JP2009043562A - Optical film which has pattern of two or more color tones, manufacturing method of the optical film, color conversion filter using the optical film, and multi-color light-emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film superior in forming a pattern of a plurality of color tones, to provide a manufacturing method of the optical film capable of cost reduction in a short process, to provide a color conversion filter using the optical film, and to provide a multi-color light-emitting device. <P>SOLUTION: This is the optical film containing a binder resin (A), a light activator (B) selected from a group consisting of a photo acid-generating agent and a photo base-generating agent, and a color tone variable color material (C) as essential components in which the color tone changes by acid or base, and the optical film in which two regions of which the color tones are different are formed by light irradiation against its one part. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical film excellent in forming a plurality of color tone patterns, a method for producing the engineering film, and a device using the optical film. More specifically, the present invention relates to a color conversion filter that enables multicolor display with high definition, high brightness, high efficiency, and excellent productivity, and a multicolor light emitting device using the color conversion filter. The present invention relates to a color conversion filter for display and a multicolor light emitting device such as an image sensor, a personal computer, a word processor, audio, video, car navigation, a telephone, a portable terminal, and an industrial measuring instrument.

  The optical film is usually produced by a photolithography method, that is, a method of applying a photosensitive resin composition on a support, exposing and developing. For example, Patent Document 1 discloses a polymer binder, a monomer, a photopolymerization initiator that generates radicals by visible light having a wavelength of 400 to 700 nm, a photoacid generator that generates acid by light having a wavelength of 200 to 380 nm, and an acid A photosensitive resin composition containing a compound that develops color when present, and a photosensitive lithographic printing plate using the photosensitive resin composition are disclosed. However, including the developing process has a problem that the process becomes complicated and the cost increases. Also, a method for patterning the color conversion layer using photo bleaching has been proposed. However, there are problems that two types of optical systems are required, the apparatus is complicated, and the patterning time is long.

  In recent years, organic EL light emitting devices (OLEDs) have been actively researched and developed for practical use. Since organic EL light-emitting elements can achieve high current density at a low voltage, they are expected to achieve higher light emission luminance and light emission efficiency than inorganic EL light-emitting elements, and are particularly applicable to thin and light flat panel displays. Expected. In-vehicle green single-color organic EL displays have already been commercialized by Pioneer in November 1997, but in the future, high-brightness, high-definition full-color display is possible and long-term stable in order to respond to diversifying social needs. There is an urgent need for practical use of an organic EL color display having high performance and high speed response.

  As a method for producing a full color display using an organic EL light emitting element, a “three-color light emitting system” in which elements that emit light in red, blue, and green by applying an electric field, and white light emission with a color filter are used. “Color filter method” that cuts and expresses red, blue, and green, absorbs near-ultraviolet light, blue light, blue-green light, or white light, and performs wavelength distribution conversion to emit light in the visible light range. A “color conversion method” using a color conversion dye as a filter has been proposed (see Patent Documents 2 to 3).

  Above all, it is said that the color conversion method can realize high color reproducibility and efficiency, and unlike the three-color light emission method, the organic EL light emitting element may be a single color, so that it is difficult to enlarge the screen. Promising as a candidate for next generation display. In the color conversion method, since the light emission color of the organic EL light emitting element is not limited to white, an organic EL light emitting element with higher luminance can be applied to the light source. In a color conversion method using a blue light emitting organic EL light emitting element, green light and red light are obtained by wavelength conversion of blue light. However, since there is a step of forming a color conversion layer, the number of processes increases, resulting in a problem that costs increase.

  An onium salt photoacid generator that generates an acid by the action of light, a dye precursor that develops a color by the action of an acid, and a photochromic composition obtained by dispersing a solid sensitizer in an aqueous solution of a water-soluble resin. It has been proposed (see Patent Document 4). However, this photochromic composition is used as a color display element, and cannot provide transparency suitable for use as an optical film that absorbs or converts light that has passed through.

JP-A-8-240908 JP-A-8-279394 JP-A-8-286033 JP 2006-297774 A JP-A-11-52103 Journal of Photopolymer science and Technology, 16, 81-82 (2003) Macromolecules, 30, 1304-1310 (1997) Chem. Commun., 1996, 605-606 Eur. J. Med. Chem., 24, 391-396 (1989)

  An object of the present invention is to provide an optical film excellent in the formation of a plurality of color tone patterns, a method for producing the optical film, and an optical filter for image display using the optical film. Furthermore, it is providing the color conversion filter excellent in pattern formation and cost, and the multicolor light emitting device containing the said filter.

  As a result of diligent research in view of the above problems, it has been found that a film containing a binder resin, a photoactive agent, and a dye compound having a specific structure is excellent in forming a pattern having a plurality of colors, and can be produced at low cost. did. The obtained optical film can be used as a color conversion layer in a color conversion filter. Furthermore, it has been found that by using the color conversion filter, it is possible to provide a multicolor light emitting device that is superior in pattern formability and cost as compared with a conventional color conversion device.

  The optical film according to the first embodiment of the present invention has a color tone due to a binder resin (A), a photoactive agent (B) selected from the group consisting of a photoacid generator and a photobase generator, and an acid or a base. An optical film containing a color tone variable color material (C) that changes as an essential component, wherein two regions having different color tones are formed by light irradiation on a part thereof. Here, the color tone variable color material (C) may be colored from colorless to colored with an acid or a base. Moreover, when using a photo-acid generator (B1) as a photoactive agent (B), it is desirable that the color tone variable color material (C) is an acid-colorable color material (C1) that is colored from colorless to colored with an acid. Furthermore, it is desirable that the acid-colorable coloring material (C1) is a leuco dye, particularly a rhodamine dye. In the above configuration, it is desirable that the color tone variable color material (C) has fluorescence in a colored state, and further absorbs light in a specific wavelength region and emits light in another wavelength region in the colored state. .

  The method for producing an optical film according to the second embodiment of the present invention includes: a binder resin (A), a photoactive agent (B) selected from the group consisting of a photoacid generator and a photobase generator, and an acid or base A step of preparing a coating liquid composition containing, as essential components, a color tone variable color material (C) whose color tone changes depending on the organic solvent (D); a step of applying the coating liquid composition to a support; Removing the solvent (D); irradiating a region of a predetermined pattern with active energy rays to change the color tone of the color tone variable color material (C) to form two regions having different color tones; It is characterized by including. Here, the color tone variable color material (C) may be colored from colorless to colored with an acid or a base. Moreover, when using a photo-acid generator (B1) as a photoactive agent (B), it is desirable that the color tone variable color material (C) is an acid-colorable color material (C1) that is colored from colorless to colored with an acid. Furthermore, it is desirable that the acid-colorable coloring material (C1) is a leuco dye, particularly a rhodamine dye. In the above configuration, it is desirable that the color tone variable color material (C) has fluorescence in a colored state, and further absorbs light in a specific wavelength region and emits light in another wavelength region in the colored state. . The support used in this embodiment may be a transparent support. The method of this embodiment may further include the step of removing the support.

  A color conversion filter according to a third embodiment of the present invention includes a transparent substrate, a color filter in which at least two kinds of color filter layers that transmit light of different wavelength ranges are independently arranged, and the color And a protective layer disposed on the upper surface of the filter, wherein the protective layer is the optical film of the first embodiment. In the present embodiment, an optical film that functions as a color conversion layer by absorbing light in a specific wavelength region and emitting light in another wavelength region when the color tone variable color material (C) is in a colored state is used.

  A multicolor light emitting device according to a fourth embodiment of the present invention includes the color conversion filter and the light source according to the third embodiment. Here, the light source may be an organic EL light emitting element.

  A binder resin (A), a photoactive agent (B), and a resin composition containing a color tone variable color material (C) as essential components by an acid or base, and controlling the pH of the resin composition by light irradiation. In an optical film to be changed, a pattern having a plurality of color tones can be formed with high definition. Moreover, the optical film of this invention can be used as a color conversion layer by using the color tone variable color material (C) which absorbs light in a specific wavelength region and emits light in another wavelength region in a colored state. . By using such an optical film, a color conversion filter and a multicolor light emitting device can be provided.

