WO2014069197A1

WO2014069197A1 - Alkali developable photosensitive composition

Info

Publication number: WO2014069197A1
Application number: PCT/JP2013/077445
Authority: WO
Inventors: 洋介前田; 清水　正晶
Original assignee: 株式会社Adeka
Priority date: 2012-11-01
Filing date: 2013-10-09
Publication date: 2014-05-08
Also published as: TWI619760B; TW201430040A; JP6333727B2; KR20150082113A; CN104395824B; KR102093446B1; JPWO2014069197A1; CN104395824A

Abstract

This alkali developable photosensitive composition contains an infrared absorbing dye (A), a polymerizable compound (B) having an ethylenically unsaturated bond and an alkali-soluble substituent group that imparts alkali developability, a photopolymerization initiator (C) and a solvent (D), wherein the photopolymerization initiator (C) contains an oxime ester compound. The aforementioned photopolymerization initiator (C) preferably contains a compound represented by general formula (I). (Refer to the description for definitions of R¹, R², R³, R⁴, X, a and b in the formula.)

Description

Alkali-developable photosensitive composition

The present invention relates to an alkali-developable photosensitive composition containing an infrared-absorbing dye, and a near-infrared absorbing filter using the alkali-developable photosensitive composition.

Photosensitive compositions containing infrared absorbing dyes are used in various applications.
Patent Document 1 discloses a color filter using a photosensitive coloring composition that is cured by irradiation with near-infrared light, and Patent Document 2 discloses a plasma display panel that can block wavelengths in the near-infrared region. A filter is disclosed. Patent Document 3 discloses an infrared-sensitive lithographic printing plate using a particulate matting agent containing an alkali-soluble resin and an infrared-absorbing dye. Patent Document 4 discloses a near-infrared light. A near infrared absorption filter using a curable composition containing an absorbing dye is disclosed.
However, the photosensitive compositions described in these documents are not satisfactory in terms of light resistance.

JP-A-9-230126 US2004090170A1 US2008035000A1 US2011070407A1

Accordingly, an object of the present invention is to provide an alkali-developable photosensitive composition having excellent light resistance. Another object of the present invention is to provide a near-infrared absorption filter using the alkali-developable photosensitive composition.

As a result of intensive studies, the present inventors have found that a cured product of an alkali-developable photosensitive composition using an oxime ester compound as a photopolymerization initiator is excellent in light resistance, and the alkali-developable feeling described above. The present inventors have found that the light composition is suitable for a near-infrared absorption filter, and have reached the present invention.

The present invention relates to an infrared-absorbing dye (A), a polymerizable compound (B) having an alkali-soluble substituent that imparts alkali developability, an ethylenically unsaturated bond, a photopolymerization initiator (C), and a solvent (D). And an alkali developable photosensitive composition in which the photopolymerization initiator (C) contains an oxime ester compound.

The present invention also provides a cured product of the alkali-developable photosensitive composition and a near-infrared absorbing filter formed using the cured product.

According to the present invention, the alkali-developable photosensitive composition containing an oxime ester compound as a photopolymerization initiator is excellent in light resistance. In addition, a near-infrared absorption filter formed using the cured product has a low transmittance at a wavelength of 900 to 1100 nm, effectively blocks infrared rays, and has excellent photolithography characteristics because the cured product has high alkali resistance.

Hereinafter, the alkali-developable photosensitive composition of the present invention will be described based on preferred embodiments.

The alkali-developable photosensitive composition of the present invention comprises an infrared-absorbing dye (A), a polymerizable compound (B) having an ethylenically unsaturated bond, having an alkali-soluble substituent that imparts alkali developability, and a photopolymerization initiator. (C) and a solvent (D) are contained. Hereinafter, each component will be described in order.

<Infrared absorbing dye (A)>
As the infrared absorbing dye (A) used in the alkali-developable photosensitive composition of the present invention, those having characteristic absorption in the infrared region and conventionally used as infrared absorbing dyes can be used. For example, cyanine compounds , Squarylium compound, porphyrin compound, metal dithiol complex, chromium, cobalt metal complex salt compound, anthraquinones, phthalocyanine compound, naphthalocyanine compound, diimonium compound, inorganic oxide particles, etc., among which diimonium compound has infrared absorption ability It is preferable because of high transparency in the visible light region.

