WO2019111700A1 - Matériau de formation de film transmettant les infrarouges, film transmettant les infrarouges et procédé pour le former, plaque protectrice pour dispositifs d'affichage, et dispositif d'affichage - Google Patents

Matériau de formation de film transmettant les infrarouges, film transmettant les infrarouges et procédé pour le former, plaque protectrice pour dispositifs d'affichage, et dispositif d'affichage Download PDF

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Publication number
WO2019111700A1
WO2019111700A1 PCT/JP2018/042899 JP2018042899W WO2019111700A1 WO 2019111700 A1 WO2019111700 A1 WO 2019111700A1 JP 2018042899 W JP2018042899 W JP 2018042899W WO 2019111700 A1 WO2019111700 A1 WO 2019111700A1
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resin
compound
infrared
transmitting film
group
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PCT/JP2018/042899
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English (en)
Japanese (ja)
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直征 牧内
大吾 一戸
勝也 長屋
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Jsr株式会社
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Publication of WO2019111700A1 publication Critical patent/WO2019111700A1/fr

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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • 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.
  • 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.
  • 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
  • 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.
  • an infrared ray transmitting film 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.
  • 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).
  • 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.
  • 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.
  • a protective plate for a display device 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 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).
  • 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.
  • the transparent substrate 100 is a substrate formed of a transparent material.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a resin as a base material.
  • 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.
  • a photosensitive resin composition containing an inorganic black pigment may be coated and formed through exposure and heating.
  • the separately formed frame portion 110 may be laminated on the surface of the transparent substrate 100.
  • 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.
  • 2 mm or more and 4 mm or less is more preferable.
  • 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.
  • 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.
  • 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.
  • the infrared ray transmitting film 120 one formed of an infrared ray transmitting film forming material described below can be suitably used.
  • 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.
  • the said display apparatus protective plate further has a coating layer laminated
  • 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.
  • An infrared transmitting film forming material 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.
  • 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 is at least one of [A1] resin and [A2] compound.
  • the resin is a transparent or opaque resin.
  • the resin may have two or more polymerizable groups in one molecule.
  • 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.
  • 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.
  • 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
  • X 0 a monomer represented by the following formula
  • Y 0 a monomer represented by the following formula
  • 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.
  • 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).
  • 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.
  • 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.
  • Aromaatic 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.
  • 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.
  • 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.
  • 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).
  • 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;
  • 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).
  • 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
  • the fluorene polycarbonate resin can be synthesized, for example, by the method described in JP-A-2008-163194.
  • 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.
  • 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 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.
  • 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 As a commercial item of silsesquioxane type UV curing resin, "Silplus” of Nippon Steel Chemical Co., Ltd. etc. are mentioned, for example.
  • resin [A1] cyclic olefin resins and (modified) acrylic resins are preferable.
  • resin which has polymeric groups, such as a cyclic ether group, a vinyl group, a (meth) acryloyl group, is also preferable.
  • [A1] resin 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.
  • 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).
  • 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.
  • a radical polymerizable group a radical polymerizable group
  • a cation reactive group a group that undergoes a polyaddition reaction.
  • 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.
  • the polyaddition reaction group include a hydroxyl group and an isocyanate group.
  • 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.
  • 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.
  • radically polymerizable compound a compound having two or more radical polymerizable groups
  • cation reactive compound a compound having two or more cation reactive groups
  • addition reactive compounds compounds having two or more groups undergoing polyaddition reaction
  • thermally polymerizable compounds compounds having two or more thermally polymerizable groups
  • 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.
  • 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.
  • (meth) acrylic is a description that means acrylic and / or methacrylic.
  • 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
  • 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.
  • cyclic ether compounds are preferable, and oxirane ring-containing compounds and oxetane ring-containing compounds are more preferable.
  • 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.
  • "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 [
