JP2022096687A - Infrared absorbing composition and near-infrared cut filter - Google Patents

Abstract

To provide an infrared absorbing composition which offers sufficient development speed in photolithography and provides high heat resistance and light resistance when used for a near-infrared cut filter.SOLUTION: An infrared absorbing composition is provided, comprising a squarylium compound having a maximum absorption wavelength in a range between 700 and 900 nm, a resin-type dispersant, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, where the squarylium compound is at least a compound represented by a general formula below.SELECTED DRAWING: None

Description

The present invention relates to an infrared absorbing composition.

The near-infrared cut filter is used for infrared absorbing films and infrared absorbing plates that block heat rays for energy saving, agricultural infrared absorbing films for the selective use of sunlight, and recording media that use the absorbed heat of infrared rays. Infrared cut filter for electronic devices, infrared filter for photography, protective glasses, sunglasses, heat ray blocking film, dye for optical recording, optical character reading and recording, for preventing copying of confidential documents, electrophotographic photosensitive member, laser fusion, biometric authentication (fingerprint) Sensors for authentication and infrared authentication) are known.

Further, CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), which are solid-state image pickup elements for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Since the solid-state image sensor uses a silicon photodiode that is sensitive to infrared rays in its light receiving portion, it is necessary to correct the visual sensitivity, and a near-infrared cut filter is often used for this.

Squalylium compounds, phthalocyanine compounds, cyanine compounds, and diimonium compounds are known as typical infrared absorbing compounds used in infrared absorbing compositions that form near-infrared cut filters. As the phthalocyanine compound, a phthalocyanine compound or a naphthalocyanine compound having a substituent, a phthalocyanine compound having an amino group, a phthalocyanine compound having an aryloxy group, a fluorine-containing phthalocyanine compound and the like are known.

Patent Document 1 discloses an infrared absorbing composition.

Japanese Unexamined Patent Publication No. 2016-164670

However, the near-infrared cut filter is required to have further improvement in heat resistance and light resistance in addition to infrared shielding property. In addition, coloring due to heating or light irradiation during the manufacture of the near-infrared cut filter is unlikely to occur, and excellent visible transparency is required. Moreover, the development speed of the conventional infrared absorbing composition was not at a satisfactory level.

An object of the present invention is to provide an infrared absorbing composition capable of forming a near-infrared cut filter having sufficient development speed by a photolithography method and having high heat resistance and light resistance.

The infrared-absorbing composition of the present invention comprises a squarylium compound (A), a resin-type dispersant (B), an alkali-soluble resin (C), and a polymerization having a maximum absorption wavelength in the wavelength range of 400 to 1000 nm between 700 and 900 nm. An infrared-absorbing composition comprising a sex compound (D) and a photopolymerization initiator (E).
The squarylium compound (A) is at least one of the compounds represented by the following general formulas (1) and (2).
An infrared-absorbing composition in which the alkali-soluble resin (C) is a resin having a cyclic structure-containing unit in the main chain.

(In the general formula (1), X ₁₀₁ to X ₁₁₀ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. May have an aryl group, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group,-. SO ₂ NR ₁₀₁ R ₁₀₂ , -COOR ₁₀₁ , -CONR ₁₀₁ R ₁₀₂ , represents a nitro group, a cyano group or a halogen atom. R ₁₀₁ and R ₁₀₂ may independently have a hydrogen atom and a substituent, respectively. Representing an alkyl group. In X ₁₀₁ to X ₁₁₀ , substituents may be bonded to each other to form a ring.
In the general formula (2), Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. If Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, then X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ shall not be present.
R ₁ to R ₅ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M ⁺ , or a halogen atom. M ⁺ represents an inorganic or organic cation.
Each of X ₂₀₁ to X ₂₀₈ independently contains a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₆ R ₇ , sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , represents a nitro group, a cyano group or a halogen atom. X ₂₀₁ to X ₂₀₈ may be coupled to each other to form a ring.
R ₆ to R ₁₂ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. R ₆ and R ₇ , R ₈ and R _{9, and} R ₁₁ and R ₁₂ may be coupled to each other to form a ring. )

INDUSTRIAL APPLICABILITY According to the above invention, it is possible to provide an infrared absorbing composition capable of forming a near-infrared cut filter having sufficient development speed by a photolithography method and having high heat resistance and light resistance, and a near-infrared cut filter.

Hereinafter, each constituent component of the coloring composition of the present invention will be described.
When the term "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" is used herein, the description thereof is particularly described. Unless otherwise indicated, they represent "acrylloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid", respectively. .. "CI" is a color index (CI). The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, a (meth) acryloyl group, and an allyl group. The monomer is a polymerizable unsaturated group-containing compound.

<Squarylium compound (A)>
The infrared absorbent composition of the present invention contains a squarylium compound (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 700 and 900 nm. Since the maximum absorption wavelength is 700 to 900 nm, light in the near-infrared region detected as noise can be widely cut to the long wavelength side. The value of the maximum absorption wavelength of the squalylium compound (A) is a value measured by the method described in Examples described later.

The content of the squarylium compound (A) is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass, based on 100 parts by mass of the non-volatile content of the infrared absorbing composition. Appropriate infrared absorption can be obtained by containing an appropriate amount.

The squalylium compound (A) has (I2) / (I1) of 0.5 or less when the absorbance at the maximum absorption wavelength in the range of 400 to 1000 nm is (I1) and the absorbance at 650 nm is (I2). Is preferable.

The squarylium compound (A) is at least one of the compounds represented by the following general formulas (1) and (2). Squalylium compounds, which are usually classified as cyanine compounds, have low heat resistance, but the compounds represented by the general formulas (1) and (2) have high heat resistance.

(Compound represented by the general formula (1))

Each of X ₁₀₁ to X ₁₁₀ independently contains a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁₀₁ R ₁₀₂ ,- Represents COOR ₁₀₁ , -CONR ₁₀₁ R ₁₀₂ , a nitro group, a cyano group or a halogen atom. R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom and an alkyl group which may have a substituent. In X ₁₀₁ to X ₁₁₀ , substituents may be bonded to each other to form a ring.

In X ₁₀₁ to X ₁₁₀ , the "alkyl group which may have a substituent" includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group and a 2-ethylhexyl group. , Stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Among these, a methyl group, an ethyl group and an n-propyl group are preferable from the viewpoint of imparting durability and difficulty in synthesis, and a methyl group is particularly preferable.

In X ₁₀₁ to X ₁₁₀ , the "alkenyl group which may have a substituent" includes, for example, a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and the like. Examples thereof include 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like. Among these, a vinyl group and an allyl group are preferable from the viewpoint of imparting durability and difficulty in synthesizing.

