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WO2016204148A1 - Composition photosensible, composition photosensible pour filtre coloré et filtre coloré - Google Patents

Composition photosensible, composition photosensible pour filtre coloré et filtre coloré Download PDF

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Publication number
WO2016204148A1
WO2016204148A1 PCT/JP2016/067688 JP2016067688W WO2016204148A1 WO 2016204148 A1 WO2016204148 A1 WO 2016204148A1 JP 2016067688 W JP2016067688 W JP 2016067688W WO 2016204148 A1 WO2016204148 A1 WO 2016204148A1
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WO
WIPO (PCT)
Prior art keywords
group
photosensitive composition
compound
monomer
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/067688
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English (en)
Japanese (ja)
Inventor
彩子 宮本
進 白鳥
ニシャド ペルール
宗大 和田
山田　和則
彰 平野
嘉孝 寺島
洋文 二井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyocolor Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyocolor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Ink SC Holdings Co Ltd, Toyocolor Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Priority to KR1020177037437A priority Critical patent/KR20180017055A/ko
Priority to CN201680034749.5A priority patent/CN107735728A/zh
Publication of WO2016204148A1 publication Critical patent/WO2016204148A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to a photosensitive composition capable of obtaining a film or fine pattern excellent in chemical resistance.
  • the photosensitive composition of the present invention is a color liquid crystal display device, a color organic EL display device, a color filter used for a solid-state imaging device, a black matrix, a color filter protective film, a photo spacer, a protrusion for liquid crystal alignment, a microlens, a touch panel. It can be used in a wide range of applications including adhesives for electronic materials, adhesive sheets, and the like in the vicinity of insulating films and flexible printed wiring boards.
  • liquid crystal display elements for organic EL display devices (particularly WRGB system combining white light-emitting organic EL and color filters), liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc., color filters, black matrices, color filter protective films, photo spacers, A projection for liquid crystal alignment, or a film such as a microlens or an insulating film for a touch panel, or a fine pattern is provided. While these films or fine patterns are required to have optical properties such as transparency, chemical resistance and the like are required when performing subsequent processes such as formation and assembly of other members. Therefore, it is known that a film or a fine pattern having excellent chemical resistance is formed by adding a thermal crosslinking agent to the photosensitive composition in advance and performing photocuring and thermosetting. (For example, Patent Documents 1 and 2)
  • the epoxy resin, blocked isocyanate, and melamine resin described in 2 have the following problems.
  • the photosensitive composition can be thermoset at 180 ° C. or higher to impart chemical resistance.
  • the blocking agent remains in the cured product, adversely affecting the insulation, and degassing may occur. It may occur and cause a dark spot in the organic EL element.
  • the blocking agent may be scattered in the air during heat curing, which may adversely affect the operator or the environment, and may cause a decrease in optical characteristics.
  • many blocked isocyanates have poor compatibility with acrylic photosensitive compositions, and whitening may occur.
  • melamine resin can also be given chemical resistance even at low temperature curing of 150 ° C or lower, but formaldehyde is generated during and after heat curing. ⁇ There are concerns about adverse environmental impacts. In addition, many melamines that can be cured at low temperature are highly polar, have poor compatibility with acrylic photosensitive compositions, and may cause whitening.
  • a diene structure and a dienophile structure can be cured at a low temperature of 150 ° C. or less to provide chemical resistance and as a cross-linking system having good compatibility with an acrylic photosensitive composition without degassing.
  • the use of the Diels-Alder reaction is disclosed (for example, Patent Document 3).
  • Patent Document 3 discloses a method of forming a pattern using a heat stamp or a photothermal conversion material that absorbs infrared rays.
  • Patent Document 3 discloses a method of forming a pattern using a heat stamp or a photothermal conversion material that absorbs infrared rays.
  • the present invention has been made in view of the above-described present situation, and an object thereof is to provide a photosensitive composition that can impart chemical resistance even at a low curing temperature and has no problem of degassing or compatibility.
  • one embodiment of the present invention is a color filter photosensitizer containing a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), and a colorant. Relates to the composition.
  • one embodiment of the present invention relates to the above-described photosensitive composition for a color filter, which is alkali-soluble.
  • one embodiment of the present invention relates to the above photosensitive composition for a color filter, wherein the compound (A) containing a furyl group contains a carboxyl group.
  • the compound (A) containing a furyl group includes a monomer (a-1) containing a furyl group and a monomer (a-2) containing a carboxyl group.
  • the present invention relates to the above-described photosensitive composition for a color filter, which is a polymer (A-1) obtained by radical polymerization of a monomer (a).
  • one embodiment of the present invention relates to the above photosensitive composition for a color filter, wherein the furyl group-containing monomer (a-1) contains furfuryl methacrylate.
  • Another embodiment of the present invention relates to the above photosensitive composition for a color filter, wherein the monomer (a-2) containing a carboxyl group contains a compound represented by the following general formula [6].
  • General formula [6] [Wherein R 11 represents a hydrogen atom or a methyl group, and R 12 and R 13 represent a linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms and a divalent alicyclic carbon group. It is a hydrogen group or a divalent aromatic hydrocarbon group, and R 12 and R 13 may be the same or different. ]
  • One embodiment of the present invention also relates to the above-described photosensitive composition for a color filter, wherein the monomer (a) further contains methyl methacrylate and / or a compound represented by the following general formula [7].
  • General formula [7] [Wherein R 14 represents a hydrogen atom or a methyl group, and R 15 represents a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic group.
  • a hydrocarbon group, and R 16 represents a linear or branched divalent aliphatic hydrocarbon group, divalent alicyclic hydrocarbon group, or divalent aromatic hydrocarbon having 1 to 8 carbon atoms. It is a group.
  • Another embodiment of the present invention relates to the above color filter photosensitive composition, wherein the polymer (A-1) has a weight average molecular weight of 2,000 to 70,000.
  • one embodiment of the present invention relates to the above photosensitive composition for a color filter, wherein the photopolymerizable functional group includes a (meth) acryloyl group and / or a maleimide group.
  • one embodiment of the present invention relates to the above photosensitive composition for a color filter, wherein the photopolymerizable functional group contains an acryloyl group.
  • one embodiment of the present invention relates to the above photosensitive composition for a color filter, wherein the compound (B) containing a photopolymerizable functional group contains a trifunctional or lower monomer or oligomer.
  • one embodiment of the present invention relates to the above color filter photosensitive composition, wherein the content of the colorant is 10% by mass or more of the total nonvolatile content of the color filter photosensitive composition.
  • R 1 represents an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon Represents an aralkyl group having 7 to 30 carbon atoms or an alkaryl group having 7 to 30 carbon atoms
  • X represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms
  • R 2 , R 3 and R 4 are each independently an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms Group, an aralky
  • mode of this invention contains the compound (A) containing a furyl group, the compound (B) containing a photopolymerizable functional group, and a photoinitiator (C),
  • a compound (A) containing a furyl group radically polymerizes a monomer (a) containing a monomer (a-1) containing a furyl group and a monomer (a-2) containing a carboxyl group.
  • a polymer (A-1) The monomer (a-2) containing a carboxyl group relates to a photosensitive composition containing a compound represented by the following general formula [6].
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 and R 13 represent a linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms and a divalent alicyclic carbon group. It is a hydrogen group or a divalent aromatic hydrocarbon group, and R 12 and R 13 may be the same or different.
  • one embodiment of the present invention relates to the above photosensitive composition, wherein the photopolymerizable functional group includes a (meth) acryloyl group and / or a maleimide group.
  • one embodiment of the present invention relates to the above photosensitive composition, wherein the photopolymerizable functional group includes an acryloyl group.
  • one embodiment of the present invention relates to the photosensitive composition according to any one of the above, further containing a colorant.
  • Another embodiment of the present invention includes a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), and a colorant.
  • the photopolymerizable functional group relates to a photosensitive composition containing an acryloyl group.
  • one embodiment of the present invention relates to the above photosensitive composition, wherein the content of the colorant is 10% by mass or more of the total nonvolatile content of the photosensitive composition.
  • one embodiment of the present invention relates to a color filter including a filter segment or a black matrix formed from the above photosensitive composition for a color filter or the above photosensitive composition on a transparent substrate.
  • one embodiment of the present invention relates to a color filter including a filter segment or a black matrix formed from the above photosensitive composition for a color filter or the above photosensitive composition on a flexible transparent substrate.
  • one embodiment of the present invention relates to the above color filter for an organic EL display device.
  • (meth) acrylate means acrylate and / or methacrylate
  • (meth) acrylic acid means acrylic acid and / or methacrylic acid.
  • the photosensitive composition of this embodiment contains the compound (A) containing a furyl group, the compound (B) containing a photopolymerizable functional group, and a photopolymerization initiator (C) as essential components.
  • the photosensitive composition of the present embodiment only needs to satisfy the above-described configuration, and is not limited to the action or the curing process. Can be raised. The effect is presumed as follows.
  • the reaction in photocuring is radical polymerization by irradiation with active energy rays such as ultraviolet rays, and it is widely known that the reaction rate of the photopolymerizable functional group in the compound (B) does not reach 100% at this stage. ing. This is one of the causes that the chemical resistance of the cured product is not sufficient.
  • the unreacted photopolymerizable functional group in the compound (B), the unreacted photopolymerization initiator (C), and the furyl group in the compound (A) undergo thermal radical addition reaction.
  • the Dienophile structure in the unreacted photopolymerizable functional group in the compound (B) and the diene structure in the furyl group in the compound (A) undergo Diels-Alder reaction.
  • the chemical resistance of the cured product can be improved by the thermal radical addition reaction and / or the Diels-Alder reaction.
  • the radical polymerization reaction occurs when radicals are generated from the photopolymerization initiator (C) by ultraviolet rays and the photopolymerizable functional groups in the compound (B) undergo radical polymerization.
  • the photopolymerizable functional group include acryloyl group, methacryloyl group, maleimide group, styryl group, maleic anhydride residue, vinyl ether group, allyl ether group, alkenyl group having 2 to 10 carbon atoms, and alkynyl group having 2 to 10 carbon atoms. (Meth) acryloyl group is preferable.
  • the thermal radical addition reaction is a reaction in which the photopolymerization initiator (C) is cleaved by heat to generate radicals, radical polymerization of the photopolymerizable functional group occurs, and radicals at the polymerization growth terminal are added to the furyl group. It is guessed.
  • Such a reaction is described in, for example, Non-Patent Document 1 (N. Davidenko et al., “Activity of the Furyring Ring in the Free radical Polymerization of Acely Monomers, Journey of the Principal Polymers, J. -2766 (1996)) also describes the mechanism.
  • the present inventors have cross-linked by thermal radical addition reaction between a photopolymerizable functional group and a compound containing a furyl group (A) even in thermal curing of the photosensitive composition, in particular, low temperature curing such as 80 to 150 ° C. It has been found that the density is improved and the chemical resistance is improved.
  • the Diels-Alder reaction does not have a problem of degassing because there is no leaving group accompanying the reaction.
  • the reaction does not occur by photoexcitation but proceeds only by heat.
  • a Lewis acid which will be described later, may be added as a catalyst.
  • the reaction temperature of the Diels-Alder reaction is determined by the combination of the diene structure and the dienophile structure.
  • a low temperature thermosetting temperature for example, 80 to 150 can be obtained by using a furyl group as the diene structure. It can be cured at 0 ° C.
  • thermosetting can be improved more by using maleimide among photopolymerizable functional groups as a dienophile structure.
  • the photopolymerizable functional group in the compound (B) includes a (meth) acryloyl group that is easily radical-polymerized by photocuring, an acryloyl group that easily undergoes radical addition reaction with a furyl group by thermosetting, a furyl group, and Diels.
  • a maleimide group that easily undergoes Alder reaction is preferable because of good reactivity during photocuring and / or heat curing.
  • the use of the photosensitive composition of the present embodiment is not particularly limited, but by imparting developability, it can be used as a negative photoresist and a fine pattern can be produced by photolithography.
  • the photosensitive composition is partially photocured by pattern exposure using a photomask, the uncured portion is dissolved and developed with an organic solvent, and the remaining photocured portion is heated. And heat curing.
  • An organic solvent or an alkaline aqueous solution can be used in the development process of photolithography.
  • the photosensitive composition of the present embodiment When the photosensitive composition of the present embodiment is used as a negative photoresist, it is possible to achieve both pattern resolution and chemical resistance regardless of whether the development is alkali development or solvent development.
  • photocuring can be performed by increasing the concentration of a photopolymerizable functional group or a photopolymerization initiator or increasing the exposure amount in order to increase chemical resistance. It is necessary to increase the crosslinking density.
  • a photopolymerization reaction diffuses out of the opening of the mask and occurs in a range larger than the mask size, resulting in a pattern larger than the mask size after development. The tendency to be strengthened.
  • unreacted photopolymerizable functional groups in the photocuring process are not resistant to chemicals in heat curing because heat polymerization does not proceed sufficiently at temperatures as low as 80 to 150 ° C in the heat curing process following exposure and development. Improvement effect is difficult to obtain. Therefore, in order to improve the chemical resistance, it is necessary to rely on a design that promotes the photopolymerization reaction, and there is a trade-off between the resolution of the pattern and the chemical resistance.
  • the color filter photosensitive composition is required to have excellent developability, but on the other hand, since it contains a colorant, it is difficult for photocuring to proceed, and particularly excellent chemical resistance is obtained under conditions of low-temperature curing. It is difficult. For this reason, it is very difficult to achieve both developability and chemical resistance.
  • the photosensitive composition of the present embodiment containing the compound (A) containing a furyl group when used, the concentration of the photopolymerizable functional group and the photopolymerization initiator is not increased, and the exposure amount of the pattern exposure part is during development.
  • the concentration of the photopolymerizable functional group and the photopolymerization initiator is not increased, and the exposure amount of the pattern exposure part is during development.
  • the chemical resistance can be improved by performing a radical addition reaction and / or a Diels-Alder reaction, and the trade-off between pattern resolution and chemical resistance can be eliminated. Therefore, although the photosensitive composition of this embodiment can be applied to a wide range of uses, it can be suitably used for a photosensitive composition for color filters.
  • the photopolymerization initiator (C) is preferably used in an amount of 0.01 to 60 parts by mass, and preferably 0.1 to 10 parts by mass in a total of 100 parts by mass of the solid content of the photosensitive composition. Is more preferable, and 0.5 to 5.0 parts by mass is even more preferable.
  • the photosensitive composition is preferably alkali-soluble, and for this purpose, the compound (A) containing a furyl group and / or the compound (B) containing a photopolymerizable functional group may contain an alkali-soluble functional group. Then, the compound (D) containing an alkali-soluble functional group (except for the case of the compound (A) or the compound (B)) may be further added to the photosensitive composition.
  • An alkali-soluble functional group is a functional group that is neutralized with an inorganic alkali aqueous solution such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine, and swells / dissolves in the aqueous solution.
  • an inorganic alkali aqueous solution such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine, and swells / dissolves in the aqueous solution.
  • organic alkali such as dimethylbenzylamine or triethanolamine
  • the compound (A) containing a furyl group of the present embodiment is chemically resistant to the photosensitive composition by a thermal radical addition reaction or a Diels-Alder reaction in a thermosetting step with the photopolymerizable functional group in the photosensitive composition. It is presumed that there is an effect of imparting.
  • the compound (A) containing a furyl group is not particularly limited in its structure as long as it contains a furyl group (a group obtained by removing one hydrogen atom from furan).
  • JP1994-271558, JP1994-293830, JP1996-239421, JP1998-508655, JP2000-001529, JP2003-183348, JP2006-193628, JP Known compounds described in 2007-186684, JP-A 2010-265377, JP-A 2011-170069 and the like can be used, and they may be low-molecular or high-molecular.
  • the low molecular weight compound include a monomer containing a furyl group, a compound obtained by reacting a polyfunctional isocyanate and an alcohol containing a furyl group, and the like.
  • a polymer is more preferable, and specific examples include poly (meth) acrylate, polyurethane, polyester, polyamide, polyimide, polycarbonate, polyolefin, polystyrene, polysiloxane, polysiloxane having a furyl group.
  • examples include ethers, copolymers containing maleic anhydride, epoxy resins, furan resins (condensation polymers of furfuryl alcohol and formaldehyde). These may be used alone, or a mixture may be used.
  • the polymer may be linear, branched or star-shaped, and may be either thermoplastic or thermosetting.
  • the photopolymerizable functional group may further be included in the compound (A) containing a furyl group.