  • the addition reactive compound examples include compounds having a hydroxyl group and an isocyanate group in the molecule.
  • 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.
  • polyfunctional isocyanate "VESTANAT T1890 / 100" of Evonik Japan Ltd. etc. can be mentioned.
  • the polyol there can be mentioned "Duranol T5652” (polycarbonate diol) of Asahi Kasei Corp. and the like.
  • an aromatic compound may be preferable.
  • the aromatic compound refers to a compound having an aromatic ring.
  • the aromatic ring-containing [A2] compound By using the aromatic ring-containing [A2] compound, the adhesion to the frame portion containing the inorganic black pigment can be further enhanced.
  • 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.
  • the said infrared rays permeable film formation material contains both [A1] resin and an [A2] compound as a [A] component.
  • 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.
  • the compound is a compound containing an element (X).
  • the compound may have one or more elements (X).
  • the [B] compound may be of one type or of two or more types.
  • 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) .
  • 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).
  • 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.
  • 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.
  • 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.
  • the compound preferably has a hydrolyzable group containing an element (X).
  • the adhesion of the infrared ray transmitting film can be further improved by the compound having a hydrolyzable group containing the element (X).
  • 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.
  • a phosphoric acid ester the compound etc. which are represented by following formula (P) are mentioned, for example.
  • 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.
  • 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 ( ⁇ ) 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.
  • a polymeric group what was illustrated as a polymeric group which the said [A2] compound has, for example is mentioned.
  • the polymerizable group a radical polymerizable group is preferable, and a (meth) acryloyl group is more preferable.
  • 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.
  • 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.
  • n is the above value, in addition to the adhesion of the formed infrared transmitting film, the light resistance is also enhanced.
  • the [B] compound containing phosphorus a polymer of a compound in which R is represented by the above formula is also preferable.
  • sulfur-containing [B] compounds examples include thioether-based silane coupling agents and the like.
  • titanium-containing [B] compounds examples include titanium-based coupling agents and the like.
  • Examples of the [B] compound containing zirconium include a zirconium-based coupling agent and the like.
  • the compound represented by the formula (P) is preferable as the compound [B].
  • the adhesiveness of the infrared rays permeable film obtained can be improved more.
  • the adhesion to the transparent substrate can be further enhanced.
  • 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.
  • the colorant is a substance that gives color by absorption or emission of visible light.
  • 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.
  • the colorant is preferably used in combination of two or more, in order to match the color tone with the black frame portion.
  • 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.
  • 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.
  • blue dyes examples include xanthene dyes, triarylmethane dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, tetraazaporphyrin dyes, indigo dyes and the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ( ⁇ max) of the compound (C1-1) is 466 nm
  • the maximum absorption ( ⁇ max) of the compound (C2-1) is 549 nm.
  • 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.
  • triarylmethane dyes are particularly preferable from the viewpoint of heat resistance.
  • triarylmethane dyes examples include compounds represented by the following formula (C3) (hereinafter, also referred to as “compound (C3)”) and the like.
  • 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.
  • 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.
  • 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 ( ⁇ max) of the compound (C3-1) is 604 nm.
  • yellow and green pigments examples 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.
  • 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.
  • squalilium dyes examples include compounds represented by the following formula (C4) (hereinafter, also referred to as “compound (C4)”) and the like.
  • 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.
  • 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 ( ⁇ max) of the compound (C4-1) is 712 nm.
  • phthalocyanine dyes examples include compounds represented by the following formula (C5) (hereinafter, also referred to as “compound (C5)”) and the like.
  • 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.
  • a metal oxide VO, TiO etc. are mentioned, for example.
  • 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 ( ⁇ max) of the compound (C5-1) is 738 nm.
  • 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.
  • 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.
  • the said infrared rays permeable film formation material contains a [C] coloring agent
  • 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.
  • 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.
  • 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.
  • 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
  • acyl phosphine oxide compound examples include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide and the like.
  • 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-morpholinoph
  • 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- Nzo
  • benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.
  • 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.
  • 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.
  • an acyl phosphine oxide compound, an oxime compound and a phenone compound are preferable as the photo radical generator.
  • an onium salt compound 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.
  • onium salt compound examples include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like.
  • 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