  By using the method for producing an optical film of the present invention, an optical film having a plurality of color tone patterns can be easily produced by a simple process of coating, drying (solvent removal), and light irradiation. Further, in this method, since a complicated photolithography method including a developing process is not used, the total number of steps can be reduced, and a high yield and a low manufacturing cost can be realized. Therefore, when this method is applied to the production of a color conversion layer, it is possible to produce the color conversion layer with a smaller number of steps than in the conventional method, with a high yield and a low production cost.

  Furthermore, the method for producing an optical film of the present invention makes it possible to produce a multicolor light emitting device with a smaller number of steps than in the conventional method, with a high yield and a low production cost. Moreover, since the color conversion layer formed from the optical film of this invention is manufactured without using the process of generating the unevenness | corrugation of a surface, the upper surface of a color conversion layer is flat. Therefore, it is possible to omit the formation of a planarization layer that is generally used in a conventional color conversion device. Also from this point, the optical film of the present invention and the manufacturing method thereof can manufacture a multicolor light emitting device with a high yield.

  The optical film according to the first embodiment of the present invention has a color tone due to a binder resin (A), a photoactive agent (B) selected from the group consisting of a photoacid generator and a photobase generator, and an acid or a base. An optical film containing a color tone variable color material (C) that changes as an essential component, wherein two regions having different color tones are formed by light irradiation on a part thereof. That is, acid or base is generated from the photoactive agent (B) by light irradiation, and the pH in the film is changed. In response to the change in pH, the color tone variable color material (C) changes to a different color tone state, and two regions having different color tones are formed. Depending on the type of color tone variable color material (C) to be used, in the two regions, a part of the light passing therethrough is absorbed or a part of the light passing through is converted. The optical film of this embodiment is useful for display applications.

  A typical configuration of the optical film of the present embodiment is shown in FIG. The optical film 1 includes a first color tone portion 2 that is not irradiated with light and a second color tone portion 3 that is irradiated with light. When the color tone variable member (C) that changes from colorless to colored by an acid or base is used, the first color tone portion 2 is colorless and the second color tone portion 3 is colored. When the color tone variable member (C) that changes from colored to colorless by an acid or base is used, the first color tone portion 2 is colored and the second color tone portion 3 is colorless. When the color tone variable member (C) that changes from a color to a color having a different color tone by an acid or a base is used, the first color tone portion 2 and the second color tone portion 3 are colored portions having different color tones.

  The optical film of the present embodiment may be a self-supporting film or a non-self-supporting film formed on a support. As the support for the non-self-supporting film, a transparent support or a support in which an optical functional element such as a color filter is provided on the transparent support can be used.

  The binder resin (A) used in the present invention is urethane resin, polyester urethane resin, nylon resin, polyamide resin, vinyl acetate resin, vinyl chloride resin, chlorinated polypropylene, polyvinylidene chloride, acrylate resin, styrene- Acrylic copolymer resins, acrylic polyol resins, acrylic-polyester resins, polyacrylamide resins, urethane acrylate resins, silicone acrylate resins, alicyclic acrylic resins and other acrylic resins, vinyl chloride-vinyl acetate copolymer resins, Maleic acid resin, polyester resin, styrene resin, styrene copolymer resin, polyolefin resin, acrylic modified polyolefin resin, norbornene resin, polycarbonate resin, epoxy resin, polyethersulfone resin, polyester Terketone resin, polyetherimide resin, polyoxyethylene resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and emulsions of these resins including. Alternatively, the binder resin (A) is casein, starch, cellulose derivative, alginic acid, polyvinyl alcohol, gelatin, urea resin, phenol resin, epoxy resin, vinyl ester resin, diallyl phthalate resin, silicone resin, phosphorus-containing resin, amino resin. , Alkyd resin, hydrogenated petroleum resin, hydrogenated terpene resin, polyvinyl acetal resin, polyvinyl pyrrolidone, phenoxy resin, ketone resin, fluorine resin, styrene-butadiene-styrene block copolymer, styrene-ethylene-butadiene-styrene block copolymer Including polymers, styrene-butadiene rubber, styrene-isoprene-styrene block copolymers, chlorosulfonated polyethylene, and the like. These resins may be a single polymer or a copolymer, and may be a mixture.

  Alternatively, a known curable resin may be used as the binder resin (A) of the present invention. The curable resin that can be used includes a thermosetting resin, an energy ray sensitive resin, and the like. The thermosetting resin may be a resin that utilizes a crosslinking reaction of a prepolymer such as a melamine resin, a urethane resin, or an epoxy resin, or a silane resin (see Patent Document 5).

  The energy ray sensitive resin is a resin containing a cationic polymerizable resin and an energy ray sensitive cationic polymerization initiator, and optionally containing a radical polymerizable resin and an energy ray sensitive radical polymerization initiator. The energy ray-sensitive resin can be cured by applying a coating solution containing the resin on an appropriate support and irradiating with active energy rays. The cationic polymerizable resin and the radical polymerizable resin may be selected according to the color tone variable color material according to the present invention. If the color tone variable color material changes color depending on the base, the cationic polymerizable resin and the radical polymerizable resin are used. A radically polymerizable resin can be used when the color tone variable color material changes its color tone with an acid.

  The cationically polymerizable resin means a uniform mixture of one or more kinds of cationically polymerizable organic substances. The cationically polymerizable organic material contains a compound that undergoes polymerization or crosslinking reaction by an energy ray-sensitive cationic polymerization initiator activated by irradiation with energy rays. For example, the cationically polymerizable organic material is an epoxy compound, an oxetane compound, a lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, a vinyl compound, an oxolane compound, a cyclic acetal compound, a lactone compound, a thiirane compound, or a thietane compound. , Cyclic thioether compounds, vinyl ether compounds, spiro orthoester compounds obtained by reaction of epoxy compounds with lactones, ethylenically unsaturated compounds such as styrene, vinylcyclohexene, isobutylene, polybutadiene, and derivatives thereof. Cationic polymerizable group-modified silicone oil or the like may be used as the cationic polymerizable organic substance.

The energy ray-sensitive cationic polymerization initiator used in the present invention includes any compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays. Preferably, the energy ray-sensitive cationic polymerization initiator is a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Typical examples of such compounds include cation and anion salts represented by the general formula [A] ^{m +} [B] ^m- .

Here, the cation [A] ^{m +} is preferably onium, and the structure thereof can be represented by, for example, the general formula [(R ³ ) _a Q] ^{m +} . R ³ has 1 to 60 carbon atoms, is an organic group that may contain any number of atoms other than carbon atoms, and a is an integer of 1 to 5. R ³ may be the same or different for each occurrence. Moreover, it is preferable that at least one of R ³ has an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. When the valence of Q in the cation [(R ³ ) _a Q] ^{m +} is q, it is necessary that the relationship m = a−q holds (provided that when Q is N = N, Value q = 0).

Further, the anion [B] ^m− is an organic boronic acid anion such as tetraphenylborate [B (C ₆ H ₅ ) ₄ ] ⁻ , tetrakis (pentafluorophenyl) borate [B (C ₆ F ₅ ) ₄ ] ^−, etc. Or a halide complex, and the structure of the halide complex can be represented by, for example, a general formula [LX _b ] ^m- or [LX _b-1 (OH)] ^m- . L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr , Mn, Co and the like. X is a halogen atom, b is an integer of 3-7. Further, when the valence of L in the anion [LX _b ] ^m− or [LX _b−1 (OH)] ^m− is p, it is necessary that the relationship m = b−p holds. Anions having the general formula [LX _b ] ^m− include, for example, tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate ( AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

The anions [B] ^m− that can be used are perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluenesulfone. Acid anions, trinitrobenzenesulfonate anions, camphor sulfonates, nonafluorobutane sulfonates, hexadecafluorooctane sulfonates, tetraaryl borates, tetrakis (pentafluorophenyl) borates and the like. One of these anions may be used alone, or two or more may be mixed and used.

