TW201430040A - Alkali developable photosensitive composition - Google Patents

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

Alkaline developing 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.

The photosensitive composition containing an infrared absorbing dye can be used for various uses.

Patent Document 1 discloses a color filter using a photosensitive coloring composition which is cured by irradiation with near-infrared light, and Patent Document 2 discloses a filter for a plasma display panel which can shield a wavelength in a near-infrared region. Patent Document 3 discloses an infrared photosensitive lithographic printing plate using a particulate matting agent containing an alkali-soluble resin and an infrared absorbing dye, and Patent Document 4 discloses the use of a hardening combination containing a near-infrared absorbing dye. Near-infrared absorption filter for matter.

However, the photosensitive compositions described in these documents are not satisfactory in terms of light resistance.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-230126

Patent Document 2: US2004090170A1

Patent Document 3: US2008035000A1

Patent Document 4: US2011070407A1

Therefore, an object of the present invention is to provide an alkali-developable photosensitive composition which is excellent in light resistance. Further, another object of the present invention is to provide a near-infrared absorption filter using the above-described alkali-developable photosensitive composition.

As a result of intensive studies, the inventors of the present invention have obtained an excellent viewpoint of light resistance of a cured product of an alkali-developable photosensitive composition using an oxime ester compound as a photopolymerization initiator, and obtained the above-described alkali-developed photosensitive light. The composition is suitable for the insight of a near-infrared absorbing filter to complete the present invention.

The present invention provides an alkali-developable photosensitive photo composition comprising an infrared absorbing dye (A), a polymerizable compound (B) having an alkali-soluble substituent which provides alkali developability and having an ethylenically unsaturated bond, and photopolymerization The initiator (C) and the solvent (D), and the above photopolymerization initiator (C) contains an oxime ester compound.

Moreover, the present invention provides a cured product of the above-described alkali-developable photosensitive composition, and a near-infrared absorption filter formed using the cured product.

According to the invention, the alkali-developable photosensitive composition containing an oxime ester compound as a photopolymerization initiator is excellent in light resistance. Further, the near-infrared absorption filter formed using the cured product has a low transmittance at a wavelength of 900 to 1100 nm, and effectively shields infrared rays, and the cured product has high alkali resistance, so that the light lithography characteristics are excellent.

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 contains an infrared absorbing dye (A), an alkali-soluble substituent which provides alkali developability, and a polymerizable property having an ethylenically unsaturated bond. Compound (B), photopolymerization initiator (C) and solvent (D). Hereinafter, each component will be described in order.

<Infrared absorbing pigment (A)>

The infrared absorbing dye (A) used in the alkali-developable photosensitive composition of the present invention can be used for infrared absorption in the infrared region and used as an infrared absorbing dye, for example, a cyanine compound or a squary squary compound. a porphyrin compound, a metal dithiol complex, a chromium, a cobalt metal salt compound, an anthracene, a phthalocyanine compound, a naphtholphthalate compound, a diimonium compound, an inorganic oxide particle, etc., wherein the diimmonium The compound has a high infrared absorbing ability and a high transparency in the visible light region, which is preferable.

Among the above-described diimmonium compounds, those represented by the following formula (II) are more preferred because they have excellent light resistance of the cured product of the photosensitive composition.

(wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent or an amine group which may have a substituent, and a methylene group in the above alkyl group The base can be interrupted by -O- or -CH=CH-, t represents the number from 1 to 4, An ^q- represents the q-valent anion, q represents 1 or 2, and p represents the coefficient that keeps the charge neutral.

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 in the above formula (II) may have a substitution. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group, tert-butyl group, isobutyl group, pentyl group and isoprene. Base, third amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, third octyl, 2-B Hexyl, trifluoromethyl, trichloromethyl, tribromomethyl, 1,2-dichloroethyl, 3,3,3-trifluoropropyl, prop-1-en-1-yl, etc. 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, and may be represented by R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ . The amine group of the substituent may, for example, be an amine group, an ethylamino group, a dimethylamino group, a diethylamino group, a butylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, or twelve. Alkylamino, anilino, chlorophenylamino, toluidine, methoxyaniline, N-methyl-aniline , diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, ethylamino, benzhydrylamine, formamylamine , trimethylethenylamine, laurylamine, amine carbylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, Polinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino , phenoxycarbonylamino, aminesulfonylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonate Amino group and the like.