  • the compound (A) containing a furyl group is preferably used in an amount of 5 to 95 parts by mass, more preferably 100 parts by mass in total of the solid content of the photosensitive composition. Is 5 to 70 parts by mass, more preferably 5 to 50 parts by mass.
  • the compound (A) containing a furyl group removes a coloring agent from a photosensitive composition.
  • the total solid content of the components is preferably 5 to 95 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 15 to 40 parts by mass.
  • the point that the furyl group can be easily introduced the point that the introduction amount of the furyl group is easy to control, the control of the developability of the photosensitive composition by controlling the molecular weight and the copolymer composition.
  • the radical polymer (A-1) is more preferable from the viewpoints of being easy to handle and the transparency of the photosensitive composition being excellent.
  • the radical polymer (A-1) containing a furyl group is a polymer obtained by radical polymerization of a monomer having a double bond capable of radical polymerization, and has a structure containing a furyl group.
  • the manufacturing method is Method [1-1] Method for Polymerizing Monomer (a) Containing Monomer (a-1) Containing Furyl Group Method [1-2] Monomer (a-3) Containing Reactive Functional Group And a method in which a monomer (a) containing a polymer is polymerized and the resulting polymer (prepolymer) is reacted with a reactive compound (a-4) containing a furyl group.
  • the method [1-1] is preferable in that the number of synthesis reaction processes can be reduced.
  • the polymer (A-1) may be a homopolymer or a copolymer with other monomers, but the polymer Tg, the viscosity of the photosensitive composition, and the phase with other components. In order to adjust the solubility, it is preferable to copolymerize with a monomer other than (a-1) or (a-3).
  • Examples of the monomer (a-1) containing a furyl group include monomers represented by the following general formulas [1] to [5], furfuryl vinyl ether, furfuryl allyl ether, and the like.
  • the monomer of the general formula [1] it is preferable to use the monomer of the general formula [1], and the stability of the monomer itself. It is more preferable to use furfuryl methacrylate in view of the above points and obtaining good polymerizability.
  • Examples of the reactive functional group in the monomer (a-3) containing a reactive functional group used in the method [1-2] include a carboxyl group, an epoxy group, an isocyanate group, and a carboxylic anhydride group.
  • a radical containing a furyl group A polymer (A-1) can be obtained.
  • Examples of the monomer (a-3) containing a reactive functional group include monomers containing a carboxyl group, an epoxy group, an isocyanate group, a carboxylic acid anhydride group, and the like.
  • the monomer containing a carboxyl group the same monomer as the monomer (a-2) containing a carboxyl group described later can be used.
  • the monomer containing a carboxylic anhydride group include maleic anhydride, itaconic anhydride, 4-[(2-methacryloyloxyethoxy) carbonyl] phthalic anhydride, and the like.
  • Monomers containing epoxy groups include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxybutyl (meth) acrylate, 3-methyl- 3,4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxy Hexyl (meth) acrylate, ⁇ -ethyl acrylate glycidyl, allyl glycidyl ether, crotonyl glycidyl ale, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, N- (3,5 -Dimethyl
  • Monomers containing isocyanate groups and blocks thereof include (meth) acryloyl isocyanate, 2-isocyanatoethyl (meth) acrylate, 2- (meth) acryloyloxyethoxyethyl isocyanate, 1,1- (bis (meth) And acryloyloxymethyl) ethyl isocyanate, m- (meth) acryloylphenyl isocyanate, ⁇ , ⁇ -dimethyl-4-isopropenylbenzyl isocyanate and the like.
  • Examples of the reactive compound (a-4) containing a furyl group include furfuryl alcohol, furfurylamine, furfuryl mercaptan, furfural and the like.
  • the monomer (a-3) containing a reactive functional group and the reactive compound (a-4) containing a furyl group one kind of compound may be used, or two or more kinds of compounds may be used in combination.
  • the concentration of the furyl group in the polymer (A-1) is preferably 0.5 to 6.0 mmol, more preferably 1.0 to 4.0 mmol per 1 g of the polymer. If the concentration of the furyl group is 0.5 mmol or more, preferably 1.0 mmol or more, the photosensitive composition is excellent in chemical resistance, and if it is 6.0 mmol or less, preferably 4.0 mmol or less, the polymer (A-1) Excellent in stability over time.
  • the radical polymer (A-1) containing a furyl group preferably contains an alkali-soluble functional group. Since the solubility in the photosensitive composition is increased, the transparency of the photosensitive composition is improved, and the chemical resistance is improved due to the reaction with the compound (B) containing a photopolymerizable functional group. It is also preferable from the point of becoming.
  • the monomer (a) is polymerized in the above method [1-1] or [1-2], the monomer (a-1) containing a furyl group or the monomer containing a reactive functional group (a In addition to -3), an alkali-soluble functional group can be introduced into the polymer (A-1) by using a monomer containing an alkali-soluble functional group. That is, as a method for producing the radical polymer (A-1) containing an alkali-soluble functional group and containing a furyl group, the following method may be mentioned.
  • Examples of the monomer containing an alkali-soluble functional group include a monomer (a-2) containing a carboxyl group, a monomer containing a phosphate group, and a monomer containing a sulfonic acid group.
  • the monomer (a-2) containing is preferably used.
  • Examples of the monomer (a-2) containing a carboxyl group include (meth) acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, ⁇ - (hydroxymethyl) (meth) acrylic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ⁇ - Addition reaction of carboxyethyl (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, ⁇ -carboxypolycaprolactone (meth) acrylate, p-vinylbenzoic acid, and carboxylic acid anhydride with monomer containing hydroxyl group And the like.
  • Examples of the carboxylic acid anhydride used for the monomer obtained by addition reaction of the carboxylic acid anhydride and the monomer containing a hydroxyl group include succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, and phthalic acid.
  • Dicarboxylic anhydrides such as anhydride, glutaric anhydride, dodecenyl succinic anhydride, and chlorendic anhydride; 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride, 1,3, Aliphatic tricarboxylic acid anhydrides such as 4-cyclopentanetricarboxylic acid anhydride; Benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], trimellitic anhydride chloride [4-chloroformylphthalic acid Anhydride], naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene
  • a carboxylic acid anhydride containing two or more acid anhydride groups in one molecule such as tetracarboxylic dianhydride
  • the carboxylic acid anhydride 1 Two or more monomers containing a hydroxyl group are added to a molecule, and two or more radical polymerizable functional groups are contained in one molecule. As a result, the copolymer may be gelled. Therefore, when using a carboxylic acid anhydride containing two or more acid anhydride groups in one molecule, preferably 3 mol% or less of the entire carboxylic acid anhydride. More preferably, it is 2 mol% or less, and it may be preferable not to use it.
  • Examples of the monomer containing a hydroxyl group used as a monomer obtained by addition reaction of a carboxylic acid anhydride and a monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2 (or 3) Hydroxyhydroxy (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and ethyl- ⁇ -hydroxymethyl acrylate (Meth) acrylates having a hydroxyl group such as alkyl- ⁇ -hydroxyalkyl acrylate; N- (hydroxyalkyl) (meth) acrylamide, such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide (Meth) acrylamides having
  • (meth) acrylates having a hydroxyl group (meth) acrylamides having a hydroxyl group, vinyl ethers having a hydroxyl group, and allyl ethers having a hydroxyl group.
  • alkylene oxide to be added ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination of two or more of these are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block.
  • lactone to be added examples include ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these. What added both alkylene oxide and lactone may be used.
  • the polymer (A-1) When a structure obtained by addition reaction of a carboxylic acid anhydride and a monomer containing a hydroxyl group is introduced into the polymer (A-1), an addition reaction between the carboxylic acid anhydride and the monomer containing a hydroxyl group is performed.
  • the monomer may be synthesized in advance and used as the monomer (a-2) containing a carboxyl group to be produced by the methods [2-1], [2-2], etc.
  • a monomer containing a hydroxyl group and another monomer may be copolymerized in advance and then a carboxylic acid anhydride may be added. This method is preferable in that the reaction process of synthesis can be shortened.
  • the monomer (a-2) containing a carboxyl group in particular, methacrylic acid and / or a monomer represented by the following general formula [6] is used in that the dissolution rate during alkali development can be increased.
  • 2-Methacryloyloxyethyl succinic acid is more preferable from the viewpoint that the development speed can be increased by using a smaller amount.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 and R 13 represent a linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms and a divalent alicyclic group. It is a hydrocarbon group or a divalent aromatic hydrocarbon group, and R 12 and R 13 may be the same or different.
  • linear or branched divalent aliphatic hydrocarbon groups examples include alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, and octane; Alkenes such as ethylene, propylene, butylene, pentene, hexene, heptene, octene, etc .; Examples include groups obtained by removing two hydrogen atoms from a compound such as alkyne such as ethyne, propyne, butyne, pentyne, hexyne, peptin, octyne, and the like.
  • alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, and octane
  • Alkenes such as ethylene, propylene, butylene, pentene, hexene, he
  • divalent alicyclic hydrocarbon group examples include cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclohexene, methylcyclohexene, norbornane, norbornene, bicyclo Examples thereof include groups obtained by removing two hydrogen atoms from a compound such as octane and bicyclooctene.
  • divalent aromatic hydrocarbon group examples include groups obtained by removing two hydrogen atoms from a compound such as benzene, toluene, xylene, ethylbenzene, dimethylbenzene, and the like. More preferably, R 12 and R 13 are each independently an alkylene group having 1 to 5 carbon atoms.
  • Examples of the monomer containing a phosphoric acid group include 2-phosphonooxyethyl (meth) acrylate, 2-phosphonooxypropyl (meth) acrylate, 3-phosphonooxypropyl (meth) acrylate, and 4-phosphonooxy.
  • Examples of the monomer containing a sulfonic acid group include vinyl sulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfo-1-propyl (meth) acrylate, 1-sulfo-2-propyl (meth) acrylate, 3- Sulfopropyl (meth) acrylate, 1-sulfo-2-butyl (meth) acrylate, 3-sulfo-2-butyl (meth) acrylate, 3-bromo-2-sulfo-2-propyl (meth) acrylate, 3-methoxy -1-sulfo-2-propyl (meth) acrylate, 4-((meth) acryloylamino) benzenesulfonic acid, N- (1,1-dimethyl-2-sulfoethyl) (meth) acrylamide, ((meth) acrylamide ) Methanesulfonic acid, 2-((meth)
  • the alkali-soluble functional group is preferably a carboxyl group from the viewpoint that the photosensitive composition is stable.
  • the carboxyl group is obtained by reacting a carboxylic anhydride group with a hydroxyl group or an amino group to form a half ester or half amide, for example, in the polymer (A-1) by the following method. Can be introduced.
  • Method [2-3] A monomer (a) containing a furyl group-containing monomer (a-1) and a hydroxyl group-containing monomer or an amino group-containing monomer (a) are polymerized.
  • Method of reacting carboxylic acid anhydride with the obtained prepolymer [2-4] A monomer containing a monomer containing a carboxylic acid anhydride group (a-3) containing a reactive functional group (a-3) Method of polymerizing a) and reacting the resulting prepolymer with a compound containing a hydroxyl group or a compound containing an amino group as a reactive compound containing a furyl group (a-4) [2-5] Including a furyl group Monomer (a-1) and monomer (a) containing a monomer containing a carboxylic anhydride group are polymerized, and the resulting prepolymer contains a compound containing water or a hydroxyl group or a compound containing an amino group Among these, the method [2-1] is It is preferable from the viewpoint that the synthesis process can be reduced and the side reaction can be reduced and the synthesis can be performed stably.
  • the same ones as described above can be used.
  • the monomer containing an amino group examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 1- (t-butylamino) ethyl (meth) acrylate, 2- ( t-butylamino) ethyl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, N- (2,2,6,6-tetramethylpiperidinyl) (meth)
  • Examples include acrylamide.
  • the acid value is preferably 10 to 200 mgKOH / g, more preferably 40 to 130 mgKOH / g.
  • the acid value is 10 mgKOH / g or more, the developing speed when the photosensitive composition is subjected to alkali development is not too slow, and when the acid value is 200 mgKOH / g or less, the photosensitive composition tends to have a low viscosity. This is because coating becomes easy.
  • the acid value in the present embodiment is the number of mg of potassium hydroxide necessary to neutralize the acid group contained in 1 g of the polymer (A-1) containing no solvent. The value calculated
  • the radical polymer (A-1) containing a furyl group may contain a photopolymerizable functional group.
  • a photopolymerizable functional group By including a photopolymerizable functional group, it may be possible to improve chemical resistance of the photosensitive composition or to adjust patternability in a direction in which the development speed is high and the pattern size is large.
  • the photopolymerizable functional group is preferably a (meth) acryloyl group or a maleimide group, but when it is included in the polymer (A-1), a (meth) acryloyl group is more preferable from the viewpoint of stability.
  • a reactive functional group such as a carboxyl group, an epoxy group, an isocyanate group, a carboxylic acid anhydride group, or a hydroxyl group is added.
  • a monomer (a-) containing a reactive functional group capable of reacting with the reactive functional group is introduced into the prepolymer by copolymerizing the monomer (a-3) containing the reactive functional group. By further reacting 3), a photopolymerizable functional group can be introduced into the polymer (A-1).
  • the radically polymerizable double bond in the monomer (a-3) containing a reactive functional group capable of reacting with the reactive functional group is incorporated into the polymer (A-1) without being reacted.
  • this double bond has a function as a photopolymerizable functional group. That is, as a method for producing the radical polymer (A-1) containing a photopolymerizable functional group and containing a furyl group, the following method may be mentioned.
  • Method [3-1] A monomer (a) containing a monomer (a-1) containing a furyl group and a monomer (a-3) containing a reactive functional group is polymerized, and the resulting pre-polymer is obtained.
  • the photopolymerizable property in the polymer (A-1) is obtained. Both functional groups and alkali-soluble functional groups can be introduced.
  • the polymer (A-1) is further reacted with a carboxylic acid anhydride. Both photopolymerizable functional groups and alkali-soluble functional groups can be introduced therein.
  • a monomer (a) containing a furyl group-containing monomer (a-1) and a carboxyl group-containing monomer (a) are polymerized, and the resulting pre-polymer is obtained.
  • Method for reacting a monomer containing an epoxy group with a part of a carboxyl group of a polymer A monomer (a) containing a monomer containing a furyl group (a-1) and a monomer containing an epoxy group Method of polymerizing and reacting a monomer containing a carboxyl group with the epoxy group of the resulting prepolymer, and reacting a carboxylic acid anhydride with the generated hydroxyl group Monomer containing a furyl group (a- 1) A monomer (a) containing a carboxyl group-containing monomer and a hydroxyl group-containing monomer (a) is polymerized, and a part or all of the hydroxyl groups of the resulting prepolymer contain an isocyanate group.
  • a monomer (a-1) containing a furyl group and a monomer containing a monomer containing a carboxylic anhydride group ( ) was polymerized, the prepolymer obtained, a method of reacting a monomer containing a monomer or an amino group containing hydroxyl groups of the monomer containing a reactive functional group (a-3)
  • Examples of the monomer (a-3) containing a reactive functional group include the above-mentioned monomers containing a hydroxyl group, monomers containing an amino group, monomers containing an isocyanate group, and acid anhydride groups.
  • a monomer containing an epoxy group a monomer containing a carboxyl group (a-2), and the like.
  • the functional group to be reacted is preferably a combination of a hydroxyl group or amino group and an isocyanate, or a combination of an epoxy group and a carboxyl group.
  • the photosensitive composition of the present embodiment contains the compound (B) containing a photopolymerizable functional group as an essential component
  • the polymer (A-1) may contain no photopolymerizable functional group.
  • the functional group equivalent also referred to as a double bond equivalent
  • the double bond equivalent is 200 g / mol or more, the temporal stability of the polymer (A-1) tends to be good, and when the double bond equivalent is 5000 g / mol or less, the photosensitivity of the photosensitive composition is good. It is because it becomes easy to become.
  • the functional group equivalent in this embodiment is the mass per 1 mol of the functional group of the polymer (A-1) not containing a solvent (unit: g / mol).
  • Examples of other monomers that can be used as the monomer (a) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, 4-t-butyl Cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxye (
  • Polyalkylene glycols such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and ethoxypolypropylene glycol (meth) acrylate
  • a monomer comprising: (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutyl (meth) acrylamide, t-butyl Unsubstituted or N-substituted (meth) acrylamides such as (meth) acrylamide, t-octyl (meth) acrylamide, 2-hydroxye
  • the monomer (a) a monomer represented by the following general formula [7] is used in that the dissolution rate during alkali development can be increased and the chemical resistance of the photosensitive composition can be increased. From the viewpoint of stability during polymerization of the polymer (A-1), it is more preferable to use those in which R 14 is a methyl group.