Among the above diimonium compounds, those represented by the following general formula (II) are more preferable because they are excellent in light resistance of a cured product of the photosensitive composition.

(In the formula, R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently has 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. Represents an alkyl group, and each of R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ independently has a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent or a substituent. An methylene group in the alkyl group may be interrupted by —O— or —CH═CH—, t represents a number of 1 to 4, and An ^q− represents a q valence. Q represents 1 or 2, and p represents a coefficient for keeping the charge neutral.)

In the above general formula (II), substituents represented by R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ Examples of the alkyl group having 1 to 10 carbon atoms that may have are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, cyclohexyl Methyl, cyclohexylethyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, trifluoromethyl, trichloromethyl, tribromomethyl, 1,2-dichloroethyl, 3,3,3 -Trifluoropropyl, prop-1-en-1-yl and the like,
Examples of the halogen atom represented by R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the amino group which may have a substituent represented by R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ include amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecyl Amino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoyl Amino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-but Cicarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, etc. Can be mentioned.

Examples of the q-valent anion represented by pAn ^q- in the general formula (II) include methanesulfonate anion, dodecylsulfonate anion, benzenesulfonate anion, toluenesulfonate anion, trifluoromethanesulfonate anion, naphthalenesulfone. Acid anion, diphenylamine-4-sulfonic acid anion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid anion, 2-amino-5-nitrobenzenesulfonic acid anion, JP-A-10-235999, JP-A-10-337959 No. 1, JP-A No. 11-102808, JP-A No. 2000-108510, JP-A No. 2000-168223, JP-A No. 2001-209969, JP-A No. 2001-322354, JP-A No. 2006-248180 , JP 2 Organic sulfonic acids such as sulfonate anions described in Japanese Patent Application Laid-Open No. 06-297907, Japanese Patent Application Laid-Open No. 8-253705, Japanese Patent Application Publication No. 2004-503379, Japanese Patent Application Laid-Open No. 2005-336150, International Publication No. 2006/28006, etc. In addition to anions, chloride ions, bromide ions, iodide ions, fluoride ions, chlorate ions, thiocyanate ions, perchlorate ions, hexafluorophosphate ions, hexafluoroantimonate ions, tetrafluoroborate ions, Octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphonate ion, tetrakis (penta Fluorophenyl) borate ion, sulfur Phosphonimide anion, quencher anion that has the function of deexciting (quenching) active molecules in the excited state, and anionic groups such as carboxyl, phosphonic acid, and sulfonic acid groups on the cyclopentadienyl ring And metallocene compound anions such as ferrocene and luteocene.

Specific examples of the compound represented by the general formula (II) according to the present invention include the following compound No. 1-1 to 1-8. In addition, in the following illustration, it has shown with the cation which excluded the anion.

The said infrared absorption pigment | dye (A) can be used individually or in combination of multiple types.
In the infrared absorbing dye (A), the content of the compound represented by the general formula (II) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass. When the content of the compound represented by the general formula (II) is less than 50% by mass, the solubility in a solvent may be lowered, or the stability of a cured product may be lowered.

The content of the infrared absorbing dye (A) is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass in the alkali-developable photosensitive composition of the present invention.

The infrared absorption dye (A) preferably has a maximum absorption wavelength (λmax) of the cured product of 700 nm or more, more preferably 780 to 850 nm. If the maximum absorption wavelength (λmax) of the cured product is less than 700 nm, it does not absorb light of the target wavelength, which is not preferable.