As the q-valent anion represented by pAn ^q- in the above formula (II), except for the methanesulfonic acid anion, the dodecylsulfonate anion, the benzenesulfonic acid anion, the toluenesulfonic acid anion, the trifluoromethanesulfonate anion, Naphthalenesulfonate anion, diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5-nitrobenzenesulfonate anion, Japanese patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2001-209969, JP-A-2001-322354, JP-A-2006-248180, JP-A-2006-297907, JP-A-8-253705, and JP-A In addition to the organic sulfonic acid anion such as a sulfonic acid anion described in the above-mentioned Japanese Patent Publication No. Hei. No. 2005-336150, and the like, the chloride ion and the bromide ion, Iodide ion, fluoride ion, chlorine Acid ion, thiocyanate ion, perchlorate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroboric acid ion, 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(pentafluorophenyl)borate ion, sulfonyl group a quinone imine anion, a quenching anion having a function of de-exciting (quenching) an active molecule in an excited state, or an anionic group having a carboxyl group or a phosphonic acid group or a sulfonic acid group on the cyclopentadienyl ring A metallocene compound anion such as ferrocene or ferrocene.

Specific examples of the compound represented by the above formula (II) of the present invention include the following compounds No. 1-1 to 1-8. Further, in the following examples, the cation obtained by removing an anion is represented.

[Chemical 2]

The above infrared absorbing dye (A) may be used singly or in combination of plural kinds.

In the infrared absorbing dye (A), the content of the compound represented by the above formula (II) is preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass. When the content of the compound represented by the above formula (II) is less than 50% by mass, the solubility in a solvent may be lowered or the stability of the cured product may be lowered.

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

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

<Polymerizable compound (B) having an alkali-soluble substituent which provides alkali developability and having an ethylenically unsaturated bond>

The polymerizable compound (B) having an alkali-soluble substituent which provides an alkali developability and having an ethylenically unsaturated bond is not particularly limited, and a user who has previously used an alkali-developable photosensitive composition can be used, for example, Use (meth)acrylic acid, α-chloroacrylic acid, methylene succinic acid, maleic acid, methyl maleic acid, fumaric acid, bicycloheptene dicarboxylic acid, crotonic acid, isobutylene Acid, vinyl acetate, allyl acetic acid, cinnamic acid, hexadienoic acid, mesaconic acid, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) Acryloxyethyl]ester, ω-carboxypolycaprolactone mono(meth)acrylate is equivalent to a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, and a hydroxyl group (meth)acrylate Ester-maleate, hydroxypropyl (meth)acrylate-maleate, dicyclopentadiene-maleate or have one carboxyl group and two or more (methyl An unsaturated polybasic acid such as a polyfunctional (meth) acrylate such as acrylonitrile; pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. a polyfunctional acrylate having a hydroxyl value of a hydroxyl group-containing polyfunctional acrylate and a reaction product of a dibasic acid anhydride such as succinic anhydride, phthalic anhydride or tetrahydrophthalic anhydride; methyl (meth)acrylate, Ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate Ester, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)acrylic acid (meth)acrylates such as esters, 2-hydroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate; N-vinylpyrrolidone; styrene and its derivatives, α-methyl Styrene such as styrene; (meth) acrylamide, hydroxymethyl (meth) acrylamide, alkoxy hydroxymethyl (meth) acrylamide, diacetone (meth) acrylamide, etc. Acrylamides; other vinyl compounds such as (meth)acrylonitrile, ethylene, propylene, butene, vinyl chloride, vinyl acetate, and polymethyl methacrylate macromonomers, polystyrene macromonomers, etc. Monomeric, tricyclodecane skeleton monomethacrylate, N-phenyl maleimide, methacryloxymethyl-3-ethyloxetane, etc. Copolymer of acrylic acid and copolymer of (meth)acrylic acid obtained by reacting the isocyanate compound having an unsaturated bond such as Karenz MOI and AOI manufactured by Showa Denko Co., Ltd., or phenol and/or cresol novolac Varnish epoxy resin, novolac epoxy resin with biphenyl skeleton, naphthalene skeleton, bisphenol A novolak epoxy compound, dicyclopentadiene A novolak type epoxy compound such as an aldehyde varnish type epoxy compound, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy group such as an epoxy compound represented by the following formula (1) A resin obtained by the action of an unsaturated monobasic acid and further with a polybasic acid anhydride. These monomers may be used alone or in combination of two or more. Further, 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 represents a direct bond, a methylene group, an alkylene 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), which may be substituted by a halogen atom, R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the above alkane a base, an alkoxy group and an alkenyl group may be substituted by a halogen atom, and m is an integer of 0 to 10)