  • the amount of the monomer represented by the general formula [7] is such that the ratio of the structure derived from the monomer in 100 parts by mass of the solvent-free polymer (A-1) is 5 to 40 parts by mass. The amount is preferably 10 to 30 parts by mass.
  • the amount is 5 parts by mass or more, preferably 10 parts by mass or more, the development speed when alkali-developing the photosensitive composition is increased, and the chemical resistance is excellent.
  • the amount is 40 parts by mass or less, preferably 30 parts by mass or less, the photosensitive composition tends to have a low viscosity and coating becomes easy.
  • R 14 represents a hydrogen atom or a methyl group
  • R 15 represents a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic group
  • R 16 is a linear or branched divalent aliphatic hydrocarbon group, divalent alicyclic hydrocarbon group, or divalent aromatic group having 1 to 8 carbon atoms. It is a hydrocarbon group.
  • linear or branched aliphatic hydrocarbon groups examples include alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, and octane; Alkenes such as ethylene, propylene, butylene, pentene, hexene, heptene, octene, etc .; Examples include groups obtained by removing one hydrogen atom from a compound such as alkyne such as ethyne, propyne, butyne, pentyne, hexyne, peptin, octyne, and the like.
  • alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, and octane
  • Alkenes such as ethylene, propylene, butylene, pentene, hexene, heptene
  • the alicyclic hydrocarbon group includes cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclohexene, methylcyclohexene, norbornane, norbornene, bicyclooctane, and bicyclooctene.
  • groups obtained by removing one hydrogen atom from a compound such as.
  • aromatic hydrocarbon group examples include groups obtained by removing one hydrogen atom from a compound such as benzene, toluene, xylene, ethylbenzene, dimethylbenzene and the like.
  • the linear or branched divalent aliphatic hydrocarbon group, divalent alicyclic hydrocarbon group, or divalent aromatic hydrocarbon group is as described above in the description of the general formula [6]. The same can be mentioned.
  • R 15 is more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 16 is more preferably an alkylene group having 1 to 5 carbon atoms.
  • hydroxyethyl (meth) acrylate Preferred are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, alkoxyethyl (meth) acrylate, and more preferred are hydroxyethyl methacrylate and methoxyethyl methacrylate.
  • methyl methacrylate from the point which hardens a coating film and can raise the chemical resistance of a photosensitive composition.
  • the amount of methyl methacrylate used is preferably such that the proportion of the structure derived from methyl methacrylate in 100 parts by mass of the solvent-free polymer (A-1) is 5 to 40 parts by mass. Is more preferable.
  • the amount is 5 parts by mass or more, preferably 10 parts by mass or more, the chemical resistance of the photosensitive composition is excellent.
  • the amount is 40 parts by mass or less, preferably 30 parts by mass or less, the photosensitive composition tends to have a low viscosity and coating becomes easy.
  • the mass average molecular weight (Mw) of the polymer (A-1) is preferably from 2000 to 70000, more preferably from 4000 to 50000.
  • the weight average molecular weight is 2000 or more, the chemical resistance of the photosensitive composition is excellent.
  • the weight average molecular weight is 70000 or less, the photosensitive composition tends to be low in viscosity and easy to apply, and alkali development is also possible. This is because the developing speed during the process does not become too slow.
  • the weight average molecular weight in this embodiment is a value obtained by gel permeation chromatography (GPC) and converted to polystyrene. More specifically, the values obtained by the measurement methods described in Examples described later are shown.
  • the radical polymer (A-1) containing a furyl group can be produced by the methods [1-1] to [3-5] described above.
  • Polymerization step as a step common to these methods Step modification of polymerizing monomer (a-1) containing furyl group-containing monomer (a-1) or monomer (a-3) containing a reactive functional group
  • Polymerization of the monomer (a-1) containing a furyl group (a-1) or the monomer (a-3) containing a reactive functional group (a-3) can be carried out by a known method. That is, it can be carried out by optionally mixing the monomer (a) with a polymerization initiator and heating.
  • the polymerization temperature is 40 to 150 ° C, preferably 50 to 120 ° C.
  • a polymerization initiator In the polymerization, 0.001 to 15 parts by mass of a polymerization initiator can be arbitrarily used with respect to 100 parts by mass of the monomer (a).
  • a polymerization initiator an azo compound and an organic peroxide can be used.
  • azo compounds examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like.
  • organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide And diacetyl peroxide.
  • These polymerization initiators can be used alone or in combination of two or more.
  • a chain transfer agent may be used for the purpose of adjusting the molecular weight. 0.001 to 15 parts by mass of a chain transfer agent can be arbitrarily used with respect to 100 parts by mass of the monomer (a).
  • the chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used.
  • octyl mercaptan n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid Mercaptans such as thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butylthioglycolate; dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, Disulfides such as tetraethylthiuram disulfide and
  • an organic solvent can be used as a polymerization solvent.
  • the organic solvent for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, 3-methoxy-1-butanol and the like are used. However, it is not limited to these.
  • These polymerization solvents may be used as a mixture of two or more kinds, but are preferably used for final use.
  • the step of reacting the monomer (a-3) containing a reactive functional group capable of reacting with a group, or a carboxylic acid anhydride comprises reacting the reactive functional group introduced into the prepolymer with the compound used for modification. It is preferable to select appropriate reaction conditions depending on the combination with the reactive functional group, and each example will be described.
  • Suitable catalysts include, for example, amines such as triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and salts thereof, tetrabutyl titanate, dibutyltin dilaurate, tin octylate. And metal salts and complexes.
  • a base catalyst or an amine catalyst it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C.
  • a gas having a polymerization inhibiting effect is introduced into the reaction system during the reaction, or a polymerization inhibitor is added. May be. By introducing a gas having a polymerization inhibition effect into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented.
  • Examples of the gas having an effect of inhibiting radical polymerization include a gas containing oxygen that does not enter the explosion range of the substance in the system, for example, air, a mixed gas of air and nitrogen, and the like.
  • radical polymerization inhibitor known ones can be used and are not particularly limited.
  • These polymerization inhibitors may be used alone or in combination of two or more.
  • the amount of the polymerization inhibitor used is preferably 0.005 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the reaction system. Most preferred is 1.5 parts by weight.
  • the compound (B) containing a photopolymerizable functional group of the present embodiment does not contain a furyl group, and the structure thereof is not particularly limited as long as it contains a photopolymerizable functional group. It can be used by mixing. It may be a low molecule or a polymer, and the low molecule and the polymer can be used separately or in combination according to the viscosity required for the photosensitive composition, the hardness, adhesion, and patterning properties of the cured product. The ratio can be adjusted.
  • an alkali-soluble functional group in the compound (B) containing a photopolymerizable functional group as mentioned above.
  • the photopolymerizable functional group include acryloyl group, methacryloyl group, maleimide group, styryl group, maleic anhydride residue, vinyl ether group, allyl ether group, alkenyl group having 2 to 10 carbon atoms, and alkynyl group having 2 to 10 carbon atoms. Etc. From the viewpoint of chemical resistance of the photosensitive composition, it is preferable to use an acryloyl group or a maleimide group.
  • the photosensitive composition when used as a negative photoresist, it is more preferable to use a methacryloyl group and an acryloyl group or a maleimide group in combination from the viewpoint of achieving both pattern resolution and chemical resistance.
  • Different functional groups such as an acryloyl group and a maleimide group may be contained in one compound as the photopolymerizable functional group, or a compound having one kind of functional group may be used as a mixture. Since the acryloyl group and the maleimide group have good reactivity with the compound (A), the acryloyl group and the maleimide group can be particularly suitably used in an embodiment in which it is desired to cure the photosensitive composition at a low temperature.
  • the photocurability is lowered because the photosensitive composition contains a colorant, an effect of improving chemical resistance is easily obtained.
  • the acryloyl group is particularly preferable from the viewpoint of balance between chemical resistance, reduction of degassing, storage stability and the like.
  • the compound (B) containing a photopolymerizable functional group is preferably used in an amount of 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, out of a total of 100 parts by mass of the solid content of the photosensitive composition. More preferred is 70 parts by mass.
  • the compound (B) containing a photopolymerizable functional group is preferably used in an amount of 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, out of a total of 100 parts by mass of the solid content of the photosensitive composition. More preferred is 70 parts by mass.
  • an amount of 5 parts by mass or more chemical resistance is easily obtained, and the exposed part is difficult to dissolve in the developer during the photolithography development process.
  • 95 parts by mass or less curing shrinkage at the time of exposure is suppressed and adhesion to the substrate is likely to be good, and chemical resistance is improved because the amount of the compound (A) containing a furyl group is sufficiently used. This is because excessive photopolymerization is suppressed at the time of
  • the photosensitive composition of this embodiment is used as a negative photoresist
  • the compound (B) containing a photopolymerizable functional group when the compound (B) containing a photopolymerizable functional group has a low molecular weight, it contains an acrylate group and / or a maleimide group, It is preferable to use 5 to 80 parts by mass, more preferably 10 to 50 parts by mass, out of a total of 100 parts by mass of the solid content of the composition.
  • the compound (B) containing a photopolymerizable functional group has a high molecular weight, it contains an acrylate group and / or a methacrylate group, further contains a carboxyl group in the compound (B), and contains a solid content of the photosensitive composition. It is preferably used in an amount of 3 to 70 parts by mass, more preferably 5 to 60 parts by mass, further preferably 5 to 40 parts by mass, out of a total of 100 parts by mass.
  • the photosensitive composition of the present embodiment is used as a photosensitive composition for a color filter described later, when the compound (B) containing a photopolymerizable functional group has a low molecular weight, the photosensitive composition for a color filter It is preferably used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the colorant.
  • the compound (B) containing a photopolymerizable functional group has a high molecular weight, it is preferably used in an amount of 20 to 400 parts by weight, and in an amount of 50 to 250 parts by weight with respect to 100 parts by weight of the colorant. Is more preferable.
  • the ratio of the compound (A) containing a furyl group and the compound (B) containing a photopolymerizable functional group is effective for efficiently performing both photocuring and thermosetting, and improving the chemical resistance of the photosensitive composition.
  • the number of moles of furyl group is preferably 0.05 to 2 and more preferably 0.05 to 0.5 with respect to 1 mole of the photopolymerizable functional group.
  • Use of 0.05 or more tends to cause thermal curing due to furyl groups and tends to improve chemical resistance.
  • Use of 2 or less facilitates radical polymerization of photopolymerizable functional groups at the stage of photocuring. There is a tendency to improve chemical resistance.
  • the low molecular weight compounds may include monofunctional or polyfunctional monomers or oligomers, and the chemical resistance is improved.
  • An oligomer is preferable.
  • the photopolymerizable functional group is preferably a (meth) acryloyl group or a maleimide group
  • the compound containing a (meth) acryloyl group include those exemplified as the monomer (a) used in the synthesis of the radical polymer (A-1) containing a furyl group, (Meth) acryloyl monomer excluding the body (a-1), ⁇ -carboxy-polycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxy Monofunctional (meth) acrylates such as triethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate
  • a tri- or lower functional monomer or oligomer is preferable.
  • trimethylolpropane tri (meth) acrylate is most preferable because it is excellent in chemical resistance.
  • polyfunctional (meth) acrylates obtained by reacting a polyfunctional isocyanate and a hydroxyl group-containing (meth) acrylate monomer as a low molecular weight compound (B) containing a photopolymerizable functional groupcan be mentioned.
  • Polyfunctional isocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, tolidine isocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexyl.
  • Bifunctional isoforms such as methane diisocyanate, isopropylidenebis (cyclohexyl isocyanate), 3- (2'-isocyanatocyclohexyl) propyl isocyanate, dianisidine isocyanate, diphenyl ether diisocyanate, dimer diisocyanate, tetramethylxylylene diisocyanate Cyanates; Trifunctional isocyanates such as lysine triisocyanate, tris (isocyanatophenyl) methane, tris (isocyanatophenyl) thiophosphate; Biuret, uretdione, isocyanurate, adduct body, etc.
  • the compound containing a (meth) acryloyl group can be obtained by reacting dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a polyfunctional isocyanate and a (meth) acrylate monomer containing a hydroxyl group.
  • Polyfunctional (meth) acrylates are preferred.
  • the compound containing a (meth) acryloyl group may have an alkali-soluble functional group.
  • a hydroxyl group-containing poly (meth) acrylate which is a reaction product of a polyhydric alcohol and (meth) acrylic acid, and a dicarboxylic acid
  • Examples include esterified products with acids, esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth) acrylates, and the like.
  • Monohydroxy oligo (meth) acrylates such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and malonic acid, succinic acid, glutaric acid, terephthalic acid, etc.
  • Monoesterified products containing free carboxyl groups with dicarboxylic acids Propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene Free carboxyl group-containing oligoesters of tricarboxylic acids such as 1,3,5-tricarboxylic acid and monohydroxy mono (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate And the like.
  • Examples of the compound containing a maleimide group include: o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, N, N ′-(toluene-2,6-diyl) bismaleimide), 4, 4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'- Diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, polyphenylmethanemaleimide (CAS NO: 67784-74-1), consisting of formaldehyde and aniline Polymer and male
  • polyfunctional maleimide obtained by making a polyfunctional amine and maleic anhydride react is mentioned.
  • a polyfunctional amine Isophoronediamine, dicyclohexylmethane-4,4′-diamine, manufactured by Huntsman Corporation, Jeffamine D-230, HK-511, D-400, XTJ-582, D-2000 having a terminally aminated polypropylene glycol skeleton, XTJ-578, XTJ-509, XTJ-510, T-403, T-5000, XTJ-500 having a terminal aminated ethylene glycol skeleton, XTJ-501, XTJ-502, XTJ-504, XTJ-511, XTJ- 512, XTJ-590, Examples thereof include XTJ-542, XTJ-533, XTJ-536, XTJ-548, and XTJ-559 having a terminal aminated polytetramethylene glyco
  • polyfunctional maleimide obtained by making the polyfunctional isocyanate mentioned above and the maleimide monomer containing the hydroxyl group mentioned later react can be mentioned.
  • the compound containing a maleimide group easily reacts with the compound (A) containing a furyl group without a catalyst without Diels-Alder reaction, stability with time may be deteriorated depending on the storage conditions of the photosensitive composition.
  • the compound containing a maleimide group is preliminarily reacted with a compound having a diene structure to protect the maleimide group to improve the stability over time, and the compound having a diene structure at the stage of thermosetting the photosensitive composition.
  • Examples of the compound having a diene structure used for protecting the maleimide group include compounds having a 1,3-butadiene structure, a furan structure, and an anthracene structure. Among these, the maleimide group is efficiently protected during storage. Furan, 2,5-dimethylfuran, furfuryl alcohol, cyclopentadiene and the like are preferable because they are efficiently deprotected at the stage of thermosetting.
  • Examples of the compound containing a maleimide group include 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, a polyfunctional isocyanate described above and a maleimide monomer containing a hydroxyl group described below. The polyfunctional maleimide obtained by the above and a compound in which the maleimide group is protected are preferred.
  • the compound (B) containing a photopolymerizable functional group include Monomers other than the (meth) acryloyl monomer among the monomers (a) used in the synthesis of the radical polymer (A-1) containing the furyl group, Compounds having a vinyl ether group such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether; Allyl ether groups such as diallyl phthalate, allyl glycidyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin monoallyl ether, diallyldimethylammonium chloride, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, methoxypolyethylene glycol allyl ether And the like.
  • a vinyl ether group such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether
  • the amount of the photopolymerizable functional group is preferably 80 to 1000, more preferably 90 to 600, as a double bond equivalent (unit: g / mol).
  • it is 80 or more, curing shrinkage at the time of exposure is suppressed and adhesion to the substrate is easily improved, and excessive photopolymerization is suppressed at the time of photolithography exposure, and the resolution of the pattern is easily improved.
  • it is 1000 or less, chemical resistance is easily obtained, and the exposed portion is hardly dissolved in the developer in the photolithography development step.
  • the double bond equivalent is a measure of the amount of the photopolymerizable functional group contained in the compound (B) containing the photopolymerizable functional group.
  • the double bond that is, the mass per 1 mol of the photopolymerizable functional group (unit: g / mol), and the smaller the double bond equivalent value, the higher the photopolymerizable functional group concentration in the compound.