The energy ray-sensitive cationic polymerization initiator used in the present invention is preferably the following compound:
(A) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate;
(B) Diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4- (1,1-dimethylethyl) phenyl) iodonium hexafluorophosphate, tricumyliodonium tetrakis (pentafluorophenyl) ) Diaryliodonium salts such as borates;
(C) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4, 4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4′-bis [di ( β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] pheny Sulfide-bis-hexafluorophosphate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- Triarylsulfonium salts such as (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate;
(D) a mixture of diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate and 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate;
(F) (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron-hexafluorophosphate, etc. And (e) a mixture of an aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and a silanol such as triphenylsilanol. including.

  The radical polymerizable resin means a uniform mixture of one or more kinds of radical polymerizable organic substances. The radical polymerizable organic substance is a compound that is polymerized or cross-linked by an energy ray-sensitive radical polymerization initiator activated by irradiation with energy rays, and preferably has at least one unsaturated group in one molecule. Has a double bond. The radical polymerizable organic material includes, for example, an acrylate compound, a methacrylate compound, an allyl urethane compound, an unsaturated polyester compound, a styrenic compound, and a radical polymerizable group-modified silicone oil. Depending on the desired performance, two or more of these radically polymerizable organic substances can be blended and used.

  The energy ray-sensitive radical polymerization initiator means a compound capable of initiating radical polymerization when irradiated with energy rays. The energy ray sensitive radical polymerization initiator includes, for example, ketone compounds such as acetophenone compounds, benzyl compounds, and thioxanthone compounds. Depending on the desired performance, two or more kinds of energy ray sensitive radical polymerization initiators can be blended and used.

  Examples of acetophenone compounds that can be used as an energy ray-sensitive radical polymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 4′-isopropyl-2-hydroxy-2- Methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p- (1,1-dimethylethyl) Dichloroacetophenone, p- (1,1-dimethylethyl) trichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propanone, 2-benzyl-2-di Methylamino-1- (4-morpholinophenyl) -1-butanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxy Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like.

  Benzyl compounds that can be used as an energy ray-sensitive radical polymerization initiator include benzyl, anisyl and the like.

  Examples of benzophenone compounds that can be used as an energy ray-sensitive radical polymerization initiator include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl- 4'-methyldiphenyl sulfide and the like.

  Examples of thioxanthone compounds that can be used as an energy ray-sensitive radical polymerization initiator include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

  Alternatively, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyru-1-yl)] titanium, etc. are used in the energy of the present invention. It may be used as a line-sensitive radical polymerization initiator.

  As energy rays for activating the energy ray-sensitive cationic polymerization initiator and the energy ray-sensitive radical polymerization initiator, ultraviolet rays having a wavelength of 190 to 380 nm, electron beams, X-rays, radiation, high frequencies, and the like can be used. Ultraviolet light is most preferred economically. As the ultraviolet light source, an ultraviolet laser, a mercury lamp, a xenon laser, a metal halide lamp, or the like can be used.

  The photoactive agent (B) used in the present invention is a compound that decomposes by the action of active energy rays (such as light or electron beam) on the substance itself or a resin composition containing the substance to generate active species. means. The photoactive agent (B) of the present invention includes a photoacid generator (B1) that generates an acid as an active species, or a photobase generator (B2) that generates a base as an active species. By using these photoacid generator (B1) or photobase generator (B2), the pH in the resin composition can be controlled.

The photoacid generator (B1) that can be used in the present invention preferably absorbs light having a wavelength of 200 to 800 nm, more preferably ultraviolet light having a wavelength of 200 to 400 nm, and directly or indirectly generates an acid. It is a compound. The acid generated from the photoacid generator (B1) acts on the color tone variable colorant (C) described below to cause a reaction such as cleavage of the acid labile group or ring closure, thereby changing the color tone of the compound. Change. As will be described later, when the acid-colorable color material (C1) is used, the acid-colorable color material (C1) changes from a colorless state to a colored state due to the acid generated from the photoacid generator (B1). In the present invention, one type of photoacid generator (B1) may be used, or two or more types of photoacid generators (B1) may be used in combination. The photoacid generator (B1) that can be used in the present invention includes triazine compounds, acetophenone derivative compounds, benzophenone compounds, halogen-containing compounds, sulfone compounds, diazomethane compounds, diazoketone compounds, diazonaphthoquinone compounds, and sulfonic acid derivative compounds. , Sulfonimide compounds, dialkylphenacylsulfonium salts, aromatic tetracarboxylic acid esters, nitrobenzyl esters, oxime sulfonic acid esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, thiazoles, imidazoles, isocyanuric acid compounds Azole compounds, phosphine oxides, thioxanthone compounds, iron arene complexes, aromatic silanol / aluminum complexes, and the like can be used. Not. Alternatively, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salt of onium type ions such as diazonium, ammonium, iodonium, sulfonium, phosphonium, oxonium, pyridinium, etc. May be used as the photoacid generator (B1).

  Triazine compounds that can be used as the photoacid generator (B1) are 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl)- 1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- (benzo [d] 1,3-dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Methoxystyryl) -4 , 6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis (trichloro) Methyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  The acetophenone derivative compounds that can be used as the photoacid generator (B1) include acetophenone, methoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 4-diphenoxydichloro. Acetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and the like.

  The benzophenone compounds that can be used as the photoacid generator (B1) are benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, diphenoxy. Contains benzophenone and the like.

  The halogen-containing compound that can be used as the photoacid generator (B1) is a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, or the like, preferably 1,1-bis (4-chlorophenyl) -2,2,2 -Trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine and the like.

  The sulfone compounds that can be used as the photoacid generator (B1) are β-ketosulfone compounds, β-sulfonylsulfone compounds, etc., preferably 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like. including.

  Diazomethane compounds that can be used as the photoacid generator (B1) include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2 , 4-Xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) Examples include diazomethane and phenylsulfonyl (benzoyl) diazomethane.

  Diazoketone compounds that can be used as the photoacid generator (B1) include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. The diazonaphthoquinone compound is an ester of 1,2-naphthoquinonediazide-4-sulfonic acid and 2,3,4,4′-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1, Esters with 1-tris (4-hydroxyphenyl) ethane, amides with 1,2-naphthoquinonediazide-4-sulfonic acid and diaminodiphenyl ether, 1,2-naphthoquinonediazide-5-sulfonic acid and 2,3,4 , 4′-tetrohydroxybenzophenone, methyl gallate, ester with 1,1,1-tris (4-hydroxyphenyl) ethane, amide with diaminodiphenyl ether and the like.

  The sulfonic acid derivative compound that can be used as the photoacid generator (B1) is an alkyl sulfonate ester, a haloalkyl sulfonate ester, an aryl sulfonate ester, an imino sulfonate, etc., preferably benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9. , 10-diethoxyanthracene-2-sulfonate and the like.

  The sulfonimide compounds that can be used as the photoacid generator (B1) are N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N -(Trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N (Camphorsulfonyloxy) succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2 .1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenyl) Sulfonyloxy) phthalimide, N- 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyl) Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5 6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenyl) Sulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfo) Nyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyl) Oxy) phthalimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3 -Dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide and the like.

  The phosphine oxides usable as the photoacid generator (B1) are 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphinate. Ester, 2,6-dichlorobenzoylphenylphosphine oxide, 2,6-dimethyoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.

  The thioxanthone compound that can be used as the photoacid generator (B1) includes 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, and the like.

  Examples of onium compound salts that can be used as the photoacid generator (B1) include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodoniumpyrenesulfonate, diphenyliodoniumdodecylbenzenesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, and diphenyliodonium. Bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p- (1,1-dimethylethyl) phenyl) iodonium hexafluorophosphate, bis (p- (1,1- Dimethylethyl) phenyl) iodonium mesylate, bis (p- (1,1- Methylethyl) phenyl) iodonium tosylate, bis (p- (1,1-dimethylethyl) phenyl) iodonium trifluoromethanesulfonate, bis (p- (1,1-dimethylethyl) phenyl) iodonium tetrafluoroborate, bis (p -(1,1-dimethylethyl) phenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tri (p-methoxyphenyl) ) Sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, Phenylphosphonium chloride, triphenylphosphonium bromide, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, tri (p-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexa Fluorophosphonate, tri (p-ethoxyphenyl) phosphonium tetrafluoroborate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, and the like.