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

(wherein Y ² and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, and may be substituted by a halogen atom An aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an aralkenyl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, may pass through a halogen atom a substituted aralkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom, or a halogen atom, and an alkyl group in the above alkyl group and aralkyl group may be omitted Saturated bond, -O- or -S-interrupt, Z ² can be adjacent to Z ² to form a ring, p represents an integer from 0 to 4, q represents an integer from 0 to 8, r represents an integer from 0 to 4, and s represents 0. An integer of ~4, the sum of r and s is an integer from 2 to 4)

Examples of the unsaturated monobasic acid which acts on the epoxy group of the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, hexadienoic acid, hydroxyethyl methacrylate-maleic acid hydroxyB. Ester and the like. Mention may be made of: hydroxyethyl acrylate-hydroxyethyl methacrylate, hydroxypropyl methacrylate-hydroxypropyl methacrylate, hydroxypropyl acrylate-hydroxypropyl maleate, dicyclopentane Diene-maleate and the like.

Further, examples of the polybasic acid anhydride which acts after the action of the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, and trimellitic anhydride. , pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol double-dehydrated trimellitic acid ester, triglyceride trimellitic acid ester, hexahydroorthophthalate Formic anhydride, methyltetrahydrophthalic anhydride, ceric acid anhydride, methylic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-di Side oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl Succinic anhydride, methyl bicycloheptene dicarboxylic anhydride, and the like.

The reaction molar of the above epoxy compound, the above unsaturated monobasic acid, and the above polybasic acid anhydride is preferably as follows. In other words, it is preferred to use an epoxy resin having a structure in which 0.1 to 1.0 of the carboxyl group of the unsaturated monobasic acid is added to one epoxy group of the epoxy compound, and the epoxy resin is formed with respect to the epoxy. One hydroxyl group of the adduct, and the acid anhydride structure of the above polybasic acid anhydride is in a ratio of 0.1 to 1.0.

The reaction of the above epoxy compound, the above unsaturated monobasic acid, and the above polybasic acid anhydride can be carried out in accordance with a usual method.

Development of an alkali-developable photosensitive composition of the present invention for adjusting the acid value As the above, the compound (B) having an alkali-soluble substituent which provides alkali developability and having an ethylenically unsaturated bond can be used, and a monofunctional or polyfunctional epoxy compound is further used. The alkali-developable compound having an ethylenically unsaturated bond preferably has an acid value of the solid content of 5 to 120 mgKOH/g, and the monofunctional or polyfunctional epoxy compound is preferably used to satisfy the above acid value. The way to make a choice.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, and butyl shrinkage. Glyceryl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, sulfhydryl Glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, fifteen Alkyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidol Ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyltolyl glycidyl ether, 4-mercapto Phenyl glycidyl ether, benzyl glycidyl , p-Phenylphenyl phenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate Ester, vinyl cyclohexane oxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, decene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the following Compound No. A2, No. A3, and the like.

When one or more selected from the group consisting of a bisphenol epoxy compound and a glycidyl ether are used as the polyfunctional epoxy compound, an alkali-developable photosensitive composition having better characteristics can be obtained. good. In addition to the epoxy compound represented by the above formula (1), a bisphenol epoxy compound such as a hydrogenated bisphenol epoxy compound can be used as the bisphenol epoxy compound. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. 8-octanediol diglycidyl ether, 1,10-nonanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, three Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, 1,1,1-tris (glycidol) Oxymethyl)propane, 1,1,1-tris(glycidoxymethyl)ethane, 1,1,1-tris(glycidoxymethyl)methane, 1,1,1,1- Tetrakis(glycidoxymethyl)methane.

In addition to this, a phenol novolac type epoxy compound, a biphenol novolak type epoxy compound, a cresol novolac type epoxy compound, a bisphenol A novolac type epoxy compound, a dicyclopentadiene novolac type varnish may also be used. Novolac type epoxy compound such as epoxy compound; 3,4-epoxy-6-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexylmethyl ester, 3,4-epoxy An alicyclic epoxy compound such as cyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester or 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, four Glycidyl esters such as hydrogen diglycol diglycidyl ester and dimer acid glycidyl ester; tetraglycidyldiamine diphenylmethane, triglycidyl p-aminophenol, N,N-diglycidyl Alkaloids and other shrinkage Glycosylamines; 1,3-diglycidyl-5,5-dimethylhydantoin, heteroglycidyl compounds such as triglycidyl isocyanurate; dicyclopentadiene dioxide An oxide compound; a naphthalene type epoxy compound, a triphenylmethane type epoxy compound, a dicyclopentadiene type epoxy compound, or the like.

