WO2019078175A1 - Plaque de protection pour dispositif d'affichage ainsi que procédé de fabrication de celle-ci, composition pour formation de film de transmission des rayons infrarouges, film de transmission des rayons infrarouges - Google Patents

Plaque de protection pour dispositif d'affichage ainsi que procédé de fabrication de celle-ci, composition pour formation de film de transmission des rayons infrarouges, film de transmission des rayons infrarouges Download PDF

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WO2019078175A1
WO2019078175A1 PCT/JP2018/038378 JP2018038378W WO2019078175A1 WO 2019078175 A1 WO2019078175 A1 WO 2019078175A1 JP 2018038378 W JP2018038378 W JP 2018038378W WO 2019078175 A1 WO2019078175 A1 WO 2019078175A1
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Prior art keywords
resin
composition
group
transmitting film
infrared
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PCT/JP2018/038378
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English (en)
Japanese (ja)
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直征 牧内
大吾 一戸
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Jsr株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a method of manufacturing a protective plate for a display device, a composition for forming an infrared transmitting film, an infrared transmitting film, and a protective plate for a display.
  • Infrared light has the advantage of being less likely to scatter because it has a longer wavelength than visible light, and so it is used in applications such as distance measurement, three-dimensional measurement, and face recognition.
  • an infrared transmission filter that blocks visible light and transmits infrared light is applied in order to further improve the sensitivity of near infrared light (see, for example, Patent Documents 1 to 3).
  • the infrared ray transmission filter is produced, for example, by applying a resin composition containing carbon black or the like that shields visible light on a glass substrate or the like to form a visible light shielding layer.
  • a front plate cover glass
  • a protective plate of a screen is provided on the outermost surface of a display device such as a mobile phone (see, for example, Patent Document 4).
  • the front plate is provided with a frame portion (bezel) made of a material having a high light shielding property for concealing wiring and the like in the peripheral portion.
  • a frame portion bezel
  • infrared communication unit for performing communication with other mobile phones, face authentication, etc. are widely used. In this case, infrared communication is performed on a part of the frame portion. The opening of is formed.
  • the frame portion of the front plate of a mobile phone or the like is black, and it may not be preferable from the aspect of design when the opening provided in the frame portion is noticeable. Therefore, it has been considered to provide an infrared transmitting film of the same color as that of the frame portion in the opening for infrared communication.
  • another layer such as an antireflective layer may be further laminated to the infrared ray transmitting film.
  • the infrared ray transmitting film is formed by the composition for forming an infrared ray transmitting film, the infrared ray transmitting film is deteriorated by heat or moisture in the film forming process of other layers. It occurs. The deterioration of the infrared ray transmitting film causes a change in light transmittance, a color, etc. and a decrease in adhesion.
  • the present invention has been made based on the above circumstances, and the object of the present invention is to provide a method of manufacturing a protective plate for a display device, in which the deterioration of the infrared ray transmitting film is suppressed, and such a manufacturing method.
  • An object of the present invention is to provide a composition for forming an infrared ray transmitting film, an infrared ray transmitting film whose deterioration is suppressed, and a protective plate for a display device provided with such an infrared ray transmitting film.
  • the invention made to solve the above problems is a substrate, a frame portion provided on one surface side of the substrate and having an opening for infrared communication, and an infrared transmitting film provided in the opening. And a step of forming a coating film in the opening with the composition for forming an infrared ray transmitting film, wherein the composition for forming an infrared ray transmitting film comprises a binder component and a silane.
  • a protective plate for a display device, which comprises a coupling agent, and the content of the silane coupling agent relative to 100 parts by mass of the binder component in the composition for forming an infrared transmitting film is 0.05 parts by mass or more and 7 parts by mass or less Manufacturing method.
  • composition (A) for infrared penetration film formation used for a manufacturing method of a protection plate for the above-mentioned display.
  • compositions for forming an infrared transmitting film provided in an opening for infrared communication formed in a frame portion of a protective plate for a display device
  • a composition for forming an infrared transmitting film comprising a binder component and a silane coupling agent, wherein the content of the silane coupling agent per 100 parts by mass of the binder component is 0.05 parts by mass or more and 7 parts by mass or less It is.
  • composition (A) for the above-mentioned composition for infrared ray transmitting film formation or composition (B) for the above-mentioned composition for infrared rays transmitting film formation.
  • a further invention made to solve the above problems is a substrate, a frame portion provided on one side of the substrate and having an opening for infrared communication, and a frame portion provided in the opening. It is a protective plate for display apparatuses provided with the said infrared rays permeable film.
  • a method of manufacturing a protective plate for a display device in which the deterioration of the infrared ray transmitting film is suppressed a composition for forming an infrared ray transmitting film which can be used for such a manufacturing method, an infrared ray transmitting film And a protective plate for a display device provided with such an infrared transmitting film.
  • FIG. 1 is a plan view showing a protective plate for a display device according to an embodiment of the present invention.
  • FIG. 2 is an A-A 'cross-sectional view of the display device protective plate of FIG.
  • FIG. 3 is a transmission spectrum of the infrared ray transmitting film obtained from the composition for forming an infrared ray transmitting film of Example 1.
  • composition for forming an infrared transmitting film according to an embodiment of the present invention
  • composition contains a binder component and a silane coupling agent.
  • the composition preferably further comprises a coloring agent, and / or a generator (at least one selected from an acid generator and a base generator).
  • the composition can further include other components.
  • the said composition is a composition used for formation of the infrared rays permeable film provided in the opening part for infrared rays communication formed in the frame part of the protection plate for display apparatuses. That is, the said composition is used as a hole-filling material of the opening part (hole part) currently formed in the frame part of the protective plate for display apparatuses. Details will be described below.
  • the binder component is a component which forms a matrix in the obtained infrared ray transmitting film and holds other components.
  • the binder component is usually composed of a resin, a compound having a polymerizable group, and the like, and is preferably a resin, a compound having a polymerizable group, or a combination thereof.
  • the silane coupling agent is not included in the binder component.
  • the binder component can be used alone or in combination of two or more.
  • the resin is not particularly limited as long as it does not impair the effect of the infrared ray transmitting film to be obtained.
  • the resin for example, the thermal stability and the solvent stability are ensured, and the glass transition temperature (Tg) is such that it is applied to a display device etc. and shows resistance to a heating production process of 100 ° C. or more
  • Preferred is a resin having a temperature of 110 ° C. to 380 ° C., more preferably 110 ° C. to 370 ° C., still more preferably 120 ° C. to 360 ° C.
  • the glass transition temperature (Tg) is, for example, a value measured at a temperature rising rate of 20 ° C./minute under a nitrogen stream using a differential scanning calorimeter (DSC 6200) manufactured by SII Nano Technologies Inc. Can.
  • the resin is preferably a transparent resin.
  • the total light transmittance (JIS K 7105) at a thickness of 0.1 mm is preferably 75% to 95%, more preferably 78% to 95%, and still more preferably 80% to 95%.
