diacrylate of Shin-Nakamura Chemical Co., Ltd. A2-4: "VESTANAT T1890 / 100" (polyfunctional isocyanate) of Evonik Japan Ltd.
A2-5: "Duranol T5652" (polycarbonate diol) from Asahi Kasei Corporation

[[B] compound]
B-1: “KAYAMER PM-21” (a compound represented by the following formula (B-1), a = b = 1.5), manufactured by Nippon Kayaku Co., Ltd.
B-2: “KAYAMER PM-2” (a compound represented by the following formula (B-2), n = 0, a = b = 1.5), manufactured by Nippon Kayaku Co., Ltd.
B-3: Shin-Etsu Chemical's "X-12-1056 ES" (compound represented by the following formula (B-3))
B-4: “Prenact AL-M” (acetoalkoxyaluminum diisopropylate, a compound represented by the following formula (B-4)) from Ajinomoto Fine Techno Co., Ltd.
B-5: "Orgatics TC-100" (Titanium diisopropoxy bis (acetylacetonate), Ti (Oi-C ₃ H ₇ ) ₂ (C ₅ H ₇ O ₂ ) ₂ ) from Matsumoto Fine Chemical Co., Ltd.
B-6: "Orgatics ZA-45" (Zirconium tetra n-propoxide, Zr (On-C ₃ H ₇ ) ₄ ) from Matsumoto Fine Chemical Co., Ltd.

[[B] compound]
b-1: JNC's "S510" (3-glycidoxypropyl trimethoxysilane)
b-2: JNC's "S710" (3-methacryloxypropyl trimethoxysilane)
b-3: "S340" (N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine from JNC

[[C] Colorant]
C-1: A mixture of a compound represented by the following formula (C1-1) and a compound represented by (C2-1) (dye A). The mixing ratio (mass) is 1: 1.
C-2: Compound (dye B) represented by the following formula (C3-1)
C-3: A mixture of a compound represented by the following formula (C4-1) and a compound represented by (C5-1) (dye C). The mixing ratio (mass) is 1: 1.

[[D] Photosensitizer]
D-1: "Omnirad 184" of IGM (photoradical generator represented by the following formula (D-1))
D-2: “Omnirad 819” (bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, a photoradical generator represented by the following formula (D-2)) manufactured by IGM
D-3: "Irgacure OXE02" (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) of BASF, light Radical generator)
D-4: SAN-APRO Co. "CPI-210S" (the following formula _{^{(D-4) (X -}} = (Rf n PF 6-n) - photo-cation generator represented by))
D-5: "Omnirad 379" (2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, photobase generator) manufactured by IGM
D-6: 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (photocation generator)

Example 1
In a container, as the component (A), 50 parts by mass of (A1-1) as the resin [A1] and 40 parts by mass of the component (A2-1) as the compound [A2] (B-1) as the compound [B] 10 parts by mass, 3 parts by mass of (C-1) as a [C] colorant, 1 part by mass of (C-2) and 2 parts by mass of (C-3), and (D-1 as a [D] photosensitizer 3 parts by mass were mixed to obtain an infrared ray transmitting film forming material (S-1). The viscosity at 25 ° C. of the obtained infrared transmitting film forming material (S-1) was 400 mPa · sec.

[Examples 2 to 10 and Comparative Examples 1 to 5]
Infrared ray transmitting film forming materials (S-1) to (S-10) and (CS-1) to (CS-) in the same manner as in Example 1 except that each component of the type and amount shown in Table 1 was used. 5) was prepared. The viscosities at 25 ° C. of the respective infrared ray transmitting film forming materials obtained are as shown in Table 1.

<Formation of infrared ray permeable film>
The above prepared infrared ray transmitting film forming material is coated on a smooth glass substrate or a substrate on which a carbon black (containing 20 parts by mass of carbon black with respect to 100 parts by mass of acrylic resin) containing frame portion is formed by screen printing And dried at 23 ° C. for 8 hours, and further dried at 50 ° C. under reduced pressure for 3 hours to obtain a coated film. The coated film is exposed on the entire surface of the coated film without using a mask by using an exposure machine ("MPA-600FA" by Canon Inc .: an ultra-high pressure mercury lamp is used), and then 30 at 150 ° C using a hot plate. By heating for a minute, an infrared transmitting film with a thickness of 10 μm was formed.

<Evaluation>
The following items were evaluated by the following method about the infrared rays permeable film formed above. The evaluation results are shown in Table 1 below.

[appearance]
The appearance of the infrared ray transmitting film formed on the glass substrate was visually observed. The appearance is black enough if it is not black on the coated surface sufficiently, and it is black if it is black enough if some surface roughness is observed, but it is black but surface roughness is strong. In the case, the case was evaluated as "poor" (slightly good) and "poor" (poor) when the surface was thin and non-black or blackish and rough.