Among the above-mentioned polymerizable compounds (B) having an alkali-soluble substituent which provides an alkali-developable alkali-soluble substituent, it is preferably unsaturated in terms of compatibility, alkali developability and heat resistance. A polybasic acid, a polyfunctional acrylate having an acid value, a resin obtained by allowing an epoxy group to react with an unsaturated monobasic acid, and further a polybasic acid anhydride, more preferably an unsaturated polybasic acid.

In the photosensitive composition of the present invention, the content of the polymerizable compound (B) having an alkali-developable alkali-soluble substituent and having an ethylenically unsaturated bond is contained in the alkaline-developable photosensitive composition of the present invention. The solid content of the solid content is preferably from 30 to 99% by mass, particularly preferably from 60 to 95% by mass. When the content of the polymerizable compound (B) having an alkali-soluble substituent which provides an alkali developability and having an ethylenically unsaturated bond is less than 30% by mass, the mechanical strength of the cured product is insufficient to cause cracking or development failure. In the case where the content of the polymerizable compound (B) having an alkali-soluble substituent which provides an alkali developability and the ethylenically unsaturated bond is more than 99% by mass, the hardening due to exposure may be insufficient to cause wrinkles. Or the development time becomes longer and the hardened portion is also damaged by the alkali.

<Photopolymerization initiator (C)>

As the photopolymerization initiator (C), a previously known compound can be used, and examples thereof include an acetophenone compound, a benzophenone compound, a benzoin compound, a benzoin compound, a benzyl ketal compound, and an oxime ester. Compound, mercaptophosphine compound, three Compound, Ketone compound, 9-oxo sulfur a compound, a benzoquinone compound, an anthraquinone compound, a disulfide compound, a biimidazole compound, 4,4-azobisisobutyronitrile, camphorquinone, benzoyl peroxide, etc., as a commercial item, N- 1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (manufactured by Adeka Corporation), IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF Corporation), and the like.

Among the photopolymerization initiators (C), an oxime ester compound is preferred from the viewpoint of sensitivity and color tone, and a compound represented by the following formula (I) is further preferred.

(wherein R ¹ and R ² each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; An aralkyl group having 7 to 30 carbon atoms having a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, and a cyanogen group. a group, a hydroxyl group, a carboxyl group, R ⁵ , OR ⁶ , SR ⁷ , NR ⁸ R ⁹ , COR ¹⁰ , SOR ¹¹ , SO ₂ 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 represent an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent. An aralkyl group having 7 to 30 carbon atoms having a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, and 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 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group or a carbon atom which may have a substituent Aralkyl of 7 to 30, the above alkyl or aralkyl group of the methylene groups may be interrupted with ^{-O-, R 15, R 16, R} 17 and R ¹⁸ may be independently with any of a benzene ring adjacent to the Form a ring, a represents an integer from 0 to 4, and b represents an integer from 1 to 5)

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 in the} above formula (I) The alkyl group having 1 to 20 carbon atoms represented by R ¹⁷ and R ¹⁸ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group or a third butyl group. Base, pentyl, isopentyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, fluorenyl, isodecyl , undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and the like.

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 in the} above formula (I) Examples of the aryl group having 6 to 30 carbon atoms represented by R ¹⁷ and R ¹⁸ include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and a aryl group. Any of the above alkyl-substituted phenyl, biphenyl, naphthyl, anthryl and the like.

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 in the} above formula (I) Examples of the aralkyl group having 7 to 30 carbon atoms represented by R ¹⁷ and R ¹⁸ include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and the like. .

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 in the} above formula (I) Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ¹⁷ and R ¹⁸ include, for example, a pyridyl group, a pyrimidinyl group, a furyl group, a thienyl group, a tetrahydrofuranyl group, a dioxolyl group, and a benzo group. Zyridin-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, tetrahydrothiazolyl, isotetrahydrothiazolyl, oxazolidine, isoxazolidine, piperidinyl, piperidine A 5- to 5-membered heterocyclic ring such as a pyridyl group or a morpholinyl group.

The ring in which R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ in the above formula (I) can be formed together with an adjacent benzene ring, for example, a cyclopentane ring, a cyclohexane ring or a cyclopentane is preferably exemplified. 5~7 member rings such as olefin ring, benzene ring, piperidine ring, morpholine ring, lactone ring and indoleamine ring.

