WO2017056831A1 - Composition photosensible, film durci, filtre de blocage infrarouge, filtre de transmission infrarouge, procédé de production de film durci, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, procédé de production d'élément d'imagerie à semi-conducteurs, et procédé de fabrication de capteur infrarouge - Google Patents

Composition photosensible, film durci, filtre de blocage infrarouge, filtre de transmission infrarouge, procédé de production de film durci, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, procédé de production d'élément d'imagerie à semi-conducteurs, et procédé de fabrication de capteur infrarouge Download PDF

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WO2017056831A1
WO2017056831A1 PCT/JP2016/075432 JP2016075432W WO2017056831A1 WO 2017056831 A1 WO2017056831 A1 WO 2017056831A1 JP 2016075432 W JP2016075432 W JP 2016075432W WO 2017056831 A1 WO2017056831 A1 WO 2017056831A1
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group
photosensitive composition
compound
cured film
infrared
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PCT/JP2016/075432
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English (en)
Japanese (ja)
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俊人 空花
大貴 瀧下
嶋田　和人
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a photosensitive composition, a cured film, an infrared cut filter, an infrared transmission filter, a cured film manufacturing method, a solid-state imaging device, an image display device, a solid-state imaging device manufacturing method, and an infrared sensor manufacturing method.
  • Patent Documents 1 to 4 In producing a cured film using a photosensitive composition containing a radical polymerizable compound and a photo radical polymerization initiator, after the exposure, the cured film is produced by further heat treatment (Patent Documents 1 to 4). 4). Heating after exposure is a process for sufficiently curing the film, and is often performed at a relatively high temperature of about 200 ° C.
  • JP 2010-224204 A International Publication No. 2013/065653 JP 2008-0665319 A JP 2013-097187 A
  • a cured film may be manufactured on a thin glass substrate or the like from the viewpoint of miniaturization of various apparatuses. Further, a cured film may be formed on an organic semiconductor layer such as an organic electro-renaissance (OLED), an organic field effect transistor (OFET), or an organic solar cell (OPV). Since such a base material is inferior in heat resistance, in recent years, it is required to produce a cured film on the base material inferior in heat resistance. In producing a cured film on a substrate having poor heat resistance, it is desirable to produce a cured film by, for example, a low temperature process of 150 ° C. or lower to suppress thermal damage to the substrate.
  • OLED organic electro-renaissance
  • OFET organic field effect transistor
  • OOV organic solar cell
  • an object of the present invention is to provide a photosensitive composition capable of producing a cured film in which wrinkles are less likely to occur, a cured film, an infrared cut filter, an infrared transmission filter, a method for producing a cured film, a solid-state imaging device, an image display device, a solid
  • An object of the present invention is to provide a method for manufacturing an image sensor and a method for manufacturing an infrared sensor.
  • the present invention is as follows.
  • the thermosetting compound contains a compound having an epoxy group.
  • thermosetting compound contains an epoxy resin.
  • thermosetting temperature of the thermosetting compound is 90 to 260 ° C.
  • thermosetting temperature of the thermosetting compound is 90 to 260 ° C.
  • content of the radical polymerizable compound is 1 to 80% by mass in the total solid content of the photosensitive composition.
  • ⁇ 6> The photosensitive composition according to any one of ⁇ 1> to ⁇ 5>, further containing an alkali-soluble resin.
  • ⁇ 8> The photosensitive composition according to any one of ⁇ 1> to ⁇ 7>, further containing an infrared absorber.
  • ⁇ 9> The photosensitive composition according to ⁇ 8>, which is used for producing an infrared cut filter.
  • ⁇ 10> The photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a colorant that transmits at least part of light in the infrared region and shields light in the visible region. .
  • ⁇ 11> The photosensitive composition according to ⁇ 10>, further comprising an infrared absorber.
  • ⁇ 12> The photosensitive composition according to ⁇ 10> or ⁇ 11>, which is used for producing an infrared transmission filter.
  • ⁇ 13> The photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, further containing inorganic particles.
  • ⁇ 14> A cured film obtained using the photosensitive composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> The cured film according to ⁇ 14>, wherein the cured film has a thickness of 2.5 to 100 ⁇ m.
  • ⁇ 16> An infrared cut filter obtained using the photosensitive composition according to ⁇ 9>.
  • ⁇ 17> An infrared transmission filter obtained using the photosensitive composition according to ⁇ 12>.
  • Method. ⁇ 19> A solid-state imaging device having the cured film according to ⁇ 14> or ⁇ 15>.
  • ⁇ 20> An infrared sensor having the cured film according to ⁇ 14> or ⁇ 15>.
  • a method for producing a solid-state imaging device comprising: producing a cured film by the production method according to ⁇ 18>; and heating the cured film to a temperature of 150 ° C. or higher and 300 ° C. or lower.
  • the manufacturing method of an infrared sensor including the process of heating a cured film to the temperature exceeding 150 degreeC and 300 degrees C or less.
  • Photosensitive composition capable of producing cured film that is less likely to cause wrinkles, cured film, infrared cut filter, infrared transmission filter, method for producing cured film, solid-state imaging device, image display device, method for producing solid-state imaging device, and infrared sensor It has become possible to provide a manufacturing method.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • light means actinic rays or radiation.
  • Actinic light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • exposure is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. Include drawing in exposure.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
  • “(meth) acrylate” represents both and / or acrylate and methacrylate
  • “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
  • Allyl represents both and / or allyl and methallyl
  • “(meth) acryloyl” represents both and / or acryloyl and methacryloyl.
  • Infrared light refers to light (electromagnetic wave) having a maximum absorption wavelength region of 700 to 2500 nm.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by a gel permeation chromatograph (GPC) measurement.
  • the pigment means an insoluble compound that is difficult to dissolve in a specific solvent. Typically, it means a compound that exists in a dispersed state as particles in the composition.
  • the solvent illustrated in the column of the solvent mentioned later for example is mentioned.
  • the pigment used in the present invention preferably has a solubility in propylene glycol monomethyl ether acetate at 25 ° C. of 0.02% by mass or less.
  • the photosensitive composition of the present invention is a photosensitive composition containing a radical polymerizable compound, a photo radical polymerization initiator, and a thermosetting compound, and the solid content concentration of the photosensitive composition is 25 to 80.
  • the content of the thermosetting compound is 10 to 50% by mass in the total solid content of the photosensitive composition.
  • the content of the thermosetting compound and the solid content concentration of the photosensitive composition are within the above ranges, respectively, and after producing a cured film using the photosensitive composition, Furthermore, even if the cured film after production is reheated (for example, heated to a temperature exceeding 150 ° C.), the difference in thermal shrinkage between the surface and the inside of the cured film at the time of reheating can be made difficult. Generation can be suppressed.
  • a cured film produced by a low-temperature process of 150 ° C. or lower may not be sufficiently cured inside as compared with the surface. This tendency becomes more prominent as the thickness of the cured film increases.
  • the photosensitive composition of the present invention is suitable for manufacturing a cured film with a low-temperature process, or manufacturing a thick cured film.
  • the photosensitive composition of the present invention can be preferably used for the production of an infrared cut filter or an infrared transmission filter. Since the infrared cut filter and the infrared transmission filter are often required to be a film having a large thickness in order to achieve desired optical characteristics, they are manufactured using the photosensitive composition of the present invention. Suitable for that.
  • the infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and shields light having a wavelength in the infrared region (infrared light).
  • the infrared cut filter may transmit all light having a wavelength in the visible region, and transmits light in a specific wavelength region out of light having a wavelength in the visible region, and blocks light in the specific wavelength region. It may be a thing.
  • the infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits light having an infrared wavelength (infrared).
  • the photosensitive composition used for manufacture of an infrared cut filter contains an infrared absorber at least.
  • the content of the infrared absorber is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to the total solid content of the photosensitive composition.
  • the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
  • the photosensitive composition used for manufacturing the infrared cut filter may further contain a chromatic colorant.
  • a filter having functions as an infrared cut filter and a color filter can be provided.
  • the color filter refers to a filter that allows light in a specific wavelength region to pass through and blocks light in a specific wavelength region out of light having a wavelength in the visible light region.
  • the photosensitive composition used for manufacturing the infrared transmission filter is a color material that transmits at least part of light in the infrared region and shields light in the visible region (hereinafter referred to as “color material that shields the visible region”). At least).
  • color material that shields the visible region include materials described later.
  • the content of the colorant that blocks the visible region is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less, based on the total solid content of the photosensitive composition.
  • the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
  • the photosensitive composition used for the production of the infrared transmission filter further contains an infrared absorber.
  • the infrared absorber has a role of limiting the infrared region of the transmitted light (infrared rays) to the longer wavelength side.
  • the infrared absorber for example, a compound having a maximum absorption wavelength in the range of 800 to 900 nm can be preferably used.
  • a pyrrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, or the like can be preferably used.
  • the content of the infrared absorber is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to the total solid content of the photosensitive composition.
  • the lower limit may be 0.1% by mass or more, and may be 0.5% by mass or more.
  • the content of the colorant that blocks visible light is preferably 10 to 1000 parts by mass, more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the infrared absorber.
  • the photosensitive composition used for the production of the infrared transmission filter has a ratio A / B between the minimum absorbance A in the wavelength range of 400 nm to less than 580 nm and the minimum absorbance B in the wavelength range of 580 nm to 750 nm.
  • the ratio C / D between the minimum absorbance C in the wavelength range of 400 nm to 750 nm and the maximum absorbance D in the wavelength range of 1000 nm to 1300 nm is 5 or more.
  • an infrared absorber it is also preferable to further contain an infrared absorber.
  • the infrared absorber when a compound having a maximum absorption wavelength in the range of 800 to 900 nm is used as the infrared absorber, the maximum transmittance in the wavelength range of 400 to 830 nm is 20% or less, and in the wavelength range of 1000 to 1300 nm.
  • the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
  • a ⁇ ⁇ log (T ⁇ ) (1)
  • a ⁇ is the absorbance at wavelength ⁇
  • T ⁇ is the transmittance at wavelength ⁇ .
  • the absorbance value may be a value measured in a solution state or may be a value in a film formed using a photosensitive composition.
  • the photosensitive composition is applied onto a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined film thickness, and hot at 100 ° C. for 120 seconds. It is preferable to use a membrane prepared by drying on a plate.
  • the film thickness can be measured using a stylus type film thickness meter.
  • the absorbance can be measured using a conventionally known spectrophotometer.
  • Absorbance measurement conditions are not particularly limited, but in a condition where the minimum absorbance A in the wavelength range of 400 nm to less than 580 nm is adjusted to 0.1 to 3.0, in the wavelength range of 580 nm to 750 nm. It is preferable to measure the minimum absorbance B, the minimum absorbance C in the wavelength range from 400 nm to 750 nm, and the maximum absorbance D in the wavelength range from 1000 nm to 1300 nm. By measuring the absorbance under such conditions, the measurement error can be further reduced.
  • the method for adjusting the minimum absorbance A in the wavelength range of 400 nm or more and less than 580 nm to be 0.1 to 3.0 there is no particular limitation on the method for adjusting the minimum absorbance A in the wavelength range of 400 nm or more and less than 580 nm to be 0.1 to 3.0.
  • a method of adjusting the optical path length of the sample cell can be mentioned.
  • the method etc. which adjust a film thickness are mentioned.
  • a method for measuring the spectral characteristics, film thickness and the like of the film formed from the photosensitive composition of the present invention is shown below.
  • the photosensitive composition of the present invention was applied onto a glass substrate by a method such as spin coating so that the film thickness after drying was the predetermined film thickness described above, and dried on a hot plate at 100 ° C. for 120 seconds.
  • the film thickness of the film was measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the dried substrate having the film.
  • the dried substrate having this film was measured for transmittance in the wavelength range of 300 to 1300 nm using a spectrophotometer of an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
  • the photosensitive composition of the present invention has a solid content concentration of 25 to 80% by mass.
  • the lower limit is preferably 30% by mass or more, and more preferably 35% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. If solid content concentration is the above-mentioned range, it will be easy to manufacture a thick cured film. Moreover, if solid content concentration is the said range, the amount of solvent volatilization at the time of drying can be decreased. Furthermore, the drying time after application can be shortened. For this reason, it is excellent in terms of environment and tact time. Further, the higher the solid content concentration of the photosensitive composition is, the more easily wrinkles are generated. However, according to the present invention, it is possible to produce a cured film that hardly generates wrinkles even if the solid content concentration is high. For this reason, the effect of this invention is notably acquired in the photosensitive composition with high solid content concentration.
  • the photosensitive composition of the present invention contains a radical polymerizable compound (hereinafter also referred to as a polymerizable compound).
  • the polymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the action of radicals.
  • the polymerizable compound is preferably a compound having at least one radical polymerizable group such as a group having an ethylenically unsaturated bond, more preferably a compound having two or more, and even more preferably three or more.
  • the upper limit is preferably 15 or less, and more preferably 6 or less.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
  • the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is preferably 2000 or less, and more preferably 1500 or less.
  • the lower limit is preferably 150 or more, and more preferably 250 or more.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
  • Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable.
  • the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
  • the compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.
  • Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A) -DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, SR454, SR4
  • oligomer types can also be used.
  • KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical), M-315 (manufactured by Toagosei Co., Ltd.)) can also be used. Shows a preferred embodiment of the polymerizable compound.
  • the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is also preferably a compound having a caprolactone structure.
  • the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
  • trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol Mention is made of an ⁇ -caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying (meth) acrylic acid and ⁇ -caprolactone with a polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and the like.
  • a polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and the like.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O).
  • — Each independently represents an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
  • the total of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40 .
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10
  • the total of each n is an integer of 0 to 60 .
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents oxygen
  • a form in which the end on the atom side is bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups is preferable.
  • the total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • the compound represented by the general formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
  • a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Also, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. You can also.
  • urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
  • the content of the polymerizable compound is preferably 1 to 80% by mass in the total solid content of the photosensitive composition.
  • the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the upper limit is preferably 65% by mass or less, and more preferably 50% by mass or less.
  • the photosensitive composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound.
  • the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
  • T1 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.
  • the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
  • Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable.
  • One or more polyfunctional thiol compounds can be used in combination.
  • the content of the polyfunctional thiol compound is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass with respect to the total solid content of the photosensitive composition.
  • the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
  • the photosensitive composition of the present invention contains a photo radical polymerization initiator (hereinafter also referred to as a photo polymerization initiator).
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
  • Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc.
  • trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
  • compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
  • trihalomethyltriazine compound More preferred are trihalomethyltriazine compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, ⁇ -aminoketone
  • the cured film of the present invention When the cured film of the present invention is used for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, and therefore it is important that the unexposed area is developed with no residue as well as curability. . From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
  • an oxime compound as the photopolymerization initiator.
  • stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in consideration of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator used for forming a fine pattern of a solid-state imaging device.
  • paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • More preferred examples of the photopolymerization initiator include oxime compounds.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M.
  • oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No. 7,556,910, a compound described in Japanese Patent Application Laid-Open No.
  • the oxime compound is preferably a compound represented by the following formula (OX-1).
  • the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
  • these groups may have one or more substituents.
  • the substituent mentioned above may be further substituted by another substituent.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • an oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.
  • an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
  • an oxime initiator having a nitro group can be used as a photopolymerization initiator.
  • Specific examples of the oxime initiator having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Adeka Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
  • oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably those having high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
  • a known method can be used for the molar extinction coefficient of the compound. For example, in a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
  • the content of the photopolymerization initiator is preferably 0.01 to 30% by mass with respect to the total solid content of the photosensitive composition of the present invention.
  • the lower limit is preferably 0.1% by mass or more, and more preferably 1% by mass or less.
  • the upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. Within this range, better sensitivity and pattern formability can be obtained.
  • the photosensitive composition of the present invention may contain only one type of photopolymerization initiator or two or more types. When two or more types are included, the total amount is preferably within the above range.
  • thermosetting compound means a compound that is cured by heating.
  • thermosetting start temperature of the thermosetting compound is preferably 90 to 260 ° C.
  • the lower limit is preferably 110 ° C. or higher, and more preferably 130 ° C. or higher.
  • the upper limit is preferably 260 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 230 ° C. or lower. If the thermosetting start temperature of a thermosetting compound is the said range, it will be easy to manufacture the cured film by which wrinkles were suppressed.
  • the thermosetting start temperature of the thermosetting compound means that 1 mg of a sample (thermosetting compound) is heated at a rate of temperature increase of 5 ° C./min from a state of 25 ° C. It is the temperature at which the exothermic reaction of the thermosetting compound begins, measured and measured.
  • the temperature at which the exothermic reaction of the thermosetting compound begins means the temperature at which the peak of the exothermic reaction appears in the differential scanning calorimetry curve with the vertical axis representing heat flow (mW) and the horizontal axis representing temperature (° C.). To do.
  • the peak of the exothermic reaction is 2 or more, the peak of the exothermic reaction at a low temperature is defined as “the temperature at which the exothermic reaction of the thermosetting compound begins” in the present invention.
  • thermosetting compound for example, a compound having a thermosetting functional group can be used.
  • the thermosetting compound may be a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). Either is acceptable.
  • the thermosetting compound is preferably a polymer compound, more preferably a compound having a molecular weight (weight average molecular weight) of 1,000 to 100,000.
  • thermosetting compound examples include an epoxy group-containing compound (epoxy compound), an oxetanyl group-containing compound (oxetanyl compound), a methylol group-containing compound (methylol compound), and an alkoxymethyl group-containing compound (alkoxymethyl compound).
  • an oxetanyl group-containing compound (block isocyanate compound) and the like, and an epoxy compound is preferred because it is easier to effectively suppress generation of wrinkles in the cured film.
  • a thermosetting compound is a compound which does not have a radically polymerizable group. According to this aspect, generation
  • radical polymerizable group examples include a vinyl group, a styryl group, a (meth) allyl group, a (meth) acryloyl group, and a group having an ethylenically unsaturated bond such as a (meth) acryloyl group.
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the number of epoxy groups is preferably 2 to 100 per molecule.
  • the upper limit may be 10 or less, and may be 5 or less.
  • the epoxy compound may be a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more).
  • the epoxy compound is preferably an epoxy resin.
  • the weight average molecular weight of the epoxy resin is preferably 1000 to 10,000.
  • the lower limit is preferably 1500 or more, and more preferably 2000 or more.
  • the upper limit is preferably 9000 or less, and more preferably 8000 or less.
  • the epoxy resin is preferably a compound having substantially no molecular weight distribution.
  • substantially having no molecular weight distribution means that the dispersity of the compound (weight average molecular weight (Mw) / number average molecular weight (Mn)) is 1.0 to 1.5. Is preferable, and 1.0 to 1.3 is more preferable.
  • the epoxy compound is preferably a compound having an aromatic ring and / or an aliphatic ring, and more preferably a compound having an aliphatic ring.
  • the epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group.
  • the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • the epoxy group is preferably a compound formed by directly bonding (single bond) to the aliphatic ring.
  • the epoxy group is preferably a compound formed by bonding to an aromatic ring via a linking group.
  • the linking group is preferably an alkylene group or a group comprising a combination of an alkylene group and —O—.
  • the epoxy group compound a compound having a structure in which two or more aromatic rings are connected by a hydrocarbon group may be used.
  • the hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected via the connecting group.
  • examples of the epoxy compound include compounds represented by the following formula (EP1).
  • R EP1 to R EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R EP1 and R EP2 and R EP2 and R EP3 may be bonded to each other to form a ring structure.
  • QEP represents a single bond or an nEP- valent organic group.
  • R EP1 ⁇ R EP3 combines with Q EP may form a ring structure.
  • nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n EP is 2 when Q EP is a single bond.
  • R EP1 to R EP3 and Q EP can be referred to the descriptions in paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein.
  • Specific examples of the compound represented by the formula (EP1) include the compounds described in paragraph 0090 of JP-A-2014-089408, the contents of which are incorporated herein.
  • Epoxy compounds include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy.
  • a compound having an alkoxysilyl group such as silane or 3-glycidoxypropyltriethoxysilane can also be used.
  • Examples of commercially available products include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403 (manufactured by Shin-Etsu Silicone) and the like.
  • a compound having no silicon atom for example, a compound having no alkoxysilyl group
  • the epoxy compound for example, a compound having no alkoxysilyl group
  • epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
  • Commercial products may be used for these compounds.
  • bisphenol A type epoxy resin jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1051, EPICLON1051, EPICLON1051 As mentioned above, DIC Corporation) etc. are mentioned.
  • Examples of the bisphenol F type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S. (Nippon Kayaku Co., Ltd.) and the like.
  • the phenol novolac type epoxy resin includes jER152, jER154, jER157S70, jER157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON. N-775 (above, manufactured by DIC Corporation).
  • Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • ADEKA RESIN EP-4080S, EP-4085S, EP-4088S manufactured by ADEKA
  • Celoxide 2021P Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like.
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), JER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.
  • the oxetanyl compound is preferably a compound having two or more oxetanyl groups in one molecule.
  • the number of oxetanyl groups is preferably 2 to 100 per molecule.
  • the upper limit may be 10 or less, and may be 5 or less.
  • Specific examples of the compound having two or more oxetanyl groups in one molecule include Aron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by Toagosei Co., Ltd.), ETERNACOLL (registered trademark) OXMA, ETERNACOLL (registered trademark) OXBP (manufactured by Ube Industries, Ltd.) can be used.
  • alkoxymethyl compounds, methylol compounds examples include compounds in which an alkoxymethyl group or a methylol group is bonded to a carbon atom that forms a nitrogen atom or an aromatic ring.
  • Compounds having an alkoxymethyl group or a methylol group bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethyl Urea urea, methylolated urea and the like are preferable.
  • the descriptions in paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 0095 to 0126 of JP-A-2014-089408 can be referred to, and the contents thereof are incorporated in this specification.
  • Preferable structures of the compound in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include compounds represented by the following formulas (8-1) to (8-4).
  • Examples of the compound in which an alkoxymethyl group or a methylol group is bonded to a carbon atom forming an aromatic ring include those represented by the following general formulas (4) to (5).
  • X represents a single bond or a monovalent to tetravalent organic group
  • R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group
  • n is an integer of 1 to 4.
  • p and q are each independently an integer of 0 to 4.
  • two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom
  • R 13 to R 16 are each independently a hydrogen atom.
  • m and n are each independently an integer of 1 to 3
  • p and q are each independently an integer of 0 to 4.
  • Examples of commercially available products of alkoxymethyl compounds and methylol compounds include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174. , UFR65, 300 (Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, -750LM, Nicarak MS- 11, Nicalac MW-30HM, -100LM, -390 (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.
  • Block isocyanate compound Although there is no restriction
  • the blocked isocyanate group in this invention is a group which can produce
  • the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 260 ° C.
  • the skeleton of the blocked isocyanate compound is not particularly limited, and may be an aliphatic, alicyclic or aromatic polyisocyanate.
  • the description in paragraph 0144 of JP2014-238438A can be referred to, and the contents thereof are incorporated in this specification.
  • Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. Can do.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • description in paragraph 0146 of JP2014-238438A can be referred to, and the contents thereof are incorporated in the present specification.
  • the blocked isocyanate compound is available as a commercial product.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X BL3575 / 1, BL3272MPA, BL
  • the content of the thermosetting compound is preferably 10 to 50% by mass with respect to the total solid content of the photosensitive composition of the present invention.
  • the lower limit is preferably 15% by mass or more.
  • the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. If content of a thermosetting compound is the said range, generation
  • the photosensitive composition of the present invention preferably contains 1 to 400 parts by mass of a thermosetting compound with respect to 100 parts by mass of the radical polymerizable compound.
  • the lower limit is preferably 5 parts by mass or more, and more preferably 20 parts by mass or more.
  • the upper limit is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less.
  • the photosensitive composition of the present invention may contain only one type of thermosetting compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the photosensitive composition of the present invention preferably contains a resin.
  • the resin is blended, for example, for the purpose of dispersing the pigment in the composition or the purpose of the binder.
  • the resin mainly used for dispersing the pigment in the composition is also referred to as a dispersant.
  • the resin is a material different from the radical polymerizable compound and the thermosetting compound.
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 3,000 or more, and more preferably 5,000 or more.
  • the resin content is preferably 1 to 90% by mass based on the total solid content of the photosensitive composition.
  • the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the photosensitive composition of the present invention may contain only one type of resin or two or more types of resins. When two or more types are included, the total amount is preferably within the above range.
  • the photosensitive composition of the present invention preferably contains an alkali-soluble resin as a resin. By containing an alkali-soluble resin, developability and pattern formability are improved.
  • the alkali-soluble resin can also be used as a dispersant or a binder.
  • the alkali-soluble resin is a material different from the radical polymerizable compound and the thermosetting compound.
  • the molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5000 to 100,000.
  • the upper limit is preferably less than 25000, and more preferably less than 20000.
  • the number average molecular weight (Mn) is preferably 1000 to 20,000.
  • the alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.
  • the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance.
  • Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
  • Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable. Only one type of acid group may be used, or two or more types may be used.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
  • the alkali-soluble resin a polymer having a carboxyl group in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
  • a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
  • examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
  • Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
  • an alkali-soluble resin having a polymerizable group may be used as the alkali-soluble resin.
  • the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
  • the alkali-soluble resin having a polymerizable group an alkali-soluble resin containing a polymerizable group in a side chain is useful.
  • the alkali-soluble resin containing a polymerizable group include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, KS resist).
  • the alkali-soluble resin is a monomer containing a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerizing the components.
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP 2010-168539 A can be referred to.
  • ether dimer for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
  • the structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.
  • the alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring.
  • n represents an integer of 1 to 15.
  • the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
  • the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring.
  • Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
  • alkali-soluble resin examples include the following resins.
  • Me is a methyl group.
  • the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
  • the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
  • the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.
  • the content of the alkali-soluble resin is preferably 1 to 90% by mass with respect to the total solid content of the photosensitive composition.
  • the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the photosensitive composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the photosensitive composition of this invention can contain a dispersing agent as resin.