  • the resin which is can be used. If the total light transmittance is in such a range, good transparency is exhibited in the near infrared region even as an infrared transmitting film to be obtained.
  • resins examples include cyclic olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, and polyarylate resins.
  • Resin, polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, alkali soluble resin, epoxy resin, allyl ester curing There can be mentioned at least one selected from a mold resin and a siloxane resin.
  • the cyclic olefin-based resin is a polymer containing cyclic olefin as a monomer.
  • cyclic olefin resin a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X 0 ) and a monomer represented by the following formula (Y 0 ) Or a resin obtained by further hydrogenating the resin as necessary.
  • R x1 to R x4 each independently represent an atom or a group selected from the following (i) to (viii).
  • Each of k x , m x and p x independently represents 0 or a positive integer.
  • the upper limit of k x , m x and p x may be, for example, 5 or 2 or 1, respectively.
  • 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 not involved in the bonding Each independently represents an atom or a group selected from (i) to (vi) described above.
  • R x2 and R x3 represent a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding to each other, and R x1 to R x4 which are not involved in the bonding are each independently the above (i) to (i) (Vi) represents an atom or a group selected from
  • R y1 and R y2 each independently represent an atom or a group selected from the above (i) to (vi), or represent the following (ix).
  • k y and p y each independently represent 0 or a positive integer.
  • the upper limit of k y and p y may each be 5, for example, it may be two or one.
  • 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.
  • Epoxy resin is a resin having an epoxy group.
  • the epoxy group is a cyclic ether group having 2 or more carbon atoms, and is a group containing both an oxiranyl group and an oxetanyl group.
  • As the epoxy resin a resin having an oxiranyl group, a 3,4-epoxycyclohexyl group or an oxetanyl group is preferable. These groups may have some or all of hydrogen atoms substituted with a substituent such as an alkyl group.
  • Epoxy resins also include prepolymers.
  • a resin (compound) having a plurality of oxiranyl groups for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated Bisphenol polyglycidyl ethers of bisphenols such as diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl Ethers, polyglycidyl ethers of polyhydric alcohols such as polypropylene glycol diglycidyl ether; ethylene glycol Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene
  • Examples of the resin (compound) having a plurality of 3,4-epoxycyclohexyl groups include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5, 5-Spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy- 6-Methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ethylene glycol Ether, D Renbisu (3
  • resins (compounds) having a plurality of oxetanyl groups include OXT-121, OXT-221, OXT-191, OX-SQ-H, PNOX-1009, RSOX (manufactured by Toagosei Co., Ltd.), Etanacol OXBP, as commercially available products. Etanacol OXTP (made by Ube Industries, Ltd.) etc. can be mentioned.
  • Aromatic Polyether-Based Resin has at least one structure selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) It is preferred to have a unit.
  • R 1 to R 4 each independently represent a monovalent organic group having 1 to 12 carbon atoms.
  • a to d each independently represent an integer of 0 to 4;
  • an organic group means group containing a carbon atom, and a hydrocarbon group, a halogenated hydrocarbon group, a carboxy group, a cyano group etc. are mentioned.
  • R 1 ⁇ R 4 and a ⁇ d have the same meanings as R 1 ⁇ R 4 and a ⁇ d each independently of the above formula (1).
  • R 7 and R 8 each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group.
  • 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 aromatic polyether resin further has at least one structural unit selected from the group consisting 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 each independently represent a C 1-12 monovalent organic group.
  • e and f each independently represent an integer of 0 to 4; n represents 0 or 1;
  • R 7, R 8, Y, m, g and h are each R 7, R 8 in independent on the equation (2), Y, m, synonymous with g and h.
  • R 5, R 6, Z, n, e and f have the same meanings as respectively R 5, R 6, Z independently in the above formula (3) in, n, e and f.
  • the polyimide-based 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 and JP-A-2008-163107.
  • the fluorene polycarbonate resin is not particularly limited, and any polycarbonate resin containing a fluorene moiety may be used.
  • 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 method described in JP-A-2010-285505 and JP-A-2011-197450.
  • the fluorinated aromatic polymer-based resin is not particularly limited, and an aromatic ring having at least one fluorine, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond And polymers containing a repeating unit containing at least one bond selected from the group consisting of and ester bonds.
  • the fluorinated aromatic polymer resin can be synthesized, for example, by the method described in Japanese Patent Application Laid-Open No. 2008-181121.
  • the siloxane-based resin is preferably a hydrolysis condensate of a hydrolyzable silane compound.
  • the hydrolyzable silane compound is usually hydrolyzed to generate a silanol group by heating in a temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the coexistence of no catalyst and excess water.
  • a silane compound having a "hydrolyzable group" capable of forming a siloxane compound which is a hydrolytic condensate by condensation by heating or the like.
  • non-hydrolyzable group in that case refers to the group which does not hydrolyze or condense under the hydrolysis conditions as mentioned above, and exists stably.
  • part of the hydrolyzable groups may remain unhydrolyzed.
  • hydrolytic condensate of the hydrolyzable silane compound a part of hydrolyzable groups may remain unhydrolyzed, and a part of silanol groups of the hydrolyzed silane compound is uncondensed. It may remain in the state.
  • hydrolyzable silane compound a silane compound substituted with one non-hydrolyzable group and three hydrolysable groups, and two non-hydrolyzable groups and two hydrolysable groups Mention may be made of substituted silane compounds, silane compounds substituted with three nonhydrolyzable groups and one hydrolyzable group, or mixtures thereof.
  • hydrolyzable silane compounds include hydrotrimethoxysilane, hydrotriethoxysilane, and methylsilane as silane compounds substituted with one nonhydrolyzable group and three hydrolyzable groups. Trimethoxysilane, Methyltriethoxysilane, Methyltri-i-propoxysilane, Methyltributoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltri-i-propoxysilane, Ethyltributoxysilane, Butyltrimethoxysilane, Hexyl Trimethoxysilane, Hexyltriethoxysilane, Decyltrimethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Styryltrimethoxysilane, Styryltriethoxysilane, Tolyltrimethoxysilane
  • hydrolyzable silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups are particularly preferable in view of hydrolysis reactivity and condensation reactivity.
  • Specific examples of the preferred hydrolyzable silane compound include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, and ⁇ -glycidoxypropyl tri Methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane can be mentioned.
  • Such hydrolyzable silane compounds may be used alone or in combination of two or more.
  • hydrolysable silane compounds other than the said hydrolysable silane compound can also be used together.
  • hydrolyzable silane compounds include silane compounds substituted with four hydrolyzable groups; tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-silane n-propoxysilane, tetra-i-propoxysilane and the like can be mentioned.
  • hydrolyzable titanium compounds hydrolyzable aluminum compounds
  • hydrolyzable zinc compounds and the like can be used in combination.