<Polymerizable compound (B) having an ethylenically unsaturated bond having an alkali-soluble substituent that gives alkali developability>
The polymerizable compound (B) having an alkali-soluble substituent that gives alkali developability and having an ethylenically unsaturated bond is not particularly limited, and those conventionally used for alkali-developable photosensitive compositions are used. For example, (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, Both ends of sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate and hydroxyethyl (meth) acrylate of polymer having carboxy group and hydroxyl group Unsaturated polybasic compounds such as poly (meth) acrylates having one carboxyl group and two or more (meth) acryloyl groups, or thiolate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate Acid: a polyfunctional compound having an acid value that is a reaction product of a hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate and a dibasic acid anhydride such as succinic anhydride, phthalic anhydride, or tetrahydrophthalic anhydride Acrylate: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) A) Chrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) (Meth) acrylic acid esters such as acrylate; N-vinylpyrrolidone; styrene and its derivatives, styrenes such as α-methylstyrene; (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide, diacetone ( Acrylamides such as (meth) acrylamide; (meth) acrylonitrile, other vinyl compounds such as ethylene, propylene, butylene, vinyl chloride, vinyl acetate, and polymethyl methacrylate Copolymers of (meth) acrylic acid and macromonomers such as acrylate macromonomer and polystyrene macromonomer, tricyclodecane skeleton monomethacrylate, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, etc. (Meth) acrylic acid copolymer, phenol and / or cresol novolac epoxy resin, biphenyl skeleton, naphthalene skeleton obtained by reacting an isocyanate compound having an unsaturated bond such as Karenz MOI and AOI manufactured by Showa Denko KK Novolac epoxy resins, bisphenol A novolac epoxy compounds, novolac epoxy compounds such as dicyclopentadiene novolac epoxy compounds, polyphenylmethane epoxy resins having polyfunctional epoxy groups, and the following general formula Resins obtained by allowing an unsaturated monobasic acid to act on an epoxy group such as an epoxy compound represented by (1) and further causing a polybasic acid anhydride to act on it can be used. These monomers can be used individually by 1 type or in mixture of 2 or more types. The compound (B) having an alkali developability and having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

Wherein X ¹ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, —O—, —S—, —SO ₂ —, —SS—, —SO—, —CO—, —OCO—, or a substituent represented by the following formula (A), (B) or (C), wherein the alkylidene group may be substituted with a halogen atom R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl having 2 to 5 carbon atoms. Represents a group or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and m is an integer of 0 to 10.)

(Wherein Z ¹ is a hydrogen atom, a phenyl group optionally substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, or A cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms, Y ¹ is an alkyl group having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms A group, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and d is an integer of 0 to 5).

Wherein Y ² and Z ² are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. An aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a complex having 2 to 20 carbon atoms that may be substituted with a halogen atom ring group, or a halogen atom, the alkylene moiety in the alkyl group and arylalkyl group, an unsaturated bond, may be interrupted by -O- or -S-, Z ² , May form a ring with the adjacent Z ² together, p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, s is 0 ~ Represents an integer of 4, and the sum of r and s is an integer of 2 to 4.)

Examples of the unsaturated monobasic acid that acts on the epoxy group of the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, and the like. Examples thereof include hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, and dicyclopentadiene / malate.
In addition, the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride , Pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride Acid, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride Maleic anhydride adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct is It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

In order to improve the developability of the alkali-developable photosensitive composition of the present invention by adjusting the acid value, together with the compound (B) having an ethylenically unsaturated bond having an alkali-soluble substituent that gives the alkali developability, Furthermore, a monofunctional or polyfunctional epoxy compound can be used. The alkali-developable compound having an ethylenically unsaturated bond preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the use amount of the monofunctional or polyfunctional epoxy compound satisfies the acid value. It is preferable to select as follows.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl A , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl Glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4- Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following compound No.A2, No. A3 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers because an alkali-developable photosensitive composition with better characteristics can be obtained. As the bisphenol-type epoxy compound, the epoxy compound represented by the general formula (1) can be used, and for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as cyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like can also be used.

Among the polymerizable compounds (B) having an ethylenically unsaturated bond having an alkali-soluble substituent that gives the alkali developability, unsaturated polybasic acids, acids from the viewpoint of compatibility, alkali developability, and heat resistance Resins obtained by allowing an unsaturated monobasic acid to act on a polyfunctional acrylate having a valence and an epoxy group, and further causing a polybasic acid anhydride to act, are preferred, and unsaturated polybasic acids are more preferred.

