JP6787083B2 - Near-infrared absorbing composition and filter - Google Patents

Description

The present invention is characterized by comprising a near-infrared absorbing composition comprising a specific near-infrared absorbing dye, a resin-type dispersant, and an organic solvent, and the near-infrared absorbing composition. It relates to a near-infrared cut filter.

The main applications of near-infrared absorbing materials are near-infrared absorbing film and near-infrared absorbing plate that block heat rays for energy saving, agricultural near-infrared absorbing film for selective use of sunlight, and near-infrared absorbing heat. Recording media, near-infrared cut filter for electronic devices, near-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, Examples include a laser welding heating material.

Perimidine-based squarylium dyes are known as materials having excellent near-infrared absorption ability and extremely good transparency of visible light, and having relatively high heat resistance and light resistance (for example, Patent Documents 1 to 4). reference). However, the perimidine-based squarylium dye has a structure that easily aggregates, and the composition prepared by a conventionally known method does not have sufficient dispersion stability and storage stability, and causes problems such as high viscosity and dye precipitation. Therefore, they cannot be used to create a stable and uniform near-infrared cut filter. In addition, the near-infrared cut filter created by using them is not satisfactory in the transparency of visible light.

JP-A-2010-180308 Japanese Unexamined Patent Publication No. 2012-041485 International Publication 2010/09943 JP-A-2010-162431

The problem to be solved by the present invention is a near-infrared absorbing composition having low absorption in the visible region (400 nm to 700 nm), excellent near-infrared absorbing ability, high durability, and excellent dispersion stability and storage stability. , And to provide a near-infrared cut filter containing the near-infrared absorbing composition.

The present inventors have reached the present invention as a result of repeated diligent studies to solve the above-mentioned problems.
That is, the present invention is a near-infrared absorbing composition containing a near-infrared absorbing dye [A] represented by the following general formula (1), a basic resin type dispersant [B], and an organic solvent [C]. There,
The basic resin type dispersant [B] is a block copolymer composed of an A block having a tertiary amino group and a quaternary ammonium base in the side chain and a B block having no tertiary amino group and a quaternary ammonium base. Contains the basic resin-type dispersant [B1], which is
The amine value of the basic resin type dispersant [B1] in the solid content is 10 to 200 mgKOH / g, and the quaternary ammonium salt value is 10 to 90 mgKOH / g.
The present invention relates to a near-infrared absorbing composition, wherein the organic solvent [C] contains an organic solvent [C1] having a boiling point of 120 to 210 ° C. at 760 mmHg and a solubility parameter of 9.0 to 13.0.

General formula (1)

[In the general formula (1), X _{1 to} X ₁₀ 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. 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, − Represents SO ₂ NR ₁ R ₂ , -COOR ₁ , -CONR ₁ R ₂ , nitro group, cyano group or halogen atom. R ₁ and R ₂ each independently represent a hydrogen atom and an alkyl group which may have a substituent. In X _{1 to} X ₁₀ , the substituents may be bonded to each other to form a ring. ]

The present invention also relates to the near-infrared absorbing composition in which the content of the organic solvent [C1] is 10 to 100% by mass with respect to the total amount of the organic solvent [C].

The present invention also relates to the near-infrared absorbing composition, wherein the organic solvent [C1] contains at least one selected from the group consisting of cyclohexanol acetate, cyclohexanone, ethyl lactate and 3-methoxybutanol.

Further, the present invention further comprises an acidic resin-type dispersant having an aromatic carboxyl group, which is a reaction product of a polymer [E] having a hydroxyl group at one end or a side chain and an aromatic tricarboxylic acid anhydride [F] [ D] The present invention relates to the near-infrared absorbing composition containing.

Furthermore, the present invention relates to a near-infrared cut filter, which comprises the near-infrared absorbing composition.

According to the present invention, there is little absorption in the visible region (400 nm to 700 nm), excellent near-infrared absorption ability, excellent durability such as heat resistance and light resistance, and near-infrared absorption excellent in dispersion stability and storage stability. The composition can be obtained. Further, according to the present invention, it is possible to stably provide a near-infrared cut filter containing the near-infrared absorbing composition having the above-mentioned excellent properties.

Hereinafter, the present invention will be described in detail. In the present specification, "(meth) acrylic", "(meth) acrylate", "(meth) acryloyl" and the like mean "acrylic or methacrylic", "acrylate or methacrylate", "acryloyl or methacryloyl" and the like. For example, "(meth) acrylic acid" shall mean "acrylic acid or methacrylic acid".

<Near infrared absorbing dye [A]>
The near-infrared absorbing dye [A] represented by the general formula (1) of the present invention will be described in detail.