  • the conditions for hydrolyzing and condensing the hydrolyzable silane compound are as long as at least a part of the hydrolyzable silane compound is hydrolyzed to convert the hydrolyzable group into a silanol group to cause a condensation reaction, although it does not specifically limit, it can implement as follows as an example.
  • water used for hydrolysis and condensation of the hydrolyzable silane compound it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.
  • the amount of water used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 2 mol, still more preferably 0 mol per mol of the total amount of hydrolysable groups of the hydrolyzable silane compound. 0.5 mol to 1.5 mol in amount. By using such an amount of water, the reaction rate of hydrolysis and condensation can be optimized.
  • the solvent that can be used for the hydrolysis / condensation of the hydrolyzable silane compound is not particularly limited, and examples thereof include linear, branched or cyclic alkyl alcohols having 1 to 15 carbon atoms, and carbon atoms Ketones of 3 to 20, tetrahydrofuran, benzene, toluene, xylene, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propionic acid esters may be mentioned.
  • diethylene glycol dimethyl ether diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate and methyl 3-methoxypropionate are particularly preferable.
  • the hydrolysis / condensation reaction of the hydrolyzable silane compound is preferably an acid catalyst (eg, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, maleic anhydride, methane) Sulfonic acid, toluene sulfonic acid, acidic ion exchange resin, various Lewis acids, base catalyst (eg, ammonia, primary amines, secondary amines, tertiary amines, pyridine, nitrogen containing nitrogen such as pyridine, quaternary ammonium hydroxide) Compound; basic ion exchange resin; hydroxide such as sodium hydroxide and potassium hydroxide; carbonate such as sodium carbonate and potassium carbonate; carboxylate such as sodium acetate and potassium acetate; various Lewis bases) or metal Alkoxide (eg, zirconium alkoxide, titanium al
  • tetra-i-propoxyaluminum can be used as the aluminum alkoxide.
  • the amount of the catalyst used is preferably 10 ⁇ 6 mol to 0.2 mol, more preferably 0. 6 mol to 0.2 mol, per mol of the monomer of the hydrolyzable silane compound, from the viewpoint of promoting hydrolysis and condensation reaction. It is from 00001 mol to 0.1 mol.
  • the reaction temperature and reaction time in the hydrolysis / condensation of the hydrolyzable silane compound are appropriately set.
  • the reaction temperature is preferably 40 ° C. to 200 ° C., more preferably 50 ° C. to 150 ° C.
  • the reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 12 hours.
  • the reaction may be carried out in one step by adding the hydrolyzable silane compound, the solvent, water and the catalyst all at once into the reaction system, or the hydrolyzable silane compound, the solvent, water
  • the hydrolysis and condensation reactions may be carried out in multiple steps by adding any one of the catalysts and the catalyst, or an arbitrarily selected mixture, into the reaction system in several portions.
  • water and generated alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting to evaporation.
  • the siloxane compound obtained by hydrolytic condensation can be handled as a solution by not completely removing the solvent or water, or by adding an optional solvent.
  • silsesquioxane type UV cured resin etc. can also be used as siloxane type resin.
  • the alkali-soluble resin is a resin soluble in an aqueous alkali solution.
  • the alkali-soluble resin is usually a polymer containing a structural unit having an acidic group such as a carboxy group or a phenolic hydroxyl group.
  • the alkali-soluble resin is, for example, a structural unit formed of at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter also referred to as “(1-1) compound”); It is a copolymer having a structural unit formed of another unsaturated compound (hereinafter also referred to as “(1-2) compound”).
  • the alkali-soluble resin can be produced, for example, by copolymerizing the compound (1-1) giving a carboxy group-containing structural unit in a solvent and the unsaturated compound (1-2) compound in the presence of a polymerization initiator.
  • Examples of the compound (1-1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids, and the like.
  • Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid; As unsaturated dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc .; As the anhydride of unsaturated dicarboxylic acid, for example, anhydride of the compound exemplified as the above dicarboxylic acid; Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], etc. Be
  • (1-1) compounds unsaturated monocarboxylic acids and unsaturated dicarboxylic acid anhydrides are preferred, and acrylic acid, methacrylic acid and maleic anhydride are copolymerizable, soluble in alkaline aqueous solution and available It is more preferable because of ease.
  • These compounds (1-1) may be used alone or in combination of two or more.
  • the proportion of the compound (1-1) used is preferably 5% by mass to 30% by mass, and more preferably 10% by mass to 25% by mass, based on the total of all the polymerizable monomers of the alkali-soluble resin. By using it in the said range, while optimizing the solubility with respect to the aqueous alkali solution of alkali-soluble resin, the composition which is excellent in radiation sensitivity is obtained.
  • (1-2) Compounds: epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, phenolic hydroxyl group-containing unsaturated compounds, methacrylic acid linear alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid linear alkyl esters, Acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, unsaturated compound having a tetrahydrofuran skeleton and the like, and other compounds Unsaturated compounds and the like can be mentioned.
  • Examples of the epoxy group-containing unsaturated compound include unsaturated compounds having an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), and the like.
  • Such unsaturated compounds having an oxiranyl group include, for example, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, p-vinylbenzyl glycidyl ether, methacrylic acid 3,4-epoxycyclohexyl Etc.
  • Examples of the unsaturated compound having an oxetanyl group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, Methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane and the like can be mentioned.
  • Examples of the hydroxyl group-containing unsaturated compound and the phenolic hydroxyl group-containing unsaturated compound include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and (meth) acrylic And 5-hydroxypentyl acid, 6-hydroxyhexyl (meth) acrylate, p-hydroxystyrene and the like.
  • Examples of acrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate, 4-hydroxyphenyl acrylate and the like.
  • Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate, 4-hydroxyphenyl methacrylate and the like.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and (meth) acrylic acid t.
  • maleimide compound for example, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxy benzyl) maleimide, N-succinimidyl-3-maleimidobenzoate And N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.
  • unsaturated aromatic compounds include styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene and the like.
  • conjugated dienes examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
  • unsaturated compound containing a tetrahydrofuran skeleton examples include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one and the like.
  • the (1-2) compounds may be used alone or in combination of two or more.
  • the use ratio of the compound (1-2) is preferably 10% by mass to 80% by mass, based on the total of all the polymerizable monomers of the alkali-soluble resin.
  • the method of synthesizing an alkali-soluble resin can be produced, for example, by copolymerizing the above compound (1-1) and the compound (1-2) in the presence of a polymerization initiator in a solvent.
  • a solvent used for the polymerization reaction for producing an alkali soluble resin for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether And propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.
  • a polymerization initiator used for a polymerization reaction what is generally known as a radical polymerization initiator can be used.
  • a radical polymerization initiator for example, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 And azo compounds such as -methoxy-2,4-dimethylvaleronitrile) and peroxides.
  • the acid value of the alkali-soluble resin is usually 50 to 150 mg KOH / g, preferably 60 to 135 mg KOH / g, and particularly preferably 70 to 135 mg KOH / g.