  The compounding quantity of a photo-acid generator (B1) is 1-300 mass parts with respect to 100 mass parts of binder resin (A), Preferably it is chosen in the range of 2-100 mass parts. By using the blending amount within the above range, the color tone of the color tone variable color material (C) can be sufficiently changed by the generated acid, and at the same time, an optical film having excellent storage stability can be provided.

The photobase generator (B2) that can be used in the present invention absorbs light having a wavelength of 200 to 800 nm and is an amine such as an amine (NH ₃ , RNH ₂ (R is a monovalent organic group such as an alkyl group)). Compound), amine anion (NH ₂ ⁻ ), hydroxy anion (OH ⁻ ) and the like. In the present invention, one type of photobase generator (B2) may be used, or two or more types of photobase generators (B2) may be used in combination.

  Examples of the compound capable of generating an amine that can be used as the photobase generator (B2) include 4,4 ′-[bis [[(2-nitrobenzyl) oxy] carbonyl] trimethylene] dipiperidine (see Non-Patent Documents 1 and 2). ) Etc.

  The compound that generates a hydroxy anion that can be used as the photobase generator (B2) is 9-hydroxy-10-methyl-9-phenyl-9,10-dihydroacridine) (Non-patent Document 3) Reference 4).

  The photobase generator (B2) that can be used in the present invention includes transition metal complexes, compounds having a benzyl carbamate structure, compounds having an ortho-substituted nitrobenzene structure, oximes, imidazole derivatives, benzoin compounds, N-formyl. A compound having an acetylated aromatic amino group, a compound having an N-acylated aromatic amino group, a compound having an alkoxybenzyl carbamate group, a compound having a 1,4-dihydropyridine skeleton, an oxime ester, a quaternary ammonium salt, etc. Including.

  Transition metal complexes that can be used are bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt Including perchlorate, hexapropylamine cobalt perchlorate and the like.

  Compounds having a benzyl carbamate structure that can be used include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl. ) Oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] butylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] Hexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[ (Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperidine, bis [[ (Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] ethylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(α , Α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine and the like.

  Compounds having an ortho-substituted nitrobenzene structure that can be used include N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -diisopropylamine, N-{[(4,5-dimethoxy-2- Nitrobenzyl) oxy] carbonyl} -bis (3-pentyl) amine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -bis (4-heptyl) amine, N-{[( 4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -dicyclopropylamine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -dicyclobutylamine, N-{[ (4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -dicyclopentylamine, N-{[(4,5-dimethyl) Xyl-2-nitrobenzyl) oxy] carbonyl} -dicyclohexylamine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine, N-{[(4, 5-Dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpyrrolidine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethyl-4- Methyl-piperazine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylmorpholine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] Carbonyl} -2,6-dimethylthiomorpholine, N-{[(3,4-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2 6-dimethylpiperidine, N-{[(3,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2, 6-dimethylpiperidine, N-{[(3,6-dimethoxy-2-nitrobenzyl) oxy ] Carbonyl} -2,6-dimethylpiperidine, N-{[(4,6-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine, N-{[(5,6-dimethoxy- 2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine and the like.

  Acyloxyiminos that can be used are propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl acetone oxime, adipoylacetophenone oxime, adipoylacetone oxime, acryloyl acetophenone oxime, alloyl Contains benzophenone oxime, acryloylacetone oxime, etc.

  The imidazole derivatives that can be used are N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (4-chloro 2-nitrobenzyloxycarbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4,5-dimethyl-2-nitrobenzyloxycarbonyl) imidazole and the like.

  The compounding quantity of a photobase generator (B2) is 1-300 mass parts with respect to 100 mass parts of binder resin (A), Preferably it is chosen in the range of 2-100 mass parts.

  In the present invention, the photoactive agent (B) may be used in combination with a photosensitizer. By using a photosensitizer, active energy rays can be efficiently absorbed, and the sensitivity of the photoactive agent (B) can be improved. Examples of the photosensitizer include anthracene derivatives, perylene derivatives, anthraquinone derivatives, thioxanthone derivatives, and coumarins.

  The color tone-changing color material (C) of the present invention is a material in which the absorption wavelength is changed by an acid or base and the color tone is changed from colorless to colored (acid-colorable color material (C1) and base-colorable color material (C2) ), A material that changes from colored to colorless, or a material that changes from colored to different colored. The color tone-changing colorant (C) of the present invention includes, for example, triarylmethanephthalide dyes, fluoran dyes, thiofluorane dyes, phenothiazine dyes, thiazine dyes, indolylphthalide dyes, spiropyran dyes, rhodamines. Dyes, triarylmethane dyes, diphenylmethane dyes, azaphthalide dyes, chromenopyrazole dyes, methine dyes, quinazoline dyes, diacoxanthene dyes, leuco dyes such as bislactone dyes, coumarin dyes, Arylamine dyes, chromenoindole dyes, anthraquinone dyes, azine dyes, quinoline dyes, thiazole dyes, oxazine dyes, azo dyes, nitro dyes, nitroso dyes, disazo dyes, Xanthene dyes, iminonaphthoquinone colors , Including the azomethine dyes. The term “dye” in the present invention includes a so-called dye precursor which is changed into a colored state by an acid or a base in addition to a colored material.

  Materials that change from colored to colorless or different colored tones depending on the acid (base) include, for example, Victoria Pure Blue BOH, Oil Blue # 603, Patent Pure Blue, Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Triarylmethane dyes such as erythrosin B, basic fuchsin, malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminaftquinone, cyano-p-diethylaminophenylacetanilide; diphenylmethane dyes; Oxazine dyes; xanthene dyes; iminonaphthoquinone dyes; azomethine dyes; anthraquinone dyes; methyl orange, methyl violet, Le yellow, methyl red, containing thymol blue, bromothymol blue, bromophenol blue, Fel red, alizarin yellow, litmus like.

  Examples of the acid-coloring colorant (C1) that changes from colorless to colored with an acid include leuco dyes; triarylmethane dyes; p, p ′, p ″ -tris-dimethylaminotriphenylmethane, p, p ′. -Bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p, p', p Including triarylmethane dyes such as “-triaminotriphenylmethane; diphenylmethane dyes; fluorane dyes; thiazine dyes; spiropyran dyes, rhodamine dyes, etc. Base coloring colorants that change from colorless to colored with a base (C2) includes phenolphthalein, thymolphthalein and the like.

  Triarylmethane dyes that can be used as the acid-coloring colorant (C1) are 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis. (P-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2- Methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis 9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide, leucomalachite green, leucoaniline, leucomethyl violet and the like.

  Diphenylmethane dyes that can be used as the acid-coloring colorant (C1) are 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-halophenylleucooramine, N-2,4,5-tri Includes chlorophenyl leucooramine and the like.

  The fluorane dyes that can be used as the acid-coloring colorant (C1) are 3-diethylamino-6-methyl-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-7-chloro. Fluorane, 3-diethylamino-7,8-benzofluorane, 3- (N-ethyl-p-toluidino) -7-methylfluorane, 3-diethylamino-7-methylfluorane, 3- (N-ethyl- N-isoamylamino) -7-methylfluorane and the like.

  Thiazine dyes that can be used as the acid-coloring colorant (C1) include benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, and the like.

  Spiropyran dyes that can be used as the acid-coloring colorant (C1) include 3-methylspirodinaphthopyrans, 3-ethylspirodinaphthopyrans, 3,3-dichlorospirodinaphthopyrans, and 3-benzylspirodinaphtho. Including pyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 3-propyl spirobenzopyran and the like.

  The rhodamine dyes that can be used as the acid coloring material (C1) are rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (o-chloroanilino) lactam, rhodamine Bp-chloroanilino. Including lactam.

  Among these materials, leuco dyes and rhodamine dyes are preferable, fluorescent dyes that emit fluorescence in a colored state are preferable, and rhodamine dyes are particularly preferable. In particular, the optical film of the present invention can be used as a color conversion layer by using a fluorescent dye that absorbs light in a specific wavelength region and emits light in another wavelength region in a colored state.