  • the dispersant include polymer dispersants [for example, resins having amine groups (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, Modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate] and the like.
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
  • a resin having an acid value of 60 mgKOH / g or more (more preferably, an acid value of 60 mgKOH / g or more and 300 mgKOH / g or less) can also be suitably exemplified.
  • Examples of the terminal-modified polymer include a polymer having a phosphate group at the end described in JP-A-3-112992 and JP-T-2003-533455, and JP-A-2002-273191. Examples thereof include a polymer having a sulfonic acid group at the terminal and a polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
  • Examples of the graft polymer include reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like.
  • Examples thereof include a copolymer of a macromonomer and an acid group-containing monomer described in a publication.
  • Macromonomer AA-6 manufactured by Toa Gosei Co., Ltd. Acid-6
  • AS-6 polystyrene whose terminal group is a methacryloyl group
  • AN-6S a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group
  • AB-6 polyyester whose terminal group is a methacryloyl group
  • PLACEL FM5 manufactured by Daicel Corporation (2-hydroxyethyl methacrylate with 5 molar equivalents of ⁇ -caprolactone
  • FA10L 2-hydroxyethyl acrylate with 10 molar equivalents of ⁇ -caprolactone
  • polyester-based macromonomer that is particularly flexible and has excellent solvophilicity is particularly preferable from the viewpoint of dispersibility of the pigment, dispersion stability, and developability exhibited by the composition using the pigment.
  • the polyester macromonomer represented by the polyester macromonomer described in Japanese Patent Publication No. 272009 is most preferable.
  • block polymers As the block polymer, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
  • a graft copolymer containing a structural unit represented by any one of the following formulas (1) to (4) can also be used.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent organic group
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent organic group
  • R 3 represents an alkylene group
  • R 4 represents a hydrogen atom or a monovalent organic group
  • n, m, p, and q each independently represents 1 to Represents an integer of 500
  • j and k each independently represent an integer of 2 to 8
  • a plurality of R 3 may be the same or different from each other.
  • may, in the formula (4), when q is 2 ⁇ 500, X 5 and R 4 existing in plural numbers may be different
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, A methyl group is particularly preferred.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • the structure of the monovalent organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 is not particularly limited.
  • an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group examples thereof include an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable.
  • the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
  • R 3 represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms.
  • p is 2 to 500, a plurality of R 3 may be the same or different.
  • R 4 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group is not particularly limited in terms of structure.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group.
  • R 4 is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 1 to 20 carbon atoms is preferable.
  • linear alkyl groups having 1 to 6 carbon atoms are particularly preferable.
  • q is 2 to 500
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can be used.
  • the oligoimine-based dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain.
  • a resin having at least one basic nitrogen atom is preferred.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
  • the oligoimine dispersant is represented by, for example, a structural unit represented by the following formula (I-1), a structural unit represented by the formula (I-2), and / or a formula (I-2a). Examples thereof include a dispersant containing a structural unit.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms).
  • a independently represents an integer of 1 to 5; * Represents a connecting part between structural units.
  • R 8 and R 9 are the same groups as R 1 .
  • L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms).
  • an imino group preferably having a carbon number of 0 to 6
  • an ether group preferably having a carbon number of 0 to 6
  • a thioether group preferably having a carbonyl group, or a combination group thereof.
  • a single bond or —CR 5 R 6 —NR 7 — is preferable.
  • R 5 R 6 each independently represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms).
  • R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • L a is a structural site ring structure formed together with CR 8 CR 9 and N, it is preferable together with the carbon atom of CR 8 CR 9 is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom of CR 8 CR 9 and N (nitrogen atom), more preferably a 5-membered non-aromatic heterocyclic ring. It is a structural part to be formed and is particularly preferably a structural part to form pyrrolidine. This structural part may further have a substituent such as an alkyl group.
  • X represents a group having a functional group of pKa14 or less.
  • Y represents a side chain having 40 to 10,000 atoms.
  • the dispersant (oligoimine-based dispersant) further comprises at least one copolymer component selected from structural units represented by formula (I-3), formula (I-4), and formula (I-5) It may contain as.
  • the dispersant contains such a structural unit, the dispersion performance can be further improved.
  • R 1 , R 2 , R 8 , R 9 , L, La, a and * are as defined in the formulas (I-1), (I-2) and (I-2a).
  • Ya represents a side chain having an anionic group having 40 to 10,000 atoms.
  • the structural unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed.
  • oligoimine-based dispersant the description in paragraphs 0102 to 0174 of JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification.
  • resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.
  • a resin containing a structural unit represented by the following formula (P1) can also be used.
  • the dispersibility of the infrared absorber (particularly the pyrrolopyrrole compound represented by the formula (1)) can be further improved.
  • R 1 represents hydrogen or a methyl group
  • R 2 represents an alkylene group
  • Z represents a nitrogen-containing heterocyclic structure.
  • the alkylene group represented by R 2 is not particularly limited, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, 2-hydroxypropylene group, a methyleneoxy group, an ethyleneoxy group, methyleneoxy carbonyl Group, a methylenethio group, etc. are mentioned suitably, A methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, and a methylenethio group are more preferable.
  • the nitrogen-containing heterocyclic structure represented by Z is, for example, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone Examples thereof include a ring, an anthraquinone ring, a benzimidazole structure, a benzotriazole structure, a benzothiazole structure, a cyclic amide structure, a cyclic urea structure, and a cyclic imide structure.
  • the nitrogen-containing heterocyclic structure represented by Z is preferably a structure represented by the following general formula (P2) or (P3).
  • X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR—, and — Any one selected from the group consisting of C ( ⁇ O) —.
  • R represents a hydrogen atom or an alkyl group.
  • R represents an alkyl group
  • examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples thereof include t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
  • X is preferably a single bond, a methylene group, —O— or —C ( ⁇ O) —, and particularly preferably —C ( ⁇ O) —.
  • ring A, ring B, and ring C each independently represent an aromatic ring.
  • the aromatic ring include benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, phenothiazine.
  • Ring, phenoxazine ring, acridone ring, anthraquinone ring, etc. among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.
  • the resin containing the structural unit represented by the general formula (P1) may further include a structural unit represented by any one of the above formulas (1) to (4) of the resin. Further, in the above-mentioned resins (I-1), (I-2), (I-2a), (I-3), (I-4), and (I-5) A structural unit represented by any of them may be further included.
  • the dispersant is also available as a commercial product.
  • examples of such a dispersant include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 111 (containing an acid group) manufactured by BYK Chemie.
  • Copolymer 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”, EFKA Corporation “EFKA 4047, 4050-4010-4165 (polyurethane)”, EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (Fatty acid polyester), 6745 (phthalosy Nin derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No.
  • DA-705, DA-725 “ Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”manufactured by Kao Corporation,“ Homogenol L- 18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (Polymer) "Oxyethylene nonylphenyl ether)", “Acetamine 86 (stearylamine acetate)", “Solsperse 5000 (phthalocyanine derivative)", 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, manufactured by Nippon Lubrizol Co., Ltd.
  • Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester
  • anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401 manufactured by Morishita Sangyo Co., Ltd.
  • dispersants may be used alone or in combination of two or more.
  • the alkali-soluble resin described above can also be used.
  • Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain.
  • the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable.
  • An alkali-soluble resin containing is also preferred.
  • the content of the dispersing agent is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the pigment.
  • the photosensitive composition of the present invention may contain a pigment derivative.
  • the pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group.
  • a pigment derivative having an acidic group or a basic group is preferable from the viewpoint of dispersibility and dispersion stability of the pigment.
  • Organic pigments for constituting the pigment derivative include pyrrolopyrrole pigment, diketopyrrolopyrrole pigment, quinacridone pigment, anthraquinone pigment, dianthraquinone pigment, benzoisoindole pigment, thiazineindigo pigment, azo pigment, quinophthalone pigment, phthalocyanine pigment , Naphthalocyanine pigments, dioxazine pigments, perylene pigments, perinone pigments, benzimidazolone pigments, benzothiazole pigments, benzimidazole pigments and benzoxazole pigments.
  • a sulfonic acid group As an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable.
  • the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
  • Specific examples of the pigment derivative include the following.
  • the description of paragraphs 0111 to 0175 in JP-A-2015-063593 can be referred to, and the contents thereof are incorporated in this specification.
  • the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass with respect to the mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
  • the photosensitive composition of the present invention can contain a chromatic colorant.
  • the chromatic colorant means a colorant other than the white colorant and the black colorant.
  • the chromatic colorant is preferably a colorant having a maximum absorption wavelength in a wavelength range of 400 nm or more and less than 650 nm.
  • the chromatic colorant may be a pigment or a dye, and a pigment is preferred.
  • the pigment preferably has an average particle diameter (r) of preferably 20 nm ⁇ r ⁇ 300 nm, more preferably 25 nm ⁇ r ⁇ 250 nm, and particularly preferably 30 nm ⁇ r ⁇ 200 nm.
  • the “average particle size” here means the average particle size of secondary particles in which primary particles of the pigment are aggregated.
  • the particle size distribution of the secondary particles of the pigment that can be used (hereinafter also simply referred to as “particle size distribution”) is such that the secondary particles falling into (average particle size ⁇ 100) nm are 70% by mass or more of the whole, Preferably it is 80 mass% or more.
  • the particle size distribution of the secondary particles can be measured using the scattering intensity distribution.
  • TEM transmission electron microscope
  • the pigment is preferably an organic pigment, and examples thereof include the following. However, the present invention is not limited to these. Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 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, 175, 176, 177, 179, 180, 181, 182, 185,
  • the dye is not particularly limited, and a known dye can be used.
  • the chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene, phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
  • an acid dye and / or a derivative thereof may be suitably used.
  • direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
  • acid dye examples include the following dyes and derivatives of these dyes.
  • acid alizarin violet N acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1, acid chroma violet K, acid Fuchsin; acid green 1,3,5,9,16,25,27,50, acid orange 6,7,8,10,12,50,51,52,56,63,74,95, acid red 1,4,8,14,17,18,26,27,29,31,34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143
  • azo, xanthene and phthalocyanine acid dyes are also preferred.
  • I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.
  • the dye triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo
  • a colorant selected from anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene is preferable. Further, pigments and dyes may be used in combination.
  • the content of the chromatic colorant is preferably 30% by mass or less, and preferably 20% by mass or less, based on the total solid content of the photosensitive composition. More preferred is 15% by mass or less.
  • the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
  • the photosensitive composition of this invention can also be made into the aspect which does not contain a chromatic color agent substantially. “Contain substantially no chromatic colorant” means that the content of the chromatic colorant is preferably 0.005% by mass or less, preferably 0.001% by mass or less, based on the total solid content of the photosensitive composition of the present invention. Is more preferable, and it is more preferable not to contain a chromatic colorant.
  • the photosensitive composition of the present invention can also contain a colorant that blocks visible light.
  • This photosensitive composition can be preferably used, for example, as a composition for forming an infrared transmission filter.
  • the color material that blocks visible light is preferably composed of a pigment. Further, in the color material that blocks visible light, the pigment content is preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 99% by mass or more with respect to the total mass of the color material that blocks visible light. Is more preferable.
  • the color material that shields visible light preferably exhibits black, gray, or a color close to them by a combination of a plurality of color materials. Moreover, it is preferable that the color material which shields a visible region is a material which absorbs light in a purple to red wavelength region.
  • the color material that blocks light in the visible range is preferably a color material that blocks light in the wavelength range of 450 to 650 nm.
  • the colorant that blocks the visible region preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies the requirement (1).
  • (2) An embodiment containing an organic black colorant.
  • the organic black colorant as a colorant for shielding the visible region means a material that absorbs light in the visible region but transmits at least part of the light in the infrared region. Therefore, in the present invention, the organic black colorant as a colorant for shielding the visible region is a material different from the black pigment described later. That is, the organic black colorant in the present invention does not include carbon black and titanium black, which are black colorants that absorb both light in the infrared region and light in the visible region.
  • Examples of chromatic colorants include those described above.
  • Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.
  • Examples of the bisbenzofuranone compounds include those described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available.
  • Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like.
  • Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.
  • the bisbenzofuranone compound is preferably a compound represented by the following general formula or a mixture thereof.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent
  • R 3 and R 4 each independently represent a substituent
  • a and b each independently represent Represents an integer of 0 to 4, and when a is 2 or more, a plurality of R 3 may be the same or different, and a plurality of R 3 may be bonded to form a ring; When b is 2 or more, the plurality of R 4 may be the same or different, and the plurality of R 4 may be bonded to form a ring.
  • the substituents represented by R 1 to R 4 are a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR 301 , —COR 302 , —COOR 303 , —OCOR 304 , —NR 305 R 306 , —NHCOR 307 , —CONR 308 R 309 , —NHCONR 310 R 311 , —NHCOOR 312 , —SR 313 , —SO 2 R 314 , —SO 2 OR 315 , —NHSO 2 R 316 or —SO 2 NR 317 R 318 , each of R 301 to R 318 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group
  • the halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group preferably has 1 to 12 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • the alkenyl group preferably has 2 to 12 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic.