  • the double bond equivalent is a theoretical value calculated from the structure of the compound or the amount of raw material charged.
  • a polymer may be used for the compound (B) containing a photopolymerizable functional group.
  • the photosensitive composition desirably has high transparency, and a polymer having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is used.
  • the polymer may be any of linear, branched, star-shaped, etc., and may be thermoplastic or thermosetting.
  • the weight average molecular weight (Mw) is preferably 2000 to 50000, more preferably 4000 to 30000. This is because when the Mw is 2000 or more, the chemical resistance of the photosensitive composition tends to be good, and when it is 50000 or less, the viscosity becomes low and coating becomes easy.
  • Poly (meth) acrylate is preferred because the developability of the photosensitive composition can be easily controlled by controlling the molecular weight and the copolymer composition, and the transparency of the photosensitive composition is excellent.
  • the poly (meth) acrylate may contain a structure derived from a comonomer other than (meth) acrylate.
  • the photopolymerizable functional group is preferably a (meth) acryloyl group or a maleimide group. From the viewpoint of chemical resistance, an acryloyl group or a maleimide group is more preferable, and from the viewpoint of balance between chemical resistance and storage stability, an acryloyl group is particularly preferable.
  • the compound (B) containing a photopolymerizable functional group contains an alkali-soluble functional group, and a carboxyl group is preferred as the alkali-soluble functional group.
  • the method for introducing the photopolymerizable functional group into the compound (B) is not particularly limited, but specifically, a method similar to the method described for the radical polymer (A-1) containing a furyl group can be used.
  • a method similar to the method described for the radical polymer (A-1) containing a furyl group can be used.
  • the prepolymer There are no particular restrictions on the prepolymer, and acrylic, urethane, polyester, polyolefin, polyether, natural rubber, block copolymer rubber, silicone, and other polymers can be used.
  • a photopolymerizable functional group for example, a carboxyl group, hydroxyl group, mercapto group, amino group, or active methylene group in a prepolymer is reacted with a monomer containing an epoxy group, an isocyanate group, or an aldehyde group. And a method using the reverse combination.
  • Examples of the method for introducing a carboxyl group include a method in which an acid anhydride group in a carboxylic acid anhydride is reacted with a hydroxyl group or an amino group in a prepolymer.
  • Examples of a method for simultaneously introducing a photopolymerizable functional group and a carboxyl group include a method in which a monomer containing a hydroxyl group, an amino group, or the like is reacted with an acid anhydride group in a prepolymer.
  • the compound (B) is preferably a (meth) acrylate copolymer, and the following methods [B-1] to [B-3] are preferable as a method for introducing a photopolymerizable functional group and a carboxyl group.
  • Method [B-1] Method of reacting a part of carboxyl groups in a (meth) acrylic copolymer containing a carboxyl group with an epoxy group in a monomer containing an epoxy group
  • [B-2] Epoxy An epoxy group in a (meth) acrylic copolymer containing a group is reacted with a carboxyl group in a monomer containing a carboxyl group, and an acid anhydride in a carboxylic anhydride is generated with respect to the generated hydroxyl group.
  • a furyl group is used as a compound to be reacted with a functional group in the prepolymer and a monomer copolymerized to introduce a functional group into the prepolymer by these methods [B-1] to [B-3].
  • a furyl group is used as a compound to be reacted with a functional group in the prepolymer and a monomer copolymerized to introduce a functional group into the prepolymer by these methods [B-1] to [B-3].
  • Those mentioned for the radical polymer (A-1) can be used.
  • the monomer containing a carboxyl group for example, the compounds described for the monomer (a-2) containing a carboxyl group can be used.
  • a carboxyl group into the prepolymer it is preferable to copolymerize (meth) acrylic acid from the viewpoint of easily increasing the amount of copolymerizable and photopolymerizable functional groups introduced.
  • (meth) acrylate group by modifying the prepolymer it is preferable to use (meth) acrylic acid from the viewpoint of easily increasing the concentration of the introduced (meth) acrylate group.
  • the compound etc. which were mentioned by the monomer containing the said epoxy group can be used, for example.
  • glycidyl (meth) acrylate In order to introduce an epoxy group into the prepolymer, and to introduce a (meth) acrylate group by modifying the prepolymer, glycidyl (meth) acrylate, 4-hydroxybutyl ( It is preferable to copolymerize (meth) acrylate glycidyl ether, and glycidyl (meth) acrylate is more preferable from the viewpoint of easily increasing the concentration of the photopolymerizable functional group to be introduced.
  • the compounds mentioned for the monomer containing a hydroxyl group can be used.
  • the concentration of the photopolymerizable functional group to be introduced can be easily increased.
  • Ethyl (meth) acrylate is preferred.
  • the compounds mentioned for the carboxylic acid anhydride can be used.
  • two or more anhydride groups are contained in one molecule, there is a risk of gelation when reacting with a hydroxyl group or the like in the prepolymer.
  • a compound containing one anhydride group in one molecule for example, Dicarboxylic acid anhydrides and tricarboxylic acid anhydrides are preferred.
  • tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferred.
  • the monomer containing a carboxylic acid anhydride group for example, the compounds mentioned for the monomer containing a carboxylic acid anhydride group can be used.
  • the concentration of the photopolymerizable functional group to be introduced can be easily increased.
  • Maleic anhydride and itaconic anhydride are preferably used, and maleic anhydride is more preferable from the viewpoint of good copolymerizability to a prepolymer and good polymerizability of the introduced photopolymerizable functional group.
  • the monomer containing an isocyanate group As the monomer containing an isocyanate group, the above-mentioned monomer containing an isocyanate group and the compounds mentioned in the block thereof can be used.
  • the concentration of the photopolymerizable functional group to be introduced can be easily increased. Natoethyl (meth) acrylate is preferred.
  • Examples of the monomer containing a mercapto group include N- (4-mercaptophenyl) methacrylamide, 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithiol (dithione). Tautomers) and the like.
  • the monomer containing an amino group those having a secondary amine among the compounds mentioned as the monomer containing an amino group can be used.
  • the compounds mentioned for the monomer containing an active methylene group can be used.
  • Examples of the monomer containing an aldehyde group include monomers such as (meth) acrolein, 3-formylstyrene, 4-formylstyrene, vinylformamide, and monomers having the aldehyde group protected with acetal. Can be mentioned.
  • the amount of the photopolymerizable functional group is preferably 300 to 1000, more preferably 400 to 800, as a double bond equivalent (unit: g / mol).
  • it is 300 or more, curing shrinkage at the time of exposure is suppressed and adhesion to the substrate is likely to be good, and excessive photopolymerization is suppressed at the time of photolithography exposure, and the pattern resolution is likely to be good.
  • it is 1000 or less, chemical resistance is easily obtained, and the exposed portion is hardly dissolved in the developer in the photolithography development step.
  • (meth) acrylate copolymer containing a photopolymerizable functional group and a carboxyl group other copolymerizable monomers can be copolymerized, and known ones can be used without limitation. .
  • Photoinitiator (C) The structure of the photopolymerization initiator (C) of this embodiment is particularly limited as long as radicals are generated by ultraviolet irradiation and used to initiate polymerization of the photopolymerizable functional group in the photosensitive composition. Is not to be done.
  • Transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, aluminate complexes such as compounds described in JP-A-3-209477, carbon tetrabromide, and JP-A 59-107344 Organic halogen compounds such as these compounds, and sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347.
  • photopolymerization initiators (C) can be used singly or as a mixture of two or more at any ratio as required.
  • the photopolymerization initiator (C) is preferably 0.01 to 60 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.03 parts in 100 parts by weight of the solid content in the photosensitive composition. ⁇ 7 parts by mass. It is preferably 0.01 parts by mass or more from the viewpoint of photopolymerization, that is, the progress of the polymerization reaction, suppression of decrease in transparency due to the influence of yellowing of the initiator, and pattern resolution due to excessive photopolymerization during exposure From the viewpoint of suppressing the decrease in the amount, it is preferably 10 parts by mass or less.
  • the photosensitive composition of this embodiment can contain a sensitizer.
  • sensitizers include: Unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthenes Derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, Squarylium derivatives, porphyrin derivatives, t
  • Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC).
  • a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
  • the sensitizer may contain two or more sensitizers in any ratio.
  • the sensitizer is preferably used in an amount of 0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, with respect to 100 parts by weight of the photopolymerization initiator (C) in the photosensitive composition. Is more preferable.
  • the mass [Ia] of the photopolymerization initiator (C) and the photopolymerizable functionality Of the compound (B) containing a group is preferably 0.03 to 1.00, preferably 0.04 to 0.95. It is more preferable.
  • the photosensitive composition for color filters contains a sensitizer, the total mass [Ib] of a photoinitiator (C) and a sensitizer, and the compound (B) containing a photopolymerizable functional group.
  • the ratio [Ib / M] with respect to the mass [M] of low molecular weight is preferably 0.04 to 1.50, and more preferably 0.05 to 1.45.
  • [Ia / M] is 0.03 or more and [Ib / M] is 0.04 or more, the sensitivity is high and good. Further, when [Ia / M] is 1.00 or less and [Ib / M] is 1.50 or less, the linearity and resolution of the pattern shape are more excellent.
  • the compound (D) containing an alkali-soluble functional group (but not containing a furyl group and a photopolymerizable group) is used for imparting alkali developability when patterning a photosensitive composition by photolithography.
  • the photosensitive composition is used as an alkali development type negative photoresist, and the compound (A) containing a furyl group and / or the compound (B) containing a photopolymerizable functional group, which are essential components, are alkali-soluble. When it does not contain a functional group, it is essential to use the compound (D), but in other cases it can be used arbitrarily.
  • the structure (D) containing an alkali-soluble functional group is not particularly limited as long as it does not contain a furyl group and a photopolymerizable group and contains an alkali-soluble functional group.
  • it may be a low molecule or a polymer, it is preferably a polymer having an alkali-soluble functional group at the terminal and / or side chain, and more preferably a polymer containing a carboxyl group.
  • the polymer may be linear, branched or star-shaped, and may be thermoplastic or thermosetting.
  • Examples thereof include poly (meth) acrylate, polyurethane, polyester, polyamide, polyimide, polycarbonate, polyolefin, polystyrene, polysiloxane, polyether, a copolymer containing maleic anhydride, and an epoxy resin. These may be used alone, or a mixture may be used.
  • the polymer may be linear, branched or star-shaped, and may be either thermoplastic or thermosetting.
  • Poly (meth) acrylate is more preferable from the viewpoint of excellent transparency of the photosensitive composition.
  • a copolymer or the like can be used.
  • the photosensitive composition of this invention contains the silane compound (E) represented by following General formula (1). It is presumed that the site that blocks the isocyanate group is removed by heating, and the chemical resistance is imparted to the coating film by reacting with the carboxyl group or hydroxyl group in the photosensitive composition in the thermosetting step.
  • R 1 is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number.
  • X represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms
  • R 2 , R 3 and R 4 are independently of each other an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • examples of the siloxane group having a substituent in the formula include a polysiloxane structure (—O — (— Si (R 5 ) 2 —O—) n —SiR 6 3 ).
  • R 5 and R 6 may be the same or different from each other, and examples of R 5 and R 6 include groups defined as R 2 , R 3 and R 4 in the general formula (1) ( (Excluding siloxane having a substituent).
  • R 1 is more preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group.
  • X is more preferably an alkylene group having 2 to 8 carbon atoms or an arylene group having 2 to 20 carbon atoms.
  • R 2 , R 3 and R 4 are more preferably each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a siloxane group having a substituent.
  • Examples of the silane compound (E) represented by the general formula (1) include (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, and (3-carbamateethyl) propyltripropoxysilane.
  • the silane compound (E) represented by the general formula (1) may be a silanol compound obtained by hydrolysis thereof, or a polyorganosiloxane compound in which they are condensed.
  • a silanol compound obtained by hydrolysis thereof or a polyorganosiloxane compound in which they are condensed.
  • (3-carbamateethyl) propyltriethoxysilane and (3-carbamateethyl) propyltrimethoxysilane are the most preferable because they easily react at low temperatures and improve chemical resistance.
  • the alkoxylene group refers to a divalent group represented by —OR— (R represents an alkylene group).
  • X may have a substituent such as an alkyl group having 1 to 3 carbon atoms, or may be a group in which two or more of the above divalent groups are linked.
  • the weight average molecular weight (Mw) of the silane compound (E) is preferably 100 or more and less than 5000, and the content of the silane compound (E) in the total solid content of 100% by mass of the photosensitive composition is 1% by mass or more and 20% by mass. It is preferable that it is less than%.
  • the weight average molecular weight (Mw) of the silane compound (E) is preferably 100 or more from the viewpoint of chemical resistance, and in the case of 5000 or more, it is preferably less than 5000 from the viewpoint of suppressing an increase in heating temperature at which the block site is desorbed. Further, the content is preferably 1% by mass or more from the viewpoint of chemical resistance, and is preferably less than 20% by mass from the viewpoint of suppressing the development residue.
  • the weight average molecular weight (Mw) of the silane compound (E) is more preferably 200 or more and less than 500 from the viewpoint of the block site desorption temperature, and the silane in the total solid content of 100% by mass of the photosensitive composition.
  • the content of the compound (E) is more preferably 3% by mass or more and less than 20% by mass from the viewpoint of chemical resistance.
  • Isocyanate group-containing silane compounds such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatepropyltripropoxysilane are present in the photosensitive composition depending on the amount and combination with other components. May react with other solvents, resins, monomers, and moisture to become cloudy or gel. In addition, the cured coating film may not stably develop high chemical resistance. In contrast, since the silane compound (E) represented by the general formula (1) does not have a highly reactive site such as an isocyanate group, it is thermally and chemically stable. Therefore, the silane compound (E) has excellent temporal stability even in the photosensitive composition, and can stably exhibit high chemical resistance.
  • the photosensitive composition of the present embodiment can further contain the following materials as long as the object of the invention is not impaired.
  • the photosensitive composition of this embodiment may contain the other resin which does not contain any of a furyl group, a photopolymerizable functional group, and an alkali-soluble functional group as needed.
  • a thermoplastic resin and a thermosetting resin are mentioned.
  • the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin.
  • thermosetting resin examples include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, a phenol resin, and ⁇ -hydroxyalkylamide described in JP2012-198527. Etc.
  • a catalyst may be added to accelerate the Diels-Alder reaction that occurs during thermal curing of the photosensitive composition to lower the reaction temperature.
  • the catalyst include Lewis acid.
  • Lewis acid aluminum chloride, tin tetrachloride, iron trichloride, titanium trichloride, titanium tetrachloride, boron trifluoride, alkylaluminum compounds (such as trimethylaluminum), polyaluminoxane compounds (polymethyl) Aluminoxane, sulfonimide-modified polyaluminoxane compound, sulfonic acid-modified polyaluminoxane compound, reaction product of polymethylaluminoxane and bistrifluoromethanesulfonimide), scandium compound (scandium (III) perfluorooctane sulfonate, etc.) It is done.
  • strong alkaline salts of weak acids such as aliphatic or aromatic esters, chloroacetic esters, ethers, ketones, carbonates and nitro compounds, amines, organic carboxylic acids and phosphoric acids (sodium acetate) , Disodium hydrogen phosphate, etc.), alkali metal or alkaline earth metal oxides, hydroxides, carbonates, bicarbonates (calcium oxide, magnesium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, etc.), etc. Can be used.
  • An organic solvent may be used in order to improve handling when the photosensitive composition is applied.
  • An organic solvent may be used in order to improve handling when the photosensitive composition is applied.
  • the amount of the organic solvent used is preferably such that the solid content concentration of the photosensitive composition is 5 to 50% by mass.
  • the solid content concentration of the photosensitive composition is 5 to 50% by mass.
  • a dry film is formed on a transparent substrate such as a glass substrate or a film substrate. It is applied so that the thickness is 0.2 to 10 ⁇ m. An organic solvent is used to facilitate this.
  • the die coating method, the screen printing method, the offset printing method, the gravure printing method, etc. preferably contain a high boiling point solvent of 160 ° C. or higher, for example, 3-methoxy-3-methyl- 1-butanol (bp 174 ° C.), 1,3-butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl Ketone (bp 168.1 ° C.), ethylene glycol monobutyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203.