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

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

[化8]

[Chemistry 9]

In the alkaline-developable photosensitive composition of the present invention, the content of the photopolymerization initiator (C) is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 30% by mass, based on the alkali-developable photosensitive composition of the present invention. 0.5 to 10% by mass. When the content of the photopolymerization initiator (C) is less than 0.1% by mass, the curing due to exposure may be insufficient, and if the content of the photopolymerization initiator (C) is more than 30% by mass, there is The case where the photopolymerization initiator (C) is precipitated in the alkali-developable photosensitive composition.

The ratio of the oxime ester compound in the above photopolymerization initiator (C) to alkaline development The solid content component of the composition is preferably from 0.1 to 30% by mass, and more preferably from 0.5 to 10% by mass.

<Solvent (D)>

Further, a solvent (D) can be further added to the alkali-developable photosensitive composition of the present invention. The solvent is usually a solvent which can dissolve or disperse the above-mentioned respective components (the infrared absorbing dye (A) of the present invention) as needed, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, diacetone alcohol; diethyl ether, two An ether solvent such as an alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Isopropyl ester, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, TEXANOL (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), etc. An ester solvent; a cellulosic solvent such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; an alcohol solvent such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol or pentanol; Ethylene glycol monoacetate, ethylene glycol monoacetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate , an ether ester solvent such as ethoxyethyl propionate; BTX (benzene, toluene, xylene, benzene, toluene, xylene) solvent such as benzene, toluene or xylene; hexane, heptane, octane, cyclohexane An aliphatic hydrocarbon solvent such as an alkane; a terpene hydrocarbon oil such as turpentine, D-limonene or decene; a paraffinic solvent such as mineral oil, Swazol #310 (Cosmo pine oil), Solvesso #100 (Exxon Chemical); Carbon chloride, chlorine a halogenated aliphatic hydrocarbon solvent such as trichloroethylene, dichloromethane or 1,2-dichloroethane; a halogenated aromatic hydrocarbon solvent such as chlorobenzene; a carbitol solvent, aniline, triethylamine, pyridine, acetic acid , acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine, water, etc., such solvents can be used Or use it as a mixed solvent of two or more types. Among these, ketones, ether ester solvents, and the like are, in particular, propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, dimethylacetamide, methyl ethyl ketone, diacetone alcohol, and the like. It is preferable that the alkali-developable photosensitive composition has good compatibility with a resist and a photopolymerization initiator.

In the alkaline-developable photosensitive composition of the present invention, the solvent (D) is preferably used in an amount of 5 to 30% by mass, and less than 5% by mass, based on the solvent (D). In this case, it is difficult to increase the thickness of the film, and it is not possible to sufficiently absorb the light of the desired wavelength, and therefore it is not preferable. When the content exceeds 30% by mass, the storage property of the composition is lowered or the viscosity is improved due to precipitation of the composition. Sexual decline, so it is not good.

Further, 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 may be used singly or in combination of two or more.

As the inorganic color material and/or the organic color material, for example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, or the like can be used. a compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, an isoindolinone compound, an isoporphyrin compound, a quinacridone compound, an indolinone compound, a purple ring ketone compound, an anthraquinone compound , diketopyrrolopyrrole compounds, thioindigo compounds, two Compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; carbon black obtained by furnace method, channel method, thermal method Or carbon black such as acetylene black, ketjen black or lamp black; the epoxy black is used to adjust and coat the carbon black, and the carbon black is dispersed in a solvent with a resin in advance and adsorbed with a resin of 20 to 200 mg/g. The product obtained by subjecting the carbon black to an acidic or alkaline surface treatment, having an average particle diameter of 8 nm or more and DBP (Dibutyl Phthalate) having an oil absorption of 90 ml/100 g or less, according to 950 ° C The total oxygen amount calculated from the CO and CO ₂ in the volatile component is 9 mg or more per 100 m ² of the surface area of the carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon Nano angle, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chrome oxide green, milorie blue, cobalt green, cobalt blue, manganese, ferrocyanide, Phosphate ultramarine, iron blue, ultramarine blue, sky blue, chrome green, emerald green Lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, synthetic iron black, umber inorganic or organic pigment.

Further, the alkali-developable photosensitive composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, cerium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, cerium oxide, and aluminum oxide; layered clay minerals and rice. Lolita Blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum citrate, calcium citrate, hydrogen Alumina, platinum, gold, silver, copper, etc., among these, titanium oxide, cerium oxide, layered clay mineral, silver, etc. are preferable.

These inorganic compounds can be used, for example, as a filler, an antireflection agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength improving agent, a special wavelength absorber, an ink repellent, and the like.