In X ₁₀₁ to X ₁₁₀ , the "aryl group which may have a substituent" is, for example, a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, or 4-bromo. Examples thereof include a phenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group and the like. Among these, a phenyl group and a 4-methylphenyl group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

Examples of the "aralkyl group which may have a substituent" in X ₁₀₁ to X ₁₁₀ include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like. Among these, a benzyl group is preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X ₁₀₁ to X ₁₁₀ , the "alkoxy group even if it has a substituent" is, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, or 2-ethylhexyl. Examples thereof include an oxy group, a trifluoromethoxy group, a cyclohexyloxy group and a stearyloxy group. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X ₁₀₁ to X ₁₁₀ , the "aryloxy group which may have a substituent" is, for example, a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2. -Methylphenyloxy group, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group and the like can be mentioned. Among these, a phenoxy group and a naphthyloxy group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X ₁₀₁ to X ₁₁₀ , the "substituted amino group" is, for example, a methylamino group, an ethylamino group, an isopropylamino group, an n-butylamino group, a cyclohexylamino group, a stearylamino group, a dimethylamino group, a diethylamino group, or a dibutylamino. Groups, N, N-di (2-hydroxyethyl) amino groups, phenylamino groups, naphthylamino groups, 4-tert-butylphenylamino groups, diphenylamino groups, N-phenyl-N-ethylamino groups and the like can be mentioned. .. Among these, a dimethylamino group and a diethylamino group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

Examples of the "halogen atom" in X ₁₀₁ to X ₁₁₀ include fluorine, bromine, chlorine and iodine.

In X ₁₀₁ to X ₁₁₀ , substituents can be bonded to each other to form a ring. The ring has, for example, the following structures, but is not limited thereto.

In R ₁₀₁ and R ₁₀₂ , the "alkyl group which may have a substituent" has the same meaning as, for example, X ₁₀₁ to X ₁₀₈ .

X ₁₀₁ to X ₁₁₀ preferably contain an unsubstituted alkyl group, and at least one of X ₁₀₃ , X ₁₀₄ , X ₁₀₇ and X ₁₀₈ is more preferably an unsubstituted alkyl group, and X ₁₀₃ and X ₁₀₇ are Unsubstituted alkyl groups are more preferred. The unsubstituted alkyl group is preferably, for example, a methyl group.

(Method for producing compounds represented by general formulas (1) and (2))
The compound represented by the general formula (1) can be produced, for example, by the method described in JP-A-2019-211764. Further, the compound represented by the general formula (2) can be produced, for example, by the method described in JP-A-2019-1983.

<Dye derivative>
A dye derivative can be used in the infrared-absorbing composition of the present invention, if necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group and the like in the organic dye residue. The dye derivative has, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and a basic substituent such as an amine salt, a sulfonamide group, or a tertiary amino group at the terminal thereof. Examples thereof include compounds and compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.

Specifically, the diketopyrrolopyrrole dye derivative is JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine-based. For dye derivatives, JP-A-2007-226161, WO2016 / 163351 pamphlet, JP-A-2017-165820, JP-A-5753266, and for anthraquinone-based dye derivatives, JP-A-63-246674, JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet, quinacridone-based dye derivatives are JP-A-48-54128, JP-A-48-54128. JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 for dioxazine-based dye derivatives, JP-A-2007-314785 for thiazine indigo-based dye derivatives, Triazine-based dye derivatives. Is JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681. , Benzoisoindole-based dye derivatives are JP-A-2009-57478, and quinophthalone-based dye derivatives are JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012. -226110, naphthol-based dye derivatives are JP-A-2012-208329, JP-A-2014-5439, and azo-based dye derivatives are JP-A-2001-172520, JP-A-2012-1722092, acidic. Substituents are referred to in JP-A-2004-307854, and basic substituents are referred to in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. Examples include the described dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

The dye derivative can be used alone or in combination of two or more.

The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the squarylium compound (A).

<Resin type dispersant (B)>
The resin-type dispersant has a squarylium compound (A) affinity site having a property of adsorbing to the squarylium compound (A) and a relaxation site that has a high affinity with components other than the squalylium compound (A) and causes steric repulsion between dispersed particles. And have. The resin type dispersant is preferably a resin having a controlled molecular structure such as a graft type (comb type) or a block type.

In terms of resin-based dispersants, for example, urethane-based dispersants such as polyurethane, polycarbonic acid esters such as polyacrylates, unsaturated polyamides, polycarbonic acid, polycarbonic acid (partial) amine salts, and ammonium polycarbonic acid salts, Polycarbonic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarbonic acid esters and their modifications; formed by the reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group. Amid and its salts; (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc .; polyester, modification Examples thereof include polyacrylates, ethylene oxide / propylene oxide addition compounds, and phosphate ester-based compounds.

In terms of ionicity, examples of the resin-type dispersant include an acidic resin-type dispersant and a basic resin-type dispersant.

The resin-type dispersant (B) used in the infrared-absorbing composition is preferably a basic resin-type dispersant. The basic resin type dispersant is a resin containing a basic group such as a tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocycle. The basic group is preferably an amino group or a quaternary ammonium base, and more preferably contains both. Examples of the resin include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers, and urethane-based polymer dispersants.

A preferred embodiment of the basic resin type dispersant is from an A block having a tertiary amino group and a quaternary ammonium base, and a B block which is a monomer polymer containing a (meth) acrylic acid alkyl ester as a main component. It is a block copolymer. The A block functions as an adsorption site for the squarylium compound (A), whereas the B block functions as a steric repulsion site. The basic resin type dispersant has A block and B block, which greatly improves the dispersion stability of the squarylium compound (A). Specifically, the basic resin type dispersant described in JP-A-2019-211764 can be preferably used.

Further, in addition to the basic resin type dispersant, an acidic resin type dispersant may also be used in combination.

Examples of the acidic resin-type dispersant include resin-type dispersants having an aromatic carboxylic acid structure. This dispersant is used in WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481. , Japanese Patent Application Laid-Open No. 2007-23195, Japanese Patent Application Laid-Open No. 1996-143651, and the like.

The content of the resin-type dispersant is preferably 3 to 200% by mass, more preferably 5 to 100% by mass, based on 100 parts by mass of the squarylium compound (A). Dispersion stability is improved when an appropriate amount is contained.

The amine value of the basic resin type dispersant is preferably 45 to 150 mgKOH / g. The quaternary ammonium salt value is preferably 10 to 90 mgKOH / g. Here, the amine value and the quaternary ammonium salt value represent values obtained by converting the number of mg of HCl required to neutralize 1 g of the dispersant into the equivalent of KOH. The amine value is more preferably 50 to 100 mgKOH / g. As a result, in addition to further improving dispersion stability and storage stability, absorption in the visible region (400 nm to 700 nm) is suppressed. The quaternary ammonium salt value is preferably 15 to 50 mgKOH / g. This gives the same effect as the amine value. The basic resin type dispersant (B) preferably has no acid value from the viewpoint of dispersion stability and storage stability.

The molecular weight of the resin-type dispersant is preferably 4,000 to 40,000 in terms of polystyrene-equivalent weight average molecular weight (hereinafter, may be referred to as “Mw”), and from the viewpoint of dispersion stability, 5,000 to 20, 000 is more preferable.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti- Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, etc. 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, manufactured by BASF Japan. 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Examples thereof include Ajinomoto Fine Techno Co., Ltd.'s Azispar PA111, PB711, PB821, PB822, PB824 and the like.