  • the alkynyl group preferably has 2 to 12 carbon atoms.
  • the alkynyl group may be linear or branched.
  • the aryl group preferably has 6 to 12 carbon atoms.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • the alkenyl group has preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic.
  • the alkynyl group has preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkynyl group may be linear or branched.
  • the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and most preferably 6 to 12 carbon atoms.
  • the alkyl part of the aralkyl group is the same as the above alkyl group.
  • the aryl part of the aralkyl group is the same as the above aryl group.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.
  • the heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
  • the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12.
  • the colorant that blocks light in the visible range has an A / B that is a ratio of the minimum absorbance A in the wavelength range of 450 to 650 nm and the minimum absorbance B in the wavelength range of 900 to 1300 nm, for example. It is preferable that it is 4.5 or more.
  • the above characteristics may be satisfied by one kind of material, or may be satisfied by a combination of a plurality of materials. For example, in the case of the above aspect (1), it is preferable that a plurality of chromatic colorants are combined to satisfy the spectral characteristics.
  • the chromatic colorant is a chromatic colorant, a red colorant, a green colorant, a blue colorant, a yellow colorant, or a purple color. It is preferable that it is a colorant chosen from an agent and an orange colorant.
  • Examples of combinations of chromatic colorants in the case of forming a color material that shields the visible region from a combination of two or more chromatic colorants include the following. (1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant and a red colorant. (2) Embodiment containing yellow colorant, blue colorant and red colorant (3) Embodiment containing yellow colorant, purple colorant and red colorant (4) Embodiment containing yellow colorant and purple colorant (5) Embodiment containing green colorant, blue colorant, purple colorant and red colorant (6) Embodiment containing purple colorant and orange colorant (7) Green colorant, purple colorant and red coloration (8) A mode containing a green colorant and a red colorant.
  • Specific examples of the above aspect (1) include C.I. I. Pigment Yellow 139 or 185 and C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment Violet 23 and C.I. I. And an embodiment containing Pigment Red 254 or 224.
  • Specific examples of the aspect (2) include C.I. I. Pigment Yellow 139 or 185 and C.I. I. Pigment Blue 15: 6 and C.I. I. And an embodiment containing Pigment Red 254 or 224.
  • Specific examples of the above aspect (3) include C.I. I. Pigment Yellow 139 or 185 and C.I. I. Pigment Violet 23 and C.I. I. And an embodiment containing Pigment Red 254 or 224.
  • Specific examples of the above aspect (4) include C.I. I.
  • Specific examples of the above aspect (5) include C.I. I. Pigment Green 7 or 36 and C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment Violet 23 and C.I. I. And an embodiment containing Pigment Red 254 or 224.
  • Specific examples of the above aspect (6) include C.I. I. Pigment Violet 23 and C.I. I. The aspect containing Pigment Orange 71 is mentioned.
  • Specific examples of the above (7) include C.I. I. Pigment Green 7 or 36 and C.I. I. Pigment Violet 23 and C.I. I. And an embodiment containing Pigment Red 254 or 224.
  • Specific examples of the above (8) include C.I. I. Pigment Green 7 or 36 and C.I. I. And an embodiment containing Pigment Red 254 or 224.
  • ratio (mass ratio) of each colorant examples include the following.
  • the content of the color material that blocks visible light is preferably 30% by mass or less based on the total solid content of the photosensitive composition. 20 mass% or less is more preferable, and 15 mass% or less is still more preferable.
  • the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
  • the photosensitive composition of this invention can also be set as the aspect which does not contain the coloring material which light-shields visible light substantially. “Containing substantially no chromatic colorant” means that the content of the colorant that blocks visible light is preferably 0.005% by mass or less in the total solid content of the photosensitive composition of the present invention, and 0.001. It is more preferable that the content is not more than mass%, and it is more preferable that no chromatic colorant is contained.
  • the photosensitive composition of the present invention can contain an infrared absorber.
  • This photosensitive composition can be preferably used, for example, as a composition for forming an infrared cut filter or an infrared transmission filter.
  • the infrared absorber has absorption in the wavelength region of the infrared region (preferably, a wavelength range of 700 to 1200 nm) and has a wavelength in the visible region (preferably, a wavelength range of 400 to 650 nm).
  • a compound that transmits light is preferably a compound having a maximum absorption wavelength in the range of 700 to 1200 nm, more preferably a compound having a range of 700 to 1000 nm.
  • the infrared absorber used in the composition for forming an infrared transmission filter for example, a compound having a range of 800 to 900 nm is preferable.
  • infrared absorbers examples include copper compounds, cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, diimmonium compounds, thiol complex compounds, transition metal oxide compounds, quaterrylene compounds, and croconium compounds.
  • a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a diimmonium compound are preferred, a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound are more preferred, and a pyrrolopyrrole compound Is more preferable.
  • the pyrrolopyrrole compound may be a pigment or a dye.
  • Examples of the pyrrolopyrrole compound include pyrrolopyrrole compounds described in JP-A 2009-263614, paragraphs 0016 to 0058, and the like.
  • As the cyanine compound, phthalocyanine compound, diimmonium compound, squarylium compound, and croconium compound the compounds described in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used, the contents of which are incorporated herein. .
  • cyanine compound for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. It is.
  • phthalocyanine-based compound the description in paragraphs 0013 to 0029 of JP2013-195480A can be referred to, and the contents thereof are incorporated herein.
  • the pyrrolopyrrole compound is preferably a compound represented by the following formula (1).
  • This compound is excellent in near-infrared absorptivity and invisibility.
  • R 1a and R 1b each independently represent an alkyl group, an aryl group or a heteroaryl group
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent
  • R 2 and R 3 are They may be bonded to each other to form a ring
  • each R 4 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR 4A R 4B , or a metal atom
  • R 4 represents R At least one selected from 1a , R 1b and R 3 may be covalently or coordinately bonded, and R 4A and R 4B each independently represent a substituent.
  • R 1a and R 1b each independently represents an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
  • the alkyl group represented by R 1a and R 1b preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • the number of carbon atoms of the aryl group represented by R 1a and R 1b is preferably 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12.
  • the number of carbon atoms constituting the heteroaryl group represented by R 1a and R 1b is preferably from 1 to 30, and more preferably from 1 to 12.
  • hetero atom which comprises a heteroaryl group
  • a nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned, for example.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2.
  • the heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the alkyl group, aryl group, and heteroaryl group described above may have a substituent, may have a substituent, or may be unsubstituted. It preferably has a substituent.
  • the substituent examples include the groups exemplified for the substituent T described later. Of these, an alkoxy group and a hydroxy group are preferable.
  • the alkoxy group is preferably an alkoxy group having a branched alkyl group.
  • the group represented by R 1a or R 1b is preferably an aryl group having an alkoxy group having a branched alkyl group as a substituent or an aryl group having a hydroxy group as a substituent.
  • the branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.
  • R 1a and R 1b in the general formula (1) may be the same as or different from each other.
  • R 2 and R 3 each independently represents a hydrogen atom or a substituent.
  • R 2 and R 3 may combine to form a ring.
  • At least one of R 2 and R 3 is preferably an electron withdrawing group.
  • R 2 and R 3 preferably each independently represent a cyano group or a heteroaryl group.
  • Examples of the substituent include those described in JP-A 2009-263614, paragraphs 0020 to 0022. The above contents are incorporated in the present specification.
  • the following substituent T can be mentioned as an example of a substituent.
  • Alkyl group (preferably 1 to 30 carbon atoms), alkenyl group (preferably 2 to 30 carbon atoms), alkynyl group (preferably 2 to 30 carbon atoms), aryl group (preferably 6 to 30 carbon atoms), amino group (Preferably 0 to 30 carbon atoms), alkoxy group (preferably 1 to 30 carbon atoms), aryloxy group (preferably 6 to 30 carbon atoms), heteroaryloxy group (preferably 1 to 30 carbon atoms), acyl A group (preferably having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms), an acyloxy group (preferably having 2 to 30 carbon atoms), Acylamino group (preferably having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms), aryloxycarbonylamino group Preferably 7 to 30 carbon atoms
  • the carboxyl group may be dissociated from a hydrogen atom (that is, a carbonate group) or may be in a salt state.
  • the sulfo group may be dissociated from hydrogen atoms (that is, a sulfonate group) or may be in a salt state.
  • these groups may further have a substituent. Examples of the substituent include the groups described above for the substituent T.
  • At least one of R 2 and R 3 is preferably an electron-withdrawing group.
  • a substituent having a positive Hammett ⁇ p value acts as an electron withdrawing group.
  • a substituent having a Hammett ⁇ p value of 0.2 or more can be exemplified as an electron withdrawing group.
  • the ⁇ p value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more.
  • the upper limit is not particularly limited, but is preferably 0.80.
  • cyano group (0.66), carboxyl group (—COOH: 0.45), alkoxycarbonyl group (—COOMe: 0.45), aryloxycarbonyl group (—COOPh: 0.44), carbamoyl.
  • a group (—CONH 2 : 0.36), an alkylcarbonyl group (—COMe: 0.50), an arylcarbonyl group (—COPh: 0.43), an alkylsulfonyl group (—SO 2 Me: 0.72), or And arylsulfonyl group (—SO 2 Ph: 0.68).
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • the Hammett's substituent constant ⁇ value for example, paragraphs 0017 to 0018 of JP 2011-68731 A can be referred to, and the contents thereof are incorporated herein.
  • R 2 and R 3 are bonded to each other to form a ring, it is preferable to form a 5- to 7-membered ring (preferably a 5- or 6-membered ring).
  • the ring formed is preferably a merocyanine dye that is used as an acidic nucleus, and specific examples thereof can include, for example, paragraphs 0019 to 0021 of JP 2011-68731 A, the contents of which are incorporated herein. It is.
  • R 2 represents an electron-withdrawing group (preferably a cyano group), and R 3 preferably represents a heteroaryl group.
  • the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
  • the heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heteroaryl group preferably has one or more nitrogen atoms.
  • the number of carbon atoms constituting the heteroaryl group is preferably 1 to 30, and more preferably 1 to 12.
  • Specific examples of the heteroaryl group include imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, triazyl group, quinolyl group, quinoxalyl group, isoquinolyl group, indolenyl group, furyl group, thienyl group, benzoxazolyl group.
  • the heteroaryl group may have a substituent or may be unsubstituted.
  • substituents include the groups described above for the substituent T.
  • an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned.
  • Two R 2 in the formula (1) may be the same as or different from each other, and two R 3 may be the same as or different from each other.
  • R 4 represents an alkyl group, an aryl group, or a heteroaryl group
  • the alkyl group, aryl group, and heteroaryl group have the same meanings as those described for R 1a and R 1b , and the preferred ranges are also the same.
  • R 4A and R 4B each independently represent a substituent.
  • substituent represented by R 4A and R 4B include the substituent T described above, and a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, and an alkyl group, an aryl group, or a hetero group is preferable.
  • An aryl group is more preferable, and an aryl group is particularly preferable.
  • Specific examples of the group represented by —BR 4A R 4B include difluoroboron, diphenylboron, dibutylboron, dinaphthylboron, and catecholboron. Of these, diphenylboron is particularly preferred.
  • R 4 represents a metal atom
  • examples of the metal atom include magnesium, aluminum, calcium, barium, zinc, tin, aluminum, zinc, tin, vanadium, iron, cobalt, nickel, copper, palladium, iridium, and platinum.
  • Aluminum, zinc, vanadium, iron, copper, palladium, iridium and platinum are particularly preferable.
  • R 4 may be covalently bonded or coordinated to at least one of R 1a , R 1b and R 3 , and it is particularly preferable that R 4 is coordinated to R 3 .
  • R 4 is preferably a hydrogen atom or a group represented by —BR 4A R 4B (particularly diphenylboron). Two R 4 in the formula (1) may be the same or different.
  • the compound represented by the formula (1) is more preferably a compound represented by the following formula (1A).
  • each R 10 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR 14A R 14B or a metal atom.
  • R 10 may be covalently bonded or coordinated to R 12 .
  • R 11 and R 12 each independently represent a hydrogen atom or a substituent, at least one of which is a cyano group, and R 11 and R 12 may combine to form a ring.
  • R 13 each independently represents a hydrogen atom or a branched alkyl group having 3 to 30 carbon atoms.
  • R 10 has the same meaning as R 4 described in the above formula (1), and the preferred range is also the same.
  • a hydrogen atom or a group represented by —BR 14A R 14B (particularly diphenylboron) is preferred, and a group represented by —BR 14A R 14B is particularly preferred.
  • R 11 and R 12 have the same meanings as R 2 and R 3 described in (1) above, and preferred ranges are also the same. More preferably, one of R 11 and R 12 is a cyano group and the other is a heteroaryl group.
  • R 14A and R 14B have the same meanings as R 4A and R 4B described in (1) above, and preferred ranges are also the same.
  • R 13 each independently represents a hydrogen atom or a branched alkyl group having 3 to 30 carbon atoms. The number of carbon atoms in the branched alkyl group is more preferably 3-20.