[Lightfastness]
The infrared ray transmitting film formed on the glass substrate was irradiated for 100 hours using a xenon lamp, and the average transmittance of visible light (400 nm to 700 nm) was measured before and after the irradiation to determine the change rate of the average transmittance. . When the change rate is less than 0.1%, the light resistance is “優 れ る” (excellent), and when the change rate is 0.1% or more and less than 1%, “o” (good), 1% or more and less than 5% The evaluation was evaluated as “Δ” (slightly good), and in the case of 5% or more, as “×” (defect).

[Adhesiveness with carbon black containing frame part]
The adhesion between the infrared transmitting film and the carbon black-containing frame portion was evaluated by the cross cut tape peeling test and the adhesion area ratio after the tape peeling. The adhesion is “◎” (excellent) when the adhesion area ratio is 100%, “○” (good) when 90% or more and less than 100%, and “Δ” when 50% or more and less than 90%. (Slightly good) and less than 50% were evaluated as "x" (defect).

As can be seen from the results in Table 1, the infrared ray transmitting film formed from each infrared ray transmitting film forming material of Examples is excellent in appearance and adhesion with the frame portion containing carbon black which is an inorganic black pigment. Moreover, the infrared rays permeable film formed from each infrared rays permeable film forming material of an Example is also favorable in light resistance.

The protective plate for a display device of the present invention can be suitably used as a protective plate for a display device such as a cellular phone.

100 Transparent substrate 110 Frame part (Bezel)
120 infrared permeable film 130 opening

Claims (15)

1. An infrared transmitting film forming material for forming an infrared transmitting film provided in an opening for infrared communication formed in a frame portion containing an inorganic black pigment provided in a protective plate for a display device
   At least one of a resin and a first compound having two or more polymerizable groups in one molecule (excluding a compound containing at least one element selected from phosphorus, sulfur, aluminum, titanium and zirconium);
   An infrared-permeable film-forming material comprising: a second compound containing at least one element selected from phosphorus, sulfur, aluminum, titanium and zirconium.
2. The infrared rays permeable film formation material of Claim 1 which further contains 2 or more types of coloring agents.
3. The infrared ray transmission according to claim 1 or 2, wherein the polymerizable group of the first compound is at least one selected from the group consisting of cyclic ether group, (meth) acryloyl group, vinyl group, hydroxyl group and isocyanate group. Film forming material.
4. The infrared rays permeable film formation material of any one of Claim 1 to 3 which further contains a photosensitive agent.
5. The resin is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, polysulfone resin, Polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester curable resin, The material for forming an infrared transmitting film according to any one of claims 1 to 4, which is at least one selected from the group consisting of silsesquioxane type ultraviolet curing resin, polystyrene type resin and phenol resin.
6. The infrared rays permeable film formation material of any one of Claim 1 to 5 containing the compound represented by following formula (P) as said 2nd compound.
   

   

   (In formula (1), R is a monovalent organic group having 1 to 30 carbon atoms. A is 1 or 2. When a is 2, two R may be the same or different. .)
7. The infrared permeable film forming material according to any one of claims 1 to 6, wherein the viscosity at 25 ° C is 100 mPa · sec or more and 1,000 mPa · sec or less.
8. The infrared rays permeable film formed from the infrared rays permeable film formation material of any one of Claims 1-7.
9. A step of applying the infrared ray transmitting film forming material according to any one of claims 1 to 7 to an opening for infrared communication formed in a frame portion containing an inorganic black pigment,
   Exposing the coated film formed by the coating step;
   And heating the coated film after the exposure step.
10. The infrared rays permeable film formed by the formation method of the infrared rays permeable film of Claim 9.
11. A protective plate for a display device, comprising: a transparent substrate; and a frame portion disposed on the periphery of one surface of the transparent substrate and containing an inorganic black pigment, wherein the frame portion is formed with an opening for infrared communication. In
    It has an infrared ray transmitting film provided in a region where the opening is formed on one surface of the transparent substrate,
    The protective plate for a display device, wherein the infrared ray transmitting film contains at least one element selected from the group consisting of phosphorus, sulfur, aluminum, titanium and zirconium.
12. The protective plate for a display device according to claim 11, wherein the infrared ray transmitting film is the infrared ray transmitting film according to claim 8.
13. The protective plate for a display device according to claim 11, wherein the infrared ray transmitting film is the infrared ray transmitting film according to claim 10.
14. The protective plate for a display device according to any one of claims 11 to 13, further comprising a coating layer laminated on the infrared ray transmitting film and having a refractive index of 1.4 or less.
15. The display apparatus provided with the protective plate for display apparatuses of any one of Claims 11-14.

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