The resin type dispersant (B) can be used alone or in combination of two or more.

<Alkali-soluble resin (C)>
The alkali-soluble resin (C) is a resin suitable for a photolithography method and has a cyclic structure-containing unit in the main chain. As a result, developability (development speed is sufficient, and heat resistance and light resistance when used as a near-infrared cut filter are improved. Alkali solubility is developed and dissolved in, for example, an alkali development step at the time of producing a near-infrared cut filter. It is intended to impart properties and requires an acidic group. The alkali-soluble resin (C) has a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm when a film having a thickness of 2 μm is formed. It is a resin. The permeability is preferably 95% or more.

The alkali-soluble resin (C) preferably contains a structural unit in which a cyclic structure is formed due to any of the following general formulas (3) to (5).
General formula (3)

(In the general formula (3), R ¹³ and R ¹⁴ represent hydrocarbon groups having 1 to 20 carbon atoms which may independently have hydrogen atoms or substituents, respectively.)

Specific examples of R ¹³ and R ¹⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, t-amyl group, stearyl group, lauryl group and cyclo. There are a xyl group, an ethylhexyl group, a methoxyethyl group, an ethoxyethyl group, a benzyl group and the like, and among them, a methyl group, an ethyl group, a cyclohexyl group and a benzyl group are more preferable. These can be used alone or in combination of two or more.

General formula (4)

(In the general formula (4), R15 represents a hydrocarbon group having ¹ to 25 carbon atoms which may have a hydrogen atom or a substituent.)

^In the above formula, R15 is a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl and the like. Alyl groups such as phenyl; alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; 1-methoxyethyl, 1- Examples thereof include an alkyl group substituted with an alkoxy such as ethoxyethyl; an alkyl group substituted with an aryl group such as benzyl; and the like. Among these, hydrocarbon groups such as methyl, ethyl, cyclohexyl, and benzyl, which are difficult to be desorbed by acid or heat, are particularly preferable in terms of heat resistance.

General formula (5)

(In the general formula (5), R ¹⁶ represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.)

In the above formula, R ¹⁶ includes a phenyl group, a benzyl group, a naphthal group, a cyclohexyl group, a methyl group, an ethyl group, a propyl group and the like. It is preferable because it is excellent.

The compound of the general formula (3) reacts at the time of the polymerization reaction to form the cyclic structure-containing unit of the following general formula (6) in the main chain.
General formula (6)

The compound of the general formula (4) reacts at the time of the polymerization reaction to form the structural unit of the following general formula (7) in the main chain.
General formula (7)

The compound of the general formula (5) is ring-opened to form the following structural units.
General formula (8)

Examples of the constituent monomer unit other than the constituent units of the general formulas (3) to (5) include an acid group-containing monomer unit, an alicyclic hydrocarbon group-containing monomer unit, and other monomer units.

As for the content of each structural unit in the alkali-soluble resin (C), the cyclic structure-containing unit formed due to any of the general formulas (3) to (5) is 0 in 1 mol of all the monomer units. 0.05 to 0.5 mol, acid group-containing monomer unit is 0.05 to 0.3 mol, alicyclic hydrocarbon group-containing monomer unit is up to 0.25 mol, and other monomer units are 0. It is preferable to use less than 7. mol in terms of heat resistance and development speed.

(Acid group-containing monomer unit)
When the acid group-containing monomer unit is contained, the infrared-absorbing composition improves the surface hardness of the coating film at the time of curing, and also improves the adhesion to the substrate and the alkali solubility. Further, the developability is improved.

The acid group of the acid group-containing monomer forming the acid group-containing monomer unit is neutralized with a base such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, or a sulfonic acid group. Examples include functional groups. Among these, a carboxyl group and a carboxylic acid anhydride group are preferable, and a carboxyl group is more preferable.

The acid group-containing monomer is, for example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, silicic acid, vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. Unsaturated polyvalent carboxylic acids; unsaturated monocarboxylic acids having a chain extension between an unsaturated group such as monosuccinic acid mono (2-acryloyloxyethyl) and monosuccinic acid mono (2-methacryloyloxyethyl) and a carboxyl group. Examples thereof include unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and phosphate group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) are preferable, and unsaturated monocarboxylic acids are preferable from the viewpoint of versatility and availability. More preferably, acrylic acid and methacrylic acid are further preferable.
The acid group-containing polymer may have only one kind or two or more of the above-mentioned ones as the acid group-containing monomer unit.

(Alicyclic hydrocarbon group-containing monomer unit)
When the alicyclic hydrocarbon group-containing monomer unit is contained, the infrared-absorbing composition improves the heat resistance of the film after curing.

The alicyclic hydrocarbon group-containing monomer forming the alicyclic hydrocarbon group-containing monomer unit is not limited as long as it has an alicyclic hydrocarbon group, but the alicyclic hydrocarbon group has 3 to 12 carbon atoms. A hydrocarbon group is preferable, and an alicyclic hydrocarbon group having 7 to 10 carbon atoms is more preferable. The alicyclic hydrocarbon group is, for example, a monocyclic hydrocarbon group such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloheptyl, cyclobutenyl, cyclopentenyl, cyclohexenyl; dicyclopentanyl, dicyclo Examples thereof include polycyclic hydrocarbon groups such as pentenyl, tricyclodecanyl, adamantyl and isobornyl. Among these, a polycyclic hydrocarbon group is preferable in terms of further improving heat resistance, more preferably dicyclopentanyl, dicyclopentenyl, and isobornyl, and even more preferably dicyclopentanyl.

(Other monomer units)
Other monomers constituting other monomer units include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and the like. Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl ( (Meta) such as meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate. ) Acrylate,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrene or styrenes such as α-methyl styrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate. And so on.

Further, the alkali-soluble resin (C) may be a photosensitive resin having a polymerizable unsaturated group.

The monomers and the like used for the synthesis of the alkali-soluble resin (C) can be used individually or in combination of two or more.

The weight average molecular weight (Mw) of the alkali-soluble resin (C) is preferably 10,000 to 100,000, more preferably 10,000 to 80,000. The number average molecular weight (Mn) is preferably 5,000 to 50,000. The value of Mw / Mn is preferably 10 or less.

The acid value of the alkali-soluble resin (C) is preferably 20 to 300 mgKOH / g, more preferably 50 to 200 mgKOH / g. Having an appropriate acid value makes it possible to achieve both developer solubility and fine pattern formation.

The content of the alkali-soluble resin (C) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the squarylium compound (A). When an appropriate amount is contained, a film can be easily formed.

(Other alkali-soluble resins)
In the present specification, other alkali-soluble resin can be used in combination with the alkali-soluble resin (C). Examples of other alkali-soluble resins include thermoplastic resins and alkali-soluble photosensitive resins. The photosensitive resin is a thermoplastic resin having a polymerizable unsaturated group.