  • the squarylium compound is preferably a compound represented by the following formula (11). This compound is excellent in near-infrared absorptivity and invisibility.
  • a 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by the following General Formula (12);
  • Z 1 represents a nonmetallic atom group forming a nitrogen-containing heterocycle
  • R 2 represents an alkyl group, an alkenyl group or an aralkyl group
  • d represents 0 or 1
  • a 1 and A 2 in the general formula (11) each independently represent an aryl group, a heteroaryl group or a group represented by the general formula (12), and a group represented by the general formula (12) is preferable.
  • the number of carbon atoms of the aryl group represented by A 1 and A 2 is preferably 6 to 48, more preferably 6 to 24, and particularly preferably 6 to 12. Specific examples include a phenyl group and a naphthyl group. When the aryl group has a substituent, the carbon number of the aryl group means the number excluding the carbon number of the substituent.
  • the heteroaryl group represented by A 1 and A 2 is preferably a 5-membered ring or a 6-membered ring.
  • the heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations, a single ring or a condensed ring.
  • a condensed ring having 2 or 3 is more preferable.
  • a hetero atom which comprises a heteroaryl group a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, and a nitrogen atom and a sulfur atom are preferable.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2.
  • aryl group and heteroaryl group may have a substituent.
  • substituents include the substituent T described in the above-described pyrrolopyrrole compound.
  • the substituent that the aryl group and heteroaryl group may have is preferably a halogen atom, an alkyl group, a hydroxy group, an amino group, or an acylamino group.
  • the halogen atom is preferably a chlorine atom.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5, and most preferably 1 to 4.
  • the alkyl group is preferably linear or branched.
  • the amino group is preferably a group represented by —NR 100 R 101 .
  • R 100 and R 101 each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl group is preferably linear or branched, and more preferably linear.
  • the acylamino group is preferably a group represented by —NR 102 —C ( ⁇ O) —R 103 .
  • R102 represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
  • R 103 represents an alkyl group.
  • the number of carbon atoms of the alkyl group represented by R 102 and R 103 is preferably 1-20, more preferably 1-10, still more preferably 1-5, and particularly preferably 1-4.
  • the plurality of substituents may be the same or different.
  • R 2 represents an alkyl group, an alkenyl group or an aralkyl group, and an alkyl group is preferable.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms.
  • the alkyl group and the alkenyl group may be linear, branched or cyclic, and are preferably linear or branched.
  • the aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms.
  • the nitrogen-containing heterocycle formed by Z 1 is preferably a 5-membered ring or a 6-membered ring.
  • the nitrogen-containing heterocycle is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations. Or the condensed ring of 3 is more preferable.
  • the nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to the nitrogen atom.
  • the nitrogen-containing heterocycle may have a substituent. Examples of the substituent include the groups described in the above-described substituent T.
  • a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable.
  • the halogen atom is preferably a chlorine atom.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms.
  • the alkyl group is preferably linear or branched.
  • the group represented by the general formula (12) is preferably a group represented by the following general formula (13) or (14).
  • R 11 represents an alkyl group, an alkenyl group or an aralkyl group
  • R 12 represents a substituent
  • m is 2 or more
  • R 12 are linked to each other.
  • X may represent a nitrogen atom or CR 13 R 14
  • R 13 and R 14 each independently represent a hydrogen atom or a substituent
  • m is an integer of 0 to 4
  • the wavy line represents the connecting hand with the general formula (11).
  • R 11 in the general formulas (13) and (14) has the same meaning as R 2 in the general formula (12), and the preferred range is also the same.
  • R 12 in the general formulas (13) and (14) represents a substituent.
  • the substituent include the groups described above for the substituent T.
  • a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable.
  • the halogen atom is preferably a chlorine atom.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms.
  • the alkyl group is preferably linear or branched.
  • R 12 may be linked to form a ring.
  • the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring.
  • the ring may be monocyclic or multicyclic.
  • the linking group is a group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. They can be linked by a divalent linking group selected from the above.
  • R 12 are connected to each other to form a benzene ring.
  • X in the general formula (13) represents a nitrogen atom or CR 13 R 14
  • R 13 and R 14 each independently represent a hydrogen atom or a substituent.
  • substituents include the groups described above for the substituent T.
  • an alkyl group etc. are mentioned.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1.
  • the alkyl group is preferably linear or branched, and particularly preferably linear.
  • m represents an integer of 0 to 4, preferably 0 to 2.
  • squarylium compound examples include compounds described in JP-A-2011-208101, paragraphs 0044 to 0049, the contents of which are incorporated herein.
  • the cyanine compound is preferably a compound represented by the following formula (A). This compound is excellent in near-infrared absorptivity and invisibility.
  • Formula (A) In the general formula (A), Z 1 and Z 2 are each independently a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed, and R 1 and R 2 are Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, L 1 represents a methine chain having an odd number of methine groups, and a and b each independently represent 0 or 1 And
  • X 1 represents an anion
  • c represents the number necessary for balancing the charge
  • the site represented by Cy in the formula is an anion moiety.
  • X 1 represents a cation
  • c represents a number necessary
  • Z 1 and Z 2 each independently represent a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed.
  • the nitrogen-containing heterocycle may be condensed with another heterocycle, aromatic ring or aliphatic ring.
  • the nitrogen-containing heterocycle is preferably a 5-membered ring. More preferably, a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring.
  • nitrogen-containing heterocycle examples include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazodibenzobenzofuran ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenine ring, Examples include benzoindolenin ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolizine ring, imidazoquinoxaline ring, quinoxaline ring, quinoline ring, indolenine ring Benzoindolenine ring, benzoxazole ring, benzothiazole ring and benzimi
  • the nitrogen-containing heterocyclic ring and the ring condensed thereto may have a substituent.
  • substituents include the substituents described in G A and G B of the general formula (15) described above. Specifically, halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, —OR 10 , —COR 11 , —COOR 12 , —OCOR 13 , — NR 14 R 15 , —NHCOR 16 , —CONR 17 R 18 , —NHCONR 19 R 20 , —NHCOOR 21 , —SR 22 , —SO 2 R 23 , —SO 2 OR 24 , —NHSO 2 R 25 or —SO 2 NR 26 R 27 may be mentioned.
  • R 10 to R 27 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group.
  • R 12 of —COOR 12 is hydrogen (ie, a carboxyl group)
  • the hydrogen atom may be dissociated (ie, a carbonate group) or may be in a salt state.
  • R 24 of —SO 2 OR 24 is a hydrogen atom (ie, a sulfo group)
  • the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in a salt state.
  • the alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted.
  • substituents include the groups described in the above-mentioned substituent group T, preferably a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amino group, etc., more preferably a carboxyl group and a sulfo group, and a sulfo group.
  • the group is particularly preferred.
  • the carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state.
  • R 1 and R 2 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkynyl group has preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 25 carbon atoms.
  • the alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the alkyl part of the aralkyl group is the same as the above alkyl group.
  • the aryl part of the aralkyl group is the same as the above aryl group.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.
  • the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group.
  • a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable.
  • the carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state.
  • L 1 represents a methine chain having an odd number of methine groups.
  • L 1 is preferably a methine chain having 3, 5, or 7 methine groups, and more preferably a methine chain having 5 or 7 methine groups.
  • the methine group may have a substituent.
  • the methine group having a substituent is preferably a central (meso-position) methine group.
  • Specific examples of the substituent include a substituent that the nitrogen-containing heterocycle of Z 1 and Z 2 may have, and a group represented by the following formula (a). Further, two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.
  • * represents a connecting part with a methine chain
  • a 1 represents an oxygen atom or a sulfur atom.
  • a and b are each independently 0 or 1. When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. Both a and b are preferably 0. When both a and b are 0, the general formula (A) is expressed as follows.
  • X 1 is an anion
  • c is represents a number necessary to balance the charge.
  • anions include halide ions (Cl ⁇ , Br ⁇ , I ⁇ ), para-toluenesulfonate ions, ethyl sulfate ions, PF 6 ⁇ , BF 4 ⁇ or ClO 4 ⁇ , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF 3 SO 2 ) 3 C ⁇ ), di (halogenoalkylsulfonyl) imide anion (for example, (CF 3 SO 2 ) 2 N ⁇ ), tetracyanoborate anion and the like can be mentioned.
  • X 1 represents a cation
  • c is represents a number necessary to balance the charge.
  • the cation include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+ etc.), transition metal ions (Ag + , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ ), other metal ions (such as Al 3+ ), ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion, tetrabutylammonium Ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium and the like.
  • Examples of the cyanine compound include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267 and compounds described in paragraphs 0026 to 0030 of JP-A No. 2002-194040, the contents of which are described in this specification. It will be incorporated.
  • the diimmonium compound is preferably a compound represented by the following formula (Im).
  • each of R 11 to R 18 independently represents an alkyl group or an aryl group
  • each of V 11 to V 15 independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group, or a cyano group
  • X represents an anion
  • c represents a number necessary for balancing the charge
  • n1 to n5 are each independently 0 to 4.
  • R 11 to R 18 each independently represents an alkyl group or an aryl group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
  • the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the alkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above for the substituent T.
  • V 11 to V 15 each independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group or a cyano group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
  • the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkoxy group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
  • N1 to n5 are each independently 0 to 4.
  • n1 to n4 are preferably 0 to 2, and more preferably 0 or 1.
  • n5 is preferably from 0 to 3, and more preferably from 0 to 2.
  • diimmonium compound examples include compounds described in JP-T-2008-528706, and the contents thereof are incorporated in the present specification.
  • the phthalocyanine compound is preferably a compound represented by the following formula (PC).
  • X 1 to X 16 each independently represents a hydrogen atom or a substituent, and M 1 represents Cu, V ⁇ O, or Ti ⁇ O.
  • Examples of the substituent represented by X 1 to X 16 include the groups described above for the substituent T, and are preferably an alkyl group, a halogen atom, an alkoxy group, a phenoxy group, an alkylthio group, a phenylthio group, an alkylamino group, and an anilino group. .
  • the number of substituents is preferably 0 to 16, more preferably 0 to 4, still more preferably 0 to 1, and particularly preferably 0.
  • M 1 is preferably Ti ⁇ O.
  • oxytitanium phthalocyanine (a compound in which M 1 in the formula (PC) is Ti ⁇ O) is preferable. Further, for example, there are compounds described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated herein.
  • the naphthalocyanine compound is preferably a compound represented by the following formula (NPC).
  • NPC general formula
  • X 1 to X 24 each independently represents a hydrogen atom or a substituent
  • M 1 represents Cu or V ⁇ O.
  • substituent represented by X 1 to X 24 include the groups described in the above-mentioned substituent group T, and include an alkyl group, a halogen atom, an alkoxy group, a phenoxy group, an alkylthio group, a phenylthio group, an alkylamino group, and an anilino group.
  • Examples of naphthalocyanine compounds include the compounds described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated herein.
  • the content of the infrared absorber is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the photosensitive composition. 15% by mass or less is more preferable.
  • the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
  • the photosensitive composition of the present invention contains a chromatic colorant and an infrared absorber, the total content of the chromatic colorant and the infrared absorber is based on the total solid content of the photosensitive composition. 30 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is still more preferable.
  • the lower limit may be 0.1% by mass or more, and may be 0.5% by mass or more.
  • the photosensitive composition of the present invention contains a colorant that blocks visible light and an infrared absorber
  • the total content of the colorant and infrared absorber that blocks visible light is determined by the photosensitive composition.
  • the total solid content is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
  • the lower limit may be 0.1% by mass or more, and may be 0.5% by mass or more.
  • the content of the coloring material that blocks visible light is preferably 10 to 1000 parts by mass, more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the infrared absorber.
  • the photosensitive composition of this invention can also be made into the aspect which does not contain an infrared absorber substantially.
  • Constaining substantially no infrared absorber means that the content of the infrared absorber is preferably 0.005% by mass or less and more preferably 0.001% by mass or less in the total solid content of the photosensitive composition of the present invention. Preferably, no chromatic colorant is contained.
  • the photosensitive composition of the present invention may contain inorganic particles.
  • the inorganic particles include black pigments, white pigments, and transparent particles.
  • the white pigment is not particularly limited, and known pigments can be used.
  • basic lead carbonate (2PbCO 3 Pb (OH) 2 so-called silver white
  • zinc oxide ZnO, so-called zinc white
  • titanium oxide TiO 2 , so-called titanium white
  • Strontium titanate SrTiO 3 , so-called titanium strontium white
  • hollow particles and the like.
  • Titanium oxide has a smaller specific gravity than other white pigments, a large refractive index, and is chemically and physically stable. Therefore, it has high hiding power and coloring power as a pigment. Excellent environmental durability. Therefore, it is preferable to use titanium oxide as the white pigment. Of course, other white pigments (may be other than the listed white pigments) may be used as necessary.
  • Titanium oxide is not particularly limited, and can be appropriately selected from known titanium oxides used as white pigments. Both rutile titanium oxide and anatase titanium oxide can be used, but rutile titanium oxide is preferably used because of its low catalytic activity and excellent stability over time. Titanium oxide is commercially available.