  • the acid value is within the above range from the improvement of the residual film rate after development because the solubility in an alkali developer is improved and the sensitivity is improved as well as the unexposed area is easily dissolved. Is preferred.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the alkali-soluble resin, and can usually be determined by titration using an aqueous potassium hydroxide solution. .
  • polyimide system resin "Neoprim L” by Mitsubishi Gas Chemical Co., Ltd. etc. can be mentioned, for example.
  • polycarbonate system resin Teijin Ltd. make “Pure ace” etc. can be mentioned, for example.
  • examples of commercially available products of fluorene polycarbonate-based resins include “Iupizeta EP-5000” manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • fluorene polyester-type resin Osaka Gas Chemical Co., Ltd. "OKP4HT” etc. can be mentioned, for example.
  • alkali-soluble resin acrylic resin
  • polyester polyol resin for example, "Polylight OD-X-2585” manufactured by DIC Corporation can be mentioned.
  • silsesquioxane type UV cured resin "Nichiplus Chemical Co., Ltd. make” sil plus "etc. can be mentioned, for example.
  • the molecular weight of the resin is not particularly limited, but the lower limit of the weight average molecular weight is preferably 500, more preferably 600, still more preferably 1,000, and even more preferably 5,000.
  • the upper limit of the weight-average molecular weight is preferably 300,000, more preferably 200,000, and even more preferably 100,000 or 10,000.
  • the siloxane-based resin has a relatively small weight average molecular weight, such as a range of 600 to 5,000.
  • the alkali-soluble resin is in a relatively large weight average molecular weight range, such as in the range of 5,000 to 300,000.
  • the number average molecular weight of the resin is, for example, 1,000 or more and 1,000,000 or less, and may be 1,500 or more and 10,000 or less.
  • the molecular weight of the resin can be measured by the following method (a) or (b) in consideration of the solubility of each resin in the solvent and the like.
  • GPC Gel permeation chromatography
  • the logarithmic viscosity can be, for example, 0.5 or more and 2 or less.
  • the logarithmic viscosity is a value measured by the following method (c).
  • the binder component preferably contains a compound having a polymerizable group. By using such a compound, it is possible to further suppress deterioration of the obtained infrared ray permeable film due to heat, moisture and the like.
  • the compound having a polymerizable group preferably has two or more polymerizable groups.
  • At least 1 sort (s) chosen from the group which consists of an epoxy group, an alicyclic epoxy group, and a vinyl group is preferable, and an epoxy group is more preferable.
  • an epoxy group oxiranyl group and oxetanyl group are preferable.
  • the alicyclic epoxy group include 3,4-epoxycyclohexyl group and 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl group.
  • the binder component may be a mixture of a compound having a polymerizable group and a compound having no polymerizable group.
  • the compound having a polymerizable group may be a resin or another compound. That is, as the resin, a resin having a polymerizable group can be used.
  • a resin having a polymerizable group can be used.
  • an epoxy resin, an alkali-soluble resin having a polymerizable group such as an epoxy group, a siloxane resin having a polymerizable group such as an epoxy group, and the like are compounds having a polymerizable group.
  • the compound having a polymerizable group other than the resin having a polymerizable group may be, for example, a compound having a molecular weight of less than 2,000 or less than 1,000.
  • epoxy resin As a compound which has an epoxy group or an alicyclic epoxy group as a polymeric group, the compound mentioned above as a specific example of epoxy resin can be mentioned.
  • Examples of the compound having a vinyl group as a polymerizable group include ethylene glycol divinyl ether, diethylene glycol divinyl ether, divinyl benzene, 1,6-bis (ethenyloxy) hexane and the like.
  • the compound having a vinyl group may be a compound having a (meth) acryloyl group.
  • the lower limit of the content ratio of the compound having a polymerizable group in the binder component contained in the composition is preferably 1% by mass, more preferably 5% by mass, still more preferably 10% by mass, and still more preferably 20% by mass. Preferably, 30 wt%, 50 wt% and 80 wt% may be even more preferred.
  • the upper limit of the content ratio may be 100% by mass, and 80% by mass and 60% by mass may be preferable.
  • the lower limit of the content of the binder component in the solid content of the composition is, for example, 50% by mass, preferably 70% by mass, more preferably 80% by mass, and even more preferably 90% by mass.
  • an upper limit of the content rate of this binder ingredient 99 mass% is preferred, 97 mass% is more preferred, and 95 mass% is still more preferred.
  • solid content means all the components other than the solvent in the said composition.
  • the silane coupling agent is used to improve adhesion to a substrate or the like and to suppress deterioration.
  • the silane coupling agent is usually a silicon compound having a hydrolyzable group and a non-hydrolyzable group having a polymerizable group.
  • a silane coupling agent the compound represented, for example by a following formula (A) can be mentioned.
  • X n -Si-Y 4-n (A)
  • X is a hydrolyzable group.
  • Y is a non-hydrolyzable group having a polymerizable group.
  • n is an integer of 1 to 3.
  • hydrolysable group represented by X alkoxy groups, such as a methoxy group and an ethoxy group, are mentioned.
  • non-hydrolyzable group having a polymerizable group represented by Y include a polymerizable group such as a vinyl group, and a group having a hydrogen atom of a hydrocarbon group substituted by the polymerizable group.
  • the polymerizable group include those described above as the polymerizable group of the “compound having a polymerizable group”, an amino group, an isocyanurate group, a ureido group, a mercapto group, an isocyanate group and the like.
  • the polymerizable group which a silane coupling agent has may be in the state protected by the protective group.
  • the above n is preferably 3.
  • silane coupling agent examples include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (Methacrylopropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-2-aminoethyl-3- Aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, vinyltrimethoxy
  • the lower limit of the content of the silane coupling agent is 0.05 parts by mass, preferably 0.1 parts by mass, further preferably 0.3 parts by mass, with respect to 100 parts by mass of the binder component. Parts are even more preferred.
  • the upper limit of the content is 7 parts by mass, preferably 5 parts by mass.
  • the infrared rays permeable film in which degradation was suppressed can be obtained, and there is little change of the average transmittance
  • a coloring agent is a substance which gives a color by absorption or emission of visible light, is a concept including both an inorganic compound and an organic compound, and includes both a dye and a pigment.
  • the composition preferably contains three or more colorants. Furthermore, the composition comprises a colorant A having an absorption maximum in a wavelength range of 400 nm to 580 nm, a colorant B having an absorption maximum in a wavelength range of 581 nm to 700 nm, and an absorption maximum in a wavelength range of 701 nm to 800 nm. It is preferable to contain the coloring agent C which has. By including such a coloring agent, it is possible to achieve shielding of the visible region continuously.
  • the composition may contain a plurality of colorants other than the above three colorants.
  • the colorant A having an absorption maximum in the wavelength range of 400 nm to 580 nm will be described below.