General formula (1)

In the general formula (1), X _{1 to} X ₁₀ may independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Aryl group, aralkyl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, amino group, substituted amino group, sulfo group, -SO ₂ Represents NR ₁ R ₂ , -COOR ₁ , -CONR ₁ R ₂ , nitro group, cyano group or halogen atom. R ₁ and R ₂ each independently represent a hydrogen atom and an alkyl group which may have a substituent. In X _{1 to} X ₁₀ , the substituents may be bonded to each other to form a ring.

In X _{1 to} X ₁₀ , the "alkyl group which may have a substituent" includes 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. Examples thereof include 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. Of 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 _{1 to} X ₁₀ , the "alkenyl group which may have a substituent" includes 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 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 can be mentioned. Among these, a vinyl group and an allyl group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X _{1 to} X ₁₀ , the "aryl group which may have a substituent" includes a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, and a 4-bromophenyl group. Groups, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like can be mentioned, and among these, the phenyl group and the 4-methylphenyl group impart durability and synthesize. It is preferable from the viewpoint of difficulty.

Examples of the "aralkyl group which may have a substituent" in X _{1 to} X ₁₀ include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like, and among these, the benzyl group is durable. It is preferable from the viewpoint of granting and synthesis difficulty.

In X _{1 to} X ₁₀ , "alkoxy groups having substituents" include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group and 2-ethylhexyloxy. Examples thereof include a group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group and the like, and 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 _{1 to} X ₁₀ , the "aryloxy group which may have a substituent" includes a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group and a 4-chloro-2-. Examples thereof include a methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group, and among these, a phenoxy group and a naphthyloxy group. However, it is preferable from the viewpoint of imparting durability and difficulty in synthesizing.

In X _{1 to} X ₁₀ , the "substituted amino group" includes a methyl amino group, an ethyl amino group, an isopropyl amino group, an n-butyl amino group, a cyclohexyl amino group, a stearyl amino group, a dimethyl amino group, a diethyl amino group and a dibutyl amino group. , N, N-di (2-hydroxyethyl) amino group, phenylamino group, naphthylamino group, 4-tert-butylphenylamino group, diphenylamino group, N-phenyl-N-ethylamino group and the like. Of 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 _{1 to} X ₁₀ include fluorine, bromine, chlorine and iodine.

In X _{1 to} X ₁₀ , substituents may be bonded to each other to form a ring, and examples thereof include, but are not limited to, the following structures.

In R ₁ and R ₂ , the "alkyl group which may have a substituent" has the same meaning as X _{1 to} X ₁₀ .

X _{1 to} X ₁₀ preferably contain an unsubstituted alkyl group, more preferably at least one of X ₃ , X ₄ , X ₇ and X ₈ is an unsubstituted alkyl group, and X ₃ and X ₇ Is particularly preferably an unsubstituted alkyl group. The unsubstituted alkyl group is preferably a methyl group.

The near-infrared absorbing composition of the present invention comprises a near-infrared absorbing dye [A] represented by the general formula (1), a specific basic resin-type dispersant [B], and a specific organic solvent [C]. Is an essential component, and is composed of an acidic resin type dispersant [D], a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a sensitizer, and other auxiliary components.

In the near-infrared absorbing composition of the present invention, the near-infrared absorbing dye [A] can be used alone or in admixture of two or more at an arbitrary ratio, if necessary.

The content of the near-infrared absorbing dye [A] of the present invention can be adjusted as needed, but is preferably contained in the near-infrared absorbing composition in an amount of 0.01 to 50% by mass, preferably 0.1. It is more preferable to contain ~ 30% by mass. Within this range, the near-infrared absorbing ability can be more preferably imparted, and at the same time, invisibility can be imparted.

In the near-infrared absorbing composition of the present invention, it is desirable that the near-infrared absorbing dye [A] is dispersed with a basic resin-type dispersant [B] and used in a fine particle-dispersed state. By using the compound in a dispersed state, there is an advantage that the durability of the compound is improved. The near-infrared absorbing dye [A] used in the present invention preferably has an average primary particle diameter of 1 to 500 nm at the time of dispersion, more preferably 10 to 200 nm, and particularly preferably 10 to 100 nm. When the average primary particle size of the fine particles is 10 nm or more, the surface energy of the particles is small, so that the particles are less likely to aggregate, the fine particles are easily dispersed, and the dispersed state is easily maintained, which is preferable. Further, when the average primary particle diameter of the fine particles is 200 nm or less, the influence of particle scattering is reduced and the absorption spectrum becomes sharp, which is preferable.

The average primary particle size of the near-infrared absorbing dye [A] was measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each dye were measured, and the average was taken as the particle size of the dye primary particles. Next, for 100 or more dye particles, the volume (weight) of each particle was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was defined as the average primary particle size.

(Manufacturing method of near-infrared absorbing dye [A])
As a method for producing the near-infrared absorbing dye [A], 1,8-diaminonaphthalene and cyclohexanones represented by the following general formula (2) are heated under reflux in a solvent together with a catalyst to be condensed, and then condensed as described below. 3,4-Dihydroxy-3-cyclobutene-1,2-dione represented by the formula (3) is added and further heated under reflux to condense to obtain a near-infrared absorbing dye [A] represented by the general formula (1). Although a production method can be considered, the near-infrared absorbing dye [A] used in the present invention is not limited to these production methods.