<Thermoplastic resin>
The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, a polyurethane resin, and the like. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

<Alkali-soluble photosensitive resin>
The alkali-soluble photosensitive resin has photosensitive because it has a polymerizable unsaturated group. The alkali-soluble photosensitive resin may be alkali-soluble and may have photosensitivity, and a known resin can be used. Therefore, the resin synthesized by the following methods (i) and (ii) is preferable. When the alkali-soluble photosensitive resin is used, it is three-dimensionally crosslinked by light irradiation to increase the crosslink density, so that the chemical resistance of the coating film is improved.

[Method (i)]
In method (i), for example, first, an epoxy group-containing monomer and a polymer of other monomers are synthesized. Next, a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin can be mentioned. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

Epoxy group-containing monomers include, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 3,4-. Epoxycyclohexyl (meth) acrylate can be mentioned. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity.

The monocarboxyl group-containing monomer is, for example, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted. Examples thereof include monocarboxylic acids such as the body.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-. Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) (Meta) acrylates such as acrylates, benzyl (meth) acrylates, phenoxyethyl (meth) acrylates, phenoxydiethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates, or ethoxypolyethylene glycol (meth) acrylates,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrene or styrenes such as α-methyl styrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate. And so on.

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Hexanoart, N-substituted maleimides such as N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimideacridin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethyleneoxide (EO) -modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, PO-modified (meth) acrylate of nonylphenol, etc. Can be mentioned.

In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin can be mentioned.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth). Examples thereof include hydroxyalkyl methacrylates such as acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by superpolymerizing hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Polyester mono (meth) acrylate to which 12-hydroxystearic acid or the like is added can also be mentioned. Among these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable, and glycerol mono (meth) acrylate is more preferable.

Examples of the isocyanate group-containing monomer include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate.

Examples of the monomer that can be used other than the above-mentioned monomer include a phosphoric acid ester group-containing monomer and the like in addition to the other monomers exemplified in the above-mentioned method (i).

The phosphoric acid ester group-containing monomer is, for example, a compound obtained by reacting a hydroxyl group of a hydroxyl group-containing monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

<Polymerizable compound (D)>
The polymerizable compound (D) is a monomer (monomer) or an oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (D) include an acid group-containing monomer, a urethane bond-containing monomer, and other monomers.

Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

The acid group-containing monomer is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyhydric carboxylic acid and a monohydroxyalkyl (meth). ) Examples thereof include esterified products with acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

(Urethane bond-containing monomer)
The urethane bond-containing monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a (meth) acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further having a hydroxyl group. Examples thereof include polyfunctional urethane acrylate obtained by reaction.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethyl propandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanthry (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate , Gloxydimethacrylate, 2-hydroxy-3-acryloylpropylmethacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, a hydroxyl group-containing polyol polyacrylate and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth). ) Acrylate, Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Triethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Trimethylol propanthry (meth) acrylate, Phenoxy Tetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, isocianul Acid EO modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A Diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, methylol Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, and urethane acrylate of melamine and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta. Examples thereof include erythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

The polymerizable compound (D) can be used alone or in combination of two or more.

The blending amount of the polymerizable compound (D) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile content of the infrared absorbing composition. When an appropriate amount is blended, curability and developability are further improved.

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-. On, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) ) Phenyl] -2- (phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Acetphenone compounds such as butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2 -Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloro). Methyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) Triazine compounds such as -6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl- , 2- (O-benzoyloxime)], or ethane, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. Oxime ester compounds; phosphin compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphinoxide; 9,10-phenanthlenquinone, camphorquinone , Ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; titanosen compounds and the like. Among these, oxime ester compounds are preferable.

(Oxime ester compound)
The oxime ester compound breaks the NO bond of the oxime by absorbing ultraviolet rays, and produces an iminyl radical and an arcroxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the concentration of the colorant in the infrared-absorbing composition is high, the ultraviolet transmittance of the film may be low and the degree of curing of the film may be low, but the oxime ester-based compound is preferably used because it has high quantum efficiency.

The oxime ester-based compound is described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, and the like. Examples thereof include ester-based photopolymerization initiators.

The photopolymerization initiator (E) can be used alone or in combination of two or more.

The content of the photopolymerization initiator (E) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the squarylium compound (A). When an appropriate amount is contained, the photocurability and developability are further improved.

<Sensitizer>
The infrared absorbing composition may further contain a sensitizer.
Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives. , Azulene derivative, Azurenium derivative, Squalylium derivative, Porphyrin derivative, Tetraphenylporphyrin derivative, Triarylmethane derivative, Tetrabenzoporphyrin derivative, Tetrapyrazinoporphyrazine derivative, Phthalocyanin derivative, Tetraazaporphyrazine derivative, Tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anuren derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal arene complexes, organic ruthenium complexes, or Mihiler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylgrioxylates, benzyls, 9,10-phenanslenquinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like can be mentioned.
Among these, a thioxanthone derivative, a Michler ketone derivative, and a carbazole derivative are preferable. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis ( Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N -Ethylcarbazole and the like are more preferable.

The sensitizer can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (E). When an appropriate amount is contained, curability and developability are further improved.

<Thermosetting compound>
The infrared absorbent composition can contain a thermosetting resin. This can further improve the heat resistance. The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.

Examples of the thermosetting compound include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Of these, epoxy compounds and oxetane compounds are preferable.

<Thiol chain transfer agent>
The infrared absorbing composition can contain a thiol-based chain transfer agent as the chain transfer agent. When thiol is used in combination with a photopolymerization initiator, chiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the sensitivity of the infrared-absorbing composition is improved.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, it becomes easier to photo-cure from the surface of the film to the deepest part.

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylolpropane Tristhioglycolate, Trimethylolpropane Tristhiopropionate, Trimethylolpropanetris (3-mercaptobutyrate), Pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, Tristrimercaptopropionate (2-Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine And the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the non-volatile content of the infrared absorbing composition. When an appropriate amount is contained, the light sensitivity and the tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating film.

<Polymerization inhibitor>
The infrared absorbing composition can contain a polymerization inhibitor. As a result, the exposure due to the diffracted light of the mask can be suppressed at the time of exposure by the photolithography method, so that a pattern having a desired shape can be easily obtained.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl. Catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert -Alkyl catechol compounds such as butyl catechol, 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol and other alkylresorcinol compounds, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 , 5-Di-tert-alkylhydroquinone compounds such as butylhydroquinone, phosphinic compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide and the like. Examples thereof include phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100% by mass of the non-volatile content of the infrared absorbing composition. When an appropriate amount is contained, the linearity of the pattern and the resolution of the pattern are improved, and wrinkles can be suppressed on the surface of the coating film.

<UV absorber>
The infrared absorbing composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. The ultraviolet absorber may be an oligomer or a polymer.

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the infrared absorbing composition. When an appropriate amount is contained, the adhesion between the substrate and the coating film is further improved, and good resolution can be obtained.

Benzotriazole compounds include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3, 5-Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy) -5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1- Mixture of dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol , 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (3-) Reaction product of (2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole-2-yl) -4- (1, 1,3,3-Tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2H-benzotriazole-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole-2-yl) -6-t-butyl-4-methylphenol, 2- (3, 5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3-tert -Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro) -2H-benzotriazole-2-yl) phenyl] propionate can be mentioned.