  • coloring agent A a coloring agent having an absorption maximum in the wavelength range of 430 nm to 560 nm is preferable.
  • colorants 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.
  • Such a cyanine dye is a dye containing, as a colorant, only a compound having in its molecule a conjugated double bond of an odd number of methine groups between two heterocyclic rings.
  • a cyanine dye the compound shown by following formula (C1) and (C2) can be mentioned.
  • Z 1 represents an alkyl group having 1 to 12 carbon atoms or a phenyl group.
  • Z 2 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a naphthyl group, and one or more hydrogen atoms of the phenyl group and the naphthyl group may be substituted with a halogen or an alkyl group having 1 to 12 carbon atoms .
  • the Z 3 and Z 4 each independently represent a hydrogen atom, an alkyl group or a phenyl group having 1 to 12 carbon atoms.
  • n is an integer of 1 to 12.
  • X - represents a counter anion.
  • X - it includes the counter anion, 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 anion, organic sulfonyl A methide acid anion etc. are mentioned.
  • halide ion Cl ⁇ , Br ⁇ , I ⁇ and the like can be mentioned.
  • the organic carboxylate anion include benzoate ion, alkanoate ion, trihaloalkanoate ion, and nicotinate ion.
  • organic sulfonate anion examples include benzenesulfonate ion, naphthalenesulfonate ion, p-toluenesulfonate ion, alkanesulfonate ion and the like.
  • Lewis acid anion tetrafluoroborate ion, hexafluoroantimonate ion, tetrakis (pentafluorophenyl) boron anion and the like can be mentioned.
  • pigments described in [0072] of JP-A-2017-090780 and [0049] of JP-A-2016-07030 can be used, and preferably “CI Pigment Blue 15: 6, 16, 79.
  • the content of the coloring agent A is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the binder component. It is. By using the coloring agent A in such a range, it is possible to form an infrared transmitting film having a low transmittance in the visible light region and a high transmittance in the near infrared light region.
  • Colorant B a coloring agent having an absorption maximum in the wavelength range of 590 nm to 660 nm is preferable.
  • Colorant B includes yellow and green dyes, yellow and green pigments. 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.
  • Z 5 each independently represent a hydrogen atom, an alkyl group or a phenyl group having 1 to 12 carbon atoms.
  • Ring T represents an aromatic group or heterocyclic group having 3 to 10 carbon atoms which may have a substituent.
  • X - represents a counter anion. Specific counter anions include halide ions, perchlorate ions, hydroxide ions, organic carboxylate anions, organic sulfonate anions, Lewis acid anions, organic metal complex anions, dye-derived anions, organic sulfonylimidate anions And organic sulfonyl methide acid anions and the like.
  • a compound (C3-1) represented by the following formula can be mentioned.
  • the maximum absorption ( ⁇ max) of the compound (C3-1) is 604 nm.
  • JP-A-2017-116767 the paragraph [0013] of JP-A-2016-191047, and [0042] of JP-A-2016-038584.
  • the pigment described in the paragraph [0027] of JP-A-2015-045736 and the paragraph [0025] of JP-A-2014-215416 can be used, and among them, particularly preferably “CI Pigment Yellow”. 129, 138, 139, 150, 185, 231.
  • C.I. I. Pigment green 7, 36, 58, 59, 62, 63, etc. preferably C.I. I. Pigment green 7, 36, 58, 59.
  • the content of the coloring agent B is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the binder component. It is. By using the coloring agent B in such a range, it is possible to form an infrared transmitting film having a low transmittance in the visible light region and a high transmittance in the near infrared light region.
  • the colorant C having an absorption maximum in the wavelength range of 701 nm to 800 nm will be described.
  • a coloring agent having an absorption maximum in a wavelength range of 710 nm to 760 nm is preferable.
  • a red dye and a red pigment are preferably used. Examples of red dyes include squarylium dyes and phthalocyanine dyes.
  • X each independently represents a methylene group in which one or more hydrogen atoms may be substituted with an alkyl group or alkoxyl group having 1 to 12 carbon atoms, or an alkylene group having 2 to 12 carbon atoms .
  • Z 6 , Z 7 and Z 8 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group.
  • Z 9 each independently represents a fluorinated alkyl group having an alkyl group or a carbon number from 1 to 12 carbons 12.
  • a compound (C4-1) represented by the following formula can be mentioned.
  • the maximum absorption ( ⁇ max) of the compound (C4-1) is 712 nm.
  • each Z 10 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group.
  • M represents metal free (in a form in which two hydrogen atoms are bonded), metal or metal oxide.
  • the metal include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe.
  • the metal oxide include VO, TiO, and the like.
  • a compound (C5-1) represented by the following formula can be mentioned.
  • the maximum absorption ( ⁇ max) of the compound (C5-1) is 738 nm.
  • the content of the colorant C is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the binder component. It is. By using the colorant C in such a range, it is possible to form an infrared transmitting film having a low transmittance in the visible light region and a high transmittance in the near infrared light region.
  • the difference between the absorption maximum wavelengths of the coloring agent A and the coloring agent B be 40 nm or more and 200 nm or less, and the difference between the absorption maximum wavelengths of the coloring agent B and the coloring agent C be 80 nm or more and 200 nm or less.
  • the difference of the absorption maximum wavelength of coloring agent A and coloring agent B, coloring agent B, and coloring agent C when 2 or more types with which absorption maximum wavelengths differ are used, the difference of the absorption maximum wavelength of coloring agent A and coloring agent B, coloring agent B, and coloring About the difference of the absorption maximum wavelength of the agent C, at least one of the combination of several coloring agents should just satisfy the said conditions.
  • the composition may or may not contain one or more other colorants other than the above three colorants A to C.
  • the upper limit of the content of the other coloring agent is preferably 10 parts by mass, more preferably 1 part by mass, and still more preferably 0.1 parts by mass with respect to 100 parts by mass in total of the coloring agents A to C.
  • the generator (at least one selected from an acid generator and a base generator) usually functions as an initiator for ionic polymerization (cationic polymerization or anionic polymerization) of a compound having a polymerizable group.
  • ionic polymerization cationic polymerization or anionic polymerization
  • a compound having a polymerizable group By containing an acid or a base generator in the composition, polymerization is promoted by irradiation with radiation (visible light, ultraviolet light, far ultraviolet light, etc.), heating, etc. to form an infrared transmitting film having excellent curability. can do.
  • These generators may generate an acid or a base upon irradiation with radiation, or may generate an acid or a base upon heating, but generate an acid or a base upon irradiation with radiation. Is preferred.
  • the generator there are an ionic compound and a nonionic compound, but a nonionic compound is preferable.
  • a non-ionic generator it is possible to enhance the resistance to heat and humidity of the obtained cured film and the light transmittance.
  • Examples of the acid generator include oxime sulfonate compounds, sulfoneimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, onium salts and the like.