<Basic resin type dispersant [B]>
The near-infrared absorbing composition of the present invention contains a basic resin-type dispersant [B]. Among them, a block copolymer composed of an A block having a tertiary amino group and a quaternary ammonium base in the side chain and a B block having no tertiary amino group and a quaternary ammonium base is contained in the block copolymer. It contains a basic resin-type dispersant [B1] having an amine value of 10 to 200 mgKOH / g in solid content and a quaternary ammonium salt value of 10 to 90 mgKOH / g. The basic resin type dispersant [B] may contain a basic resin type dispersant other than [B1].

The A block having a tertiary amino group and a quaternary ammonium base in the side chain of the basic resin type dispersant [B1] is an ethylenically unsaturated monomer having a tertiary amino group and an ethylenic having a quaternary ammonium base. It is obtained by preparing a copolymer containing an unsaturated monomer in the copolymer composition, but instead of containing an ethylenically unsaturated monomer having a quaternary ammonium salt in the copolymer composition, it has a tertiary amine. After polymerizing a copolymer containing an ethylenically unsaturated monomer, the polymer is reacted with a halogenated hydrocarbon compound such as benzyl chloride, and a tertiary amino group is partially quaternary ammonium chloride to form A. You may create a block.

The ethylenically unsaturated monomer having a tertiary amino group contained in the A block of the basic resin type dispersant [B1] is represented by the following general formula (4).

General formula (4)

[In the general formula (4), R ⁵¹ and R ⁵² each independently represent a chain or cyclic hydrocarbon group which may have a hydrogen atom or a substituent, and R ⁵¹ and R ⁵² are bonded to each other. May form an annular structure. R ⁵³ represents a hydrogen atom or a methyl group, and X ¹⁰¹ represents a divalent linking group. ]

As R ⁵¹ and R ⁵² in the above general formula (4), an alkyl group having 1 to 4 carbon atoms which may have a substituent is more preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are particularly preferable. ..

Among the substituents on the hydrocarbon groups represented by R ⁵¹ and R ⁵² of the general formula (4), the substituents on the chain hydrocarbon group include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. And so on. Examples of the substituent on the cyclic hydrocarbon group include a chain alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group. Further, the chain hydrocarbon groups represented by R ⁵¹ and R ⁵² include both linear and branched chain chains.

Further, in the above general formula (4), as the cyclic structure in which R ⁵¹ and R ⁵² are bonded to each other, for example, a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a condensed ring formed by condensing two of them. Can be mentioned. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specifically, for example, the following can be mentioned.

These cyclic structures may further have substituents.

Further, in the above general formula (4), the divalent linking group X ¹⁰¹ includes, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R ⁵⁸ -group, and -COO-R ^59. -Groups [However, R ⁵⁸ and R ⁵⁹ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)] and the like. preferably ^{-COO-R 59} - a group.

The ethylenically unsaturated monomer having a tertiary amino group represented by the above general formula (4) is, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylamino. Examples thereof include propyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate is preferable.

The ethylenically unsaturated monomer having a quaternary ammonium base contained in the A block of the basic resin type dispersant [B1] is represented by the following general formula (6).

General formula (6)

[In the general formula (6), R ^{54 to} R ⁵⁶ independently represent a chain or cyclic hydrocarbon group which may have a hydrogen atom or a substituent, and 2 of R ^{54 to} R ⁵⁶ . One or more may be bonded to each other to form a cyclic structure. R ⁵⁷ represents a hydrogen atom or a methyl group, X ¹⁰² represents a divalent linking group, and L ⁻ represents a counter anion. ]

As R ^{54 to} R ⁵⁶ in the above general formula (6), an alkyl group having 1 to 4 carbon atoms which may have a substituent is more preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are particularly preferable. ..

Among the substituents on the hydrocarbon groups represented by R ^{54 to} R ⁵⁶ of the general formula (6), the substituents on the chain hydrocarbon group include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. And so on. Examples of the substituent on the cyclic hydrocarbon group include a chain alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group. Further, the chain hydrocarbon groups represented by R ^{54 to} R ⁵⁶ include both linear and branched chain chains.

Further, in the above general formula (6), as a cyclic structure formed by bonding two or more of R ^{54 to} R ⁵⁶ to each other, for example, a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or two of them. Examples thereof include a fused ring formed by condensation. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specifically, for example, the following can be mentioned.

In the above formula (7), R is any one of R ^{54 to} R ⁵⁶ . These cyclic structures may further have substituents.