  • halogen containing compound a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound etc. are mentioned, for example.
  • haloalkyl group-containing hydrocarbon compound examples include 1,10-dibromo-n-decane and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.
  • haloalkyl group-containing heterocyclic compound examples 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.
  • sulfone compounds include ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds, ⁇ -diazo compounds of these compounds, and the like.
  • sulfone compound 4-trisphenacyl sulfone, mesityl phenacyl sulfone and bis (phenacylsulfonyl) methane are preferable.
  • the sulfonic acid compound examples include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates and the like.
  • a sulfonic acid compound benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate and o-nitrobenzyl p-toluenesulfonate are preferable.
  • 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.
  • diazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and the like.
  • 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-morpholinophen
  • 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.
  • 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.
  • any one may be used alone, or two or more may be mixed and used.
  • antioxidants examples 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.
  • a hindered amine compound etc. are mentioned, for example.
  • a 2,2 ', 6,6'-tetraalkylpiperidine derivative is preferable.
  • 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.
  • 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.
  • 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.
  • solvent is used in the concept including both the dispersion medium and the solvent.
  • 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
  • ethers such as ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate
  • esters such as methyl acetate
  • the said infrared rays permeable film formation material contains a solvent
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • the said infrared rays permeable film formation material is coated in the opening part formed in the frame part.
  • 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.
  • 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.
  • 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 .
  • 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).
  • g-ray wavelength 436 nm
  • i-ray wavelength 365 nm
  • 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.
  • 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.
  • a method using a heating device such as a hot plate or an oven may, for example, be mentioned.
  • 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.
  • the formation method of the said infrared rays permeable film is not limited to the said method.
  • a coating solution for forming a covering layer is applied on the formed infrared ray transmitting film.
  • a commercially available coating solution for an antireflective layer such as Arakawa Chemical Opstar TU 2359 or TU 2361 can be used.
  • 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.
  • the inkjet method is preferable as the coating method.
  • the ink droplets are emitted at, for example, 2 to 16 pl.
  • 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 .
  • a display device is a display device provided with the display device protective plate.
  • 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.
  • the opening infrared ray transmitting window
  • the appearance design
  • 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.
  • 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.
  • 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.
  • 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.).
  • 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-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.
  • 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-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.
  • 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.
  • Example 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.
  • 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 ⁇ m was formed.
  • 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. .
  • the change rate is less than 0.1%
  • the light resistance is “ ⁇ ⁇ ⁇ ” (excellent)
  • 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 “ ⁇ ” (slightly good), and in the case of 5% or more, as “ ⁇ ” (defect).
  • 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 “ ⁇ ” when 50% or more and less than 90%. (Slightly good) and less than 50% were evaluated as "x" (defect).
  • 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.
  • 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.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optical Filters (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne: un matériau de formation de film transmettant les infrarouges qui est capable de former un film transmettant les infrarouges présentant une excellente apparence et une excellente adhérence à une partie de cadre qui contient un pigment noir inorganique; un film transmettant les infrarouges qui présente une excellente apparence et une excellente adhérence à une partie de cadre qui contient un pigment noir inorganique; un procédé de formation dudit film transmettant les infrarouges; une plaque protectrice pour dispositifs d'affichage, qui comporte ce film transmettant les infrarouges; et un dispositif d'affichage muni de cette plaque protectrice pour dispositifs d'affichage. La présente invention concerne un matériau de formation de film transmettant les infrarouges servant à former un film transmettant les infrarouges qui est placé sur une ouverture servant à la communication infrarouge, qui est formée dans une partie de cadre d'une plaque protectrice pour dispositifs d'affichage, ladite partie de cadre contenant un pigment noir inorganique. Le présent matériau de formation de film transmettant les infrarouges contient au moins une résine et/ou un premier composé (à l'exclusion d'un composé qui contient au moins un élément choisi parmi le phosphore, le soufre, l'aluminium, le titane et le zirconium) qui comprend au moins deux groupes polymérisables dans chaque molécule, et un second composé qui contient au moins un élément choisi parmi le phosphore, le soufre, l'aluminium, le titane et le zirconium.
PCT/JP2018/042899 2017-12-04 2018-11-20 Matériau de formation de film transmettant les infrarouges, film transmettant les infrarouges et procédé pour le former, plaque protectrice pour dispositifs d'affichage, et dispositif d'affichage WO2019111700A1 (fr)