The triazine compound is, for example, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4. 6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4 -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-( Hexyloxy) Phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6- Examples thereof include tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone. , 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadesiloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, Examples thereof include 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of the salicylic acid ester-based compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate.

<Antioxidant>
The infrared absorbing composition can be an antioxidant. The antioxidant improves the transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the infrared absorbing composition from oxidizing and yellowing due to the thermal process during thermal curing or ITO annealing. can. In particular, when the concentration of the squarylium compound (A) is high, the amount of the film cross-linking component decreases, so the yellowing of the thermal process becomes stronger due to the use of highly sensitive cross-linking components and the increase in the amount of the photopolymerization initiator. Can be seen. Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and obtain a high transmittance of the film.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable from the viewpoint of achieving both the transmittance and the sensitivity of the coating film.

The antioxidant can be used alone or in combination of two or more.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the infrared absorbing composition. This further improves the transmittance, spectral characteristics, and sensitivity.

<Leveling agent>
The infrared absorbing composition can contain a leveling agent. This further improves the wettability of the coating film to the substrate and the drying property of the coating film. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and the like.

The leveling agent can be used alone or in combination of two or more.

The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the non-volatile content of the infrared absorbing composition. By containing an appropriate amount, the balance between coatability, adhesion, and transmittance is further improved.

<Storage stabilizer>
The infrared absorbing composition may contain a storage stabilizer to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, organic acids such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples include phosphine and phosphite.

The content of the storage stabilizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the squarylium compound (A).

<Adhesion improver>
The infrared external ray absorbing composition may contain an adhesion improver. This improves the adhesion between the coating and the base material. In addition, it becomes easy to form a pattern having a narrow width by the photolithography method. Examples of the adhesion improver include a silane coupling agent and the like.

Examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. (Meta) acrylic silanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-) Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Melcaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like. Examples thereof include sulfides and isocyanates such as 3-isocyanatepropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the squarylium compound (A). When an appropriate amount is contained, the light sensitivity is improved, and the adhesion of the coating film and the resolution of the pattern are improved.

<Manufacturing method of infrared absorbing composition>
The infrared-absorbing composition is subjected to a dispersion treatment using, for example, a squarylium compound (A), a resin-type dispersant (B), a solvent, or the like to prepare a dispersion. When the dye derivative is used in combination during the dispersion treatment, the squarylium compound (A) can be dispersed more finely.
Next, the alkali-soluble resin (C), the polymerizable compound (D) and the photopolymerization initiator (E) are blended with the dispersion and mixed to obtain an infrared-absorbing composition. Needless to say, the timing of blending each material is arbitrary.

For the dispersion treatment, for example, a disperser such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor can be used.

<Solvent>
The infrared absorbent composition can contain a solvent. As a result, the viscosity of the infrared absorbing composition can be easily adjusted, so that a film having a smooth surface can be easily formed. The solvent may be appropriately selected according to the purpose of use and may contain an appropriate amount.

The solvent is, for example, an ester solvent (solvent containing -COO- in the molecule and not containing -O-), an ether solvent (solvent containing -O- in the molecule and not containing -COO-), and an ether ester solvent. (Solvent containing -COO- and -O- in the molecule), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O -, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Among these, a solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable in terms of coatability and drying property. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are further preferable.

<Removal of coarse particles>
The infrared absorbing composition has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm by means such as centrifugation at a gravity acceleration of 3000 to 25000 G and filtration by a sintering filter or a membrane filter. It is preferable to remove the above coarse particles and mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Manufacturing method of near infrared cut filter>
The near-infrared cut filter of the present invention preferably includes a substrate and a film formed of the infrared-absorbing composition.
The near-infrared cut filter can be produced by a printing method or a photolithography method. The most preferred photolithography method is described herein.

When a pattern is formed by a photolithography method, the dry film thickness is about 0.2 to 5 μm by applying a spray coat, a spin coat, a slit coat, a roll coat, or the like on a substrate. Apply so that If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. After that, a desired pattern can be formed by immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion. In order to promote the polymerization of the polymerizable compound, heating can be applied as needed.

The base material is preferably a sheet-shaped, film-shaped or plate-shaped transparent base material. The material of the transparent base material is a highly transparent material, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or triacetyl cellulose (TAC). Examples thereof include acrylic resins such as methyl methacrylate-based copolymers, styrene resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, vinyl chloride resins, polymethacrylicimide resins, and glass plates.

For development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

The near-infrared cut filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an inkjet method, or the like in addition to the above methods.

<Use>
The infrared absorbing composition of the present invention can be used, for example, for a sensor for biometric authentication (fingerprint authentication or vein authentication), or a touch sensor or touch panel incorporating the sensor.
For example, smartphones, tablet PCs, etc., bank ATMs, multimedia terminals, etc. are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication for security protection. In particular, the development of fingerprint authentication technology used for smartphones and tablet PCs is rapid, and as the authentication range increases to the screen size (full screen), fingerprint authentication sensors with built-in displays have been developed for organic EL displays, liquid crystal displays, etc. There is.
However, since many fingerprint sensors with a built-in display irradiate the fingerprint with various light sources installed in the display and sense the reflected light, illegal external light (such as sunlight or LED lighting) is used. When a sensor has a wide range of wavelengths and is subject to strong light), there is a problem of noise during imaging, and there is some concern about accuracy when using it outdoors. The coloring composition of the present invention is effective in solving these problems by absorbing and preventing the incident of an external illegal light on the sensor.
Further, since the infrared absorbing composition of the present invention has excellent heat resistance, it can be preferably used in terms of a process for manufacturing a sensor, a touch sensor incorporating the sensor, and a touch panel.
In addition, the external light that becomes noise in biometric authentication applications is light of 650 nm to 1000 nm that passes through the living body, and in particular, light of 650 nm to 800 nm overflows in the living space, so it is possible to cut light in this wavelength region. Increase the accuracy of biometric authentication.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. The "part" is a "mass part". Further, "PGMAC" is propylene glycol monomethyl ether acetate.

(Method for identifying squarylium compound (A))
The MALDI TOF-MS spectrum was used for the identification of the squalylium compound (A). For the MALDI TOF-MS spectrum, the obtained compound was identified by matching the molecular ion peak of the obtained mass spectrum with the mass number obtained by calculation using the MALDI mass spectrometer autoflex III manufactured by Bruker Daltonix. rice field.

(Acid value of resin type dispersant and alkali-soluble resin)
The acid value of the resin-type dispersant and the alkali-soluble resin was determined by a potentiometric titration method using a 0.1 N potassium hydroxide / ethanol solution. The acid value of the resin and the resin type dispersant indicates the acid value of the non-volatile component.

(Weight average molecular weight (Mw) of resin-type dispersant and alkali-soluble resin)
The weight average molecular weight (Mw) of the resin-type dispersant and the alkali-soluble resin is a GPC (Tosoh, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh), and THF is used as a developing solvent. It is a polystyrene-equivalent weight average molecular weight measured using.