  • a high boiling point solvent 160 ° C. or higher, for example, 3-methoxy
  • diethyleneglyco Rumonomethyl ether (bp 194.0 ° C.), diethylene glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2) ° C), propylene glycol diacetate (bp 190.0 ° C), dipropylene glycol monomethyl ether (bp 187.2 ° C), dipropylene glycol monoethyl ether (bp 197.8 ° C), dipropylene glycol monopropyl ether (bp 212.0 ° C) ), Dipropylene glycol dimethyl ether (bp 175 ° C.), tripropylene glycol monomethyl ether (bp 206.3 ° C.), 3-ethoxypro Ethyl onate (bp 169.7 °
  • the organic solvent is preferably used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive composition for color filters.
  • ⁇ Colorant> In order to color the photosensitive composition of this embodiment and use it for a color filter or the like, a colorant may be added. Below, the coloring agent preferably used for the photosensitive composition for color filters is demonstrated.
  • organic or inorganic pigments and dyes can be used alone or in admixture of two or more.
  • pigments pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used, but are not limited thereto.
  • specific examples of organic pigments that can be used for the production of color filter segments and black matrices are shown by color index numbers.
  • red photosensitive composition for forming the red filter segment examples include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 166, 168, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 207, 208, 209, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, Red pigments such as 228, 240, 242, 246, 254, 255, 264, 269, 272, and 279 can be used.
  • a yellow pigment and an orange pigment can be used in combination with the red photosensitive composition.
  • red dyes such as xanthene, azo, disazo, and anthraquinone can be used.
  • C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.
  • the green pigment mentioned later can be used together for chromaticity adjustment.
  • the red pigment a diketopyrrolopyrrole pigment, an anthraquinone pigment, an azo pigment, or a perylene pigment is preferable.
  • diketopyrrolopyrrole pigments include C.I. I. Pigment Red254 is preferable, and as an anthraquinone pigment, C.I. I. Pigment Red177 and perylene pigments include C.I. I. Pigment Red 179 is preferable because excellent coloring power can be obtained.
  • the azo pigment is preferably a naphthol azo pigment represented by the following general formula (1).
  • A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group.
  • R 1 represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 7 or —COOR 8 .
  • R 2 to R 6 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 9 , —COOR 10 , —CONHR 11 , —NHCOR 12 or —SO 2 NHR 13 is represented.
  • R 7 to R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, it is excluded when R 4 is —NHCOR 12 and A, R 2 , R 3 , R 5 , and R 6 are hydrogen atoms and R 1 is a halogen atom. ]
  • An azo pigment of 12 is preferred because it is easy to make the pigment particles finer and has an excellent contrast ratio.
  • a naphthol azo pigment represented by the general formula (1) when represented by a color index (CI) number, C.I. I. Pigment Red 31, 32, 146, 147, 150, 184, 187, 188, 210, 238.2245.247, 266, 268, 269, C.I. I. Violet 25, 50, etc. are mentioned. Among these, from the viewpoint of hue and lightness, C.I. I. Pigment Red 150, 170, 187, 266, 268, and 269 are preferable.
  • the “substituent” of the phenyl group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, cyano Group, trifluoromethyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or monovalent to acidic group selected from sulfo group Trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.) and the like can be mentioned.
  • Trivalent metal salts for example, sodium salt, potassium salt, aluminum salt, etc.
  • the “substituent” of the heterocyclic group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, trifluoro group or the like.
  • “Heterocycle” means an atom in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a single ring or a condensed ring.
  • the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring.
  • the heterocyclic group means a monovalent radical derived by removing a hydrogen atom from these heterocycles. Therefore, specific examples of the heterocyclic group which may have a substituent include 2- Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2- Oxazolyl group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, And N-carbazolyl group.
  • halogen atom in R 2 to R 6 and R 14 examples include fluorine, chlorine, bromine and iodine.
  • alkyl group having 1 to 4 carbon atoms in R 1 to R 14 may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group. , Sec-butyl group, and tert-butyl group.
  • A is a phenyl group which may have a substituent from a viewpoint of brightness.
  • R 1 is preferably an alkyl group having 1 to 4 carbon atoms or —OR 7 , and more preferably R 1 is a methyl group or a methoxy group.
  • the colorant of the present embodiment may have a chemical structure of the general formula (1) or a tautomer thereof, or may be a pigment having any crystal form, and is called any so-called polymorph. It may be a mixed crystal of pigments having a crystal form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.
  • Naphthol azo pigment is a water-insoluble pigment having excellent fastness to solvent and light, and by using this pigment, the color composition for color filter is excellent in both brightness and contrast ratio. Can be obtained.
  • Naphtholazo pigments can be used alone or in admixture of two or more.
  • a naphthol azo pigment in which at least one of R 2 to R 6 is a trifluoromethyl group is preferable because it can be easily miniaturized.
  • R 5 is preferably a -trifluoromethyl group
  • R 2 is preferably a -Cl group.
  • naphthol azo pigment examples include the following naphthol azo pigments, but the present invention is not limited thereto.
  • the naphthol azo pigment [A2] in which at least one of R 2 to R 6 is —NHCOR 12 is preferable because of excellent lightness.
  • R 4 is —NHCOR 12 and A
  • R 2 , R 3 , R 5 , and R 6 are hydrogen atoms and R 1 is a halogen atom.
  • R 4 is preferably —NHCOR 12
  • R 1 is more preferably a methoxy group.
  • naphthol azo pigment examples include the following naphthol azo pigments, but the present invention is not limited thereto.
  • the range of the content of the red pigment / dye with respect to the total colorant is preferably 10 to 70% by mass, more preferably 10 to 60% by mass. It is preferable from the viewpoint of excellent color reproducibility as a color filter for an organic EL display device that the content of the red pigment / dye is within the above range.
  • yellow pigments examples include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Or the like can be used 5,176,177,179,180,181,182,185,187,
  • yellow dyes such as quinoline, azo, disazo, and methine can be used.
  • isoindoline pigments and quinophthalone pigments are preferable.
  • C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185 or a quinophthalone compound represented by the following general formula (2) is preferable because of excellent lightness and coloring power.
  • the quinophthalone compound represented by the general formula (2) will be described.
  • X1 to X13 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent.
  • An aryl group, an acidic group, or a metal salt thereof, an alkyl ammonium salt, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group is shown.
  • the adjacent groups of X1 to X4 and / or X10 to X13 together form an aromatic ring which may have a substituent.
  • examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
  • the alkyl group which may have a substituent
  • the alkyl group preferably has 1 to 10 carbon atoms (not including the carbon number of the substituent).
  • the substituent include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, and an aryl group having 6 to 18 carbon atoms, and may have two or more kinds of substituents.
  • the alkoxyl group which may have a substituent
  • the alkoxyl group preferably has 1 to 10 carbon atoms (not including the carbon number of the substituent).
  • the substituent include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, and an aryl group having 6 to 18 carbon atoms, and may have two or more kinds of substituents.
  • linear or branched alkoxyl groups such as dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2, 2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group
  • an alkoxyl group having a substituent such as a benzyloxy group.
  • the aryl group which may have a substituent
  • the aryl group preferably has 6 to 18 carbon atoms (not including the carbon number of the substituent).
  • the substituent include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, and the like. Also good.
  • Examples of acidic groups include —SO 3 H and —COOH.
  • Examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, An aluminum salt etc. are mentioned.
  • alkyl ammonium salt of acidic group quaternary alkyl such as ammonium salt of long-chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. An ammonium salt is mentioned.
  • the hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and the heteroaromatic ring includes pyridine.
  • the quinophthalone compound represented by the general formula (2) is preferably any one of the following general formulas (2A) to (2C).
  • X14 to X28, X29 to X43, and X44 to X60 each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or a substituent. May be an alkoxyl group, an aryl group which may have a substituent, a —SO 3 H group, a —COOH group, a —SO 3 H group or a —COOH group metal salt, a —SO 3 H group or a —COOH group.
  • X14 to X28, X29 to X43, and X44 to X60 in the general formulas (2A) to (2C) are a hydrogen atom or a halogen atom.
  • quinophthalone compound represented by the general formula (2) include the following quinophthalone compounds (a) to (p), but the present invention is not limited thereto.
  • yellow pigments can be used in a yellow photosensitive composition for forming a yellow filter segment, alone or in combination of two or more.
  • the red photosensitive composition for forming the red filter segment includes orange pigments such as C.I. I. Pigment orange 36, 38, 43, 51, 55, 59, 61, 71, 73, etc. can be used. Moreover, these orange pigments can be used for the orange photosensitive composition for forming an orange filter segment individually or in combination of 2 or more types.
  • Examples of the green photosensitive composition for forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37 and 58, and green pigments such as aluminum phthalocyanine pigments can be used.
  • the yellow pigment described above can be used in combination with the green photosensitive composition.
  • Examples of the blue photosensitive composition for forming the blue filter segment include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and 80 can be used. Blue photosensitive compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination. Furthermore, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used. Furthermore, the yellow pigment mentioned above can be used together for chromaticity adjustment.
  • Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and 80 can be used. Blue photosensitive compositions include C.I. I. Pig
  • Examples of the cyan photosensitive composition for forming the cyan filter segment include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 80 can be used.
  • magenta color photosensitive composition for forming the magenta color filter segment examples include C.I. I. Pigment Violet 1, 19, C.I. I. Violet pigments such as Pigment Red 81, 144, 146, 177, 169, and red pigments can be used.
  • a yellow pigment can be used in combination with the magenta photosensitive composition.
  • black photosensitive composition for forming the black matrix examples include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment black 1, 6, 7, 12, 20, 31, etc. can be used.
  • a mixture of a red pigment, a blue pigment, and a green pigment can also be used.
  • carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like.
  • a blue pigment and a purple pigment can be used together in a black photosensitive composition.
  • Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black.
  • examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders.
  • Inorganic pigments are preferably used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, and the like while balancing saturation and lightness.
  • a dye can be contained within a range that does not lower the heat resistance.
  • the preferable concentration of the colorant is 5% by mass or more, more preferably 10% by mass or more, based on the total nonvolatile components of the photosensitive composition for color filters (100% by mass). Preferably it is 15 mass% or more.
  • the concentration of the colorant component is preferably 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less. In one embodiment, the concentration of the colorant component is more preferably 25% by mass or more and 30% by mass or more based on the total nonvolatile components of the color filter photosensitive composition (100% by mass). Particularly preferred is 35% by mass or more.
  • the photosensitive composition for color filters can contain a polyfunctional thiol.
  • a polyfunctional thiol is a compound having two or more thiol (SH) groups.
  • SH thiol
  • a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation.
  • the photosensitive composition for filters becomes highly sensitive.
  • a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
  • the content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant.
  • 0.05 part by mass or more of polyfunctional thiol better development resistance can be obtained.
  • a thiol having a plurality of thiol (SH) groups development resistance can be improved.
  • the photosensitive composition for color filters can contain an ultraviolet absorber or a polymerization inhibitor.
  • an ultraviolet absorber or a polymerization inhibitor By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.
  • the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl).
  • polymerization inhibitor examples include hydroquinones such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol.
  • phenolic compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc.
  • manganese salt compounds 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine Nitroso compounds and their ammonium salts or aluminum salts and the like, and used alone or in combination.
  • the ultraviolet absorber and the polymerization inhibitor are preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the colorant in the color filter photosensitive composition. Better resolution can be obtained by using 0.01 parts by mass or more of the ultraviolet absorber or the polymerization inhibitor.
  • the photosensitive composition for a color filter can contain a storage stabilizer in order to stabilize the viscosity with time of the composition.
  • a storage stabilizer examples include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl).
  • Propionate 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, hindered phenols, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid. Used alone or in combination.
  • the storage stabilizer is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive composition for color filters.
  • the color filter photosensitive composition preferably contains an adhesion improver such as a silane coupling agent in order to enhance adhesion to the transparent substrate.
  • Adhesion improvers include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-
  • silane-based additive inclusion of a silane-based additive is preferred because adhesion to a glass substrate is improved, 3-methacryloxypropyltrimethoxysilane is more preferred, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethylsilane. Methoxysilane is particularly preferred.
  • the silane coupling agent is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive composition for color filters.
  • a leveling agent In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive composition for a color filter.
  • a leveling agent dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable.
  • dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie.
  • dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie.
  • Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination.
  • a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and having a hydrophilic group but low solubility in water, and when added to a photosensitive pigment composition It has the characteristics that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and it does not cause coating film defects due to foaming Those that can sufficiently suppress chargeability in terms of amount can be preferably used.
  • dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used.
  • the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.
  • the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used.
  • Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but is not limited thereto.
  • An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
  • Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.
  • Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.
  • the photosensitive composition for a color filter preferably contains an amine compound having a function of reducing dissolved oxygen.
  • amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.
  • additives such as a curing agent, a light stabilizer, an antioxidant, an inorganic filler, an adhesion-imparting agent, and a surfactant that are used in combination with the thermosetting resin may be added. These additives can be added in any amount as long as the purpose of the resin composition is not impaired.
  • the photosensitive composition of this embodiment includes a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), and an alkali-soluble functional group as necessary. It can produce by mixing and stirring the compound (D) containing this and other components.
  • the photosensitive composition of the present embodiment is used as a color filter, a color filter protective film, a photo spacer, a projection for liquid crystal alignment, a microlens, a coating agent for a display such as an insulating film for a touch panel, a photoresist, etc., centrifugation, It is preferable to remove coarse particles of 5 ⁇ m or more, preferably coarse particles of 1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and mixed dust and foreign matters by means of a sintered filter, a membrane filter or the like.
  • One embodiment of the present invention relates to a photosensitive composition for a color filter. Since the photosensitive composition for color filters contains a colorant, photocuring is difficult to proceed, and the problem that chemical resistance and developability are in a trade-off relationship is particularly remarkable. In particular, when low temperature curing is desired, it is difficult to achieve both excellent chemical resistance and developability. According to the photosensitive composition for a color filter of the present embodiment, both chemical resistance and developability can be achieved even under low temperature curing conditions. When a colorant is added to the photosensitive composition of this embodiment and used as a photosensitive composition for a color filter, it can be prepared in the form of a solvent development type or alkali development type colored resist material.
  • the colored resist material includes a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), a compound (D) containing an alkali-soluble functional group as necessary, and an organic material.
  • a colorant is dispersed in a composition containing a solvent.
  • the photosensitive composition for a color filter is obtained by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor in a pigment carrier such as a resin and / or a solvent such as a pigment and a dye.
  • a pigment dispersion is prepared by finely dispersing, and the pigment dispersion contains a furyl group-containing compound (A), a photopolymerizable functional group-containing compound (B), a photopolymerization initiator (C), and if necessary.
  • a compound (D) containing an alkali-soluble functional group, an organic solvent, and in some cases, a silane compound (E), a sensitizer, a polyfunctional thiol, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, and other components are mixed and stirred. Can be manufactured.
  • the photosensitive coloring composition containing 2 or more types of pigments mixes each pigment dispersion separately finely in a pigment
  • the compound (A) containing a furyl group It can be produced by mixing and stirring a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), a compound (D) containing an alkali-soluble functional group if necessary, an organic solvent, and the like.
  • the compound (A) containing a furyl group and the compound (B) containing a photopolymerizable functional group may be used as a dye carrier when producing a pigment dispersion.
  • a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, the photosensitivity for a color filter formed by dispersing the pigment in a resin and / or solvent using the dispersion aid. When the composition is used, a color filter having excellent transparency can be obtained.
  • the dispersing aid is preferably used in an amount of 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.
  • the resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and acts to stabilize the dispersion of the pigment on the dye carrier by adsorbing to the pigment. It is something to do.
  • resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines.
  • Salts polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like
  • Oil-based dispersants such as salts, water-soluble such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.
  • resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan.
  • Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Ethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adduct
  • the pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes a light yellow aromatic polycyclic compound such as naphthalene type and anthraquinone type, which is not generally called a pigment.
  • a light yellow aromatic polycyclic compound such as naphthalene type and anthraquinone type
  • Examples of pigment derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.
  • One embodiment of the present invention also relates to a method for producing a cured product using the above-described photosensitive composition.
  • the manufacturing method of this embodiment is A photosensitive composition containing a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, and a photopolymerizable initiator (C) is applied to a substrate and dried, or desired Forming into a shape of A photocuring step of irradiating at least a part of the photosensitive composition applied to a substrate and dried, or formed into a desired shape, with an ultraviolet ray; At least a thermosetting step of curing the photosensitive composition irradiated with ultraviolet rays in a temperature range of 80 to 150 ° C.
  • a development step may be included after the photocuring step.
  • the photosensitive composition of the present embodiment is applied to one or both surfaces of various substrates, or molded using a mold or the like, and dried by heating or reduced pressure as necessary, and ultraviolet rays are applied to the entire surface or photo.