  The compounding quantity of the color tone variable color material (C) in this invention is 0.1-30 mass parts with respect to 100 mass parts of binder resin (A), Preferably it is 1.0-20 mass parts.

  If necessary, the resin composition of the present invention may further contain a monomer. Monomers that can be used include the materials exemplified as the cationically polymerizable organic substance and the radically polymerizable organic substance in the aforementioned energy ray sensitive resin.

  In addition, the resin composition according to the present invention includes, if necessary, thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, tertiary butylcatechol, phenothiazine; plasticizer; adhesion promoter; filler; Dispersant; Leveling agent; Silane coupling agent; Hindered amine light stabilizer (HALS); Ultraviolet absorber; Phosphorous, phenolic and sulfur antioxidants; Nucleating agent; Flame retardant; Metal soap; Auxiliary agents: Conventional additives such as lubricants can be added.

  The optical film of the present invention includes an optical recording layer of a write-once optical disc (CD ± R, DVD ± R, next-generation high-density disc, etc.) in which the optical film is applied to a support; various lenses; an optical filter for an image display device Various filters typified by color filters and color conversion filters; or can be used as protective sealing films for organic EL light-emitting elements, inorganic EL light-emitting elements, electronic paper displays, and the like.

  For example, when the optical film 1 shown in FIG. 1 is produced using a color tone variable color material (C) that absorbs light in a specific wavelength region and emits light in another wavelength region in a colored state, wavelength conversion of light The second color tone unit 3 becomes a colored portion (color converting portion) that converts light in a specific wavelength region into light of another wavelength region. This optical film 1 is useful as a color conversion layer for adjusting the hue of light from a light source.

  When the optical film of this embodiment is used as a color conversion layer, it is advantageous to use an acid-colorable color material (C1) or a base-colorable color material (C2) that changes from colorless to colored with an acid or a base. This is because, when the color tone variable color material (C) that changes from colored to colorless is used, the photoactive agent (B) remains in the colored portion, and its energy is spectrally sensitized when irradiated with visible light. This is because it may move to the photoactive agent (B), cause decomposition of the photoactive agent (B), and affect the color stability over time. On the other hand, when the color tone variable color material (C) that changes from colorless to colored by an acid or base is used, the colorless part does not absorb visible light although the photoactive agent (B) remains in the colorless part. The photoactive agent (B) is not decomposed by the mechanism as described above. In the case where the optical film of the present invention is used as a color conversion layer, a particularly desirable constitution is that a photoacid generator (B1) is used as the photoactive agent (B), and an acid-colorable color material (C1) is used as the color tone variable color material (C). ). This is because a more sensitive photoacid generator (B1) can be used as the photoactive agent (B).

  Moreover, the optical film 1 shown in FIG. 1 was produced using the acid-coloring coloring material (C1) that absorbs light in the blue or blue-green wavelength region and emits light in the green or red wavelength region in the colored state. In this case, the first color tone portion 2 is a colorless portion that transmits blue light or blue-green light, and the second color tone portion 3 is a colored portion (color conversion portion) that converts blue light or blue-green light into longer wavelength green light or red light. ) This optical film 1 is useful as a color conversion layer combined with an organic EL light emitting element that emits blue or blue-green light. In addition, the optical film 1 is not subjected to removal of substances by etching or development, and the first color tone portion 2 and the second color tone portion 3 maintain the structural continuity with the binder resin (A). This feature is advantageous in producing a color conversion part (second tone part 3) having a fine pattern. Furthermore, since this optical film 1 has a flat upper surface, the necessity of forming a layer for planarization thereon can be eliminated.

  The second embodiment of the present invention is: (1) Binder resin (A), photoactive agent (B) selected from the group consisting of a photoacid generator and a photobase generator, and the color tone changes depending on the acid or base A step of preparing a coating liquid composition containing the color tone variable color material (C) and the organic solvent (D) as essential components; (2) a step of applying the coating liquid composition to a support; and the organic solvent (D) removing; and (3) irradiating light to a predetermined pattern area to change the color tone of the color tone variable color material (C) to form two regions having different color tones. It is a manufacturing method of an optical film containing.

  Step (1) of the present embodiment is performed by dissolving or dispersing the binder resin (A), the photoactive agent (B), and the color-change colorant (C) in the organic solvent (D). Can do.

  The organic solvent (D) used in the step (1) is not particularly limited as long as it dissolves or disperses essential components, and various known solvents can be appropriately used. Examples of the organic solvent (D) that can be used include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone ;; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Cellosolve solvents such as propylene glycol monomethyl ether acetate; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid Ester solvents such as n-propyl, isopropyl acetate, n-butyl acetate; methanol, ethanol, iso- or n-propanol, iso- or n- Alcohol solvents such as ethanol and amyl alcohol; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene carbonization such as turpentine oil, D-limonene and pinene Hydrogen oil; paraffinic solvents such as mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatics such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride Hydrocarbon solvents; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents; Aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon disulfide; N, N-dimethylformamide; . The above-mentioned solvents may be used alone, or two or more solvents may be mixed and used. In particular, it is preferable to use ketones or cellosolve solvents as the organic solvent (D).

  Next, in step (2), the coating liquid composition obtained in step (1) is subjected to dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or extrusion. It is coated on a support by a coating method. The support used in this step (2) may be a transparent support or a temporary support that is removed later. Or you may use what provided optical functional elements, such as a color filter, on the transparent support body as a support body in this process.

  Subsequently, in a process (3), an organic solvent (D) is removed from the coating film apply | coated on the support body. Removal of the organic solvent (D) is carried out by heating and / or application of reduced pressure. In this step, the organic solvent (D) may not be completely removed on condition that the properties of the obtained optical film are not affected.

  Next, in step (4), the predetermined pattern area of the coating film from which the organic solvent (D) has been removed is irradiated with light to change the color tone of the color tone variable color material (C), so that the color tone is different 2 An optical film having two regions is obtained. This step is performed by irradiating the coating film with active energy rays through a photomask having a predetermined pattern. The active energy ray includes light, an electron beam, and the like, preferably light having a wavelength of 200 to 800 nm, and particularly preferably ultraviolet light having a wavelength of 200 to 400 nm. Any active energy ray source known in the art can be used.

  When forming a self-supporting optical film in the method of the present embodiment, the method further includes a step of removing the support (that is, the temporary support). The support can be removed at the end of step (4). However, if the coating film obtained in step (2) is self-supporting, it can be removed at the end of step (2) or (3). Alternatively, when the coating film from which the organic solvent (D) obtained in the step (3) is removed has self-supporting property, the coating may be performed at the end of the step (3).

  The color tone variable color material (C) used in the method of the present embodiment may be an acid-colorable color material (C1) that changes from colorless to colored with an acid, or a base coloring that changes from colorless to colored with a base. Sexual color material (C2) may be used. A particularly desirable configuration is a combination in which the photoacid generator (B1) is used as the photoactive agent (B) and the acid-colorable color material (C1) is used as the color tone variable color material (C). This is because an optical film excellent in color stability with time can be produced, and a highly sensitive photoacid generator (B1) can be used as the photoactive agent (B).

  The acid-coloring colorant (C1) used in the method of the present embodiment is preferably a leuco dye, and particularly preferably a rhodamine dye. Furthermore, it is desirable that the color tone variable color material (C) has fluorescence in a colored state. In addition, when a material that absorbs light in a specific wavelength region and emits light in another wavelength region in a colored state is used as the color-tunable color material (C), a color conversion layer is produced by the method of this embodiment. It becomes possible to do.

  Whereas patterning by photolithography requires a development process after light irradiation, the method of this embodiment does not require a development process, and is a simple process of coating, drying (solvent removal), and light irradiation. By this, it is possible to form an optical film having two regions of different color tones. Thereby, it is possible to improve the yield in manufacturing the optical film and at the same time reduce the manufacturing cost.