In the photosensitive composition of the present invention, the content of the polymerizable compound (B) having an ethylenically unsaturated bond having an alkali-soluble substituent that imparts the alkali developability is the alkali-developable photosensitive composition of the present invention. 30 to 99 mass%, particularly 60 to 95 mass% is preferable in the solid matter. If the content of the polymerizable compound (B) having an ethylenically unsaturated bond having an alkali-soluble substituent that gives alkali developability is less than 30% by mass, the cured product has insufficient mechanical strength and cracks are formed. If it is larger than 99% by weight, curing due to exposure may be insufficient and tack may occur, or the development time may be long and the cured part may be damaged by alkali. There is.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C), conventionally known compounds can be used. For example, acetophenone compounds, benzophenone compounds, benzoin compounds, benzyl compounds, benzyl ketal compounds, oxime ester compounds, acylphosphine compounds, triazines. Compounds, xanthone compounds, thioxanthone compounds, benzoquinone compounds, anthraquinone compounds, disulfide compounds, biimidazole compounds, 4,4-azobisisobutyronitrile, camphorquinone, benzoyl peroxide, and the like. 1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (ADEKA), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGA URE OXE 02 (manufactured by BASF), and the like.
Among the photopolymerization initiators (C), an oxime ester compound is preferable from the viewpoint of sensitivity and color tone, and a compound represented by the following general formula (I) is more preferable.

(Wherein R ¹ and R ² are each independently a hydrogen atom, a cyano group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom number) An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent;
R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ⁵ , OR ⁶ , SR ⁷ , NR ⁸ R ⁹ , COR ¹⁰ , SOR ¹¹ , SO _2. Represents R ¹² or CONR ¹³ R ¹⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently has 1 to 20 carbon atoms which may have a substituent. An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a carbon atom which may have a substituent Represents a heterocyclic group of formula 2 to 20,
X represents an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁵ R ¹⁶ , CO, NR ¹⁷ or PR ¹⁸ ;
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an optionally substituted carbon atom having 6 carbon atoms. Represents an aryl group of ˜30 or an arylalkyl group of 7 to 30 carbon atoms which may have a substituent, and the methylene group in the alkyl group or arylalkyl group may be interrupted by —O—. ,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 1 to 5. )

In the above general formula (I), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁷ and R ¹⁸ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, amyl, isoamyl, and t-amyl. Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and the like.

In the above general formula (I), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ As the aryl group having 6 to 30 carbon atoms represented by R ¹⁷ and R ¹⁸ , for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted by one or more of the above alkyl groups , Biphenylyl, naphthyl, anthryl and the like.

In the above general formula (I), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ¹⁷ and R ¹⁸ include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

In the above general formula (I), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ¹⁷ and R ¹⁸ include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzooxazol-2-yl, tetrahydropyranyl, pyrrolidyl Preferred examples include 5- to 7-membered heterocycles such as imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl and the like.

In the above general formula (I), examples of the ring formed by R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ together with the adjacent benzene ring include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring and a benzene ring. Preferred examples include 5- to 7-membered rings such as a piperidine ring, a morpholine ring, a lactone ring and a lactam ring.

In the general formula (I), examples of the halogen atom represented by R ³ and R ⁴ include fluorine, chlorine, bromine and iodine.

Specific examples of the compound represented by the general formula (I) according to the present invention include the following compound No. 2-1 to 2-19.

In the alkali-developable photosensitive composition of the present invention, the content of the photopolymerization initiator (C) is 0.1 to 30% by mass, particularly 0.5 to 0.5% in the alkali-developable photosensitive composition of the present invention. 10 mass% is preferable. When the content of the photopolymerization initiator (C) is less than 0.1% by mass, curing by exposure may be insufficient, and when the content is more than 30% by mass, light is contained in the alkali-developable photosensitive composition. A polymerization initiator (C) may precipitate.

The ratio of the oxime ester compound in the photopolymerization initiator (C) is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass, based on the solid content of the alkali-developable photosensitive composition.