  • a desired cured product can be obtained by partial irradiation through a mask, development as necessary, and heat curing at 80 to 150 ° C.
  • heat curing can be performed at a temperature exceeding 150 ° C. according to the heat resistance of the substrate to be used.
  • the substrate examples include glass, ceramic, polycarbonate, polyester, urethane, acrylic, polyacetate cellulose, polyamide, polyimide, polystyrene, epoxy resin, polyolefin, polycycloolefin, polyvinyl alcohol, various metals such as stainless steel, and the like. It is done.
  • a light source such as a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, or an excimer lamp.
  • Development can be performed by immersing in a solvent or an alkaline developer, or by spraying the developer with a spray or the like to remove uncured portions and form a desired fine pattern.
  • the thickness at the time of manufacturing these display members is preferably 0.005 to 30 ⁇ m, more preferably 0.01 to 20 ⁇ m, and particularly preferably 0.1 to 10 ⁇ m in a dry state. preferable. By setting the thickness in such a range, an appropriate mechanical strength and heat resistance can be obtained, and the light transmittance is less likely to be impaired.
  • the method for applying the photosensitive composition of the present embodiment to a glass substrate, ITO, metal film, organic film or the like is not particularly limited. For example, dipping, spraying, roll coating, die coating, spin coating In addition, it can be applied by printing methods such as a screen printing method, an offset printing method, and a gravure printing method. It is also possible to form a pattern by photolithography.
  • the drying method after applying the photosensitive composition of the present embodiment to the substrate is not particularly limited, and may vary depending on the type of each component used in the photosensitive composition, the amount added (blending amount), and the like. Can do.
  • a vacuum dryer, an oven, an infrared heater or the like can be used.
  • the temperature is preferably 40 to 80 ° C., and drying is preferably performed for 1 minute to 1 hour.
  • the heating temperature is preferably 60 ° C. or less, and more preferably 50 ° C. or less.
  • the photocuring method is not particularly limited.
  • the irradiation conditions can be changed depending on the type of each component used in the photosensitive composition, the addition amount (blending amount), and the like, but the irradiation amount of ultraviolet rays is usually 10 to 500 mJ / cm 2. 20 to 300 mJ / cm 2 is more preferable.
  • thermosetting performed after photocuring although it can be changed depending on the kind of each constituent component used in the photosensitive composition, the addition amount (blending amount), etc., the furyl group in the compound (A) containing a furyl group and
  • the temperature at which the photopolymerizable functional group in the photopolymerizable functional group (B) that remains unreacted in the photocuring step is preferably cross-linked, and the temperature is 0 to 80 to 150 ° C. It is preferable to heat cure under conditions of 1 to 10 hours.
  • the thermosetting temperature is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the color filter includes a filter segment or a black matrix formed from a photosensitive composition for a color filter on a transparent substrate, and a general color filter includes at least one red filter segment and at least one green filter. A segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.
  • each color filter segment and black matrix by photolithography is performed by the following method. That is, The photosensitive film composition for color filter prepared as a solvent development type or alkali development type colored resist material is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. Apply to 2 to 10 ⁇ m. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.
  • a coating method such as spray coating, spin coating, slit coating, roll coating, etc. Apply to 2 to 10 ⁇ m. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.
  • the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, thermosetting is performed to impart chemical resistance to the filter segment and black matrix formed by development.
  • it may be desired to increase the concentration of the colorant in order to achieve suitable chromaticity and film thickness.
  • the photosensitive composition of the present embodiment as described above. Even when the concentration of the colorant is high, both developability and chemical resistance can be achieved. In applications such as UV inks and etching resists for printed wiring boards, the photosensitive composition is generally used in a film thickness exceeding 10 ⁇ m.
  • the film thickness is often limited to 5 ⁇ m or less due to structural restrictions such as a liquid crystal display device, a color organic EL display device, and a solid-state image sensor, and production process. Therefore, it is often necessary to increase the concentration of the colorant in the photosensitive composition for color filters, and it is practically meaningful that the photosensitive composition of this embodiment achieves both developability and chemical resistance. is there.
  • glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate are used.
  • resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate are used.
  • a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
  • the dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m.
  • a vacuum dryer When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. The drying conditions can be changed depending on the type of each component used in the color filter photosensitive composition and the amount added (blending amount), etc.
  • a vacuum dryer In order to perform negative photolithography, development of the unexposed portion is performed. In order not to deteriorate the properties, it is preferable to use a vacuum dryer that is not heated during drying.
  • the temperature is preferably 40 to 80 ° C., and drying is preferably performed for 1 minute to 1 hour. From the viewpoint of suppressing generation of a development residue due to crosslinking of the photosensitive composition, the heating temperature is preferably 60 ° C. or lower, more preferably 50 ° C. or lower.
  • an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used.
  • an antifoamer and surfactant can also be added to a developing solution.
  • a development processing method a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
  • a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen.
  • Ultraviolet exposure can also be performed after forming a film.
  • the organic EL display device in the present embodiment is a display device having a color filter formed of the photosensitive composition of the present embodiment and a white light-emitting organic EL element (hereinafter referred to as an organic EL element) as a light source. preferable.
  • the organic EL element used in the present embodiment has peak wavelengths ( ⁇ 1 ) and ( ⁇ 2 ) at which the emission intensity is maximized in at least a wavelength range of 430 nm to 485 nm and a wavelength range of 560 nm to 620 nm.
  • the ratio of the emission intensity I 2 in the light-emitting intensity I 1 and the wavelength lambda 2 in lambda 1 (I 2 / I 1) is preferably has an emission spectrum is 0.4 to 0.9, 0. More preferably, it is 5 or more and 0.8 or less. Most preferably, it is 0.5 or more and 0.7 or less.
  • the emission intensity I 2 ratio (I 2 / I 1 ) has an emission spectrum of 0.4 to 0.9, it is preferable because high brightness and wide color reproducibility can be obtained.
  • the light emission intensity has a maximum value or a shoulder in the wavelength range of 530 nm to 650 nm.
  • the wavelength range of 430 nm to 485 nm is preferable when the color display device including the color filter displays blue with good color reproducibility. More preferably, it is in the range of 430 nm to 475 nm.
  • An organic EL element is composed of an element in which a single layer or multiple layers of organic layers are formed between an anode and a cathode.
  • the single-layer organic EL element refers to an element composed of only a light emitting layer between an anode and a cathode
  • the multilayer organic EL element refers to a hole or a hole in the light emitting layer in addition to the light emitting layer.
  • Hole injection layer, hole transport layer, hole blocking layer, electron injection for the purpose of facilitating electron injection and smooth recombination of holes and electrons in the light emitting layer It refers to a laminate of layers.
  • typical element configurations of the multilayer organic EL element include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode.
  • Anode / hole injection layer / light emitting layer / electron injection layer / cathode (3) Anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) Anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Examples include an anode / light emitting layer / hole blocking layer / electron injection layer / cathode, and (8) an element configuration laminated in a multilayer structure such as anode / light emitting layer / electron injection layer / cathode.
  • the organic EL element used in the present invention is not limited to these.
  • each organic layer described above may be formed by a layer configuration of two or more layers, and several layers may be laminated repeatedly.
  • an element configuration called “multi-photon emission” in which a part of the multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency.
  • the charge generating layer and the light emitting unit There is a method of laminating a plurality of portions.
  • a phthalocyanine-based compound As a material that can be used for the hole injection layer, a phthalocyanine-based compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc), or the like can be used.
  • copper phthalocyanine abbreviation: CuPc
  • VOPc vanadyl phthalocyanine
  • conductive polymer compounds such as polyethylenedioxythiophene (abbreviation: PEDOT) doped with polystyrene sulfonic acid (abbreviation: PSS), polyaniline (abbreviation: PANI), or the like. You can also.
  • a thin film of an inorganic semiconductor such as molybdenum oxide (abbreviation: MoO x ), vanadium oxide (abbreviation: VO x ), nickel oxide (abbreviation: NiO x ), or inorganic insulation such as aluminum oxide (abbreviation: Al 2 O 3 ).
  • MoO x molybdenum oxide
  • VO x vanadium oxide
  • NiO x nickel oxide
  • inorganic insulation such as aluminum oxide (abbreviation: Al 2 O 3 ).
  • a substance showing acceptability for these aromatic amine compounds may be added to the aromatic amine compound.
  • 2,3,5,6-tetrafluoro-7 which is an acceptor for VOPc.
  • 7,8,8-tetracyanoquinodimethane (abbreviation: F4-TCNQ), or ⁇ -NPD to which acceptor MoO x is added may be used.
  • an aromatic amine compound is preferable, and TDATA, MTDATA, TPD, ⁇ -NPD, DNTPD, and the like described for the hole injection material can be used.
  • Examples of the electron transport material that can be used for the electron transport layer include tris (8-quinolinolato) aluminum (abbreviation: Alq3), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), bis (10-hydroxybenzo).
  • [H] -quinolinato) beryllium abbreviation: BeBq2
  • bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum abbreviation: BAlq
  • bis [2- (2-hydroxyphenyl) benzoxazola And metal complexes such as zinc (substantially: Zn (BOX) 2) and bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (substantially: Zn (BTZ) 2).
  • 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- Oxadiazole derivatives such as (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4 -Phenyl-5- (4-biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) ) -1,2,4-triazole (abbreviation: p-EtTA Z) and other triazole derivatives, 2,2 ′, 2 ′′-(1,3,5-benzenetriyl) tris
  • Materials that can be used for the electron injection layer include Alq3, Almq3, BeBq2, BAlq, Zn (BOX) 2 , Zn (BTZ) 2 , PBD, OXD-7, TAZ, p-EtTAZ, TPBI, Electron transport materials such as BPhen and BCP can be used.
  • an ultrathin film of an insulator such as an alkali metal halide such as LiF or CsF, an alkaline earth halide such as CaF 2 , or an alkali metal oxide such as Li 2 O is often used.
  • Alkali metal complexes such as lithium acetylacetonate (abbreviation: Li (acac)) and 8-quinolinolato-lithium (abbreviation: Liq) are also effective.
  • a substance exhibiting a donor property with respect to these electron injection materials may be added to the electron injection material, and alkali metals, alkaline earth metals, rare earth metals, and the like can be used as donors.
  • a material obtained by adding lithium as a donor to BCP or a material obtained by adding lithium as a donor to Alq 3 can be used.
  • hole blocking material that can prevent a hole from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer.
  • hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinato) (4-phenylphenolato) aluminum and bis (2-methyl-8-hydroxyquinolina).
  • -To) (4-phenylphenolato) gallium complex compounds such as gallium, nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP) Can be mentioned.
  • a light emitting layer which obtains white light emission For example, the following can be used. That is, the energy level of each layer of the organic EL laminated structure is defined and light is emitted using tunnel injection (European Patent No. 0390551). Similarly, a white light-emitting element is an example of an element using tunnel injection.
  • a light emitting layer having a two-layer structure Japanese Patent Laid-Open No. 2-220390 and Japanese Patent Laid-Open No. 2-216790
  • a layered material composed of materials having different emission wavelengths Japanese Patent Laid-Open No.
  • a blue light emitter fluorescent peak 380 to 480 nm
  • a green light emitter 480 to 580 nm
  • a red phosphor is included (Japanese Patent Laid-Open No. 6-207170)
  • the blue light emitting layer contains a blue fluorescent dye
  • the green light emitting layer is a red fluorescent dye. It has contained area, such as construction of those (JP-A-7-142169) and the like further containing a green phosphor.
  • the light emitting material used in the present embodiment may be a material known as a conventional light emitting material. Examples of compounds suitably used for blue, green, orange to red light emission are shown below. However, the light emitting material is not limited to those specifically exemplified below.
  • Blue light emission can be obtained by using, for example, perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivative or the like as a guest material.
  • styrylarylene derivatives such as 4,4′-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi), 9,10-di-2-naphthylanthracene (abbreviation: DNA), 9,10-bis It can also be obtained from anthracene derivatives such as (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA).
  • a polymer such as poly (9,9-dioctylfluorene) may also be used.
  • Green light is emitted from coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetyl. It can be obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material.
  • coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetyl. It can be obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material.
  • metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq 3 ), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) 2 Cl)
  • Alq 3 8-hydroxyquinoline aluminum
  • BAlq BAlq
  • Zn BZ
  • bis (2-methyl-8-quinolinolato) chlorogallium abbreviation: Ga (mq) 2 Cl
  • a polymer such as poly (p-phenylene vinylene) may be used.
  • DCM1 Luminescence of 4-o-dicyanomethylene
  • a guest material such as bis (8-quinolinolato) zinc (abbreviation: Znq2) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2).
  • Znq2 bis (8-quinolinolato) zinc
  • Znsq2 bis [2-cinnamoyl-8-quinolinolato] zinc
  • a polymer such as poly (2,5-dialkoxy-1,4-phenylene vinylene) may be used.
  • the material used for the anode of the organic EL device used in the present embodiment is preferably a material having a work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance.
  • an electrode substance include metals such as Au, and conductive materials such as CuI, ITO, SNO 2 , and ZNO.
  • a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering.
  • the anode desirably has such a characteristic that when light emitted from the light emitting layer is extracted from the anode, the transmittance of the anode for light emission is greater than 10%.
  • the sheet resistance of the anode is preferably several hundred ⁇ / cm 2 or less. Further, although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • the material used for the cathode of the organic EL element used in the present embodiment is a material having a work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, and rare earth metals.
  • This cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the transmittance of the cathode for light emission is preferably greater than 10%.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / cm 2 or less, and the film thickness is usually 10 nm to 1 ⁇ m, preferably 50 to 200 Nm.
  • an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode. May be formed.
  • an organic EL element can also be produced from the cathode to the anode in the reverse order.
  • This organic EL element is manufactured on a translucent substrate.
  • This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.
  • glass plates examples include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • synthetic resin plate examples include plates such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.
  • a dry film forming method such as vacuum deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, Wet film-forming methods such as an ink jet method, a method of vapor-depositing a light emitter on a donor film, Japanese Patent Application Laid-Open No. 2002-534782 and S.A. T.A. Lee, et al. , Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging, laser thermal transfer) described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.
  • a dry film forming method such as vacuum deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, Wet film-forming methods such as an ink jet method, a method of vapor-depositing a light emitter
  • the organic layer is particularly preferably a molecular deposited film.
  • the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state.
  • a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coating method or the like.
  • an organic layer can be formed.
  • the film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, the pinhole is Or the like, and even when an electric field is applied, it is difficult to obtain sufficient light emission luminance. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 ⁇ m, but more preferably in the range of 10 nm to 0.2 ⁇ m.
  • a protective layer may be provided on the surface of the element, or the whole element may be covered or sealed with a resin or the like.
  • a photocurable resin that is cured by light is preferably used.
  • the current applied to the organic EL element used in this embodiment is usually a direct current, but a pulse current or an alternating current may be used.
  • the current value and the voltage value are not particularly limited as long as they are within the range that does not destroy the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.
  • the driving method of the organic EL element used in this embodiment can be driven not only by the passive matrix method but also by the active matrix method.
  • the method for extracting light from the organic EL element of the present embodiment is applicable not only to the method of bottom emission for extracting light from the anode side, but also to the method of top emission for extracting light from the cathode side.
  • the main method of the full color method of the organic EL element used in this embodiment is a color filter method.
  • the color filter method uses a white light emitting organic EL element to extract light of three primary colors through a color filter. In addition to these three primary colors, a part of white light is extracted as it is and used for light emission. In addition, the luminous efficiency of the entire device can be increased.
  • the organic EL element used in this embodiment may adopt a microcavity structure.
  • the organic EL device has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode
  • This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. .
  • J.A. Yamada et al. AM-LCD Digest of Technical Papers, OD-2, p. 77-80 see J.A. Yamada et al. AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).
  • an RGB color filter layer is produced in parallel with a glass substrate, and a light emitting layer (backlight) produced using the ITO electrode layer and the organic EL element is placed on the color filter layer.
  • a light emitting layer backlight
  • color display is possible, and a color display device is obtained.
  • a color display device having a high contrast ratio can be realized by controlling the current flow during light emission by the TFT.
  • the use of the photosensitive composition of the present invention is not particularly limited.
  • a color filter protective film, a photo spacer, a protrusion for liquid crystal alignment, a touch panel interlayer insulating film, a photosensitive film It can be used to produce a conductive solder resist, microlens, optical hard coat, UV ink, photosensitive lithographic printing plate, various coatings and the like. Further, it can also be used for reinforcing plate adhesives, interlayer adhesives, coating agents, electromagnetic wave shielding adhesives, photosensitive optical waveguides, photothermal dual-curing potting agents and the like used for flexible printed wiring boards.