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JP2017-232881 2017-12-04

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002022904A (ja) * 2000-07-03 2002-01-23 Nissha Printing Co Ltd 反射防止成形品とその製造方法、加飾シート
JP2002060698A (ja) * 2000-08-15 2002-02-26 Origin Electric Co Ltd 赤外線透過層形成用組成物及び赤外線反射体並びに処理物
JP2012047948A (ja) * 2010-08-26 2012-03-08 Sumitomo Osaka Cement Co Ltd 赤外線透過黒色膜、赤外線透過黒色膜を用いた膜付き基材及び画像表示装置
JP2012150418A (ja) * 2010-12-27 2012-08-09 Dainippon Printing Co Ltd 表示用前面板、表示用前面板の製造方法、表示装置および表示装置の製造方法
WO2013094476A1 (fr) * 2011-12-21 2013-06-27 大日本印刷株式会社 Plaque de protection de surface avant pour dispositif d'affichage et dispositif d'affichage
JP2014079944A (ja) * 2012-10-16 2014-05-08 Geomatec Co Ltd 電子機器用の保護パネル、その製造方法及び電子機器
JP2014130173A (ja) * 2012-12-27 2014-07-10 Fujifilm Corp カラーフィルタ用組成物、赤外線透過フィルタ及びその製造方法、並びに赤外線センサー
JP2017097042A (ja) * 2015-11-19 2017-06-01 日本電気硝子株式会社 ディスプレイ用保護部材及びこれを用いた携帯端末
WO2017183432A1 (fr) * 2016-04-18 2017-10-26 日本電気硝子株式会社 Lame de blocage de lumière

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002022904A (ja) * 2000-07-03 2002-01-23 Nissha Printing Co Ltd 反射防止成形品とその製造方法、加飾シート
JP2002060698A (ja) * 2000-08-15 2002-02-26 Origin Electric Co Ltd 赤外線透過層形成用組成物及び赤外線反射体並びに処理物
JP2012047948A (ja) * 2010-08-26 2012-03-08 Sumitomo Osaka Cement Co Ltd 赤外線透過黒色膜、赤外線透過黒色膜を用いた膜付き基材及び画像表示装置
JP2012150418A (ja) * 2010-12-27 2012-08-09 Dainippon Printing Co Ltd 表示用前面板、表示用前面板の製造方法、表示装置および表示装置の製造方法
WO2013094476A1 (fr) * 2011-12-21 2013-06-27 大日本印刷株式会社 Plaque de protection de surface avant pour dispositif d'affichage et dispositif d'affichage
JP2014079944A (ja) * 2012-10-16 2014-05-08 Geomatec Co Ltd 電子機器用の保護パネル、その製造方法及び電子機器
JP2014130173A (ja) * 2012-12-27 2014-07-10 Fujifilm Corp カラーフィルタ用組成物、赤外線透過フィルタ及びその製造方法、並びに赤外線センサー
JP2017097042A (ja) * 2015-11-19 2017-06-01 日本電気硝子株式会社 ディスプレイ用保護部材及びこれを用いた携帯端末
WO2017183432A1 (fr) * 2016-04-18 2017-10-26 日本電気硝子株式会社 Lame de blocage de lumière

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