  In addition, the film obtained by the photolithographic method necessarily has unevenness, whereas the upper surface of the optical film obtained by the method of this embodiment is flat. Therefore, the need for forming a layer for planarization is eliminated when another functional layer is further laminated on the upper surface of the optical film to form a device. For example, in the case where an optical film obtained by the method of the present embodiment is used as a color conversion layer and an organic EL element is laminated thereon to form a multicolor light emitting device, a development step in patterning and a step of providing a flattening layer By being omissible, the manufacturing cost is reduced, and since the upper surface of the optical film is flat, a high yield can be obtained.

  A color conversion filter according to a third embodiment of the present invention includes a transparent substrate, a color filter in which at least two kinds of color filter layers that transmit light of different wavelength ranges are independently arranged, and the color And a protective layer disposed on the upper surface of the filter, wherein the protective layer is the optical film of the first embodiment. In the present embodiment, an optical film that functions as a color conversion layer by absorbing light in a specific wavelength region and emitting light in another wavelength region when the color tone variable color material (C) is in a colored state is used.

  FIG. 2 shows an example (for one pixel) of a color conversion filter for a color display according to this embodiment. In the color conversion filter shown in FIG. 2, red (R), green (G), and blue (B) color filter layers 30 </ b> R, 30 </ b> G, and 30 </ b> B are provided on the transparent substrate 10. A black black matrix 20 is provided between the color filter layers 30. On top of that, the optical film 1 of the first embodiment that functions as a protective layer and a color conversion layer is provided. In the configuration of FIG. 2, the first color tone portion 2 is a colorless portion. On the other hand, the second color tone part 3 is a colored part and functions as a red color conversion part. The light source is provided on the side of the optical film 1 of the color conversion filter, and light from the light source passes through the optical film 1, the color filter layer 30, and the transparent substrate 10 in this order, and is extracted to the outside.

  The transparent substrate 10 has excellent visible light transmittance, and does not adversely affect the formation process of the subsequent layers (the color filter layer 30 and each constituent layer of the organic EL element in the fourth embodiment, etc.). It can be formed using any material. Materials that can be used include glass and various plastics. The transparent substrate 10 may be either rigid or flexible.

  The color filter layer 30 is a layer having a function of transmitting only light in a desired wavelength range. In the present invention, at least two kinds of color filter layers 30, preferably three kinds of color filter layers 30, and more preferably three kinds of RGB color filter layers 30 are provided. The color filter layer 30 (in the configuration of FIG. 2, the red color filter layer 30R) provided at a position corresponding to the color conversion unit blocks light from the light source that has not been subjected to wavelength distribution conversion by the color conversion unit. This is effective for improving the color purity of the light subjected to wavelength distribution conversion by the conversion unit. Further, the color filter layer 30 (the green color filter layer 30G and the blue color filter layer 30B in the configuration of FIG. 2) provided at other positions transmits only light in a desired wavelength range of light from the light source. And obtaining light having desired color coordinates and color purity. Each of the color filter layers 30 can be formed using, for example, a color filter material for a liquid crystal display.

  The black matrix 20 is an optional layer that may be provided for the purpose of improving contrast. The black matrix 20 can be manufactured using any material that is commercially available for flat panel displays. The color filter composed of the transparent substrate 10, the color filter layer 30, and the optional black matrix 20 can be formed using any method known in the art.

  In FIG. 2, the structure which uses only the one optical film 1 and uses the 2nd color tone part 3 as a red conversion part was illustrated. However, the first non-irradiated first color tone portion 2 of the optical film 1 may be used as a red color conversion portion, and the light-irradiated second color tone portion 3 may be a colorless portion.

  The configuration of FIG. 2 includes a case where the light source sufficiently includes components in the blue and green wavelength ranges but does not sufficiently include the red wavelength range component (that is, a light source that emits blue to blue-green light). It is effective for. In addition, when desired (for example, when a light source that does not sufficiently contain components in the green and / or blue wavelength region is used), the second and / or third optical films 1 are laminated, and the respective optical films 1 are laminated. The second color tone portion 3 may be provided at a position corresponding to the green color filter layer 30G and / or the blue color filter layer 30B and used as a green color conversion portion and / or a blue color conversion portion, respectively.

  A color conversion filter for a color display is formed by arranging a plurality of pixels in a matrix on the substrate 10 with the RGB color filter layer 30 and the second color tone portion 3 shown in FIG. 2 as a set of pixels. I can do things. The upper surface shape and the arrangement pattern of the color filter layer 30 and the second color tone portion 3 depend on the application used. A rectangular, circular, polygonal or other top surface color filter layer 30 and the second color tone portion 3 may be formed as a set on the entire surface of the transparent substrate 10 in a matrix. Alternatively, when two or more optical films functioning as a protective layer and a color conversion layer are used, each of the second color tone portions 3 is divided into minute areas and disposed at an appropriate area ratio. A single color that cannot be achieved with this optical film may be exhibited.

  The optical film 1 used in the present embodiment may be formed using a laminate of the transparent substrate 10 / color filter layer 30 as a support. Alternatively, after the optical film 1 is formed using another temporary support, the resulting optical film 1 may be transferred or pasted onto the transparent substrate 10 / color filter layer 30. When two or more optical films 1 are used, the second color tone portion 3 can be formed at a desired position by light irradiation. Therefore, it is convenient to employ a formation method using a temporary support.

  A multicolor light emitting device according to a fourth embodiment of the present invention includes the color conversion filter and the light source according to the third embodiment.

  The light source of the present embodiment includes any light source that emits light in the near ultraviolet to visible range, preferably blue to blue-green. Examples of light sources that can be used include organic EL light-emitting elements, inorganic EL light-emitting elements, plasma light-emitting elements, cold cathode tubes, discharge lamps (such as high-pressure / ultra-high-pressure mercury lamps and xenon lamps), light-emitting diodes, and the like. Preferably, the light source is an organic EL light emitting element. When a multicolor light emitting device is used as a display, the light source has a plurality of light emitting units that can be controlled independently.

  The light source of this embodiment may be formed by directly laminating on the optical film 1 of the color conversion filter of the third embodiment. When the color conversion filter according to the third embodiment of the present invention is used, since the upper surface of the optical film 1 is flat, it is not necessary to dispose a flattening layer. Alternatively, the light source may be independently formed on another substrate. When using the light source formed independently, a light source is arrange | positioned at the optical film 1 side which is a protective layer of a color conversion filter.

  FIG. 3 shows a configuration example in which an organic EL light emitting element is directly laminated on the optical film 1. In the configuration of FIG. 3, the organic EL light emitting element includes a transparent electrode 40 composed of a plurality of stripe electrodes extending in the first direction, an organic EL layer 50, and a reflection composed of a plurality of stripe electrodes extending in the second direction. And an electrode 60. When forming an organic EL light emitting element independently on another substrate, the reflective electrode 60, the organic EL layer 50, and the transparent electrode 40 are laminated on the substrate in this order.

In the present embodiment, a gas barrier layer may be laminated on the upper surface of the color conversion filter optical film 1 (between the optical film 1 and the transparent electrode 40 in the configuration of FIG. 3). The gas barrier layer is effective for the purpose of protecting the organic EL light emitting element from moisture generated from the color conversion filter. The gas barrier layer is required to be a transparent and dense film without pinholes. As a material for forming the gas barrier layer, for example, an inorganic oxide such as SiO _x , SiN _x , SiN _x O _y , AlO _x , TiO _x , TaO _x , ZnO _x or the like can be used. The gas barrier layer can be formed by using a conventional method such as a sputtering method, a CVD method, a vacuum deposition method, or a dip method.

The organic EL light-emitting element that can be used in this embodiment has a structure in which an organic EL layer is held between a transparent electrode and a reflective electrode. The organic EL layer includes at least an organic light emitting layer and has a structure in which a hole injection layer, a hole transport layer, an electron transport layer and / or an electron injection layer are interposed as required. Alternatively, a hole injection / transport layer having both hole injection and transport functions and an electron injection / transport layer having both electron injection and transport functions may be used. Specifically, an organic EL light-emitting element having the following layer structure is employed.
(1) Anode / organic light emitting layer / cathode (2) Anode / hole injection layer / organic light emitting layer / cathode (3) Anode / organic light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / organic Light emitting layer / electron injection layer / cathode (5) Anode / hole transport layer / organic light emitting layer / electron injection layer / cathode (6) Anode / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / Cathode (7) Anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / electron injection layer / cathode (Note: the anode and the cathode are either a transparent electrode or a reflective electrode, respectively)

  In general, it is known in the art that it is easy to make the anode transparent, and it is also desirable in the present invention to use the transparent electrode 40 as an anode and the reflective electrode 60 as a cathode.