<Solvent (D)>
A solvent (D) can be further added to the alkali-developable photosensitive composition of the present invention. The solvent is usually a solvent capable of dissolving or dispersing each of the above components (the infrared absorbing dye (A) of the present invention, etc.) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl. Ketones such as ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, diacetone alcohol; ethers such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether Solvent: ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as methanol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol Ether ester solvents such as 1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; hexane, Aliphatic hydrocarbon solvents such as heptane, octane and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Mineral spirit, Swazol # 31 (Cosmo Matsuyama Petroleum), Solvesso # 100 (Exxon Chemical) and other paraffinic solvents; Carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents; Chlorobenzene and other halogens Aromatic hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water These solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, dimethylacetamide, methyl ethyl ketone, diacetone alcohol, and the like are photopolymerized with a resist in an alkali-developable photosensitive composition. It is preferable because the compatibility of the initiator is good.

In the alkali-developable photosensitive composition of the present invention, the amount of the solvent (D) used is preferably such that the concentration of the composition other than the solvent (D) is 5 to 30% by mass, and less than 5% by mass. It is not preferable because it is difficult to increase the film thickness and the light of the desired wavelength cannot be sufficiently absorbed, and when it exceeds 30% by mass, the storage stability of the composition due to precipitation of the composition is reduced, and the viscosity is improved. Therefore, handling is reduced, which is not preferable.

The alkali-developable photosensitive composition of the present invention may further contain an inorganic color material and / or an organic color material. These color materials can be used alone or in admixture of two or more.

Examples of the inorganic color material and / or organic color material include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds. Quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acids; azo dyes, metal complex compounds of cyanine dyes; lake pigments Carbon black obtained by furnace method, channel method, thermal method, or carbon black such as acetylene black, ketjen black or lamp black The carbon black prepared and coated with an epoxy resin, the carbon black previously dispersed with a resin in a solvent, adsorbed with 20 to 200 mg / g of resin, and the carbon black treated with an acidic or alkaline surface. The average particle size is 8 nm or more, the DBP oil absorption is 90 ml / 100 g or less, the total oxygen amount calculated from CO and CO ₂ in the volatile matter at 950 ° C. is 9 mg or more per 100 m ² of the surface area of the carbon black. Things: Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue, cobalt Green, cobalt blue, Ngan, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black Inorganic pigments such as amber or organic pigments can be used.

The alkali-developable photosensitive composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

In the alkali-developable photosensitive composition of the present invention, a dispersant can be added when a pigment and / or an inorganic compound is used. As the dispersant, any colorant or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used, and polyester having a basic functional group, Polymer dispersing agent made of polyether, polyurethane, nitrogen atom as basic functional group, functional group having nitrogen atom is amine and / or quaternary salt thereof, amine value is 1 to 100 mgKOH / g Those are preferably used.

In addition, the alkali-developable photosensitive composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; Antifoaming agent; Leveling agent; Surface conditioner; Antioxidant; Ultraviolet absorber; Dispersion aid; Aggregation inhibitor; Catalyst; Effect promoter; Cross-linking agent; Can do.

In the alkali-developable photosensitive composition of the present invention, an infrared-absorbing dye (A), a polymerizable compound (B) having an ethylenically unsaturated bond, having an alkali-soluble substituent that imparts alkali developability, and a photopolymerization initiator The content of optional components other than (C) (excluding the solvent (D)) is appropriately selected according to the purpose of use and is not particularly limited, but is preferably an alkali-soluble substituent that gives the alkali developability. The content of the polymerizable compound (B) having an ethylenically unsaturated bond is 50 parts by mass or less in total with respect to 100 parts by mass.

Further, by using another organic polymer together with the polymerizable compound (B) having an ethylenically unsaturated bond having an alkali-soluble substituent that gives the alkali developability, the alkali-developable photosensitive composition of the present invention. It is also possible to improve the properties of a cured product made of a product. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are included. Masui.

In the alkali-developable photosensitive composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound and the like can be further used.

Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pen Examples include erythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate, and tripropylene glycol di (meth) acrylate. It is done.