When a pigment and/or an inorganic compound is used for the alkali-developable photosensitive composition of the present invention, a dispersing agent may be added. As the dispersing agent, any dispersing agent may be used as long as it can disperse and stabilize the color material or the inorganic compound, and a commercially available dispersing agent such as BYK series manufactured by BYK-Chemie Co., Ltd., or the like can be preferably used. Using a polymer dispersant comprising a polyester having a basic functional group, a polyether, a polyurethane, a functional group having a nitrogen atom as a basic functional group, and having a nitrogen atom, and/or a quaternary salt thereof The amine value is 1 to 100 mgKOH/g.

Further, in the alkaline-developable photosensitive composition of the present invention, thermal polymerization inhibition such as para-anisole, hydroquinone, catechol, tert-butylcatechol, and phenothiazine may be added as needed. Agent; plasticizer; subsequent accelerator; filler; defoamer; leveling agent; surface conditioner; antioxidant; ultraviolet absorber; dispersing aid; anti-agglomerating agent; catalyst; effect promoter; Additives such as tackifiers.

In the alkali-developable photosensitive composition of the present invention, the infrared absorbing dye (A), the polymerizable compound (B) having an alkali-soluble substituent which provides alkali developability and having an ethylenically unsaturated bond, and photopolymerization The content of any component other than the initiator (C) (excluding the solvent (D)) can be appropriately selected depending on the purpose of use, and is not particularly limited, and it is preferably provided to provide alkali developability with respect to the above. Alkali soluble substituent and having ethylene The content of the polymerizable compound (B) of the unsaturated bond is 100 parts by mass or less in total of 50 parts by mass or less.

Further, by using the above-mentioned polymerizable compound (B) having an alkali-soluble substituent which provides alkali developability and having an ethylenically unsaturated bond, and using other organic polymer, it is also possible to improve the alkaline development and sexyness including the present invention. The properties of the cured product of the photo composition. Examples of the above organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS (Acrylonitrile Butadiene Styrene, acrylonitrile-butadiene-styrene copolymerization Resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polybutyrate, cellulose ester, polypropylene decylamine, saturated polyester, phenolic resin, phenoxy resin, poly Among them, amidoxime resin, a polyaminic acid resin, an epoxy resin, etc., among these, a polystyrene, a (meth)acrylic-methyl methacrylate copolymer, and an epoxy resin are preferable.

A monomer having a unsaturated bond, a chain transfer agent, a sensitizer, a surfactant, a decane coupling agent, a melamine compound, or the like can be further used in the alkali-developable photosensitive composition of the present invention.

Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isodecyl acrylate, and acrylic acid. Stearyl ester, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxy methacrylate Ethyl ester, 2-hydroxypropyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate , dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z condensed water sweet Oleic ether (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like.

As the chain transfer agent or the sensitizer, a compound containing a sulfur atom can be usually used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-amidinopropyl)glycolamine Acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)amine-methylhydrazine]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-( 3-mercaptopropyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercapto Ethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, nonylphenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzophenone a mercapto compound such as imidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid or the like, an alkyl iodide compound, trimethylolpropane trisole (3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylnonylbenzene, butyl Alcohol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, Trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trishydroxyethyl trithiopropionate, An aliphatic polyfunctional thiol compound such as the following compound No. C1, tris-propionic acid tris(2-hydroxyethyl)isocyanurate, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko Co., Ltd., and the like.

As the above surfactant, a fluorosurfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate; an anionic interfacial activity such as an alkali metal salt of a higher fatty acid, an alkyl sulfonate or an alkyl sulfate; a cationic surfactant such as a higher amine hydrohalide or a quaternary ammonium salt; a nonionic such as a polyethylene glycol alkyl ether, a polyethylene glycol fatty acid ester, a sorbitan fatty acid ester, or a fatty acid monoglyceride; Surfactants such as surfactants, amphoteric surfactants, and polyoxo-based surfactants can be used in combination.

As the decane coupling agent, for example, a decane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. may be used, and among them, KBE-9007, KBM-502, KBE-403, etc. having an isocyanate group, a methacryl fluorenyl group, or an epoxy group can be preferably used. Decane coupling agent.

Examples of the above melamine compound include (poly)methylol melamine, (poly)methylol glycoluril, and (poly)hydroxymethylphenylhydrazine. A compound in which all or a part (at least two) of the active methylol groups (CH ₂ OH groups) in the nitrogen compound such as (poly)hydroxymethyl urea are alkylated with an alkyl group. 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 or different from each other. Further, the methylol group which has not been subjected to alkyl etherification can be self-condensed in one molecule, or can be condensed between two molecules to form an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril or the like can be used. Among these, melamine which is alkyl etherified, such as hexamethoxymethyl melamine or hexabutoxymethyl melamine, is preferable.