Further, in the general formula (6), the divalent linking group X ¹⁰² is the same as X ¹⁰¹ in the general formula (4). Further, in the above general formula (6), examples of the counter anion L ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO4 ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

Ethyl unsaturated monomers having a quaternary ammonium base represented by the above general formula (6) are, for example, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, and (meth) acryloyl. Examples thereof include (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, and the like (meth). ) Acryloyloxyethyltrimethylammonium chloride is preferred.

In the A block of the basic resin type dispersant [B1], the ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium base are both random copolymerized and blocked. It may be contained in any aspect of polymerization. Further, two or more kinds of ethylenically unsaturated monomer having a tertiary amine and ethylenically unsaturated monomer having a quaternary ammonium salt may be contained in one A block, in which case. Each repeating unit may be contained in the A block in any mode of random copolymerization or block copolymerization.

In the A block of the basic resin type dispersant [B1], a monomer other than the above-mentioned ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium base are used. It may be included in the copolymer composition. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth). Acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, polyethylene glycol (n = 1-5) methyl ether (meth) acrylate, polyethylene glycol (n) = 1-5) Ethyl ether (meth) acrylate, polyethylene glycol (n = 1-5) propyl ether (meth) acrylate, polypropylene glycol (n = 1-5) methyl ether (meth) acrylate, polypropylene glycol (n = 1) ~ 5) (Meta) acrylic acid ester-based monomers such as ethyl ether (meth) acrylate and polypropylene glycol (n = 1-5) propyl ether (meth) acrylate; styrene-based single amounts such as styrene and α-methylstyrene. Body; (meth) acrylate-based monomers such as (meth) acrylate chloride; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allylglycidyl ether, Glycidyl crotonate ether; N-methacryloylmorpholine and the like can be mentioned. The content of the monomers other than the ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium base in the A block is preferably 0 to 50% by mass, and more. It is preferably 0 to 20% by mass, but it is most preferable that such a monomer is not contained in the A block.

Unless the B block of the basic resin type dispersant [B1] contains the above-mentioned ethylenically unsaturated monomer having a tertiary amino group and the above-mentioned ethylenically unsaturated monomer having a quaternary ammonium base, Random copolymerization, blocking, including, but not limited to, a monomer other than the above-mentioned ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium base. Copolymerization can be mentioned. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth). Acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, polyethylene glycol (n = 1-5) methyl ether (meth) acrylate, polyethylene glycol (n) = 1-5) Ethyl ether (meth) acrylate, polyethylene glycol (n = 1-5) propyl ether (meth) acrylate, polypropylene glycol (n = 1-5) methyl ether (meth) acrylate, polypropylene glycol (n = 1) -5) It is preferable to contain (meth) acrylic acid ester-based monomers such as ethyl ether (meth) acrylate and polypropylene glycol (n = 1 to 5) propyl ether (meth) acrylate. The B block of the basic resin type dispersant [B1] has a content of the above acrylic acid ester-based monomer preferably 50 to 100% by mass, more preferably 80 to 100% by mass, but 100% by mass. Most preferably.

The basic resin type dispersant [B1] is preferably an AB block copolymer or a BAB block copolymer. Regardless of whether the basic resin type dispersant [B1] is an AB block copolymer or a BAB block copolymer, the A block / B block ratio constituting the copolymer is From the viewpoint of dispersion stability and storage stability, it is preferably 5/95 to 75/25 (mass ratio), more preferably 15/85 to 65/35 (mass ratio), and 20/80. It is particularly more preferably ~ 60/40 (mass ratio).

The acid value of the basic resin-type dispersant [B1] is preferably low, particularly preferably 0 mgKOH / g, from the viewpoint of dispersion stability and storage stability. Here, the acid value represents the number of mg of KOH required to neutralize 1 g of the dispersant solid content.

The amine value of the basic resin type dispersant [B1] in the solid content is 10 or more and 200 or less (mgKOH / g), and the quaternary ammonium salt value is 10 or more and 90 or less (mgKOH / g). Here, the amine value represents a value obtained by converting the number of mg of HCl required to neutralize 1 g of the dispersant solid content into the equivalent of KOH. The quaternary ammonium salt value indicates the quaternary ammonium salt value of the solid content. Above all, the amine value is more preferably 20 or more and 160 or less (mgKOH / g) from the viewpoint of improving dispersion stability and storage stability and reducing absorption in the visible region (400 nm to 700 nm). In addition, the quaternary ammonium salt value should be 30 or more and 70 or less (mgKOH / g) from the viewpoint of improving dispersion stability and storage stability and reducing absorption in the visible region (400 nm to 700 nm). More preferred.

The molecular weight of the basic resin type dispersant [B1] is preferably in the range of 4,000 to 40,000 in terms of polystyrene-equivalent weight average molecular weight (hereinafter, may be referred to as “Mw”). When Mw is 4,000 or more, the dispersion stability is further improved, while when it is 40,000 or less, the developability is not lowered and dry foreign matter is less likely to be generated at the time of coating on the substrate.