  • the present invention relates to the subject matter of the invention described in Japanese Patent Application No. 2015-120375 filed on June 15, 2015 and Japanese Patent Application No. 2016-081168 filed on April 14, 2016, the entire disclosure thereof. The contents are incorporated herein by reference.
  • the embodiments of the present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention.
  • “part” represents “part by mass”
  • “%” represents “% by mass”.
  • the molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography). Using GPC-8020 manufactured by Tosoh Corporation, eluent was used as the eluent.
  • TSKgelSuperHM-M manufactured by Tosoh Corporation
  • IR measurement was performed using Spectrum One manufactured by PerkinElmer.
  • the acid value was measured as follows. About 1 g of the compound solution for measuring the acid value was weighed, 30 g of methyl ethyl ketone and 1 g of water were added and stirred for 10 minutes, and then potentiometric titration was performed with a 0.1 N potassium hydroxide ethanol solution. A blank test was conducted in the same manner. Measurement was performed by heating the nonvolatile content of the target product at 200 ° C.
  • the nonvolatile content means a value calculated from the sample mass after heating / the sample mass before heating when 1 g of the sample is heated at 200 ° C. for 10 minutes.
  • a value calculated based on a method specified by the manufacturer may be adopted.
  • solid content and non-volatile content are synonymous.
  • the solution was diluted with propylene glycol monomethyl ether acetate to obtain a compound solution A3 containing a furyl group having a nonvolatile content of 20%.
  • This compound does not contain an alkali-soluble group and does not contain a photopolymerizable functional group. Since a side reaction tends to occur when an isocyanate group derived from 2-methacryloyloxyethyl isocyanate in the polymer and a hydroxyl group in furfuryl alcohol are reacted, the polymer has a slightly higher molecular weight and a weight average molecular weight of 60000. .
  • This compound contains an alkali-soluble group and does not contain a photopolymerizable functional group. Since the methacrylic acid and glycidyl methacrylate in the prepolymer are likely to cause side reactions during the polymerization, the final polymer after completion of the furfuryl mercaptan modification has a weight average molecular weight of 70000.
  • the solution was diluted with propylene glycol monomethyl ether acetate to obtain a compound solution A16 containing a furyl group having a nonvolatile content of 20%.
  • This compound contains an alkali-soluble group and does not contain a photopolymerizable functional group.
  • the weight average molecular weight was 27000.
  • the solution was diluted with propylene glycol monomethyl ether acetate to obtain a compound solution A17 containing a furyl group having a nonvolatile content of 20%.
  • This compound contains an alkali-soluble group and does not contain a photopolymerizable functional group.
  • the weight average molecular weight was 28000.
  • the solution was diluted with propylene glycol monomethyl ether acetate to obtain a compound solution A18 containing a furyl group having a nonvolatile content of 20%.
  • This compound contains an alkali-soluble group and a photopolymerizable functional group.
  • the weight average molecular weight was 33,000.
  • the solution was diluted with propylene glycol monomethyl ether acetate to obtain a compound solution A20 containing a furyl group having a nonvolatile content of 20%.
  • This compound contains an alkali-soluble group and a photopolymerizable functional group.
  • the weight average molecular weight was 28000.
  • the solution was diluted with propylene glycol monomethyl ether acetate to obtain a compound solution A23 containing a furyl group having a nonvolatile content of 20%.
  • This compound contains an alkali-soluble group and a photopolymerizable functional group.
  • the weight average molecular weight was 26000.
  • a compound solution B1 ((meth) acrylate copolymer having a methacryloyl group) containing a photopolymerizable functional group having a nonvolatile content of 20%.
  • This compound contains an alkali-soluble group.
  • the weight average molecular weight was 26000.
  • a compound solution B2 (a (meth) acrylate copolymer having a methacryloyl group) containing a photopolymerizable functional group having a nonvolatile content of 20% was obtained.
  • This compound contains an alkali-soluble group.
  • the weight average molecular weight was 28000.
  • a compound solution B10 (polyfunctional maleimide compound) containing a photopolymerizable functional group having a nonvolatile content of 5% was obtained.
  • This compound does not contain an alkali-soluble group, and the maleimide group which is a photopolymerizable functional group is protected by a furyl group.
  • Irg907 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one: Irgacure 907 (manufactured by BASF) PGMAc: propylene glycol monomethyl ether acetate EHPE: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol: EHPE3150 (manufactured by Daicel) Imidazole: 2-ethyl-4-methylimidazole: 2E4MZ (manufactured by Shikoku Chemicals) b-NCO: Block of IPDI-based polyisocyanate, Solvent Naphtha 100 solution with a nonvolatile content of 65%, Potential NCO group content 8.1%: Desmodur BL4265SN (manufactured by Sumika Bayer Urethane Co., Ltd.) Melamine: Me
  • a 100 mm ⁇ 100 mm, 250 ⁇ m thick polyethylene naphthalate film obtained by fixing the photosensitive compositions of Experimental Examples 1 to 24 on a glass substrate with an adhesive has a final film thickness of 2.0 ⁇ m after drying under reduced pressure using a spin coater. After applying under pressure and drying under reduced pressure, UV exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm 2 and an exposure amount of 50 mJ / cm 2 . The coated film was heated at 100 ° C. for 20 minutes, allowed to cool, and peeled off from the glass substrate to obtain a film for evaluation.
  • the haze value of the obtained film was measured using a haze meter NDH-2000 (manufactured by Tokyo Denshoku). The rank of evaluation is as follows. ⁇ : No foreign matter or white turbidity, haze value less than 0.5%: Very good level ⁇ : No foreign matter or white turbidity, haze value 0.5% or more and less than 1.0%: Good level ⁇ : Foreign matter or white turbidity No haze value of 1.0% or more and less than 1.5%: Inferior to ⁇ , but practical level ⁇ : Foreign matter or cloudiness or Haze value of 1.5% or more: Level not suitable for practical use
  • the coated film produced in the same procedure as the evaluation of the appearance was heated at 100 ° C. or 150 ° C. for 20 minutes, allowed to cool, and peeled off from the glass substrate to obtain a film for evaluation.
  • the film thickness of the layer of the photosensitive composition was measured, and after immersing the film in propylene glycol monomethyl ether acetate for 5 minutes at room temperature, it was washed with ion-exchanged water and air-dried. Thereafter, the film was visually observed and the film thickness was measured, and the change rate of the film thickness was calculated.
  • the film thickness was measured with a stylus type film thickness meter DEKTAK-3 manufactured by ULVAC.
  • the rank of evaluation is as follows.
  • a 100 mm ⁇ 100 mm, 250 ⁇ m thick polyethylene naphthalate film obtained by fixing the photosensitive compositions of Experimental Examples 1 to 24 on a glass substrate with an adhesive has a final film thickness of 2.0 ⁇ m after drying under reduced pressure using a spin coater. It applied so that it might become, and dried under reduced pressure.
  • This film was spray-developed with an aqueous solution of sodium carbonate at 23 ° C. for different times, and the time when the coating film excluding the edge portion of the film disappeared was determined visually to determine the development time.
  • the rank of evaluation is as follows.
  • ⁇ 10 seconds to less than 20 seconds ⁇ : 20 seconds to less than 30 seconds ⁇ ⁇ : 30 seconds to less than 40 seconds ⁇ : 40 seconds to less than 60 seconds ⁇ : 60 seconds to less than 80 seconds ⁇ : 80
  • the development remains even after development for more than 2 seconds.
  • ⁇ and ⁇ are practically preferable levels, ⁇ ⁇ , ⁇ , and ⁇ ⁇ are practically usable levels, and ⁇ is a level not suitable for practical use.
  • a 100 mm ⁇ 100 mm, 250 ⁇ m thick polyethylene naphthalate film obtained by fixing the photosensitive compositions of Experimental Examples 1 to 24 on a glass substrate with an adhesive has a final film thickness of 2.0 ⁇ m after drying under reduced pressure using a spin coater. It applied so that it might become, and dried under reduced pressure.
  • the film was cooled to room temperature, and then irradiated with ultraviolet rays through a photomask having a stripe pattern of 50 ⁇ m width (pitch 100 ⁇ m) with an illuminance of 20 mW / cm 2 and an exposure amount of 50 mJ / cm 2 using an ultrahigh pressure mercury lamp.
  • the film was spray-developed using an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 100 ° C. for 20 minutes in a clean oven. After standing to cool, it peeled off from the glass substrate and obtained the film for evaluation.
  • spray development was performed for the time which added 10 second to the development time measured by evaluation of the developing speed about the film which used each photosensitive composition.
  • the obtained pattern film was observed with an optical microscope, and the width of the pattern at the 50 ⁇ m photomask portion was measured. The closer to the size of the photomask, the higher the definition and the better the photosensitive composition.
  • the rank of evaluation is as follows.
  • ⁇ : 50 ⁇ m or more to less than 53 ⁇ m ⁇ : 53 ⁇ m or more to less than 56 ⁇ m ⁇ ⁇ : 56 ⁇ m or more to less than 60 ⁇ m ⁇ : 60 ⁇ m or more to less than 65 ⁇ m ⁇ : 65 ⁇ m or more ⁇ and ⁇ are practically preferred levels, and ⁇ and ⁇ are practical Possible level, x is a level not suitable for practical use.
  • the photosensitive compositions of Experimental Examples 1 to 17 can be alkali-developed because the photosensitive compositions contain alkali-soluble functional groups, and have chemical resistance, degassing, appearance, In addition to storage stability, the development speed and development line width were good. More specifically, in Experimental Example 2, 2-hydroxyethyl methacrylate, which is one of the compounds of general formula [7], in Experimental Example 3, hydroxypropyl methacrylate, which is one of the compounds of general formula [7], Experimental Example 6 However, since 2-methoxyethyl methacrylate, one of the compounds of the general formula [7], was used, the development speed was further increased.
  • Experimental Examples 12 and 13 use a protected maleimide group and a maleimide group together, so that the storage stability is somewhat within the practical range. Although inferior, the chemical resistance tended to be good. On the other hand, in Experimental Example 14, since a methacryl group was used in combination, the reactivity with the compound (A) was low and the chemical resistance was slightly inferior.
  • the photosensitive composition of Experimental Example 19 did not contain the compound (B) containing a photopolymerizable functional group, it could not be cured by ultraviolet rays, and the chemical resistance was insufficient. Further, at the time of alkali development, the portion irradiated with ultraviolet rays through a photomask was dissolved, and a pattern could not be formed. Since the photosensitive composition of Experimental Example 20 did not contain the photopolymerization initiator (C), it could not be cured by ultraviolet rays, and the chemical resistance was insufficient. Further, at the time of alkali development, the portion irradiated with ultraviolet rays through a photomask was dissolved, and a pattern could not be formed.
  • red pigment dispersion After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, filtered through a 5 ⁇ m filter, and red A pigment dispersion PR was prepared.
  • Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, filtered through a 5 ⁇ m filter, and red A pigment dispersion PR was prepared.
  • Diketopyrrolopyrrole pigment C.I. I. Pigment Red 254: “Irga Four Red S3610 CF” manufactured by Ciba Japan Co., Ltd. 8.96 parts
  • Anthraquinone pigment C.I. I. Pigment Red 177: “Chromophthal Red L4039” manufactured by Ciba Japan Co., Ltd.
  • Nickel azo complex pigment C.I. I. Pigment Yellow 150: “E4GN” manufactured by LANXESS 1.16 parts
  • Resin-type pigment dispersant “Solsperse 20000” manufactured by Lubrizol Japan Inc. 2.29 parts Diketopyrrolopyrrole pigment derivative 2.69 parts
  • a green pigment dispersion PG was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
  • Halogenated zinc phthalocyanine pigment C.I. I. Pigment Green 58: “FASTOGEN Green A110” manufactured by DIC Co., Ltd. 7.53 parts
  • Monoazo pigment C.I. I. Pigment Yellow 150: "E4GN” manufactured by LANXESS 4.14 parts
  • Resin-type pigment dispersant "Dysperbyk 2001” manufactured by BYK Chemie Corporation 46% non-volatile content 6.09 parts
  • Compound solution D2 containing alkali-soluble functional group 5.53 parts propylene glycol monomethyl 76.71 parts of ether acetate
  • a blue pigment dispersion PB was prepared in the same manner as the red pigment dispersion, using a mixture having the following composition.
  • ⁇ -type copper phthalocyanine pigment C.I. I. Pigment Blue 15: 6: “Heliogen Blue L-6700F” manufactured by BASF 12.88 parts
  • Resin-type pigment dispersant “Solsperse 20000” manufactured by Nippon Lubrizol Corporation 5.62 parts
  • Compound solution D2 containing alkali-soluble functional group 1.50 Parts Cyclohexanone 80.00 parts
  • a black pigment dispersion PK was prepared in the same manner as the red pigment dispersion, using a mixture having the following composition.
  • Carbon black “MA77” manufactured by Mitsubishi Chemical Corporation 11.67 parts
  • Resin-type pigment dispersant “Solsperse 20000” manufactured by Nippon Lubrizol Corporation 2.80 parts
  • Compound solution D2 containing alkali-soluble functional group 5.53 parts
  • M402 Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate: Aronix M-402 (manufactured by Toa Gosei Co., Ltd.) BMI5100: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide: BMI-5100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime): Irgacure OXE02 (manufactured by BASF) PGMAc: propylene glycol monomethyl ether acetate EHPE: 1,2-epoxy-4- (2-oxiranyl) cyclohexan
  • Experimental Examples 64 to 81 are experimental examples of the embodiment of the present invention, and Experimental Examples 82 to 84 are comparative experimental examples.
  • experimental examples 85 to 98 are experimental examples of the embodiment of the present invention, and experimental example 99 is a comparative experimental example.
  • experimental examples 100 to 106 are experimental examples of the embodiment of the present invention, and experimental example 107 is a comparative experimental example.
  • the haze value of the obtained film was measured using a haze meter NDH-2000 (manufactured by Tokyo Denshoku). The rank of evaluation is as follows. ⁇ : No foreign matter or white turbidity, haze value less than 0.5%: Very good level ⁇ : No foreign matter or white turbidity, haze value 0.5% or more and less than 1.0%: Good level ⁇ : Foreign matter or white turbidity No haze value of 1.0% or more and less than 1.5%: Inferior to ⁇ , but practical level ⁇ : Foreign matter or cloudiness or Haze value of 1.5% or more: Level not suitable for practical use
  • the coated film produced in the same procedure as the appearance evaluation was heated at 100 ° C. or 150 ° C. for 20 minutes, allowed to cool, and peeled off from the glass substrate to obtain a film for evaluation.
  • the obtained film was measured for chromaticity, immersed in propylene glycol monomethyl ether acetate for 5 minutes at room temperature, washed with ion-exchanged water, and air-dried. Thereafter, the film was visually observed and the chromaticity was measured, and the color difference ⁇ E was calculated.
  • the chromaticity was measured with a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) using a C light source.
  • the rank of evaluation is as follows.
  • ⁇ 10 seconds to less than 20 seconds ⁇ : 20 seconds to less than 30 seconds ⁇ ⁇ : 30 seconds to less than 40 seconds ⁇ : 40 seconds to less than 60 seconds ⁇ : 60 seconds to less than 80 seconds ⁇ : 80
  • the development remains even after development for more than 2 seconds.
  • ⁇ and ⁇ are practically preferable levels, ⁇ ⁇ , ⁇ , and ⁇ ⁇ are practically usable levels, and ⁇ is a level not suitable for practical use.
  • the film was spray-developed using an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 100 ° C. for 20 minutes in a clean oven. After standing to cool, it peeled off from the glass substrate and obtained the film for evaluation.
  • spray development was performed for the time which added 10 second to the development time measured by evaluation of the developing speed about the film which used each photosensitive composition.
  • the obtained pattern film was observed with an optical microscope, and the width of the pattern at the 50 ⁇ m photomask portion was measured. The closer to the size of the photomask, the higher the definition and the better the photosensitive composition.
  • the rank of evaluation is as follows.
  • ⁇ 50 ⁇ m or more to less than 53 ⁇ m ⁇ : 53 ⁇ m or more to less than 56 ⁇ m ⁇ ⁇ : 56 ⁇ m or more to less than 60 ⁇ m ⁇ : 60 ⁇ m or more to less than 65 ⁇ m ⁇ : 65 ⁇ m or more ⁇ and ⁇ are practically preferred levels, ⁇ ⁇ and ⁇ are practical Possible level, x is a level not suitable for practical use.