  • Tipaque CR60-2 Tipaque A-220 (both manufactured by Ishihara Sangyo Co., Ltd.), KRONOS 1001, 1014, 1071, 1074, 1075, 1077, 1078, 1080, 1171, 2044, 2047, 2056, 2063, 2080, 2081, 2084, 2087, 2160, 2190, 2211, 2202, 2222, 2225, 2230, 2233, 2257, 2300, 2310, 2450, 2500, 3000, 3025 (all of which are KRONOS For example).
  • the white pigment may be surface-treated as necessary. Specifically, for example, silica, alumina, zinc, zirconia, or organic matter treatment is performed, and weather resistance and lipophilicity differ depending on the treatment method. In the present invention, those treated with alumina, zinc, zirconia, or basic organic substances are preferred.
  • the hollow particles include hollow polymer particles. Examples of the hollow polymer particles include resin particles in which the inside of the particles is hollow, and examples thereof include those described in JP2009-35672A. Moreover, the hollow particle is marketed, for example, SX866 (A) (made by JSR Corporation) etc. can be illustrated.
  • Black pigment The black pigment is not particularly limited, and known ones can be used. Examples thereof include carbon black, titanium black, and graphite. Carbon black and titanium black are preferable, and titanium black is particularly preferable. Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water-repellent substance as disclosed in JP-A-2007-302836 is also possible. Is possible.
  • Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small. Specifically, the average primary particle size is preferably in the range of 10 nm to 45 nm.
  • the particle diameter that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.
  • the specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is used in order that the water repellency after the surface treatment of titanium black with a water repellent becomes a predetermined performance. It is preferably 5 m 2 / g or more and 150 m 2 / g or less, and more preferably 20 m 2 / g or more and 120 m 2 / g or less.
  • Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
  • Titanium black can also be used as a dispersion.
  • a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50, and the like can be mentioned.
  • the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
  • the transparent particles are preferably one or more oxides selected from the group consisting of Si, Ti, Zr, Al and Sn, and one or more oxides selected from Ti, Al and Sn. More preferably, the oxide is one or two oxides selected from Ti and Al. Specific examples of the oxide include TiO 2 , Al 2 O 3 , SiO 2 , SnO, SnO 2 and the like.
  • the transparent particles preferably have an average particle size of 1 to 200 nm, more preferably 10 to 100 nm.
  • the average particle diameter of the colorless transparent particles can be obtained from the photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom to obtain the average particle size (usually, 300 or more particles are measured in order to obtain the average particle size).
  • the primary particle diameter of the transparent particles is preferably 1 to 100 nm, and more preferably 1 to 60 nm.
  • the refractive index of the transparent particles is preferably 1.6 to 2.8, more preferably 1.7 to 2.7, and most preferably 1.8 to 2.7.
  • the specific surface area of the transparent particles is preferably 10 to 2000 m 2 / g, more preferably 20 to 1800 m 2 / g, and most preferably 40 to 1500 m 2 / g.
  • the transparent particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as they satisfy a predetermined particle size.
  • the shape is most preferably a spherical shape, but may be a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape.
  • commercially available particles can be preferably used. For example, Ishihara Sangyo Co., Ltd.
  • TTO series TTO-51 (A), TTO-51 (C), etc.
  • TTO-S V series
  • TTO-S-1, TTO-S-2, TTO-V-3) Etc. TTO-S-1, TTO-S-2, TTO-V-3) Etc.
  • MT series MT-01, MT-05, etc. manufactured by Teika Co., Ltd.
  • the content of inorganic particles is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the photosensitive composition, 15 A mass% or less is more preferable.
  • the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
  • the total content of the inorganic particles, the chromatic colorant, and the infrared absorber described above is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the photosensitive composition. 15 mass% or less is still more preferable.
  • the lower limit may be 0.1% by mass or more, and may be 0.5% by mass or more.
  • the photosensitive composition of this invention can also be made into the aspect which does not contain an inorganic particle substantially.
  • Consing substantially no inorganic particles means that the content of inorganic particles is preferably 0.005% by mass or less, more preferably 0.001% by mass or less in the total solid content of the photosensitive composition of the present invention, More preferably, it does not contain inorganic particles.
  • the photosensitive composition of the present invention can contain a solvent.
  • the solvent include water and organic solvents.
  • the solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition, but is preferably selected in consideration of the applicability and safety of the composition.
  • Examples of organic solvents include the following.
  • Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxy Alkyl acetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (For example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
  • 2-oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • diethylene glycol dimethyl ether tetrahydrofuran
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate
  • diethylene glycol monomethyl ether diethylene glycol monoethyl ether, diethylene glycol monobutyl ether
  • propylene glycol monomethyl ether propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.
  • ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons
  • Preferred examples include toluene and xylene.
  • An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
  • the content of the solvent is preferably such that the total solid content of the photosensitive composition is 25 to 80% by mass.
  • the lower limit is preferably 30% by mass or less, and more preferably 35% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the photosensitive composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the crosslinkable compound during the production or storage of the composition.
  • Polymerization inhibitors include hydroquinone, para-methoxyphenol, di-tert-butyl-para-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Of these, para-methoxyphenol is preferred.
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive composition.
  • the photosensitive composition of this invention may contain various surfactant from a viewpoint of improving applicability
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the coating thickness uniformity and liquid-saving properties are further improved.
  • Can do That is, in the case of forming a film using a coating liquid to which a photosensitive composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid is reduced, and the coating surface is wetted. The coating property is improved and the coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactant examples include MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
  • the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Lubrizol Japan Ltd.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101, NCW-1001, NCW-10
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.
  • silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
  • the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the photosensitive composition of the present invention.
  • the photosensitive composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber is preferably a conjugated diene compound, more preferably a compound represented by the following general formula (1).
  • this conjugated diene compound is used, fluctuations in development performance after exposure, especially when low-illuminance exposure is performed, can be suppressed, and exposure illuminance dependence related to pattern formability such as pattern line width, film thickness, and spectral spectrum can be reduced. It can suppress more effectively.
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 may be the same or different from each other. However, it does not represent a hydrogen atom at the same time.
  • R 3 and R 4 represent an electron withdrawing group.
  • the electron withdrawing group is a group having Hammett's substituent constant ⁇ p value (hereinafter, simply referred to as “ ⁇ p value”) of 0.20 or more and 1.0 or less.
  • ⁇ p value Hammett's substituent constant
  • R 3 and R 4 are preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group, particularly an acyl group.
  • a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferred.
  • the description of paragraph numbers 0148 to 0158 in JP2010-049029A can be referred to, and the contents thereof are incorporated in the present specification.
  • Specific examples of the compound represented by the general formula (1) include the following compounds. Further, the compounds described in paragraph Nos. 0160 to 0162 of JP 2010-049029 A are included in this specification. As a commercial item of an ultraviolet absorber, UV503 (Daito Chemical Co., Ltd.) etc. are mentioned, for example.
  • the content of the ultraviolet absorber is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content of the photosensitive composition of the present invention.
  • the photosensitive composition of the present invention may contain an antioxidant.
  • the antioxidant include a phenol compound, a phosphite compound, and a thioether compound.
  • a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. You may use these in mixture of 2 or more types.
  • the phenol compound any phenol compound known as a phenol-based antioxidant can be used.
  • Preferable phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • phosphorus antioxidant can also be used suitably for antioxidant.
  • phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl And at least one compound selected from the group consisting of) oxy] ethyl] amine, and ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).
  • the content of the antioxidant is preferably 0.01 to 20% by mass and more preferably 0.3 to 15% by mass with respect to the total solid content of the photosensitive composition. Only one type of antioxidant may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
  • additives for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, and the like can be blended with the photosensitive composition of the present invention as necessary.
  • additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
  • the photosensitive composition may contain a metal element, but from the viewpoint of suppressing the occurrence of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the photosensitive composition is 50 ppm or less. And is preferably controlled to 0.01 to 10 ppm. Further, the total amount of the inorganic metal salt in the photosensitive composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.
  • the total amount of monochlorobenzene and methyl tert-butyl ether is preferably 2 ppm or less, more preferably 1 ppm or less, based on the total mass of the photosensitive composition. More preferably, it is substantially free of monochlorobenzene and methyl tert-butyl ether. By setting it as such a structure, it can be set as the photosensitive composition excellent in safety
  • substantially free of monochlorobenzene and methyl tert-butyl ether means that the total amount of monochlorobenzene and methyl tert-butyl ether is, for example, 0.8% relative to the total mass of the photosensitive composition. 5 ppm or less is preferable, 0.1 ppm or less is more preferable, and it is still more preferable not to contain.
  • the photosensitive composition of the present invention can be prepared by mixing the aforementioned components.
  • each component may be blended at once, or may be blended sequentially after each component is dissolved and dispersed in a solvent.
  • the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
  • any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
  • PTFE polytetrafluoroethylene
  • nylon eg nylon-6, nylon-6,6)
  • polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
  • polypropylene including high density polypropylene
  • nylon are preferable.
  • the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m.
  • a fiber-shaped filter medium examples include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) can do.
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the filtering with the first filter may be performed only with the dispersion liquid, and after the other components are mixed, the filtering with the second filter may be performed.
  • the cured film of the present invention is formed using the above-described photosensitive composition of the present invention.
  • the cured film of the present invention can be used for a color filter, an infrared cut filter, an infrared transmission filter, a white film, a light shielding film, a transparent film, and the like.
  • a cured film suitable for a color filter or the like can be manufactured by using a photosensitive composition containing a chromatic colorant.
  • the photosensitive composition containing an infrared absorber can be manufactured by using the photosensitive composition containing an infrared absorber.
  • the cured film suitable for an infrared transmission filter etc. can be manufactured by using the photosensitive composition containing the coloring material which shields visible light.
  • the cured film suitable for a white film etc. can be manufactured by using the photosensitive composition containing a white pigment.
  • the cured film suitable for a light shielding film etc. can be manufactured by using the photosensitive composition containing a black pigment.
  • the cured film suitable for a transparent film etc. can be manufactured by using the photosensitive composition which does not contain any of a chromatic colorant, an infrared absorber, a white pigment, and a black pigment.
  • the cured film of the present invention may have a pattern or may be a film (flat film) having no pattern.
  • the infrared cut filter of this invention uses the photosensitive composition (photosensitive composition containing at least an infrared absorber) of this invention mentioned above.
  • the infrared rays transmission filter of this invention uses the photosensitive composition of this invention mentioned above.
  • a chromatic colorant may or may not be contained, but in addition to the infrared absorber, a chromatic colorant is further contained.
  • a filter having functions as an infrared cut filter and a color filter can also be used.
  • the cured film of the present invention When used as an infrared transmission filter, it preferably has the following spectral characteristics (1) or (2). According to this aspect, it is possible to form a film that can transmit infrared rays with less visible light-derived noise.
  • the maximum value of the light transmittance in the thickness direction of the film is 20% or less in the wavelength range of 400 to 750 nm, and the minimum value of the light transmittance in the thickness direction of the film is 900 to 1300 nm. 80% or more.
  • a cured film having such spectral characteristics can be preferably used as an infrared transmission filter that blocks light in the wavelength range of 400 to 750 nm and transmits light having a wavelength of 800 nm or more.
  • the light transmittance in the thickness direction of the film is 20% or less in the wavelength range of 400 to 830 nm, and the light transmittance in the thickness direction of the film is the minimum in the wavelength range of 1000 to 1300 nm. The value is 80% or more.
  • the cured film having such spectral characteristics can be preferably used as an infrared transmission filter that blocks light in the wavelength range of 400 to 750 nm and transmits light having a wavelength of 900 nm or more.
  • the spectral characteristics of the cured film are values obtained by measuring the transmittance in the wavelength range of 300 to 1300 nm using a spectrophotometer of an ultraviolet-visible near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
  • the cured film of the present invention When the cured film of the present invention is used as an infrared cut filter or an infrared transmission filter, it can be used in combination with an infrared cut filter and an infrared transmission filter.
  • the filter By using a combination of an infrared cut filter and an infrared transmission filter, the filter can be preferably used for an infrared sensor that detects infrared rays having a specific wavelength.
  • both filters are used in combination, both the infrared cut filter and the infrared transmission filter can be formed using the photosensitive composition of the present invention, and only one of them is used with the photosensitive composition of the present invention. It can also be formed.
  • the infrared cut filter may or may not be adjacent to the color filter in the thickness direction.
  • the infrared cut filter may be formed on a base material different from the base material on which the color filter is formed.
  • Other members for example, a microlens, a flattening layer, etc. constituting the solid-state imaging device may be interposed between the filter and the filter.
  • the infrared cut filter of the present invention may further have a dielectric multilayer film or an ultraviolet absorbing layer in addition to the cured film of the present invention. Since the infrared cut filter of the present invention further includes a dielectric multilayer film, an infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be easily obtained. Moreover, it can be set as the infrared cut filter excellent in ultraviolet-shielding property because the infrared cut filter of this invention has an ultraviolet absorption layer further.
  • the ultraviolet absorbing layer for example, the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of WO2015 / 099060 can be referred to, and the contents thereof are incorporated in the present specification.