As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compound, iodoacetates such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko K.K.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403 and the like, silane cups having an isocyanate group, a methacryloyl group, and an epoxy group. A ring agent is preferably used.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. In addition, the methylol group that is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

The alkali-developable photosensitive composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, It can be applied on a supporting substrate such as paper or plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

The active light source used for curing the alkali-developable photosensitive composition of the present invention may be a light source that emits light having a wavelength of 300 to 450 nm, such as ultra-high pressure mercury, mercury vapor. An arc, carbon arc, xenon arc, or the like can be used.

Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser beam, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

The alkali-developable photosensitive composition (or cured product thereof) of the present invention is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color television, a PC monitor, a portable information terminal, a digital camera, or the like. Color filters for liquid crystal display panels for display, color filters or infrared absorption filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, resin for optical modeling, Gel coat, electronic photoresist, electroplating resist, etching resist, both liquid and dry film, solder resist, plasma display panel, electroluminescent display device, for producing color filters for various display applications, and Resist, electric for forming structure in LCD manufacturing process And compositions for encapsulating electronic components, solder resists, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, stereo Materials for producing three-dimensional objects by lithography, holographic recording materials, image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules Used for various applications such as photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct image systems, photoresist materials used for dielectric layer formation in the sequential lamination of printed circuit boards, or protective films There is no particular limitation on its use.

The alkali-developable photosensitive composition of the present invention is useful as an alkali-developable photosensitive composition for forming a near infrared absorption filter.

The near-infrared absorption filter includes (1) a step of forming a coating film of the alkali-developable photosensitive composition of the present invention on a substrate, and (2) active light through a mask having a predetermined pattern shape on the coating film. (3) a step of developing the exposed film with a developer (particularly an alkali developer), and (4) a step of heating the film after development. The alkali-developable photosensitive composition of the present invention is also useful as a photosensitive composition for an ink jet system or a transfer system without a development process.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Example 1] Alkali-developable photosensitive composition No. 1 Preparation of Compound No. 1 as component (A) 0.16 g of 1-1 bis (trifluoromethanesulfonyl) imide salt and 3.70 g of dimethylacetamide as a part of component (D) were added and dissolved by stirring. Thereafter, 4.95 g of ACA Z250 (manufactured by Daicel Cytec Co., Ltd.) as component (B) and 1.96 g of Aronix M-450 (manufactured by Toa Gosei Co., Ltd.), 0 of OXE-01 (manufactured by BASF Corp.) as component (C) 0.07 g, 2.92 g of PGMEA as a part of component (D), 0.001 g of FZ2122 (manufactured by Toray Dow Corning) as another component, and stir until insoluble matter disappears, alkali developing photosensitive Composition No. 1 was obtained.

[Examples 2 to 13 and Comparative Examples 1 to 3] Alkali-developable photosensitive composition No. 2 to No. 13 and comparative alkali-developable photosensitive composition No. 1-No. In the same procedure as in Example 1, each component was mixed with the formulation shown in [Table 1], and the alkali-developable photosensitive composition no. 2 to No. 13 and comparative alkali-developable photosensitive composition No. 1-No. 3 was obtained.

[Examples 14 to 26 and Comparative Examples 4 to 6] Near-infrared absorbing filter no. 1-No. 13 and comparative near-infrared absorption filter no. 1-No. Production of Alkali Developable Photosensitive Composition Nos. Obtained in Examples 1 to 13 and Comparative Examples 1 to 3 on a glass substrate. 1-No. 13 and comparative alkali-developable photosensitive composition No. 1-No. 3 was added dropwise, spin-coated under the conditions of 250 rpm × 10 seconds, dried at 90 ° C. for 100 seconds, exposed to 300 mJ / cm ² with a high-pressure mercury lamp, and subjected to near-infrared absorption filter no. 1-No. 13 and comparative near-infrared absorption filter no. 1-No. 3 was created.

[Evaluation Examples 1-1 to 1-13 and Comparative Evaluation Examples 1-1 to 1-2] 1-No. 13 and comparative near-infrared absorption filter no. 1-No. 2. Alkali resistance test No. 2 of near-infrared absorption filter No. obtained in Examples 14 to 26 1-No. No. 13 and Comparative Near Infrared Absorbing Filter Nos. 1-No. For No. 2, a 2.5% potassium carbonate aqueous solution was sprayed for 180 seconds, the film thickness before and after spraying was measured, and the film thickness reduction rate was calculated to make an alkali resistance test. The results are shown in [Table 2].