The alkali-developable photosensitive composition of the present invention can be known by a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, and the like. The mechanism is used on a support substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, and the like. Further, after being temporarily applied to a support substrate such as a film, it may be transferred onto another support substrate, and the application method is not limited.

Further, as a light source for the active light used for curing the alkali-developable photosensitive composition of the present invention, a light having a wavelength of 300 to 450 nm can be used, and for example, it can be used. Ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc.

Further, laser direct lithography which directly forms an image by using laser light by an exposure light source without using a reticle and based on digital information such as a computer can not only achieve productivity but also improve resolution or positional accuracy. Therefore, as the laser light, light of a wavelength of 340 to 430 nm can be preferably used, and an argon ion laser, a krypton laser, and a YAG (Yttrium Aluminum Garnet) laser can also be used. And semiconductor lasers, etc. that emit light from the visible region to the infrared region. In the case of using such lasers, a sensitizing dye that absorbs the region visible to the infrared is added.

The alkali-developable photosensitive composition of the present invention (or the cured product) can be used for a photocurable paint or varnish; a photocurable adhesive; a printed substrate, a color television, a PC display, a personal digital assistant, a digital camera, etc. Color filter in color display liquid crystal display panel; color filter or infrared absorption filter of CCD (Charge Coupled Device) image sensor; electrode material for plasma display panel, powder coating Layer, printing ink, printing plate, adhesive, dental composition, photo-forming resin, gel coating, photoresist for electronic engineering, plating resist, etching resist, liquid and dry film a solder resist, a resist for manufacturing various color filters for display purposes, or a resist for forming a structure in a plasma display panel, an electroluminescent display device, and a manufacturing step of the LCD; Sealed into electrical and electronic parts; solder resist; magnetic recording material; micro mechanical parts; waveguide; optical switch; mask for plating; etching mask; color test system; Line coating; template for screen printing; material for manufacturing three-dimensional object by stereolithography; material for holographic recording; image recording material; fine electronic circuit; decolorizing material; decolorizing material for image recording material a decolorizing material for image recording materials using microcapsules; a photoresist material for printed wiring boards; a photoresist material for UV and visible laser direct image systems; and a dielectric for successively laminating printed circuit boards There are no particular restrictions on the use of the layer of the photoresist material or the protective film for various purposes.

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 can be preferably formed by: (1) forming a coating film of the alkali-developable photosensitive composition of the present invention on a substrate; (2) passing through a shape having a specific pattern The mask irradiates the coating film with active light; (3) develops the exposed film by a developing solution (especially an alkaline developing solution); (4) heats the film after development. Further, the alkali-developable photosensitive composition of the present invention is also useful as a photosensitive composition for an inkjet method or a transfer method without a developing step.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the examples.

[Example 1] Preparation of alkaline developing photosensitive photo composition No. 1

0.16 g of bis(trifluoromethanesulfonyl) sulfinium salt of the compound No. 1-1 as the component (A) and 3.70 g of dimethylacetamide as a part of the component (D) were added and stirred. Let it dissolve. Then, 4.75 g of ACA Z250 (manufactured by Daicel-Cytec Co., Ltd.) and 1.96 g of ARONIX M-450 (manufactured by Toagosei Co., Ltd.) and OXE-01 (manufactured by BASF Corporation) as a component (C) were added as the component (B). g, 2.92 g of PGMEA as a part of the component (D), and 0.001 g of FZ2122 (manufactured by Dow Corning Toray Co., Ltd.) as another component, and stirred until the insoluble matter disappears, thereby obtaining an alkali-developable photosensitive composition No. 1.

[Examples 2 to 13 and Comparative Examples 1 to 3] Adjustment of alkaline development photosensitive composition No. 2 to No. 13 and comparative alkaline development photosensitive composition No. 1 to No. 3

In the same manner as in Example 1, the components were mixed according to the components shown in [Table 1] to obtain an alkali-developable photosensitive composition No. 2 to No. 13 and a comparative alkaline-developing photosensitive combination. Object No.1~No.3.