  • the film thickness of the cured film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 2.5 to 100 ⁇ m.
  • the lower limit may be 3 ⁇ m or more, and may be 3.5 ⁇ m or more.
  • the upper limit is more preferably 70 ⁇ m or less, further preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • wrinkles can be effectively suppressed even when the thickness is large. For this reason, when producing a cured film having a large thickness, the curing of the present invention is remarkably obtained. In particular, the effects of the present invention are remarkably obtained when a cured film of 3 to 30 ⁇ m is produced.
  • the cured film of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.
  • a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.
  • CCD Charge Coupled Device
  • CMOS Complementary Metal Oxide Semiconductor
  • the method for producing a cured film of the present invention comprises a step of forming a photosensitive composition layer on a substrate using the photosensitive composition of the present invention, a step of exposing the photosensitive composition layer in a pattern, And a step of forming a pattern by developing and removing the exposed portion, and performing at a temperature of 150 ° C. or lower throughout the entire process. Furthermore, you may provide the process (prebaking process) of baking a photosensitive composition layer, and the process (post-baking process) of baking the developed pattern as needed. In the present invention, “performed at a temperature of 150 ° C.
  • the process of forming a photosensitive composition layer on a substrate using the photosensitive composition through the process of exposing the photosensitive composition layer in a pattern, the unexposed areas are developed and removed to form a pattern.
  • the process up to is performed at a temperature of 150 ° C. or lower.
  • the process from the step of forming the photosensitive composition layer on the substrate using the photosensitive composition to the post-baking step after the step of forming the pattern is performed at a temperature of 150 ° C. or lower.
  • the process from the step of forming the photosensitive composition layer on the substrate using the photosensitive composition to the post-baking step after the post-exposure step is performed at a temperature of 150 ° C. or lower.
  • various devices such as solid-state imaging devices, image display devices, and infrared sensors
  • further processing such as dicing (dividing into chips), bonding, packaging, etc.
  • these treatments after the production of the cured film are not included in the “all steps” in the present invention. That is, in manufacturing various devices, the process after manufacturing the cured film may be performed at a temperature exceeding 150 ° C.
  • cracking and warping may occur in the thin film glass substrate when it is performed at a temperature exceeding 150 ° C. during the production of the cured film, but the temperature exceeds 150 ° C. after dicing. This is because cracking and warping are less likely to occur even when heated. Details of each step will be described below.
  • the photosensitive composition layer is formed on the substrate using the photosensitive composition of the present invention.
  • the base material comprised with glass, a silicon
  • the resin examples include polyethylene, polypropylene, vinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, acrylic, polyvinyl alcohol, vinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene.
  • a terephthalate, a fluororesin, etc. are mentioned, These can be used 1 type or in combination of 2 or more types.
  • These substrates may be formed with an organic light emitting layer, an organic semiconductor such as an organic photoelectric conversion layer, or the like.
  • organic semiconductor examples include organic electroluminescence (OLED), organic field effect transistor (OFET), and organic solar cell (OPV).
  • organic-semiconductor layer can also be used as a base material.
  • the substrate may be a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD (charge coupled device) or CMOS (complementary metal oxide semiconductor) is provided on the substrate.
  • a solid-state image sensor light receiving element
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • the present invention is carried out at a temperature of 150 ° C. or lower throughout the entire process, and therefore a substrate having poor heat resistance can be used.
  • the substrate having low heat resistance include a glass substrate having a thickness of 0.5 mm or less, a thermoplastic resin substrate, a substrate including an organic semiconductor layer (preferably a substrate having an organic semiconductor layer on the surface), and the like. Is mentioned.
  • the thermoplastic resin base material for example, in the case of a base material composed of a thermoplastic resin having a glass transition temperature of 95 ° C. or lower, the effect of the present invention is remarkable. Particularly in a flexible substrate, a glass transition temperature of 90 ° C. or less is more often used.
  • a lower temperature of 70 ° C. or less is particularly preferably used.
  • the lower limit of the glass transition temperature of the thermoplastic resin is not particularly limited. For example, it may be normal temperature (23 ° C.) or higher. Moreover, the temperature below normal temperature can also be made into a lower limit.
  • the glass transition temperature can be 0 ° C. or higher, ⁇ 50 ° C. or higher, ⁇ 100 ° C. or higher, or ⁇ 150 ° C. or higher.
  • the lower temperature is set as the value of the glass transition temperature in the present invention.
  • the upper limit of the film thickness of the glass substrate is preferably 0.5 mm or less, and more preferably 0.3 mm or less.
  • the lower limit is not particularly limited, but may be 0.1 mm or more.
  • various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be used.
  • the photosensitive composition formed on the substrate is preferably heated (prebaked).
  • the heating is performed at 150 ° C. or less, preferably 120 ° C. or less, more preferably 50 to 120 ° C., further preferably 80 to 120 ° C., and particularly preferably 90 to 120 ° C.
  • the heating time is preferably 10 seconds to 30 minutes, more preferably 40 seconds to 20 minutes, and even more preferably 80 seconds to 10 minutes. Heating can be performed with a hot plate, oven, or the like.
  • 80% or more of the radical polymerizable compound is preferably unreacted (uncured), and more preferably 90% or more is unreacted (uncured).
  • the upper limit can be 100%, 95% or less, or 90% or less.
  • 60% or more of the thermosetting compound is preferably unreacted (uncured), and more preferably 80% or more is unreacted (uncured).
  • the upper limit can be 100%, 95% or less, or 90% or less.
  • the reaction rate of the radical polymerizable compound and the thermosetting compound can be measured by FT-IR (Fourier transform infrared analyzer).
  • the photosensitive composition formed on the substrate is exposed in a pattern.
  • pattern exposure can be performed by exposing the photosensitive composition formed on the base material through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
  • 20% or more of the exposed radical polymerizable compound is preferably reacted (cured), and 30 to 70% is preferably reacted (cured).
  • 60% or more of the thermosetting compound is preferably unreacted (uncured), and more preferably 80% or more is unreacted (uncured).
  • the upper limit can be 100%, 95% or less, or 90% or less.
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected.
  • a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free).
  • a high oxygen atmosphere for example, 22% by volume, 30% by volume, 50% by volume with an oxygen concentration exceeding 21% by volume.
  • the exposure illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ).
  • Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the unexposed portion is developed and removed to form a pattern.
  • the development removal of the unexposed portion can be performed using a developer.
  • the photosensitive composition of an unexposed part elutes in a developing solution, and only the photocured part remains.
  • the developer an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
  • the temperature of the developer is preferably 20 to 30 ° C., for example.
  • the development time is preferably 20 to 180 seconds.
  • alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
  • organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
  • the inorganic alkali for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
  • a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described photosensitive composition, and a nonionic surfactant is preferable.
  • the developing solution which consists of alkaline aqueous solution generally it is preferable to wash
  • exposure post-exposure
  • the exposure amount is preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
  • 30% or more of the exposed radical polymerizable compound is preferably reacted (cured), and 40 to 80% is preferably reacted (cured).
  • 60% or more of the thermosetting compound is preferably unreacted (uncured), and more preferably 80% or more is unreacted (uncured).
  • the upper limit can be 100%, 95% or less, or 90% or less.
  • post-bake may be performed after the development step described above or after post-exposure.
  • Post-baking is a heat treatment after development for accelerating curing.
  • the heating temperature is 150 ° C. 50 to 130 ° C is preferable, and 80 to 130 ° C is more preferable.
  • the heating time is preferably 3 minutes to 180 minutes, more preferably 5 minutes to 120 minutes.
  • Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. .
  • the radical polymerizable compound is preferably reacted (cured), and 50% or more is preferably reacted (cured).
  • the upper limit can be 100%, 95% or less, or 90% or less.
  • 50% or more of the thermosetting compound is preferably unreacted (uncured), and more preferably 70% or more is unreacted (uncured).
  • the upper limit can be 100%, 95% or less, or 90% or less.
  • the solid-state imaging device of the present invention has the above-described cured film of the present invention.
  • the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the cured film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
  • the manufacturing method of the solid-state image sensor of this invention includes the process of heating a cured film to the temperature of more than 150 degreeC and 300 degrees C or less, after manufacturing a cured film with the method mentioned above.
  • An example of the heating after the production of the cured film is a heating process after dicing (dividing into chips). For example, bonding, packaging, etc. are mentioned. In these treatments, the cured film may be heated to a temperature exceeding 150 ° C. and not higher than 300 ° C.
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • Device protection consisting of silicon nitride, etc., which has a light-shielding film that opens only on the photodiode and the transfer electrode on the photodiode and the transfer electrode, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part It has a film, and has a color filter on the device protective film.
  • a configuration having a light condensing means for example, a micro lens, etc., the same applies hereinafter
  • a structure having the light condensing means on the color filter, etc. may be.
  • the cured film of this invention can be used for image display apparatuses, such as a liquid crystal display device and an organic electroluminescent display apparatus.
  • the manufacturing method of the image display apparatus of this invention includes the process of heating a cured film to the temperature of more than 150 degreeC and 300 degrees C or less, after manufacturing a cured film with the method mentioned above.
  • An example of the heating after the production of the cured film is a heating process after dicing (dividing into chips). For example, bonding, packaging, etc. are mentioned. In these treatments, the cured film may be heated to a temperature exceeding 150 ° C. and not higher than 300 ° C.
  • display devices For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the infrared sensor of the present invention has the cured film of the present invention.
  • the manufacturing method of the infrared sensor of this invention includes the process of heating a cured film to the temperature of more than 150 degreeC and below 300 degreeC, after manufacturing a cured film with the method mentioned above.
  • An example of the heating after the production of the cured film is a heating process after dicing (dividing into chips). For example, bonding, packaging, etc. are mentioned.
  • the cured film may be heated to a temperature exceeding 150 ° C. and not higher than 300 ° C.
  • the configuration of the infrared sensor of the present invention is a configuration provided with the cured film of the present invention, and is not particularly limited as long as it is a configuration that functions as an infrared sensor. Examples thereof include the following configurations.
  • a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.), a transfer electrode made of polysilicon, etc., and a photodiode on the photodiode and the transfer electrode
  • a light-shielding film made of tungsten or the like that is open only in the light-receiving part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. It is the structure which has the cured film of this invention on the top.
  • the device protective film has a condensing means (for example, a microlens etc. The same shall apply hereinafter) on the device protective film and under the cured film of the present invention (on the side close to the substrate), or condensed on the cured film of the present invention
  • a condensing means for example, a microlens etc. The same shall apply hereinafter
  • the structure etc. which have a means may be sufficient.
  • FIG. 1 shows an infrared sensor 100 including a solid-state image sensor 110.
  • the imaging area provided on the solid-state imaging device 110 has an infrared cut filter 111 and a color filter 112.
  • the infrared cut filter 111 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm), light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm,
  • the filter is preferably configured to shield light having a wavelength of 900 to 1000 nm.
  • the infrared cut filter 111 can be composed of the cured film of the present invention.
  • the color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, a color filter in which red, green, and blue pixels are formed is used. A color filter can be comprised with the cured film of this invention.
  • a region 114 where the infrared cut filter 111 is not formed is provided between the infrared transmission filter 113 and the solid-state image sensor 110. In the region 114, a resin layer (for example, a transparent resin layer) that can transmit light having a wavelength that has passed through the infrared transmission filter 113 is disposed.
  • the infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared rays having a specific wavelength.
  • the infrared transmission filter can be composed of the cured film of the present invention having the above-described spectrum.
  • a microlens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 113.
  • a planarization layer 116 is formed so as to cover the microlens 115.
  • the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110.
  • FIG. 1 the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110.
  • FIG. 1 the resin layer is disposed in
  • the thickness of the color filter 112 and the thickness of the infrared transmission filter 113 are the same, but the thickness of both may be different.
  • the color filter 112 is provided on the incident light h ⁇ side from the infrared cut filter 111.
  • the infrared cut filter 111 may be provided closer to the incident light h ⁇ than the color filter 112.
  • the infrared cut filter 111 and the color filter 112 are stacked adjacent to each other.
  • both filters are not necessarily adjacent to each other, and other layers are provided therebetween. May be. According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including three-dimensional information can be taken.
  • Colorant-containing liquid A-1 Red pigment dispersion 11.8 parts of C.I. I. Pigment Red254, 1.2 parts of the following pigment derivative A, 17.3 parts of the following dispersant A (30% propylene glycol monomethyl ether acetate (hereinafter, PGMEA) solution), and 69.7 parts of PGMEA as a solvent.
  • PGMEA propylene glycol monomethyl ether acetate
  • Colorant-containing liquid A-3 Blue pigment dispersion 11.8 parts Pigment Blue 15: 6, 1.2 parts of the following pigment derivative A, and 17.3 parts of the following dispersing agent A (30% PGMEA solution) And a mixture of 69.7 parts of PGMEA as a solvent was dispersed by a bead mill for 15 hours to prepare a colorant-containing liquid A-3.
  • Colorant-containing liquid A-4 Yellow pigment dispersion 11.8 parts Pigment Yellow 139, 1.2 parts of the following pigment derivative A, 17.3 parts of the following dispersing agent A (30% PGMEA solution), A mixed liquid composed of 69.7 parts of PGMEA as a solvent was dispersed for 15 hours by a bead mill to prepare a colorant-containing liquid A-4.