  • the photosensitive compositions of Experimental Examples 25 to 55, 64 to 81, 85 to 98, and 100 to 106 have chemical resistance, degassing, appearance, storage stability, development speed, and development line. Both widths were good.
  • the red photosensitive composition will be described in more detail.
  • Experimental Examples 28 to 35, 37, 42, and 43 A7 to A14, A16, A21, and A22 are used as the compound (A) containing a furyl group.
  • the same physical property trends as in Experimental Examples 1 to 11 were exhibited.
  • Experimental Example 57 low molecular weight A1 is used as the compound (A) containing a furyl group, whereas in Experimental Example 56, high molecular weight A2 is used, resulting in better chemical resistance.
  • Experimental Example 58 since A3 having a high molecular weight tendency was used during synthesis, the compatibility of the photosensitive composition was slightly inferior, and although it was within the practical range, the appearance was inferior.
  • Experimental Example 89 A4 is used as the compound (A), and A7 is used in Experimental Example 93. Like Experimental Examples 25 and 28, the methacrylic acid in (A) was changed to 2-methacryloyloxyethyl succinic acid. Development speed has increased. In Experimental Example 90, since D2 having a high acid value was used as the compound (D), the development speed was higher than that in Experimental Example 89 using D1. In Experimental Example 91, since hydroxyethyl methacrylate was used in the compound (D), the development speed was faster and the chemical resistance was improved as compared with Experimental Example 89.
  • Experimental Example 92 the hydroxypropyl methacrylate of the compound (D) was used and the acid value was higher, so that the development speed was higher than in Experimental Example 91.
  • M402 is used as the compound (B), but in Experimental Examples 94 to 97, a part of M402 is replaced with B6 to B9. Since B6 to B9 had a lower photopolymerizable functional group concentration than M402, Experimental Examples 94 to 97 had a narrow line width.
  • the photosensitive compositions of Experimental Examples 56 to 58 all had good chemical resistance, degassing, appearance, and storage stability, but no alkali-soluble functional group was contained in the photosensitive composition.
  • the development speed and development line width were not evaluated.
  • the photosensitive compositions of Experimental Examples 59 to 63, 82 to 84, 99, and 107 which are comparative experimental examples, resulted in poor results in any of the above physical properties, and none of them satisfied the practical level. Since the photosensitive compositions of Experimental Examples 59, 99, and 107 did not contain the compound (A) containing a furyl group, the chemical resistance was insufficient. None of the photosensitive compositions of Experimental Examples 82 to 84 contains the compound (A) containing a furyl group.
  • Experimental Example 82 the compound (A) containing the furyl group used in Experimental Example 64 was replaced with the compound (B) containing a photopolymerizable functional group, so that the chemical resistance was insufficient, and the photosensitive composition The development line width tended to be slightly thicker due to increased photopolymerization.
  • Experimental Example 83 the compound (D) containing an alkali-soluble functional group used in Experimental Example 82 was replaced with the compound (B) containing a photopolymerizable functional group.
  • Experimental Example 84 the light used in Experimental Example 83 was used. Since the amount of the polymerization initiator (C) was increased, there was a tendency that the chemical resistance increased and the development line width increased compared to Experimental Example 82. could not.
  • Photosensitive Composition for Color Filter of Organic EL Display Device >> ⁇ Production of photosensitive composition for color filter of organic EL display device>
  • ⁇ Pigment production method> ⁇ Method for producing azo pigment> (Red colorant (PR-1))
  • a mixture of 52.9 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of the amine compound of the chemical formula (14) is dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C. by adding ice, and 35% aqueous hydrochloric acid solution After adding 108.3 parts and stirring for 1 hour, an aqueous solution prepared by adding 19.9 parts of sodium nitrite to 50 parts of water was added and stirred for 3 hours.
  • aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and a diazonium salt aqueous solution was added.
  • 88.4 parts of N- [4-acetylaminophenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C. to obtain a coupler solution. did.
  • This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction.
  • the pH at this time was 4.3.
  • the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours.
  • the azo pigment represented by the formula (A2-1) and the chemical formula (A2- 141 parts of a mixture of azo pigments represented by 6) were obtained.
  • mass ratio of the mixture of azo pigments of formula (A2-1) and chemical formula (A2-6) was 80.3: 19.7.
  • Red colorant (PR-2) Commercially available C.I. I. 100 parts of Pigment Red 179 (PR179) (“Pariogen Maroon L-3920” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. for 6 hours. Kneaded and salt milled. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a red colorant (PR-2) were obtained. The average primary particle size was 40.8 nm.
  • Red colorant (PR-3) C. I. Pigment Red 179, C.I. I. Pigment Red 177 (PR177) (“chromophthal red L4039” manufactured by BASF) was used in the same manner as in the production of the red colorant (PR-2) to obtain 97 parts of the red colorant (PR-3). It was. The average primary particle size was 27.6 nm.
  • Red colorant (PR-4) C. I. Pigment Red 179, C.I. I. Pigment Red 254 (PR254) (“Irga Fore Red S3610 CF” manufactured by BASF) was used in the same manner as in the production of the red colorant (PR-2), and 97 parts of the red colorant (PR-4) was added. Obtained.
  • the average primary particle size was 33 nm.
  • Nickel azo complex pigments C.I. I. Pigment Yellow 150: 100 parts of “E4GN” manufactured by LANXESS, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A colorant (PY-1) was obtained. The average primary particle size was 42.3 nm.
  • yellow colorant (PY-2) C. I. Pigment Yellow 150, C.I. I. Except for changing to CI Pigment Yellow 139 (PY139) (“Irgafore Yellow 2R-CF” manufactured by BASF), yellow colorant (PY-2) was obtained in the same manner as in the production of yellow colorant (PY-1). It was. The average primary particle size was 40.2 nm.
  • yellow colorant (PY-4) C. I. Pigment Yellow 150, C.I. I.
  • a yellow colorant (PY-4) was obtained in the same manner as in the production of the yellow colorant (PY-1) except that it was changed to CI Pigment Yellow 185 (PY185) ("Paliogen Yellow D1155" manufactured by BASF).
  • the average primary particle size was 38.4 nm.
  • quinophthalone compound (c) 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours.
  • the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight.
  • 97 parts of a yellow colorant (PY-5) were obtained.
  • the average primary particle size was 34.1 nm.
  • Green colorant (PG-1) Halogenated zinc phthalocyanine pigment: C.I. I. Pigment Green 58: 200 parts of “FASTOGEN Green A110” manufactured by DIC, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 4 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of a green colorant (PG-1) was obtained. The average primary particle size was 50.2 nm.
  • Green colorant (PG-2) C. I. Pigment Green 58 and phthalocyanine green pigment C.I. I. Except for changing to Pigment Green 7 (PG7) (“Lionol Green YS-07” manufactured by Toyocolor Co., Ltd.), the same procedure as in the production of Green Coloring Agent (PG-1) was carried out. Got. The average primary particle size was 55.3 nm.
  • Green colorant (PG-3) C. I. Pigment Green 58, C.I. I.
  • a green colorant (PG-3) was obtained in the same manner as in the production of the yellow colorant (PG-1) except that it was changed to CI Pigment Green 36 (“CF-G-6YK” manufactured by Toyocolor Co., Ltd.).
  • the average primary particle size was 52.1 nm.
  • Green colorant (PG-4) In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene), and the temperature was raised and refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry.
  • DBU 1,8-Diazabicclo [5.4.0] undec-7-ene
  • This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following general formula (2).
  • Pigment Orange 64 (“Chromophthal Orange K 2960” manufactured by BASF)
  • 1200 parts of sodium chloride and 120 parts of diethylene glycol
  • stainless gallon kneader manufactured by Inoue Seisakusho
  • salt milling was performed.
  • the obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight.
  • 97 parts of an orange colorant (PO-1) were obtained.
  • the average primary particle size was 39 nm.
  • Blue colorant (PB-2) C. I. Pigment Blue 15: 6, C.I. I.
  • a blue colorant (PB-2) was obtained in the same manner as in the production of the blue colorant (PB-1) except that it was changed to CI Pigment Blue 15: 3 (“Lionol Blue SM” manufactured by Toyocolor Co., Ltd.).
  • the average primary particle size was 28.6 nm.
  • Blue colorant (PB-3) C. I. Pigment Blue 15: 6, C.I. I. Blue colorant (PB-3) was obtained in the same manner as the blue colorant (PB-1) except that it was changed to CI Pigment Blue 15: 1 (“Lionol Blue MG-7” manufactured by Toyocolor Co., Ltd.) It was.
  • the average primary particle size was 30.4 nm.
  • PV-1 Pigment Violet 23
  • Clariant Green Violet RL
  • diethylene glycol 1 gallon kneader
  • the mixture was poured into 5000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 118 parts of purple A colorant (PV-1) was obtained.
  • the average primary particle size was 26.4 nm.
  • C.I. A purple colorant (PV-2) comprising Acid Red 289 and the following resin B-1 having a cationic group in the side chain was produced.
  • the following resin B-1 having a cationic group in the side chain of 51 parts was added to 2000 parts of water, and after stirring and mixing sufficiently, the mixture was heated to 60 ° C.
  • An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react.
  • C.I. A purple colorant (PV-3) comprising Acid Red 52 and Resin B-1 having a cationic group in the side chain was produced.
  • the resin B-1 having a cationic group in the side chain of 51 parts was added to 2000 parts of water, and after stirring and mixing sufficiently, the mixture was heated to 60 ° C.
  • An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react.
  • Resin B-1 having a cationic group in the side chain 74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream.
  • Red Colorant Dispersion P-R1 After the mixture having the following composition is uniformly stirred and mixed, it is dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 ⁇ m filter. A red pigment dispersion P-R1 was prepared.
  • Red colorant (PR-1) 12.0 parts (azo pigment)
  • Resin type dispersant 3.0 parts
  • Compound solution D2 containing alkali-soluble functional group 20.0 parts
  • Solvent 65.0 parts Propylene glycol monomethyl ether acetate (PGMAC)
  • red colorant dispersions PR-2 to 4 green colorant dispersions PG1 to 4, blue were used in the same manner as red colorant dispersion PR-1.
  • Colorant dispersions P-B1-3, yellow colorant dispersions PY1-5, purple colorant dispersion P-V1, and orange colorant dispersion P-O1 were prepared.
  • M402 Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate: Aronix M-402 (manufactured by Toa Gosei Co., Ltd.)
  • M309 trimethylol prohan triacrylate: Aronix M-309 (manufactured by Toa Gosei Co., Ltd.)
  • OXE02 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime): Irgacure OXE02 (manufactured by BASF)
  • PGMAc Propylene glycol monomethyl ether acetate
  • a 100 mm ⁇ 100 mm, 250 ⁇ m thick polyethylene naphthalate film obtained by fixing the photosensitive compositions of Experimental Examples 108 to 176 with a pressure-sensitive adhesive on a glass substrate has a final film thickness of 2.0 ⁇ m after drying under reduced pressure using a spin coater. After applying under pressure and drying under reduced pressure, UV exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm 2 and an exposure amount of 50 mJ / cm 2 . The coated film was heated at 100 ° C. for 20 minutes, allowed to cool, and peeled off from the glass substrate to obtain a film for evaluation.
  • the haze value of the obtained film was measured using a haze meter NDH-2000 (manufactured by Tokyo Denshoku). The rank of evaluation is as follows. ⁇ : No foreign matter or white turbidity, haze value less than 0.5%: Very good level ⁇ : No foreign matter or white turbidity, haze value 0.5% or more and less than 1.0%: Good level ⁇ : Foreign matter or white turbidity No, haze value of 1.0% or more and less than 1.5%: Inferior to ⁇ , but practical level ⁇ : Foreign matter or cloudiness or Haze value of 1.5% or more: Level not suitable for practical use
  • the coated film produced in the same procedure as the appearance evaluation was heated at 100 ° C. or 150 ° C. for 20 minutes, allowed to cool, and peeled off from the glass substrate to obtain a film for evaluation.
  • the obtained film was measured for chromaticity, immersed in propylene glycol monomethyl ether acetate for 5 minutes at room temperature, washed with ion-exchanged water, and air-dried. Thereafter, the film was visually observed and the chromaticity was measured, and the color difference ⁇ E was calculated.
  • the chromaticity was measured with a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) using a C light source.
  • the rank of evaluation is as follows.
  • ⁇ 10 seconds to less than 20 seconds ⁇ : 20 seconds to less than 30 seconds ⁇ ⁇ : 30 seconds to less than 40 seconds ⁇ : 40 seconds to less than 60 seconds ⁇ : 60 seconds to less than 80 seconds ⁇ : 80
  • the development remains even after development for more than 2 seconds.
  • ⁇ and ⁇ are practically preferable levels, ⁇ ⁇ , ⁇ , and ⁇ ⁇ are practically usable levels, and ⁇ is a level not suitable for practical use.
  • the film was spray-developed using an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 100 ° C. for 20 minutes in a clean oven. After standing to cool, it peeled off from the glass substrate and obtained the film for evaluation.
  • spray development was performed for the time which added 10 second to the development time measured by evaluation of the developing speed about the film which used each photosensitive composition.
  • the obtained pattern film was observed with an optical microscope, and the width of the pattern at the 50 ⁇ m photomask portion was measured. The closer to the size of the photomask, the higher the definition and the better the photosensitive composition.
  • the rank of evaluation is as follows.
  • ⁇ 50 ⁇ m or more to less than 53 ⁇ m ⁇ : 53 ⁇ m or more to less than 56 ⁇ m ⁇ ⁇ : 56 ⁇ m or more to less than 60 ⁇ m ⁇ : 60 ⁇ m or more to less than 65 ⁇ m ⁇ : 65 ⁇ m or more ⁇ and ⁇ are practically preferred levels, ⁇ ⁇ and ⁇ are practical Possible level, x is a level not suitable for practical use.
  • the photosensitive compositions of Experimental Examples 108 to 127, 131 to 150, and 154 to 173 containing the compound (A) containing a furyl group in any combination of various colorants Chemical resistance, degassing, appearance, storage stability, development speed, and development line width were all good.
  • chemical resistance was further improved by using a trifunctional monomer (M309) for the compound (B) containing a photopolymerizable functional group.
  • the use of the silane compound (E-1) promoted internal cross-linking and further improved chemical resistance.
  • the photosensitive composition of the present invention can be used as long as it is cured by light and heat.
  • a color filter protective film, a photo spacer, for liquid crystal alignment It can be used to produce protrusions, touch panel interlayer insulating films, photosensitive solder resists, micro lenses, optical hard coats, UV inks, photosensitive lithographic printing plates, various coatings, and the like. Further, it can also be used for reinforcing plate adhesives, interlayer adhesives, coating agents, electromagnetic wave shielding adhesives, photosensitive optical waveguides, photothermal dual-curing potting agents and the like used for flexible printed wiring boards.

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Abstract

La présente invention concerne une composition photosensible qui contient un composé (A) contenant des groupes furyle, un composé (B) contenant des groupes fonctionnels photopolymérisables, ainsi qu'un initiateur de photopolymérisation (C). La présente invention permet d'obtenir une composition photosensible susceptible de présenter une pharmacorésistance même à de basses températures de durcissement et ne présentant aucun problème de dégazement et de compatibilité.
PCT/JP2016/067688 2015-06-15 2016-06-14 Composition photosensible, composition photosensible pour filtre coloré et filtre coloré Ceased WO2016204148A1 (fr)

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TWI666518B (zh) * 2016-12-30 2019-07-21 奇美實業股份有限公司 感光性樹脂組成物及其應用
JP2022008395A (ja) * 2017-03-22 2022-01-13 東洋インキＳｃホールディングス株式会社 有機ｅｌ表示装置用赤色着色組成物、有機ｅｌ表示装置用カラーフィルタ及び有機ｅｌ表示装置
CN109254498A (zh) * 2017-07-14 2019-01-22 株式会社田村制作所 感光性树脂组合物
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CN111025847B (zh) * 2019-12-31 2023-07-14 阜阳欣奕华材料科技有限公司 一种感光树脂组合物、黑色矩阵和显示设备
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CN114478590A (zh) * 2022-03-31 2022-05-13 中山大学 一种超支化聚酯及其制备方法与应用
CN114478590B (zh) * 2022-03-31 2023-08-25 中山大学 一种超支化聚酯及其制备方法与应用

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