The basic resin type dispersant [B1] can be produced by a known method, and can be produced, for example, by subjecting the above-mentioned monomer to living polymerization. Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P. et al. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K. et al. Ute, et al, Polym. J. 17,977 (1985), 18,1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36,366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46,189 (1989), M. Kuroki, T.K. Aida, J. et al. Am. Chem. Soc, 109,4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43,300 (1985), D.M. Y. Sogoh, W. et al. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be adopted.

In the present invention, another dispersant can be used in combination with the basic resin type dispersant [B1]. Other dispersants include, for example, Disperbyk-108, 161, 162, 163, 165, 167, 182, 184, 185, 2000, 2001, 2009, 2025, 2050, 2055, 2150, 2155, 2163, 2164 and the like ( (Made by Big Chemie Japan), SOLSERSE-3000, 9000, 13000, 13240, 13650, 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. (all manufactured by Japan Lubrizol), EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015. , 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 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. (above, manufactured by BASF), Azisper PA111, PB711, PB821, PB822, PB824, etc. (above, manufactured by Ajinomoto Fine Techno). ) Commercial products can be mentioned.

In the present invention, the content of the basic resin type dispersant [B] is preferably 5 to 200% by weight, preferably 5 to 200% by weight, based on the total amount of the dye in the near-infrared absorbing composition (100% by weight). From the viewpoint of characteristics and durability, it is more preferably 10 to 150% by weight. The content of the basic resin type dispersant [B1] is 50 to 100% by weight based on the total basic resin type dispersant (100% by weight) from the viewpoint of optical properties and dispersion stability. Is more preferable, 80 to 100% by weight is more preferable, and 100% by weight is particularly more preferable.

<Organic solvent [C]>
The near-infrared absorbing composition of the present invention stably maintains a state in which the dye is sufficiently dispersed in a resin or the like, and has a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. The organic solvent [C] is contained in order to facilitate the application to form the filter segment.

As the organic solvent [C], a known organic solvent can be used, for example, ethyl lactate, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3. -Butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethyl Cyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butandiol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxy Butyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o -Xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, ethylene glycol, ethylene glycol diacetate , Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diisopropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glyco Lu dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tri Propylene glycol monomethyl ether, propylene glycol, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Examples thereof include ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester.

Among them, alkyl lactates such as ethyl lactate, glycols such as ethylene glycol and propylene glycol, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Glycolacets such as diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutanol, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol dimethyl ether , Glycol ethers such as propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, aliphatic esters such as cyclohexanol acetate, lactones such as γ-butyrolactone. , Aromatic alcohols such as benzyl alcohol and ketones such as cyclohexanone are preferably used.

(Organic solvent [C1])
The near-infrared absorbing composition of the present invention maintains a state in which the dye is sufficiently dispersed in a resin or the like in a more stable manner, and has a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. The boiling point at 760 mmHg is 120 to 210 ° C., and the solubility parameter (= SP value) is 9.0 (cal / cm ³ ) ¹ in order to make it easier to form the filter segment. Contains an organic solvent [C1] that is ² or more and less than 13.0 (cal / cm ³ ) ^1/2 .

By using the organic solvent [C1] having a specific SP value, the affinity between the near-infrared absorbing dye [A] contained in the composition and the basic resin type dispersant [B] is improved, and the dispersion is stable. A near-infrared absorbing composition having better properties and storage stability can be obtained, and a near-infrared cut filter having less absorption in the visible region (400 nm to 700 nm) and having excellent near-infrared absorbing ability can be obtained. ..

Further, it is preferable to use an organic solvent [C1] having a boiling point of 120 or more because the drying property is appropriate and the solvent composition ratio and the non-volatile content are unlikely to change during production, storage, and use. Further, by using an organic solvent [C1] having a boiling point of less than 210 ° C., the drying property becomes appropriate when forming a thin film of a near-infrared cut filter. For example, when a near-infrared absorbing composition is applied by a spin coating method. This is preferable because a thin film can be formed that is smooth and has no color unevenness (film thickness unevenness) without swelling of the liquid at the edge of the substrate. The die coating method is also preferable because it can form a thin film that is smooth and has no color unevenness (film thickness unevenness) without swelling of the liquid at the coating boundary.

To exemplify the organic solvent [C1] together with (boiling point (° C.) / SP value (cal / cm ³ ) ^1/2 ), ethylene glycol monoethyl ether acetate (156 / 9.0), ethylene glycol monomethyl ether acetate (145 / 9.2), cyclohexanol acetate (173 / 9.2), ethylene glycol monobutyl ether (171 / 9.5), propylene glycol diacetate (190 / 9.6), dipropylene glycol monomethyl ether (190). /9.7), Propylene Glycol Monopropyl Ether (150 / 9.7), Propylene Glycol Monobutyl Ether (170 / 9.8), Cyclohexanone (156 / 9.9), Ethyl Lactate (154 / 10.0), Ethylene glycol diacetate (190 / 10.0), ethylene glycol monoethyl ether (135 / 10.5), diethylene glycol monoethyl ether (202 / 10.9), 3-methoxybutanol (158 / 10.9), ethylene Glycol monomethyl ether (124 / 11.4), γ-butyrolactone (204 / 12.6), propylene glycol (188 / 12.6) and the like can be mentioned, and two or more of them may be used in combination.