  • Colorant-containing liquid A-6 Solution containing a colorant that blocks visible light Colorant-containing liquid A-1, Colorant-containing liquid A-3, Colorant-containing liquid A-4, and Colorant-containing Liquid A-5 in terms of mass ratio
  • the colorant-containing liquid A-6 was prepared by mixing at a ratio of
  • (Coloring material-containing liquid A-7a) Solution containing an infrared absorber As an infrared absorber, 11.8 parts of oxytitanium phthalocyanine, 1.2 parts of the following pigment derivative A, and a 30% PGMEA solution of the following dispersant A17. A mixed material composed of 3 parts and 69.7 parts of PGMEA as a solvent was dispersed for 15 hours by a bead mill to prepare a colorant-containing liquid A-7a.
  • the colorant-containing liquid A-7 was prepared by mixing at a ratio of 6: 3: 2.
  • Coloring material-containing liquid A-8 Black pigment dispersion Titanium black (titanium oxynitride (TiOxNy)) 11.8 parts, 1.2 parts of the following pigment derivative A, and 30% PGMEA solution of the following dispersing agent A 17.
  • a mixed material composed of 3 parts and 69.7 parts of PGMEA as a solvent was dispersed for 15 hours by a bead mill to prepare a colorant-containing liquid A-8.
  • Pigment derivative A the following structure
  • Dispersant A The following structure (Mw: 24000, acid value 50 mgKOH / g)
  • Example 1 After the components shown in the following composition were mixed and stirred in the following amounts, the solution was filtered with a nylon filter having a pore size of 0.45 ⁇ m (manufactured by Nippon Pole Co., Ltd., DFA4201NXEY) to prepare a photosensitive composition. did.
  • A-composition- Colorant-containing liquid (A-1): 21.5 parts
  • Photoradical polymerization initiator (B-1): 1.6 parts Radical polymerizable compound (C-1): 11.1 parts Alkali-soluble resin (D-1) ): 43.4 parts
  • Thermosetting compound (E-1): 8.6 parts
  • Ultraviolet absorber (the following structure): 0.4 parts Polymerization inhibitor (p-methoxyphenol) 0.01 part
  • Surfactant (10% PGMEA solution of the following mixture (Mw 14000)): 0.4 part Solvent (PGMEA): 13 parts
  • Examples 2 to 28, Comparative Examples 1 to 3 The colorant-containing liquid, photoradical polymerization initiator, radical polymerizable compound, and thermosetting compound were changed to the components shown in the following table, respectively, and the solid content concentration and the color material in the total solid content of the photosensitive composition
  • the content, the content of the radical polymerizable compound in the total solid content of the photosensitive composition, and the content of the thermosetting compound in the total solid content of the photosensitive composition are as shown in the table below.
  • Each photosensitive composition was prepared by adjusting the content of each component.
  • the “coloring material content” in the table is the content of the coloring material in the total solid content of the photosensitive composition. Further, the color material is C.I.
  • “content of radical polymerizable compound” is the content of radical polymerizable compound in the total solid content of the photosensitive composition.
  • “content of a thermosetting compound” is content of the thermosetting compound in the total solid of a photosensitive composition.
  • the photosensitive composition was applied onto a glass substrate using a spin coater, and heat-treated (prebaked) for 150 seconds using a 100 ° C. hot plate.
  • an ultraviolet exposure apparatus USH-500BY / ML-501C / B, manufactured by Ushio Electric Co., Ltd.
  • exposure was performed at a dose of 1000 mJ / cm 2 through a photomask.
  • the glass substrate on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (developer, Paddle development was performed at 23 ° C.
  • the glass substrate on which the pattern has been formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is supplied from the ejection nozzle in a shower form from above the rotation center while rotating the glass substrate at a rotation speed of 50 rpm by a rotating device.
  • a rinse treatment was performed, followed by spin drying. Further, after additional exposure using an ultraviolet exposure apparatus at an exposure amount of 9000 mJ / cm 2 , heat treatment (post-bake) was performed for 90 minutes using an oven at 90 ° C. to obtain a cured film on which a pattern was formed. It was 6 micrometers when the thickness of the obtained cured film was measured with the stylus type film thickness meter (the Bruker company make, Dektak).
  • Example was able to effectively suppress the generation of soot. In contrast, wrinkles were likely to occur in the comparative example.
  • A-1 to A-9 Colorant-containing liquids (A-1) to (A-9) described above (Photo radical polymerization initiator)
  • B-1 The following compounds
  • B-2 The following compound
  • B-3 Adeka Arcles NCI-831 (manufactured by ADEKA Corporation) (Radically polymerizable compound)
  • C-1 NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • C-3 KAYARAD DCPA-20 (manufactured by Nippon Kayaku Co., Ltd.)
  • D-1 benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (molar ratio 60/20/20, 40% PGMEA solution, weight average molecular weight 14
  • Infrared sensor 110 Solid-state image sensor 111: Infrared cut filter 112: Color filter 113: Infrared transmission filter 114: Area

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Abstract

L'invention concerne : une composition photosensible qui est susceptible de produire un film durci qui n'est pas sujet à la formation de plis ; un film durci ; un filtre de blocage infrarouge ; un filtre de transmission infrarouge ; un procédé pour produire un film durci ; un élément d'imagerie à semi-conducteurs ; un dispositif d'affichage d'image ; un procédé pour produire un élément d'imagerie à semi-conducteurs ; et un procédé pour fabriquer un capteur infrarouge. Cette composition photosensible contient un composé polymérisable par voie radicalaire, un initiateur de photopolymérisation radicalaire et un composé thermodurcissable. La concentration de contenu solide de la composition photosensible est 25-80 % en masse ; et le contenu du composé thermodurcissable dans le contenu solide total de la composition photosensible est 10-50 % en masse.
PCT/JP2016/075432 2015-09-29 2016-08-31 Composition photosensible, film durci, filtre de blocage infrarouge, filtre de transmission infrarouge, procédé de production de film durci, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, procédé de production d'élément d'imagerie à semi-conducteurs, et procédé de fabrication de capteur infrarouge WO2017056831A1 (fr)

Priority Applications (1)

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JP2017543041A JPWO2017056831A1 (ja) 2015-09-29 2016-08-31 感光性組成物、硬化膜、赤外線カットフィルタ、赤外線透過フィルタ、硬化膜の製造方法、固体撮像素子、画像表示装置、固体撮像素子の製造方法および赤外線センサの製造方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018116258A (ja) * 2017-01-16 2018-07-26 東洋インキＳｃホールディングス株式会社 感光性着色組成物、カラーフィルタ用感光性着色組成物、およびカラーフィルタ
WO2019065475A1 (fr) * 2017-09-28 2019-04-04 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à semi-conducteurs et capteur d'infrarouges
JP2019113699A (ja) * 2017-12-22 2019-07-11 東洋インキＳｃホールディングス株式会社 感光性着色組成物およびカラーフィルタ
WO2020066871A1 (fr) * 2018-09-26 2020-04-02 富士フイルム株式会社 Composition durcissable, film durci, procédé de formation de motif, filtre optique et photocapteur
WO2020129807A1 (fr) * 2018-12-18 2020-06-25 三菱ケミカル株式会社 Composition colorante photosensible, produit durci, espaceur colorant et appareil d'affichage d'image
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WO2022191044A1 (fr) * 2021-03-12 2022-09-15 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à l'état solide, dispositif d'affichage d'image, capteur infrarouge, module de caméra, composé, et agent absorbant l'infrarouge
JP7219378B1 (ja) 2021-12-09 2023-02-08 東洋インキＳｃホールディングス株式会社 感光性着色組成物、光学フィルタ、画像表示装置、及び固体撮像素子

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000338322A (ja) * 1999-05-26 2000-12-08 Mitsubishi Chemicals Corp カラーフィルター用光重合性組成物およびカラーフィルター
JP2004151705A (ja) * 2002-10-09 2004-05-27 Sumitomo Chem Co Ltd カラーフィルタおよびその製造方法
JP2005114992A (ja) * 2003-10-07 2005-04-28 Mitsubishi Chemicals Corp 光硬化性組成物、並びにそれを用いた光硬化性画像形成材料、光硬化性画像形成材、及び画像形成方法
JP2007071995A (ja) * 2005-09-05 2007-03-22 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物
JP2010224204A (ja) * 2009-03-24 2010-10-07 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
JP2014199925A (ja) * 2013-03-14 2014-10-23 富士フイルム株式会社 固体撮像素子及びその製造方法、赤外光カットフィルタ形成用硬化性組成物、カメラモジュール
JP2015068945A (ja) * 2013-09-27 2015-04-13 富士フイルム株式会社 感光性樹脂組成物、赤外線透過フィルタおよびその製造方法、赤外線センサならびにカラーフィルタ。

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000338322A (ja) * 1999-05-26 2000-12-08 Mitsubishi Chemicals Corp カラーフィルター用光重合性組成物およびカラーフィルター
JP2004151705A (ja) * 2002-10-09 2004-05-27 Sumitomo Chem Co Ltd カラーフィルタおよびその製造方法
JP2005114992A (ja) * 2003-10-07 2005-04-28 Mitsubishi Chemicals Corp 光硬化性組成物、並びにそれを用いた光硬化性画像形成材料、光硬化性画像形成材、及び画像形成方法
JP2007071995A (ja) * 2005-09-05 2007-03-22 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物
JP2010224204A (ja) * 2009-03-24 2010-10-07 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
JP2014199925A (ja) * 2013-03-14 2014-10-23 富士フイルム株式会社 固体撮像素子及びその製造方法、赤外光カットフィルタ形成用硬化性組成物、カメラモジュール
JP2015068945A (ja) * 2013-09-27 2015-04-13 富士フイルム株式会社 感光性樹脂組成物、赤外線透過フィルタおよびその製造方法、赤外線センサならびにカラーフィルタ。

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JP2018116258A (ja) * 2017-01-16 2018-07-26 東洋インキＳｃホールディングス株式会社 感光性着色組成物、カラーフィルタ用感光性着色組成物、およびカラーフィルタ
WO2019065475A1 (fr) * 2017-09-28 2019-04-04 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à semi-conducteurs et capteur d'infrarouges
JPWO2019065475A1 (ja) * 2017-09-28 2020-11-05 富士フイルム株式会社 組成物、膜、光学フィルタ、固体撮像素子および赤外線センサ
JP7030275B2 (ja) 2017-12-22 2022-03-07 東洋インキＳｃホールディングス株式会社 感光性着色組成物およびカラーフィルタ
JP2019113699A (ja) * 2017-12-22 2019-07-11 東洋インキＳｃホールディングス株式会社 感光性着色組成物およびカラーフィルタ
CN111902775A (zh) * 2018-04-19 2020-11-06 富士胶片株式会社 图案的制造方法、光学滤波器的制造方法、固体摄像元件的制造方法、图像显示装置的制造方法、光固化性组合物及膜
CN111902775B (zh) * 2018-04-19 2024-01-02 富士胶片株式会社 图案及光学滤波器及固体摄像元件以及图像显示装置的制造方法、光固化性组合物及膜
WO2020066871A1 (fr) * 2018-09-26 2020-04-02 富士フイルム株式会社 Composition durcissable, film durci, procédé de formation de motif, filtre optique et photocapteur
JPWO2020066871A1 (ja) * 2018-09-26 2021-09-16 富士フイルム株式会社 硬化性組成物、硬化膜、パターンの形成方法、光学フィルタおよび光センサ
JP7059387B2 (ja) 2018-09-26 2022-04-25 富士フイルム株式会社 硬化性組成物、硬化膜、パターンの形成方法、光学フィルタおよび光センサ
WO2020129807A1 (fr) * 2018-12-18 2020-06-25 三菱ケミカル株式会社 Composition colorante photosensible, produit durci, espaceur colorant et appareil d'affichage d'image
JPWO2020129807A1 (ja) * 2018-12-18 2021-10-28 三菱ケミカル株式会社 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
JP7375773B2 (ja) 2018-12-18 2023-11-08 三菱ケミカル株式会社 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
CN113168094A (zh) * 2018-12-18 2021-07-23 三菱化学株式会社 感光性着色树脂组合物、固化物、着色间隔物及图像显示装置
CN113168094B (zh) * 2018-12-18 2024-06-11 三菱化学株式会社 感光性着色树脂组合物、固化物、着色间隔物及图像显示装置
WO2022191044A1 (fr) * 2021-03-12 2022-09-15 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à l'état solide, dispositif d'affichage d'image, capteur infrarouge, module de caméra, composé, et agent absorbant l'infrarouge
JP7219378B1 (ja) 2021-12-09 2023-02-08 東洋インキＳｃホールディングス株式会社 感光性着色組成物、光学フィルタ、画像表示装置、及び固体撮像素子
JP2023085600A (ja) * 2021-12-09 2023-06-21 東洋インキＳｃホールディングス株式会社 感光性着色組成物、光学フィルタ、画像表示装置、及び固体撮像素子

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