  • oxime sulfonate compounds, sulfoneimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds and carboxylic acid ester compounds are nonionic compounds.
  • the onium salt is an ionic compound.
  • the oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (5).
  • R B1 is an alkyl group, a cycloalkyl group or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.
  • the alkyl group of R B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group of R B1 includes a bridged alicyclic group such as an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (7, 7-dimethyl-2-oxo norbornyl group, etc., preferably a bicycloalkyl And the like) may be substituted.
  • the aryl group of R B1 is preferably an aryl group having a carbon number of 6 to 11, and more preferably a phenyl group and a naphthyl group.
  • the aryl group of R B1 may be substituted with an alkyl group of 1 to 5 carbon atoms, an alkoxy group or a halogen atom.
  • the said compound containing the oxime sulfonate group represented by the said Formula (5) is an oxime sulfonate compound represented by following formula (6).
  • R B1 has the same meaning as the description of R B1 in Formula (5).
  • X is an alkyl group, an alkoxy group or a halogen atom.
  • m is an integer of 0 to 3. When m is 2 or 3, multiple Xs may be the same or different.
  • the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • alkoxy group as X a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable.
  • the halogen atom as X is preferably a chlorine atom or a fluorine atom.
  • m is preferably 0 or 1.
  • compounds of the formula (6) in which m is 1, X is a methyl group, and the substitution position of X is ortho are preferable.
  • oxime sulfonate compound examples include, for example, compounds (6-i), compounds (6-ii) and compounds (6-iii) represented by the following formulas (6-i) to (6-v) Compound (6-iv) and compound (6-v) may, for example, be mentioned.
  • 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.
  • halogen containing compound a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound etc.
  • preferred halogen-containing compounds are: 1,10-dibromo-n-decane; 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane; 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) And s-triazine derivatives such as -2-yl) ethenyl] -4,6-bis- (trichloromethyl) -1,3,5-triazine.
  • diazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and the like.
  • sulfone compounds include ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds and ⁇ -diazo compounds of these compounds.
  • Specific examples of preferred sulfone compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone and bis (phenacylsulfonyl) methane.
  • sulfonic acid compound examples include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates and the like.
  • preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate and the like.
  • carboxylic acid ester compound examples include carboxylic acid o-nitrobenzyl ester and the like.
  • onium salt compound examples include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like.
  • preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Sulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butyl
  • nonionic acid generators are preferable, and oxime sulfonate compounds and sulfonimide compounds are more preferable.
  • Base generator As a base generator, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-an Heterocyclic group-containing base generators such as (4-morpholinophenyl) -butanone, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, 1- (anthraquinone-2-yl) ethylimidazole carboxylate; 2-Nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, o And -carbamoyl hydroxylamide, o-carbam
  • heterocyclic group-containing base generators are preferred.
  • 0.1 mass part is preferred to 100 mass parts of binder components, and 0.5 mass part is more preferred.
  • 20 mass parts is preferred, 10 mass parts is more preferred, and 3 mass parts is still more preferred.
  • the composition usually contains a solvent.
  • the solvent is not particularly limited as long as it is a dispersion medium or a solvent in which each component such as a binder component and a silane coupling agent can be stably dispersed.
  • the term "solvent" is used in the concept including both the dispersion medium and the solvent.
  • the solvent examples include alcohols such as isopropyl alcohol, n-butyl alcohol, ethyl cellosolve, methyl cellosolve, glycols such as ethylene glycol, diethylene glycol and propylene glycol, and 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 mono Ethyl 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 a
  • the amount of the solvent is preferably 10 to 5,000 parts by mass, and more preferably 30 to 2,000 parts by mass with respect to 100 parts by mass of the binder component.
  • the said composition can use the arbitrary components shown below other than the said compound.
  • Optional components include, for example, color correction dyes, leveling agents, antistatic agents, heat stabilizers, light stabilizers, antioxidants, dispersants, flame retardants, lubricants, plasticizers, thickeners, transparent nanoparticles, cured An accelerator etc. are mentioned.
  • 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 light transparency.
  • 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 or t-butyl group is preferable.
  • the hindered phenol compound may be any of monophenols, bisphenols and polyphenols.
  • a hindered amine compound can be used, for example.
  • a 2,2 ', 6,6'-tetraalkylpiperidine derivative is preferable.
  • the substituent on the nitrogen atom is preferably a hydrogen atom, an alkyl group or an alkoxy group.
  • the 2- and 6-position substituents are preferably an alkyl group or a phenyl group.
  • nanoparticles of an inorganic oxide material transparent in the infrared wavelength range may be included.
  • Such materials include Al 2 O 3 , SiO 2 , GeO 2 , Y 2 O 3 , La 2 O 3 , Ce 2 O 3 , CeO 2 , TiO 2 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 and the like.
  • the composition can also contain a surfactant.
  • a surfactant By including the surfactant, it is possible to improve the appearance, in particular, a void due to a fine bubble, a dent due to adhesion of foreign matter and the like, and a repelling during a drying step.
  • the surfactant is not particularly limited, and known ones such as cationic, anionic and nonionic surfactants can be optionally used.
  • the content ratio of the other components in the solid content of the composition, 10% by mass may be preferable, and 1% by mass Is more preferable, and 0.1% by mass may be more preferable.
  • the viscosity of the composition is preferably in the range of 15 to 1,000 mPa ⁇ s at 25 ° C., more preferably in the range of 15 to 100 mPa ⁇ s, and in the range of 20 to 50 mPa ⁇ s. More preferable. By being in this range, both coating properties and storage stability can be achieved at a high level.
  • the solid content concentration of the composition is preferably in the range of 5 to 15% by mass.
  • the infrared transmitting film according to the embodiment of the present invention is provided in an opening for infrared communication formed in a frame (bezel) of the display device protection plate.
  • the display device protection plate is a cover for protecting the screen of a display device such as a smartphone, and is provided on the surface of the screen.
  • This protective plate is also referred to as a front plate or the like.
  • the display device protection plate is not limited to the one provided on the “front surface” of the display device.
  • the protective plate has a transparent substrate and a frame portion disposed on the periphery of one surface of the transparent substrate.
  • the frame portion (bezel) is a member that protects the peripheral portion of a display device such as a display and also has the role of hiding wiring and the like.
  • the display unit protection plate will be described in detail later.
  • the lower limit of the average thickness of the infrared transmitting film 120 is preferably 1 ⁇ m, more preferably 3 ⁇ m, and still more preferably 5 ⁇ m.
  • the upper limit of the average thickness is preferably 1,000 ⁇ m, more preferably 100 ⁇ m, and still more preferably 30 ⁇ m.
  • the lower the average transmittance at a wavelength of 400 to 700 nm corresponding to visible light in the infrared transmitting film formed using the composition the better the effect of reducing visible light as sensing noise. Moreover, it becomes an infrared rays permeable film more synchronized with the frame part.