[Evaluation Examples 2-1 to 2-13 and Comparative Evaluation Example 2-1] Near-infrared absorbing filter no. 1-No. 13 and comparative near-infrared absorption filter no. Measurement of the transmittance of the near-infrared absorption filter No. 1 obtained in Examples 14 to 26. 1-No. 13 and Comparative Near Infrared Absorption Filter No. For No. 3, transmittances at 900 nm, 1000 nm, and 1100 nm were measured using an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation. The results are shown in [Table 3].

[Evaluation Examples 3-1 to 3-4 and Comparative Evaluation Example 3-1]
The near-infrared absorption filter No. obtained in Examples 14, 16, 19, 24 and Comparative Example 6 was used. 1, no. 3, no. 6, no. 9 and comparative near-infrared absorption filter no. For No. 3, a 50-hour light resistance test was carried out with Xenon Light Resistance Tester Table Sun XT-1500L manufactured by Suga Test Instruments Co., Ltd., and the change in transmittance at 900 nm was evaluated. Specifically, the amount of change is a value obtained by dividing a value obtained by subtracting the transmittance before the light resistance test from the transmittance after the light resistance test by the transmittance before the light resistance test. The transmittance before the light resistance test and after the light resistance test was measured using an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation. The evaluation results are shown in [Table 4].

From the results of [Table 3] and [Table 4], the near-infrared absorption filter formed using the cured product of the alkali-developable photosensitive composition of the present invention has low transmittance at a wavelength of 900 to 1100 nm, that is, effective. Infrared rays are also blocked and light resistance is high. In addition, since the cured product has high alkali resistance, it has excellent photolithography characteristics.

Claims

Containing an infrared-absorbing dye (A), an alkali-soluble substituent that gives alkali developability, a polymerizable compound (B) having an ethylenically unsaturated bond, a photopolymerization initiator (C), and a solvent (D);
The alkali-developable photosensitive composition, wherein the photopolymerization initiator (C) contains an oxime ester compound.
The alkali-developable photosensitive composition according to claim 1, wherein the photopolymerization initiator (C) contains a compound represented by the following general formula (I).

(Wherein R 1 and R 2 are each independently a hydrogen atom, a cyano group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom number) An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent;
R 3 and R 4 are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 5 , OR 6 , SR 7 , NR 8 R 9 , COR 10 , SOR 11 , SO 2. Represents R 12 or CONR 13 R 14 ,
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 each independently has 1 to 20 carbon atoms which may have a substituent. An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a carbon atom which may have a substituent Represents a heterocyclic group of formula 2 to 20,
X represents an oxygen atom, a sulfur atom, a selenium atom, CR 15 R 16 , CO, NR 17 or PR 18 ;
R 15 , R 16 , R 17 and R 18 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an optionally substituted carbon atom having 6 carbon atoms. Represents an aryl group of ˜30 or an arylalkyl group of 7 to 30 carbon atoms which may have a substituent, and the methylene group in the alkyl group or arylalkyl group may be interrupted by —O—. ,
R 15 , R 16 , R 17 and R 18 may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 1 to 5. )
3. The alkali-developable photosensitive composition according to claim 1 or 2, wherein the infrared absorbing dye (A) is a diimonium compound.
The alkali-developable photosensitive composition according to any one of claims 1 to 3, wherein the infrared absorbing dye (A) is represented by the following general formula (II).

(In the formula, R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 each independently has 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. Represents an alkyl group, and each of R 27 , R 28 , R 29 and R 30 independently has a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent or a substituent. An methylene group in the alkyl group may be interrupted by —O— or —CH═CH—, t represents a number of 1 to 4, and An q− represents a q valence. Q represents 1 or 2, and p represents a coefficient for keeping the charge neutral.)
A cured product of the alkali-developable photosensitive composition according to any one of claims 1 to 4.
A near-infrared absorption filter formed using the cured product according to claim 5.