  As a material of each layer constituting the organic EL layer 50, known materials can be used. For example, in order to obtain blue to blue-green light emission, fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxonium compounds, styrylbenzene compounds, aromatic dimethylidin compounds, etc. Used to form an organic light emitting layer.

  In order to form an organic EL light emitting element having an independent light emitting portion, the transparent electrode 40 and the reflective electrode 60 are formed from a plurality of striped electrodes extending in the first and second directions, respectively, and the first and second Let the direction intersect the direction. Preferably, the first and second directions are orthogonal to each other. With such a configuration, the organic EL light-emitting element can be driven in a passive matrix. That is, when a voltage is applied to the specific stripe electrode of the transparent electrode 40 and the specific stripe electrode of the reflective electrode 60, the organic EL layer 50 at the intersection of the stripe electrodes emits light.

  Alternatively, the transparent electrode 40 is a uniform planar electrode having no stripe pattern, the reflective electrode is formed from a plurality of partial electrodes corresponding to each light emitting portion, and a switching element is added to the plurality of partial electrodes constituting the reflective electrode. One-to-one connection may be used. In this configuration, so-called active matrix driving can be performed. This configuration is convenient when the organic EL light emitting element is formed on another substrate.

  Hereinafter, the present invention will be described in more detail with reference to examples, evaluation examples, and comparative examples. However, the present invention is not limited by the following examples.

[Examples and Comparative Example 1] Optical film formation 1 (Examination of photoacid generator)
As shown in Table 1, 0.05 g of polymethyl methacrylate (PMMA) as the binder resin (A), photoacid generator (B1), rhodamine B (basic) as the acid-coloring colorant (C1) ( A coating solution was formed by mixing 1.2 mg of C1-1) and 1.0 g of an organic solvent (D). Next, a coating solution was applied on a 2.5 cm × 2.5 cm glass substrate by using a spin coating method (1000 rpm / 60 seconds). The coating was then prebaked at 80 ° C. for 20 minutes. Subsequently, the coating film prebaked using a striped photomask and an ultra-high pressure mercury lamp was exposed at an exposure amount of 3000 mJ / cm ² and further heated to 210 ° C. for 1 hour to be fixed to obtain an optical film. . The obtained optical film was observed using an optical microscope (magnification 100 times) to confirm the presence or absence of pattern formation. The results are shown in Table 1. In Table 1, “◯” indicates that a pattern corresponding to the stripe of the photomask is formed, and “x” indicates that no pattern is formed.

[Example 2] Optical film formation 2 (examination of binder resin)
As shown in Table 2, a binder resin, Adekaoptomer SP-172 as a photoacid generator, Rhodamine B (basic) (C1-1) 1.2 mg, and a solvent were mixed to form a coating solution. . Using the obtained coating solution, the procedure of Example 1 was repeated to form an optical film. The evaluation results of the obtained optical film are shown in Table 2.

  (Synthesis Method of Silicone Resin of Example 2-3) After 4 mol parts of phenyltrimethoxysilane and 1 mol part of diethoxydimethylsilane were polymerized with a phosphoric acid aqueous solution catalyst, 5.5 mol parts (excess) of trimethylsilyl chloride were added. Pyridine was reacted as a reactant, the end was sealed with a trimethylsilyl group, washed with water, and then the low molecular product was removed by a reprecipitation method using a mixed solvent of toluene and hexane to obtain a silicone resin.

[Example 3] Formation 3 of optical film (examination of acid-colorable coloring material)
As shown in Table 3, PMMA as binder resin (A), Adekaoptomer SP-172 as photoacid generator (B1), acid-coloring colorant, and 1.0 g of MEK as organic solvent (D) are mixed. Thus, a coating solution was formed. In Examples 3-1 to 3-5, an optical film was formed by repeating the procedure of Example 1 except that the obtained coating solution was used and the exposure dose was changed to 300 mJ / cm ² . Moreover, in Examples 3-6 to 3-7, the procedure of Example 1 was repeated using the obtained coating solution to form an optical film. The evaluation results of the obtained optical film are shown in Table 3. Moreover, as a result of measuring the transmittance | permeability of the light of wavelength 700nm in the 1st color tone part (non-exposed part) of the optical film obtained in each Example, all the transmittance | permeability was 99.0% or more.

  As apparent from Examples 1 to 3, an optical film formed from a resin composition containing the binder resin (A), the photoacid generator (B1) and the acid-colorable colorant (C1) according to the present invention is as follows. By the acid generated from the photoacid generator (B1) by light irradiation, a colored color is observed only in the exposed portion (second color tone portion), and a pattern having two different color tones is formed without going through the development process. I was able to. On the other hand, since the resin composition of Comparative Example 1 did not contain the photoacid generator (B1), no acid was generated, no coloring was observed in the exposed area, and the film remained uniformly transparent.

Example 4 Formation of Multicolor Light-Emitting Device (Formation of Color Filter)
Color mosaic (registered trademark) CK-7001 (manufactured by Fuji Film ARCH Co., Ltd.) was applied on the transparent substrate 10 (Corning 1737 glass) and patterned by a photolithographic method to form a black matrix. Next, a color mosaic (registered trademark) CR7001 (manufactured by Fuji Film ARCH Co., Ltd.) is applied and patterned by a photolithographic method to obtain a film thickness of a plurality of stripes having a width of 0.10 mm and a pitch of 0.33 mm. A red color filter layer 30R of 0 μm was formed. Subsequently, using color mosaic (registered trademark) CG7001 and CB7001 (manufactured by Fuji Film ARCH Co., Ltd.), a plurality of stripes having a width of 0.10 mm and a pitch of 0.33 mm so that the color filter layers 30 do not overlap each other. A green color filter layer 30G and a blue color filter layer 30B having a film thickness of 1.0 μm were formed to obtain a color filter.

(Formation of protective layer and red conversion filter)
70 parts by weight of PMMA, 4 parts by weight of the acid-colorable colorant (C1-6), 3 parts by weight of the acid-colorable colorant (C1-1), and 30 parts by weight of adekatopomer SP as a photoacid generator -172 was dissolved in 1000 parts by weight of MEK to obtain a coating solution. The obtained coating solution is applied onto a color filter, and a plurality of stripes having a width of 0.1 mm and a pitch of 0.33 mm are formed on the red color filter layer 30R by exposure using a mask (exposure amount 3000 mJ / cm ² ). A second color tone portion 3 (which functions as a red color conversion portion) is formed, and an optical film 1 which functions as a protective layer and a color conversion layer is obtained. The film thickness of the obtained optical film was 10 μm.

(Formation of gas barrier layer)
Next, a gas barrier layer composed of a 0.5 μm thick SiOx film was formed on the optical film 1 by using a sputtering method, and a color conversion filter was obtained. As a sputtering apparatus, an RF-planar magnetron type apparatus provided with a SiO2 target was used. Ar was used as a sputtering gas during film formation. The substrate temperature during formation was set to 80 ° C.

(Formation of organic EL light emitting device)
Subsequently, on the obtained color conversion filter, transparent electrode 40 (anode) / organic EL layer 50 (four layers of hole injection layer / hole transport layer / organic light emitting layer / electron injection transport layer) / reflection electrode 60 An organic EL light emitting device was formed by sequentially laminating (cathode) to obtain a multicolor light emitting device.

  An ITO film having a thickness of 100 nm was formed on the entire surface of the gas barrier layer by sputtering. After applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the ITO film, patterning is performed by a photolithography method, and the light emitting portions (red, green, and blue) of each color are positioned. A transparent electrode 40 composed of a plurality of striped partial electrodes having a width of 0.094 mm, a pitch of 0.10 mm, and a film thickness of 100 nm was obtained.