  • the average transmittance of the infrared ray transmitting film at a wavelength of 400 to 700 nm is preferably 10% or less, more preferably 7% or less, and particularly preferably 5% or less.
  • the lower limit of the average transmittance is preferably substantially 0%, but may be 1%.
  • the average transmittance of the infrared ray transmitting film in the near infrared region at a wavelength of 800 to 1100 nm is preferably 80% or more, more preferably 90% or more.
  • the upper limit of the average transmittance is preferably substantially 100%, but may be 99%, 97% or 95%.
  • the protective plate for a display device of FIGS. 1 and 2 includes a substrate 100, a frame portion 110 disposed on the periphery of one surface of the substrate 100, an infrared ray transmitting film 120, Is equipped.
  • an opening 130 for infrared communication is formed (see FIG. 2).
  • An infrared transmitting film 120 is provided in the opening 130. That is, the infrared ray transmitting film 120 is laminated on the surface of the substrate 100 in which the opening 130 of the window portion which transmits infrared rays is formed.
  • the display device protection plate is provided on the surface of a screen of a display device such as a smartphone. That is, the display device protection plate is a cover that protects the screen of the display device.
  • the substrate 100 is usually a transparent substrate formed of a transparent material.
  • the 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 substrate 100 is preferably a glass substrate.
  • the average thickness of the 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 substrate 100.
  • the frame portion 110 has a role of hiding the wiring of the peripheral portion, and is usually black in many cases.
  • the black frame portion 110 generally includes a black pigment and a resin.
  • black pigments include graphite.
  • resin of the frame part 110 an acrylic resin, cycloolefin resin, a polyimide, a polyether, a polyester resin, a polyurethane resin etc. can be mentioned, for example.
  • the frame portion 110 can be formed, for example, by applying a resin composition containing a resin and graphite to the surface of the substrate 100 and heating. Alternatively, the photosensitive resin composition may be coated, and exposed and heated. In addition, the separately formed frame portion 110 may be laminated on the surface of the substrate 100.
  • the opening portion 130 is a through hole formed 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 shape of the opening 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 permeable membrane Infrared permeable membrane
  • Infrared ray transmitting film 120 is provided on the surface of substrate 100 in the area 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 of the surface of the substrate 100 where the opening 130 is provided.
  • the infrared ray permeable film 120 is formed of the composition for forming an infrared ray permeable film according to the embodiment of the present invention described above.
  • 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 substrate 100) of the infrared ray transmitting film 120 in FIGS.
  • the covering layer include an antireflection layer, an oxygen shielding layer, an ultraviolet absorbing layer and the like.
  • the display device protective plate may have an intermediate layer, for example, between the transparent substrate 100 and the infrared ray transmitting film 120 in FIGS. 1 and 2. An ultraviolet absorption layer etc. can be mentioned as this intermediate
  • the protective plate for a display device Since the infrared ray transmitting film 120 is formed of the composition, the protective plate for a display device has the deterioration of the infrared ray transmitting film suppressed, and has excellent visible light shielding properties and the like, and also the adhesion property It is good.
  • a substrate, a frame portion provided on one surface side of the substrate and having an opening for infrared communication formed therein, and the opening It is a manufacturing method of a protection plate for displays provided with an infrared rays permeable film provided, (1) The process of forming a coating film in the said opening part with the said composition for infrared rays permeable film formation is provided.
  • the manufacturing method may further include (2) heating or exposing the coating film, and (3) laminating a covering layer on the infrared transmitting film formed through the heating or exposure.
  • the composition is applied in the opening for infrared communication formed in the frame portion of the protective plate for a display device, and preferably a film is formed by removing the solvent by prebaking. .
  • the frame portion is formed on a substrate.
  • the said composition is apply
  • an appropriate method 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, a screen printing method, or an inkjet method is adopted.
  • a spin coating method, a screen printing method, and an inkjet method are preferable.
  • the conditions for pre-baking may vary depending on the types of the components contained in the composition, the content ratio thereof, and the like, but may be, for example, about 60 seconds to 100 degrees Celsius for about 30 seconds to about 10 minutes.
  • the film thickness of the coating film is preferably 1 ⁇ m as the lower limit after prebaking. Moreover, as this upper limit, 30 micrometers is preferable, 20 micrometers is more preferable, and 10 micrometers is more preferable.
  • the coating film formed in the step (1) is irradiated with radiation through a mask having a predetermined pattern.
  • radiation at this time include ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like. The entire surface of the coating may be exposed.
  • 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 light is preferred, and among the ultraviolet light, radiation containing g-line and / or i-line is particularly preferred.
  • the exposure dose is preferably, for example, 100 J / m 2 or more and 10,000 J / m 2 or less.
  • the coated film formed in the step (1) is subjected to heating and baking treatment (post-baking treatment) using a heating device such as a hot plate or an oven. Cure the coating.
  • a heating device such as a hot plate or an oven. Cure the coating.
  • 120 ° C is preferred.
  • 200 ° C is preferred, 180 ° C is more preferred, and 150 ° C is still more preferred.
  • the firing time varies depending on the type of the heating device, but is, 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. be able to. Particularly preferably, it is 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 said heating can be performed after exposure.
  • development may be performed before heating to remove a portion irradiated with radiation and form a desired pattern.
  • An alkaline aqueous solution (alkaline developer) can be used as a developer used for development processing.
  • alkali examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyl diethylamine, Dimethyl ethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3, 0] -5-nonane and the like.
  • an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above alkaline aqueous solution, or a solution containing a small amount of various organic solvents capable of dissolving the composition may be used. it can.
  • an organic solvent may be used as the developer.
  • a developing method for example, methods such as a liquid deposition method, a dipping method, a swing immersion method, a shower method and the like can be used.
  • the step (3) is a step of laminating a covering layer on the formed infrared transmitting film.
  • the covering layer include the above-described antireflective layer, oxygen shielding layer, and ultraviolet absorbing layer.
  • These coating layers can be formed by a method of applying a material for forming each coating layer and curing by heating, vapor deposition or the like.
  • the material for forming each coating layer may be a known material, or a commercially available product may be used.
  • the infrared ray transmitting film provided earlier may be deteriorated by heating, moisture and the like.
  • the protective plate for display apparatuses with which degradation of the infrared rays permeable film was suppressed can be obtained.
  • the protective plate for a display according to an embodiment of the present invention is used for a display.
  • the said display apparatus has a display apparatus main body and the protection plate for display apparatuses.
  • the display device main body a known one having a display function such as a liquid crystal display device or a flat panel display is adopted. Further, the display device protection plate is provided on the outermost surface so as to cover the display screen of the display device main 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 in the display device protection plate.
  • 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.
  • part in a description means a “mass part” unless there is particular notice.
  • number average molecular weight, weight average molecular weight, glass transition temperature and logarithmic viscosity of the synthesized resin were measured by the method described in the above-described embodiment.
  • the obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.