[Table 1]

[11]

[Examples 14 to 26 and Comparative Examples 4 to 6] Manufacturing of near-infrared absorption filters No. 1 to No. 13 and comparative near-infrared absorption filters No. 1 to No. 3

The alkali-developable photosensitive composition Nos. 1 to No. 13 obtained in Examples 1 to 13 and Comparative Examples 1 to 3 and the comparative alkaline-developable photosensitive composition No. 1 to No were dropped on the glass substrate. .3 2.5 mL, spin-coated at 250 rpm × 10 s, dried at 90 ° C for 100 seconds, and exposed to 300 mJ/cm ² using a high-pressure mercury lamp to produce a near-infrared absorbing filter No. 1 to No. And compare near infrared absorption filters No.1~No.3.

[Evaluation Examples 1-1 to 1-13 and Comparative Evaluation Examples 1-1 to 1-2] Near-infrared absorption filters No. 1 to No. 13 and comparative near-infrared absorption filters No. 1 to No. 2 Alkali resistance test

The near-infrared absorption filters No. 1 to No. 2 obtained in the near-infrared absorption filters Nos. 1 to No. 13 and Comparative Examples 4 to 5 obtained in Examples 14 to 26 were sprayed for 180 seconds 2.5. The potassium carbonate aqueous solution was measured for the film thickness before and after the spraying, and the film thickness reduction rate was calculated, thereby setting the alkali resistance test. The results are shown in [Table 2].

[Evaluation Examples 2-1 to 2-13 and Comparative Evaluation Example 2-1] Measurement of Transmittance of Near Infrared Absorption Filters No. 1 to No. 13 and Comparative Near Infrared Absorption Filter No. 3

The near-infrared absorbing filters No. 1 to No. 13 obtained in Examples 14 to 26 and the comparative near-infrared absorbing filter No. 3 obtained in Comparative Example 6 were used, and UV-visible near-infrared rays manufactured by JASCO Corporation were used. The spectrophotometer V-570 measures the transmittance at 900 nm, 1000 nm, and 1100 nm. The results are shown in [Table 3].

[Evaluation Examples 3-1 to 3-4 and Comparative Evaluation Example 3-1]

The near-infrared absorption filters No. 1, No. 3, No. 6, No. 9, and comparative near-infrared absorption filter No. 3 obtained in Examples 14, 16, 19, 24 and Comparative Example 6, The Xenon light resistance tester Table Sun XT-1500L manufactured by the Suga test machine was subjected to a 50-hour light resistance test, and the amount of change in transmittance at 900 nm was evaluated. Specifically, the amount of change is a value obtained by dividing the transmittance after the light resistance test by the transmittance before 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].

According to the results of [Table 3] and [Table 4], it is understood that the near-infrared absorption filter formed by using the cured product of the alkali-developable photosensitive composition of the present invention has a low transmittance at a wavelength of 900 to 1100 nm. The ground shields infrared rays and has high light resistance. Further, since the cured product has high alkali resistance, it is excellent in photolithographic properties.

Claims (6)

An alkali-developable photosensitive composition comprising an infrared absorbing dye (A), a polymerizable compound (B) having an alkali-soluble substituent which provides an alkali developability, and an ethylenically unsaturated bond, and light The polymerization initiator (C) and the solvent (D), and the above photopolymerization initiator (C) contains an oxime ester compound. The alkaline-developable photosensitive composition according to claim 1, wherein the photopolymerization initiator (C) contains a compound represented by the following formula (I), (wherein R ¹ and R ² each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; An aralkyl group having 7 to 30 carbon atoms having a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, and a cyanogen group. a group, a hydroxyl group, a carboxyl group, R ⁵ , OR ⁶ , SR ⁷ , NR ⁸ R ⁹ , COR ¹⁰ , SOR ¹¹ , SO ₂ 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 represent an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent. An aralkyl group having 7 to 30 carbon atoms having a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, and 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 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group or a carbon atom which may have a substituent a 7 to 30 aralkyl group, the methylene group in the above alkyl group or aralkyl group may be interrupted by -O-, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be independently and adjacent to any one of the benzene rings. Form a ring together, a represents an integer from 0 to 4, and b represents an integer from 1 to 5. The alkaline-developable photosensitive composition according to claim 1, wherein the infrared absorbing dye (A) is a diimmonium compound. The alkaline-developable photosensitive composition according to claim 1, wherein the infrared absorbing dye (A) is represented by the following formula (II). (wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent or an amine group which may have a substituent, and a methylene group in the above alkyl group The base may be interrupted by -O- or -CH=CH-, t represents the number from 1 to 4, An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral. A cured product which is a cured product of the alkali-developable photosensitive composition of claim 1. A near-infrared absorbing filter formed using the cured product of claim 5.