(Amine value of resin type dispersant)
The amine value of the resin-type dispersant was determined by a potentiometric titration method using a 0.1 N aqueous hydrochloric acid solution, and then converted to the equivalent of potassium hydroxide. The amine value of the resin type dispersant indicates the amine value of the non-volatile component.

(Quaternary ammonium salt value of resin type dispersant)
The quaternary ammonium salt value of the resin-type dispersant was determined by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to the equivalent of potassium hydroxide. The quaternary ammonium salt value of the resin type dispersant below indicates the quaternary ammonium salt value of the non-volatile component.

<Manufacturing of miniaturized squarylium compound (P)>
(Synthesis of squarylium compound (A1-1))
400 parts of toluene is mixed with 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture is heated and stirred in an atmosphere of nitrogen gas. It was refluxed for hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation.
After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, and dried under reduced pressure to give 61.9 parts (yield: 92%) of the squarylium compound (A1-1). Obtained. As a result of mass spectrometry by TOF-MS, it was identified as a squarylium compound (A1-1).

(Synthesis of squarylium compound (A1-2))
The same operation as the synthesis of the squarylium compound (A1-1) except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the synthesis of the squarylium compound (A1-1). To obtain 72.6 parts (yield: 98%) of the squarylium compound (A1-2). As a result of mass spectrometry by TOF-MS, it was identified as a squarylium compound (A1-2).

(Synthesis of squarylium compound (A1-3))
The same operation as for the synthesis of the squarylium compound (A1-1) was performed except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the synthesis of the squarylium compound (A1-1). , 67.2 parts (yield: 95%) of the squarylium compound (A1-3) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a squarylium compound (A2-3).

(Synthesis of squarylium compound (A2-1))
400 parts of toluene was mixed with 40.0 parts of 1,8-diaminonaphthalene, 46.0 parts of 9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in an atmosphere of nitrogen gas. It was refluxed for 3 hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was separated by filtration, washed successively with hexane, ethanol and acetone, and dried under reduced pressure to obtain 84.6 parts (yield: 97%) of squarylium compound (A2-1). rice field. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium compound (A2-1).

(Synthesis of squarylium compound (A2-2))
Squalylium compounds (except that 80.7 parts of 2,7-bis (trifluoromethyl) -9-fluorenone were used in place of 46.0 parts of 9-fluorenone used in the synthesis of the squalylium compound (A2-1). The same operation as in the synthesis of A2-1) was carried out to obtain 109.8 parts (yield: 91%) of the squarylium compound (A2-2). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium compound (A2-2).

(Synthesis of squarylium compound (A2-3))
With the synthesis of squalylium compound (A2-1), except that 50.1 parts of 2-hydroxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the synthesis of squalylium compound (A2-1). The same operation was carried out to obtain 83.9 parts (yield: 92%) of the squarylium compound (A2-3). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium compound (A2-3).

The structure of the obtained squarylium compound (A) is as shown in Table 1.

(Solvent treatment and miniaturization of squarylium compound (A))
[Solvent treatment process]
50 parts of the squarylium compound (A1-1) was mixed with 250 parts of N-methylpyrrolidone, and the mixture was stirred at 23 ° C. for 24 hours. Then, the mixture was filtered, washed with 150 parts of methanol, taken out, and dried at 80 ° C. for 24 hours to obtain 25 parts of powder.
[Miniaturization process]
10 parts of the obtained powder, 100 parts of sodium chloride, and 12.5 parts of ethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 12 hours. Next, the kneaded mixture is put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. for 24 hours and pulverized. As a result, 9.4 parts of a finely divided slurryylium compound (P1-1) was obtained.
[Component ratio]
5.0 mg of squarylium compound (P1-1) was placed in a 100 ml volumetric flask, tetrahydrofuran (THF) for HPLC was added, and the mixture was dissolved by irradiating with ultrasonic waves for 30 minutes to prepare a 100 ml THF solution. Using this solution, HPLC measurement of compound B was carried out under the above equipment and the above conditions.
The HPLC measurement was analyzed by reverse phase liquid chromatography under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as a mobile phase.
As a result, multiple peaks were shown.
Specifically, a peak with a retention time of 12 ± 1 minute (peak 1), a peak with a retention time of 42 ± 1 minute (peak 2), and a peak with a retention time of 46 ± 2 minutes (peak 3). It is composed of a peak with a retention time of 50 ± 2 minutes (peak 4) and a peak with a retention time of 57 ± 2 minutes (peak 5).
The area of peak 5 was 70% of the total area of peaks 1-5.

The squarylium compounds (A1-2) and (A1-3) were subjected to solvent treatment and miniaturization in the same manner as the squarylium compound (A1-1) to obtain miniaturized squarylium compounds (P1-2) and (P1-3). .. The squarylium compounds (A2-1) to (A2-3) were not treated with a solvent and were only miniaturized to obtain miniaturized squarylium compounds (P2-1) to (P2-3).

<Manufacturing method of resin type dispersant (B)>
(Resin type dispersant (B-1 to B-4) solution)
Among the basic resin type dispersants used in the examples of JP-A-2019-211764, the dispersants shown in Table 2 below were used.

Dye derivative (b0-1)

<Manufacturing of alkali-soluble resin (C) solution>
(Production of alkali-soluble resin (C1-1) solution: The main chain has a cyclic structure of the general formula (6))
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 32 parts of methacrylic acid, and methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 128 parts of methyl, 3 parts of t-butylperoxy-2-ethylhexanoate, and 40 parts of PGMAC, and well stir 6 parts of n-dodecanethiol and 24 parts of PGMAC as a chain transfer agent dropping tank. A mixture was prepared. After charging 403 parts of PGMAC into the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a polymer solution. After completion of the reaction, PGMAC was added to adjust the non-volatile content to 20% by weight to obtain an alkali-soluble resin (C1-1) solution. The weight average molecular weight of the polymer was 17,000, and the acid value was 104 mgKOH / g.

(Production of alkali-soluble resin (C1-2) solution: The main chain has a cyclic structure of the general formula (7))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.0 parts of 3-mercapto-1,2-propanediol and pyromellitic acid dianhydride (manufactured by Daicel Chemical Industry Co., Ltd.) are 9.7. 31.7 parts of PGMAC were charged and replaced with nitrogen gas. 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene was added as a catalyst, and the mixture was reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. Next, 50.0 parts of methyl methacrylate, methyl α-allyloxymethyl acrylate 50. 0 parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., a solution prepared by dissolving 0.1 part of 2,2-azobisisobutyronitrile in 45.4 parts of PGMAC was added, and the reaction was carried out for 10 hours. It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. After completion of the reaction, PGMAC was added to adjust the non-volatile content to 20% by weight, and an alkali-soluble resin having a structural unit having a cyclic structure formed on the main chain having an acid value of 43 mgKOH / g and a weight average molecular weight of 9500 ( C1-2) A solution was obtained.