Among them, it is more preferable to use cyclohexanol acetate, cyclohexanone, ethyl lactate and 3-methoxybutanol, and it is particularly more preferable to use cyclohexanol acetate, ethyl lactate and 3-methoxybutanol.

These organic solvents [C] can be used alone or in admixture of two or more. When two or more kinds of mixed solvents are used, the organic solvent [C1] is preferably contained in an amount of 10 to 100% by mass , preferably 20 to 100% by mass , based on 100 parts by mass of the total organic solvent [C]. It is more preferable to have. Further, when using an organic solvent [C] other than the organic solvent [C1], it is more preferable to use propylene glycol monomethyl ether acetate. Further, since the organic solvent [C] can adjust the near-infrared absorbing composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, 500 to 500 to 100 parts by weight of the total weight of the dye. It is preferably used in an amount of 4000 parts by weight.

<Acid resin type dispersant>
The near-infrared absorbing composition of the present invention is an acidic resin type having an aromatic carboxyl group in order to more stably maintain a state in which the dye is sufficiently dispersed in a resin or the like and to improve optical characteristics. It preferably contains a dispersant. A particularly preferable acidic resin type dispersant having an aromatic carboxyl group is an aromatic carboxyl which is a reaction product of a polymer [E] having a hydroxyl group at one end or a side chain and an aromatic tricarboxylic acid anhydride [F]. It is an acidic resin type dispersant [D] having a group.

<Acid resin type dispersant [D]>
The acidic resin-type dispersant [D] of the present invention has an aromatic carboxyl group in its molecule, and an aromatic tricarboxylic acid anhydride [F] is added to a polymer [E] having a hydroxyl group at one end or a side chain. ] Is reacted.

(Polymer [E] having a hydroxyl group at one end or side chain)
The polymer [E] used as a precursor of the dispersant having an aromatic carboxyl group of the present invention includes a polymer [E1] having a hydroxyl group at one end and a polymer [E2] having a hydroxyl group in the side chain. It is divided into. Further, as the polymer [E1] having a hydroxyl group at one end, a polymer [E3] having two hydroxyl groups at one end is preferable.

[Polymer having a hydroxyl group at one end [E1]]
First, a polymer [E1] having a hydroxyl group at one end will be described. The polymer [E1] having a hydroxyl group at one end used in the present invention includes a polyester and / or a polyether polymer [E1-1] having a hydroxyl group at one end and a vinyl polymer having a hydroxyl group at one end. [E1-2] and the like.

<< Polyester and / or polyether polymer [E1-1] >>
As the polyester and / or the polyether polymer [E1-1] having a hydroxyl group at one end, those represented by the following general formula (8) are preferable.

General formula (8):

[In the general formula (8), Y ¹ is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms.
X ¹¹ is -O-, -S-, or -N (R ¹⁰¹ )-(where R ¹⁰¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms).
Z ¹ is -OH,
G ¹ is a repeating unit represented by -R ¹⁰² O-.
G ² is a repeating unit represented by −C (= O) R ¹⁰³ O−.
G ³ is a repeating unit represented by −C (= O) R ¹⁰⁴ C (= O) −OR ¹⁰⁵ O−.
R ¹⁰² is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms.
R ¹⁰³ is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms.
R ¹⁰⁴ is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or It is an arylene group with 6 to 20 carbon atoms.
R ¹⁰⁵ is −CH (R ¹⁰⁶ ) −CH (R ¹⁰⁷ ) −
One of R ¹⁰⁶ and R ¹⁰⁷ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyl. Alkyloxymethylene groups with 1 to 20 carbon atoms in the moiety, alkenyloxymethylene groups with 2 to 20 carbon atoms in the alkenyl moiety, and 6 to 20 carbon atoms in the aryl moiety, with the aryl moiety optionally substituted with halogen atoms. Aryloxymethylene groups that may be present,
It is an N-methylene-phthalimide group and
R ¹⁰⁸ is the ^{R 102, -C (= O)} R 103 -, or ^{-C (= O) R 104 C} (= O) -OR 105 - a and,
m1 is an integer from 0 to 100 and
m2 is an integer from 0 to 60 and
m3 is an integer from 0 to 30
However, m1 + m2 + m3 is 1 or more and 100 or less.
The arrangement of the repeating units G ^{1 to} G ^{3 in} the general formula (8) does not limit the order thereof, and in the polymer represented by the general formula (8), between the group X ¹¹ and the group R ^108. Indicates that the repeating units G ^{1 to} G ³ are included in an arbitrary order, and the repeating units G ^{1 to} G ³ may be either a random type or a block type, respectively. ]

Formula (8), it Y ¹ is a linear or branched alkyl group having 1 to 18 carbon atoms is preferable from the viewpoint of dispersion stability and storage stability of the near-infrared absorbing composition.