Then, mounting the substrate formed with the transparent electrode 40 to the resistance heating deposition equipment, pressure in the vacuum tank was reduced internal pressure to 1 × 10 ^-4 Pa. A hole injection layer made of copper phthalocyanine (CuPc) with a thickness of 100 nm, and 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) with a thickness of 20 nm. Hole transport layer, organic light-emitting layer made of 4,4′-bis (2,2′-diphenylvinyl) biphenyl (DPVBi) with a thickness of 30 nm, tris (8-hydroxyquinolinato) aluminum (Alq ₃ ) with a thickness of 20 nm ) Were sequentially formed without breaking the vacuum, and the organic EL layer 50 was obtained.

  Thereafter, Mg / Ag (10: 1) having a film thickness of 200 nm is used by using a mask from which a plurality of stripes having a width of 0.30 mm and a pitch of 0.33 mm orthogonal to the stripes of the transparent electrode 40 can be obtained without breaking the vacuum. Weight ratio) layer was deposited to form a reflective electrode 60 to obtain a multicolor light emitting device.

  The obtained multicolor light emitting device was sealed with sealing glass and a UV curable adhesive (both not shown) under a dry nitrogen atmosphere in the group box (both oxygen and moisture concentrations were 10 ppm or less).

[Comparative Example 2] Formation of multicolor light emitting device by conventional method (formation of color filter)
According to the same procedure as in Example 4, a red color filter layer, a green color filter layer, and a blue color filter layer were formed on a transparent substrate to obtain a color filter.

(Formation of clear layer (blue part))
Next, “V259PAP5” (manufactured by Nippon Steel Chemical Co., Ltd.), a photopolymerizable resin, was applied and patterned by a photolithographic method. A width of 0.10 mm, a pitch of 0.33 mm, A clear layer composed of a plurality of stripe-shaped portions having a thickness of 10 μm was formed. The clear layer is a layer for preventing a difference in film thickness between the color sub-pixels when the red color conversion layer is formed.

(Formation of clear layer (green part))
Next, “V259PAP5” (manufactured by Nippon Steel Chemical Co., Ltd.), which is a photopolymerizable resin, is applied and patterned by a photolithographic method. A width of 0.10 mm, a pitch of 0.33 mm, A clear layer composed of a plurality of stripe-shaped portions having a thickness of 10 μm was formed. The clear layer is a layer for preventing a difference in film thickness between the color sub-pixels when the red color conversion layer is formed.

(Formation of red conversion layer)
Coumarin 6 (0.6 parts by weight), rhodamine 6G (0.3 parts by weight) and basic violet 11 (0.3 parts by weight) as fluorescent dyes were added to 120 parts by weight of propylene glycol monoethyl acetate (PGMEA) as a solvent. Dissolved. 100 parts by weight of a photopolymerizable resin “V259PAP5” (manufactured by Nippon Steel Chemical Co., Ltd.) was added and dissolved to obtain a coating solution. This coating solution is applied using a spin coating method, patterned by a photolithographic method, and a plurality of stripe-shaped portions having a width of 0.10 mm, a pitch of 0.33 mm, and a thickness of 10 μm on the red color filter layer. A red conversion layer was formed.

(Formation of protective layer)
A photopolymerizable resin “V259PAP5” (manufactured by Nippon Steel Chemical Co., Ltd.) was applied to the upper surface of the substrate on which the color conversion layer and the clear layer were formed as described above to form a protective layer 7 having a thickness of 5 μm.

  Thereafter, in the same manner as in Example 4, a gas barrier layer and an organic EL light emitting device (transparent electrode, organic EL layer, and reflective electrode) were formed and sealed to obtain a multicolor light emitting device.

[Evaluation example]
The multicolor light emitting devices obtained in Example 4 and Comparative Example 2 were driven with a constant current amount, and the initial luminance of each color and the driving time dependency of each color luminance were evaluated. The results are shown in Table 4. In addition, Table 4 shows the yield evaluation in the manufacturing methods of Example 4 and Comparative Example 2 and the steps that could be reduced by Example 4.

  As is apparent from Table 4, the multicolor light emitting device according to the present invention has the same performance (initial luminance and luminance retention) as the multicolor light emitting device using the conventional color conversion layer. Moreover, the manufacturing method of the multicolor light emitting device according to Example 4 of the present invention is compared with the manufacturing method of Comparative Example 2 in the development process of the red color conversion layer, the application of the clear layer (green part), the pattern exposure, and the development. And post-bake (POB) process, and clear layer (blue part) coating, pattern exposure, development and post-bake (POB) process, a total of 9 processes can be reduced, which is advantageous in terms of reducing manufacturing costs And, as shown in Table 4, the yield could be improved.

It is a schematic top view which shows the optical film of this invention. It is a schematic sectional drawing which shows 1 pixel part of the color conversion filter of this invention. It is a schematic sectional drawing which shows 1 pixel part of the multicolor light-emitting device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical film 2 1st color tone part 3 2nd color tone part 10 Transparent substrate 20 Black matrix 30 (R, G, B) Color filter layer (red, green, blue)
40 Transparent electrode 50 Organic EL layer 60 Reflective electrode

Claims (19)

  The binder resin (A), a photoactive agent (B) selected from the group consisting of a photoacid generator and a photobase generator, and a color tone variable color material (C) whose color tone changes depending on the acid or base are included as essential components. An optical film, wherein two regions having different color tones are formed by light irradiation on a part of the optical film.   The optical film according to claim 1, wherein the color tone variable color material (C) is colored from colorless to colored with an acid or a base.   The photoactive agent (B) is a photoacid generator (B1), and the color-tunable color material (C) is an acid-colorable color material (C1) that is colored from colorless to colored with an acid. The optical film according to claim 2.   4. The optical film according to claim 3, wherein the acid-colorable color material (C1) is a leuco dye.   The optical film according to claim 3 or 4, wherein the acid-colorable coloring material (C1) is a rhodamine-based pigment.   The optical film according to claim 2, wherein the color tone variable color material (C) has fluorescence in a colored state.   The optical film according to claim 6, wherein the color tone variable color material (C) absorbs light in a specific wavelength region and emits light in another wavelength region in a colored state. A binder resin (A), a photoactive agent (B) selected from the group consisting of a photoacid generator and a photobase generator, a color tone variable color material (C) whose color tone changes depending on the acid or base, and an organic solvent ( A step of preparing a coating liquid composition containing D) as an essential component; a step of applying the coating liquid composition to a support;
Removing the organic solvent (D); irradiating active energy rays to a predetermined pattern region to change the color tone of the color tone variable color material (C); and forming two regions having different color tones; The manufacturing method of the optical film characterized by including.   The method for producing an optical film according to claim 8, wherein the color tone variable color material (C) is colored from colorless to colored with an acid or a base.   The photoactive agent (B) is a photoacid generator (B1), and the color-tunable color material (C) is an acid-colorable color material (C1) that is colored from colorless to colored with an acid. Item 10. A method for producing an optical film according to Item 9.   The method for producing an optical film according to claim 10, wherein the acid-colorable colorant (C1) is a leuco dye.   The method for producing an optical film according to claim 10 or 11, wherein the acid-colorable coloring material (C1) is a rhodamine dye.   The method for producing an optical film according to claim 9, wherein the color tone variable color material (C) has fluorescence in a colored state.   14. The optical film according to claim 13, wherein the color tone variable color material (C) absorbs light in a specific wavelength region and emits light in another wavelength region in a colored state.   The method for producing an optical film according to claim 8, wherein the support is a transparent support.   The method for producing an optical film according to claim 8, further comprising a step of removing the support.   A transparent substrate, a color filter that independently transmits at least two kinds of color filter layers that transmit light of different wavelength ranges, and a protective layer that is disposed on the upper surface of the color filter, and the protection A color conversion filter, wherein the layer is the optical film according to claim 7.   A multicolor light emitting device comprising the color conversion filter according to claim 17 and a light source.   The multicolor light emitting device according to claim 18, wherein the light source is an organic EL light emitting element.

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