(Production of alkali-soluble resin (C1-3) solution: The main chain has a cyclic structure of the general formula (8))
As a reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen introduction tube was used. The monomer dropping funnel contains 74.8 parts (0.2 mol) of benzyl maleimide, 43.2 parts (0.3 mol) of acrylic acid, and 176 parts of benzyl methacrylate. After adding 0 part (0.5 mol), 4.0 parts of t-butylperoxy-2-ethylhexanoate and 40.0 parts of PGMAC, the mixture was stirred and mixed. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMAC were put into the chain transfer agent dropping tank, and the mixture was stirred and mixed. Then, 395.0 parts of PGMAC was put into the flask, the air in the flask was replaced with nitrogen, and then the temperature in the flask was raised to 90 ° C. with stirring. Then, the monomer and the chain transfer agent were added dropwise into the flask. The dropping is carried out over 2 hours while maintaining the temperature at 90 ° C. One hour after the dropping is completed, the temperature is raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube is attached to oxygen / nitrogen. = 5/95 mixed gas bubbling was started. Next, 28.4 parts (0.1 mol) of glycidyl methacrylate (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction), 2,2'-methylenebis (4-methyl-6-t-). (Butylphenol) (0.4 part) and triethylamine (0.8 part) were placed in a flask, and the reaction was continued at 110 ° C. for 8 hours. After completion of the reaction, PGMAC was added to adjust the non-volatile content to 20% by weight to obtain an alkali-soluble resin (C2-1) solution having a non-volatile acid value of 73 mgKOH / g and a weight average molecular weight of 17300.

(Manufacturing of alkali-soluble resin (C2-1) solution: does not have a cyclic structure in the main chain)
160 g of PGMAC was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, the temperature was raised to 100 ° C., and then 96.0 g of benzyl methacrylate. Azo in a mixture consisting of (0.55 mol), 17.6 g (0.21 mol) of methacrylic acid, 22.0 g (0.10 mol) of tricyclodecane skeleton-containing methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 140 g of PGMAC. A solution containing 3.6 g of bisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and the mixture was further stirred at 100 ° C. for 5 hours to have an acid value of 85 mgKOH / g and a weight average molecular weight (Mw) of 8,000. A solution of acrylic resin was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAC was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Obtained an alkali-soluble resin (C2-1) solution.

(Manufacturing of alkali-soluble resin (C2-2) solution: does not have a cyclic structure in the main chain)
160 g of PGMAC was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, the temperature was raised to 100 ° C., and then 96.0 g of benzyl methacrylate. In a mixture consisting of (0.55 mol), 17.6 g (0.21 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 140 g of PGMAC. A solution containing 3.6 g of azobisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 21.3 g [0.15 mol] of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were added into the flask, and the reaction was carried out at 110 ° C. for 6 hours. A resin solution having a non-volatile content of 37.6% and an acid value of 67.7 mgKOH / g (in terms of non-volatile content) was obtained. A solution of an acrylic resin having a polystyrene-equivalent weight average molecular weight of 9,500 measured by GPC was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAC was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Obtained an alkali-soluble resin (C2-2) solution.

<Manufacturing of resin composition containing squarylium compound>
(Squarylium compound-containing resin composition (IRP-1))
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to prepare a resin composition containing a squarylium compound. ..
Squalilium compound (A1-1): 10.0 parts resin type dispersant (B-1) solution (nonvolatile content 40%): 15.0 parts alkali-soluble resin (C1-1) solution: 35.0 parts solvent (N) ): 40.0 copies

(Squarylium compound-containing resin composition (IRP-2-14))
The squarylium compound-containing resin composition is the same as the squarylium compound-containing resin composition (IRP-1) except that the squarylium compound, the resin-type dispersant solution, the alkali-soluble resin solution, and the solvent are changed to the compositions and amounts shown in Table 3. (IRP-2-14) was adjusted.

<Manufacturing of infrared absorbing composition (IRR-1)>
[Example 1]
After stirring and mixing the following mixture so as to be uniform, 1. Filtration with a 0 μm filter gave a photosensitive infrared absorbing composition (IRR-1).
Squarylium compound-containing resin composition (IRP-1: non-volatile content 20%): 75.0 parts Alkali-soluble resin (C1-1: non-volatile content 20%) solution: 5.0 parts Thermo-curable compound (CE-1): 0.5 part thermosetting compound (CE-2): 0.5 part polymerizable compound (D): 2.0 part photopolymerization initiator (E): 1.8 part sensitizer (F): 0. 2 parts thiol-based chain transfer agent (G): 0.4 parts polymerization inhibitor (H): 0.05 parts ultraviolet absorber (I): 0.15 parts antioxidant (J): 0.1 parts leveling agent (K: Non-volatile content 3%): 1.0 part Storage stabilizer (L): 0.1 part Silane coupling agent (M): 0.2 part Solvent (N): 13.0 parts

[Examples 2 to 22, Comparative Examples 1 to 4]
Hereinafter, infrared absorbing compositions (IRR-2-26) were obtained in the same manner as the infrared absorbing composition (IRR-1) except that the compositions and blending amounts were changed to those shown in Table 4.

<Thermosetting compound (CE)>
-Epoxy compound (CE-1)
(CE-1-1) 1,2'-bis (hydroxymethyl) -1-butanol 1,2-
Epoxy-4- (2-oxylanyl) cyclohexane adduct
[EHPE-3150 (manufactured by Daicel)],
(CE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase Chemtex)],
(CE-1-3) Triglycidyl isocyanurate (CE-1-1) to (CE-1-3) were mixed in the same amount to prepare an epoxy compound (CE-1).
-Oxetane compound (CE-2):
3-Ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Polymerizable compound (D)>
(D-1) Trimethylolpropane Triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]; Trifunctional (D-2) dipentaerythritol penta and hexaacrylate (E-2)
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]; 5,6-functional (D-3) polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(D-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]; 6 sensuality

(D-5) Pentaerythritol triacrylate (432 parts, 84 parts of hexamethylene diisocyanate) was charged in a reaction vessel having a polyfunctional urethane acrylate content of 1 liter and 5 mouths according to the following, and reacted at 60 ° C. for 8 hours to (meth). A product containing a polyfunctional urethane acrylate (D-5) having an acryloyl group was obtained. The proportion of the polyfunctional urethane acrylate (D-5) in the product was 70% by mass, and the balance was other light. It is occupied by polymerizable monomer. It was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(D-6) Bifunctional bisphenol A type (meth) acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
As described above, (D-1) to (D-7) were mixed in the same amount to obtain the polymerizable compound (D).

<Photopolymerization initiator (E)>
(E-1) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one
[Irgacure 907 (manufactured by BASF Japan)]
(E-2) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(E-3) 2,4,6-trimethylbenzoyludiphenyl-phosphine oxide
[Lucillin TPO (manufactured by Ciba Japan)]
(E-4) 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole
[Viimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
(E-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(E-6) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(E-7) 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one
[Irgacure 2959 (manufactured by BASF Japan)]
(E-8) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
As described above, (E-1) to (E-8) were mixed in the same amount to prepare the photopolymerization initiator (E).

<Sensitizer (F)>
(F-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(F-2) 4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (F-1) and (F-2) were mixed in the same amount to obtain a sensitizer (F).