As another embodiment, the Y ¹ in the general formula (8) preferably has an ethylenically unsaturated double bond. In this case, the dispersant having an aromatic carboxyl group can be imparted with active energy ray curability.

Further, in the general formula (8), it is preferable that m2 is an integer of 3 to 15 from the viewpoint of reducing the viscosity and storage stability of the near-infrared absorbing composition.

Further, in the above general formula (8), when m2 = 0 and m3 = 0, Y ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms, or is an ethylenically unsaturated double bond. It preferably has a double bond.

The polyester and / or polyether polymer [E1-1] having a hydroxyl group at one end represented by the general formula (8) can be produced by a known method, and can be produced by a known method, monoalcohol, primary monoamine, and secondary. It can be easily obtained by ring-opening polymerization of a cyclic compound selected from the group of alkylene oxide, lactone, lactide, dicarboxylic acid anhydride, and epoxide using a compound selected from the group of monoamine and monothiol as an initiator.

The monoalcohol may be any compound as long as it has one hydroxyl group. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldeca Aliper monoalcohols such as ol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, or oleyl alcohol;
Monoalcohols having an aromatic ring such as benzyl alcohol, phenoxyethyl alcohol, paracumylphenoxyethyl alcohol; or
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono- 2-Ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene Glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol Monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl A. Examples thereof include tere, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and alkylene glycol monoalkyl ethers such as tetradiethylene glycol monomethyl ether.

As the monoalcohol, a monoalcohol having an ethylenically unsaturated double bond may be used. In this case, the active energy ray-curing performance can be imparted to the dispersant having an aromatic carboxyl group to be produced.

Examples of the group having an ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group (wherein this is referred to as "(meth) acryloyl" or "(meth) acrylate". Includes "acryloyl and / or methacryloyl" or "methacrylate and / or acrylate", respectively), with preference given to the (meth) acryloyl group. The type of the group having these double bonds may be one type or a plurality of types.

As the monoalcohol having an ethylenically unsaturated double bond, a compound containing 1, 2, or 3 or more ethylenically unsaturated double bonds can be used. Examples of the monoalcohol having one ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate (in the case of "(meth) acrylate", acrylate and / or methacrylate are used. The same shall apply hereinafter.), 3-Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl. (Meta) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, or 4- Hydroxybutyl vinyl ether and the like can be mentioned. Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate, glycerin di (meth) acrylate and the like. Examples of monoalcohols having 3 ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of monoalcohols having 5 ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate. Can be mentioned.

Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained as a mixture of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively, and therefore, HPLC (high performance liquid chromatography) is used to control the molecular weight of the dispersant produced. It is necessary to determine the ratio of monoalcohol by the liquid chromatography) method or the measurement of hydroxyl value. This is because the molecular weight of the dispersant is determined by the number of monoalcoholic compounds and the ratio of the raw materials forming G ^{1 to} G ³ .

Among the above monoalcohols, those having two or more ethylenically unsaturated double bonds are preferable when used in an active energy ray-curable pigment composition in terms of curability.

Examples of the primary monoamine include methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, tert-butylamine, 1-pentylamine, isopentylamine, 3-pentylamine and 1-hexylamine. , Cyclohexylamine, 4-methyl-2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2-ethylhexylamine, 1-nonylamine, isononylamine, 1-decylamine, 1-dodecylamine, 1 -Adipose primary monoamines such as myristylamine, cetylamine, 1-stearylamine, isostearylamine, 2-octyldecylamine, 2-octyldodecylamine, 2-hexyldecylamine, behenylamine, or oleylamine;
3-Methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 2-ethylhexyloxypropylamine, 3-isobutyroxypropylamine, 3-decyloxypropylamine, or 3- Alkoxyalkyl primary monoamines such as myristyloxypropylamine; or
Examples thereof include aromatic primary monoamines such as benzylamine.

Examples of the secondary monoamine include dimethylamine, diethylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisobutylamine, di-1-pentylamine, diisopentylamine, and di-1-hexylamine. , Dicyclohexylamine, di- (4-methyl-2-pentyl) amine, di-1-heptylamine, di-1-octylamine, isooctylamine, di- (2-ethylhexyl) amine, di-1-nonylamine, Diisononylamine, di-1-decylamine, di-1-dodecylamine, di-1-myristylamine, disetylamine, di-1-stearylamine, diisostearylamine, di- (2-octyldecyl) amine, di- (2) -Octyldodecyl) amine, di- (2-hexyldecyl) amine, N-methylethylamine, N-methylbutylamine, N-methylisobutylamine, N-methylpropylamine, N-methylhexylamine, piperazin, or alkyl-substituted piperazine Examples of aliphatic secondary monoamines such as.