  • ⁇ Resin synthesis example 2> In a container equipped with a stirrer, 80 parts by mass of propylene glycol monomethyl ether is charged, and then 100 parts by mass in total of hydrolyzable silane compounds (45 mol% of methyltrimethoxysilane, 30 mol% of dimethoxydimethylsilane and ⁇ - Glycidoxypropyltrimethoxysilane (25 mol%) was charged and heated until the solution temperature reached 60.degree. After the solution temperature reached 60 ° C., 0.5 parts by mass of formic acid and 25 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 3 hours.
  • hydrolyzable silane compounds 45 mol% of methyltrimethoxysilane, 30 mol% of dimethoxydimethylsilane and ⁇ - Glycidoxypropyltrimethoxysilane (25 mol%) was charged and heated until the solution temperature reached 60.degree. After the solution temperature reached 60
  • the temperature of the solution was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (hereinafter, also referred to as “resin E”).
  • the obtained resin E had a number average molecular weight of 3,000.
  • Example 1 In a container, 50 parts by mass of the resin A obtained in Synthesis Example 1 and 50 parts by mass of CS-2 ("EP1032H60" of Japan Epoxy Resins Co., Ltd.) were dissolved in ethyl acetate as binder components, and the resin (binder component) concentration was An 8% by mass resin solution was obtained.
  • Example 2 to [Example 11] and [Comparative Example 1] to [Comparative Example 6]
  • a composition was prepared in the same manner as Example 1, except that the binder components, colorants, silane coupling agents and generators of the types and amounts shown in Table 1 were used.
  • the numerical values in parentheses in the column of each composition type in Table 1 indicate the number of used parts (parts by mass) with respect to 100 parts by mass of the binder component.
  • the binder component, the colorant, the silane coupling agent and the generator used in Examples 1 to 10 and Comparative Examples 1 to 3 are the following compounds.
  • Resins A to E Resins A to E obtained in Resin Synthesis Examples 1 to 5, respectively CS-1: "Aron oxetane OXT-191" (compound represented by the following formula) from Toa Gosei Co., Ltd.
  • Coloring agent A compounds (C1-1) and (C2-1) represented by the following formula
  • Colorant C Compounds (C4-1) and (C5-1) represented by the following formula
  • CT-1 acid generator (nonionic compound) Midori Kagaku Co., Ltd.
  • NAI-105 N- (trifluoromethylsulfonyloxy) -1,8-naphthalenedicarbimide
  • CT-2 acid generator (nonionic compound) BASF "IRGACURE PAG 121" (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile)
  • CT-3 Base generator (nonionic compound) Wako Pure Chemical Industries, Ltd.
  • WPBG-140 (1- (anthraquinone-2-yl) ethyl imidazole carboxylate)
  • CT-4 acid generator (ionic compound) Benzyl (4-hydroxyphenyl) (methyl) sulfonium hexafluorophosphate
  • permeability is the value which measured 151 point
  • the transmittance at 151 points every 2 nm is measured in the range of 800 to 1100 nm, and the average value of the transmittances is obtained. The results are shown in Table 1.
  • the transmittance of the infrared transmitting film can be said to be good.
  • FIG. 3 the transmission spectrum of the infrared rays permeable film obtained from the composition of Example 1 is shown.
  • the wet heat resistance test Before and after the wet heat resistance test, when the change value of the visible average transmittance is less than 5%, the wet heat resistance is good (o), and when the change value is 5% or more, the wet heat resistance is poor (x).
  • Table 1 shows the differences in the absorption maximum wavelengths of the colorant A and the colorant B used in the examples, and the differences in the absorption maximum wavelengths of the colorant B and the colorant C.
  • the difference between the absorption maximum of the colorant A on the short wavelength side and the absorption maximum of the colorant B is shown, and when two or more colorants C are used, the long wavelength The difference between the absorption maximum of the coloring agent C on the side and the absorption maximum of the coloring agent B is shown.
  • the visible transmittance is Low, near infrared transmittance can be increased. It was found that by using the silane coupling agent in a specific range, it is possible to suppress the change in transmittance due to the heat and humidity resistance of the infrared ray transmitting film, and to maintain good adhesion. In addition, it was found that the wet heat resistance (adhesion) of the infrared ray permeable film is more excellent when the nonionic compound (CT-1 to CT-3) is used as the generator.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit un procédé de fabrication d'une plaque de protection pour dispositif d'affichage avec laquelle la dégradation d'un film de transmission des rayons infrarouges est inhibée, une composition pour formation de film de transmission des rayons infrarouges permettant d'être mise en œuvre dans un tel procédé de fabrication, un film de transmission des rayons infrarouges dont la dégradation est inhibée, et une plaque de protection pour dispositif d'affichage équipée d'un tel film de transmission des rayons infrarouges. Plus précisément, l'invention concerne un procédé de fabrication d'une plaque de protection pour dispositif d'affichage qui est équipée d'une plaque de base, d'une partie cadre agencée du côté d'une face de ladite plaque de base et formant une partie ouverture pour communication infrarouge, et d'un film de transmission des rayons infrarouges agencé à l'intérieur de ladite partie ouverture. Ce procédé de fabrication comporte une étape au cours de laquelle est formé un film de revêtement à l'intérieur de ladite partie ouverture à l'aide d'une composition pour formation de film de transmission des rayons infrarouges. Ladite composition pour formation de film de transmission des rayons infrarouges contient un composant liant et un agent de couplage de silane. La teneur en agent de couplage de silane pour 100 parties en masse dudit composant liant dans ladite composition pour formation de film de transmission des rayons infrarouges, est supérieure ou égale à 0,05 parties en masse et inférieure ou égale à 7 parties en masse.
PCT/JP2018/038378 2017-10-19 2018-10-15 Plaque de protection pour dispositif d'affichage ainsi que procédé de fabrication de celle-ci, composition pour formation de film de transmission des rayons infrarouges, film de transmission des rayons infrarouges WO2019078175A1 (fr)

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JP2017203008A JP2021012223A (ja) 2017-10-19 2017-10-19 表示パネル用基板の製造方法、感放射線性組成物及び赤外線透過膜

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JP2021056345A (ja) * 2019-09-30 2021-04-08 豊田合成株式会社 赤外線透過製品
WO2023145700A1 (fr) * 2022-01-31 2023-08-03 富士フイルム株式会社 Composition absorbant les infrarouges, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, capteur infrarouge et module de caméra

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JPWO2022210797A1 (fr) * 2021-03-29 2022-10-06
JP7466040B1 (ja) 2023-03-31 2024-04-11 ａｒｔｉｅｎｃｅ株式会社 光学積層体及びその製造方法

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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
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

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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
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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021056345A (ja) * 2019-09-30 2021-04-08 豊田合成株式会社 赤外線透過製品
WO2023145700A1 (fr) * 2022-01-31 2023-08-03 富士フイルム株式会社 Composition absorbant les infrarouges, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, capteur infrarouge et module de caméra

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