<Thiol chain transfer agent (G)>
(G-1) Trimethylolethane Etantris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(G-2) Trimethylolpropane Tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(G-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-4) Trimethylolpropane Tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-5) Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
As described above, (G-1) to (G-5) were mixed in the same amount to prepare a thiol-based chain transfer agent (G).

<Polymerization inhibitor (H)>
(H-1) 3-Methylcatechol (H-2) Methylhydroquinone (H-3) t-Butylhydroquinone or more, (H-1) to (H-3) are mixed in the same amount, and a polymerization inhibitor is added. It was designated as (H).

<Ultraviolet absorber (I)>
(I-1) 2- [4-[(2-Hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 ， 3,5-Triazine
[TINUVIN400 (manufactured by BASF Japan)]
(I-2) 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan)]
As described above, (I-1) to (I-2) were mixed in the same amount to prepare the ultraviolet absorber (I).

<Antioxidant (J)>
(J-1) Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (J-2) 3,3'-dioctadecylthiodipropanoate (J-3) Tris [2] , 4-Di- (t) -Butylphenyl] Phenyl (J-4) Bis (2,2,6,6-Tetramethyl-4-piperidyl) Sevacate (J-5) P-octylphenyl salicylate or higher, (J) -1) to (J-5) were mixed in the same amount to prepare an antioxidant (J).

<Leveling agent (K)>
Big Chemie "BYK-330" 1 copy,
DIC's "Mega Fuck F-551" 1st copy,
A mixed solution in which 1 part of Kao's "Emargen 103" is dissolved in 97 parts of PGMAc.

<Storage stabilizer (L)>
(L-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (L-1) to (L-2) were mixed in the same amount to prepare a storage stabilizer (L).

<Adhesion improver (M)>
(M-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (M-1) to (M-4) were mixed in the same amount to prepare a silane coupling agent (M).

<Solvent (N)>
(N-1) PGMAc 30 parts (N-2) Cyclohexanone 30 parts (N-3) Ethyl 3-ethoxypropionate 10 parts (N-4) Propylene glycol monomethyl ether 10 parts (N-5) Cyclohexanol acetate 10 parts (N-6) 10 parts or more of diproprene glycol methyl ether acetate and (N-1) to (N-6) were mixed in the above parts by mass to prepare a solvent (N).

<Evaluation of infrared absorbing composition>
The obtained infrared-absorbing composition was tested for average primary particle size, spectral characteristics, resistance (light resistance, heat resistance), pattern peeling property, development speed, and pattern forming property by the following methods. In the evaluation criteria, ⊚ is a very good level, ○ is a good level, Δ is a practical level, and × is a level unsuitable for practical use. The results are shown in Table 5.

(Evaluation of spectral characteristics)
The obtained infrared-absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the dry film thickness was 1.0 μm, dried at 60 ° C. for 5 minutes, and then 230 ° C. The substrate was heated for 5 minutes to prepare a coated substrate. The spectrum of the obtained coated substrate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 400 to 900 nm. The "average absorbance at 400 to 700 nm" when the absorbance at the maximum absorption wavelength was set to 1 was evaluated according to the following criteria. The maximum absorption wavelength of the squarylium compound (A) exists in the infrared region (700 to 900 nm). When this absorbance is 1, it can be said that the smaller the absorbance at 400 to 700 nm, the better the absorption ability in the infrared region and the better the transparency in the visible light region.
⊚: less than 0.05 ○: 0.05 or more, less than 0.075 Δ: 0.075 or more, less than 0.1 ×: 0.1 or more

(Light resistance test)
A coated substrate was prepared by the same procedure as the spectral characterization, placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), and left for 24 hours. The absorbance of the film at the spectroscopic maximum absorption wavelength was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The survival rate was calculated using the following formula.
Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100
⊚: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

(Heat resistance test)
A coated substrate was prepared by the same procedure as the spectral characterization, and was additionally heated at 210 ° C. for 20 minutes as a heat resistance test. The absorbance of the film at the spectroscopic maximum absorption wavelength was measured, the residual ratio to that before the heat resistance test was determined, and the heat resistance was evaluated according to the following criteria. The survival rate was calculated using the following formula.
Residual rate = (absorbance after heat resistance test) ÷ (absorbance before heat resistance test) x 100
⊚: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

(Development speed evaluation)
The obtained composition was rotationally coated on a glass substrate using a spin coater so that the dry film thickness was 1.0 μm, and dried at 70 ° C. for 20 minutes to prepare a coated substrate. 2 ml of a 2% potassium hydroxide aqueous solution was added dropwise onto the obtained film, and the time until the film was dissolved and disappeared was measured to evaluate the development speed of the film. The evaluation criteria are as follows.
⊚: less than 10 seconds 〇: 10 seconds or more, less than 15 seconds Δ: 15 seconds or more, less than 20 seconds ×: 20 seconds or more

Claims (4)

Squarylium compound (A), resin-type dispersant (B), alkali-soluble resin (C), polymerizable compound (D) and photopolymerization initiator having a maximum absorption wavelength in the range of 400 to 1000 nm between 700 and 900 nm (A). An infrared absorbing composition containing E).
The squarylium compound (A) is at least one of the compounds represented by the following general formulas (1) and (2).
An infrared-absorbing composition in which the alkali-soluble resin (C) is a resin having a cyclic structure-containing unit in the main chain.

(In the general formula (1), X ₁₀₁ to X ₁₁₀ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. May have an aryl group, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group,-. SO ₂ NR ₁₀₁ R ₁₀₂ , -COOR ₁₀₁ , -CONR ₁₀₁ R ₁₀₂ , represents a nitro group, a cyano group or a halogen atom. R ₁₀₁ and R ₁₀₂ may independently have a hydrogen atom and a substituent, respectively. Representing an alkyl group. In X ₁₀₁ to X ₁₁₀ , substituents may be bonded to each other to form a ring.
In the general formula (2), Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. If Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, then X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ shall not be present.
R ₁ to R ₅ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M ⁺ , or a halogen atom. M ⁺ represents an inorganic or organic cation.
Each of X ₂₀₁ to X ₂₀₈ independently contains a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₆ R ₇ , sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , represents a nitro group, a cyano group or a halogen atom. X ₂₀₁ to X ₂₀₈ may be coupled to each other to form a ring.
R ₆ to R ₁₂ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. R ₆ and R ₇ , R ₈ and R _{9, and} R ₁₁ and R ₁₂ may be coupled to each other to form a ring. ) The infrared absorbing composition according to claim 1, wherein the cyclic structure-containing unit is a cyclic structure formed by the reaction of any of the compounds represented by the following general formulas (3) to (5).

(In the general formula (3), R ¹³ and R ¹⁴ represent hydrocarbon groups having 1 to 20 carbon atoms, which may independently have hydrogen atoms or substituents, respectively.
In the general formula (4), R ¹⁵ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
In the general formula (5), R ¹⁶ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. ) The infrared absorbing composition according to claim 1 or 2, wherein the resin type dispersant (B) has an amine value of 45 to 150 mgKOH / g. A near-infrared cut filter comprising a substrate and a coating formed from the infrared-absorbing composition of claims 1-3.