Examples of monothiols include methylthiol, ethylthiol, 1-propylthiol, isopropylthiol, 1-butylthiol, isobutylthiol, tert-butylthiol, 1-pentylthiol, isopentylthiol, 3-pentylthiol, 1-. Hexylthiol, cyclohexylthiol, 4-methyl-2-pentylthiol, 1-heptylthiol, 1-octylthiol, isooctylthiol, 2-ethylhexylthiol, 1-nonylthiol, isononylthiol, 1-decylthiol, 1- An aliphatic monothiol such as dodecylthiol, 1-myristylthiol, cetylthiol, 1-stearylthiol, isostearylthiol, 2-octyldecylthiol, 2-octyldodecylthiol, 2-hexyldecylthiol, behenylthiol, or oleylthiol. Kind; or
Alkyl thioglycolic acids such as methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, methyl mercaptopropionate, octyl mercaptopropionate, methoxybutyl mercaptopropionate, or alkyl mercaptopropionate such as tridecyl mercaptopropionate. Esters can be mentioned.

The compound selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols referred to in the present invention is not limited to the above examples, but is not limited to the above examples, and is a hydroxyl group, a primary amino group, a secondary amino group, or a thiol. Any compound can be used as long as it has one group, and it may be used alone or in combination of two or more.

Here, the portion of the monoalcohol, the primary monoamine, the secondary monoamine, or the monothiol excluding the hydroxyl group, the primary amino group, the secondary amino group, or the thiol group is Y ¹ in the general formula (8). Configure.

From the group consisting of a compound selected from the group consisting of the above-exemplified monoalcohol, primary monoamine, secondary monoamine, and monothiol as an initiator, alkylene oxide, lactone, lactide, and a combination of dicarboxylic acid anhydride and epoxide. The selected cyclic compound can be ring-opened polymerized to produce a polymer represented by the general formula (8) in which Z ¹ is −OH. However, the combination of dicarboxylic acid anhydride and epoxide is always used at the same time and polymerized alternately.

Here, the reaction sequence of the cyclic compound selected from the group consisting of a combination of an alkylene oxide, a lactone, a lactide, and a combination of a dicarboxylic acid anhydride and an epoxide may be any, and for example, as the first step, the initiator. After polymerizing the alkylene oxide, the lactone can be polymerized in the second step, and the dicarboxylic acid anhydride and the epoxide can be polymerized alternately in the third step. In this example, the initiator for polymerizing the lactone in the second step is an alkylene oxide polymer having a hydroxyl group at one end that is polymerized in the first step. In addition, the initiator when the dicarboxylic acid anhydride and the epoxide are alternately polymerized in the third step is a block of both the alkylene oxide polymer having a hydroxyl group at one end and the lactone polymer that have been polymerized by the second step. It becomes a polymer. In the production method of the present invention, Z ¹ among the polymers represented by the general formula (8) is used as an initiator in the case of producing the polymer represented by the general formula (8) described below. -OH and the polymer represented by the general formula (10) described later can also be an initiator.

The reaction sequence of the cyclic compounds is not limited to the combination of the first step alkylene oxide, the second step lactone, the third step dicarboxylic acid anhydride and the epoxide, and the alkylene oxide, the lactone (and / or the lactide). , And the combination of dicarboxylic acid anhydride and epoxide can be carried out in any order, one or more times, respectively. Alternatively, for combinations of alkylene oxides, lactones (and / or lactides), and dicarboxylic acid anhydrides and epoxides, any cyclic compound may be selected from among them without performing all ring-opening polymerization. Ring-opening polymerization can also be carried out.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide and the like, and these are used alone. Alternatively, two or more types can be used in combination. The binding form when two or more kinds of alkylene oxides are used in combination may be either random and / or block. The number of moles of alkylene oxide polymerized per mole of initiator is preferably 0 to 100.

Polymerization of the alkylene oxide can be carried out by a known method, for example, in the presence of an alkaline catalyst at a temperature of 100 to 200 ° C. under pressure. An alkylene oxide polymer having a hydroxyl group at one end obtained by polymerizing an alkylene oxide on a hydroxyl group of a monoalcohol is commercially available. For example, there are Uniox series manufactured by Nippon Oil & Fats Co., Ltd., Blemmer series manufactured by Nippon Oil & Fats Co., Ltd. and the like. As a raw material for the dispersant having an aromatic carboxyl group of the present invention, assuming that Z ¹ is −OH and has only G ¹ among the repeating units of G ^{1 to} G ³ among the polymers represented by the general formula (8). It can be used as it is. Specific examples of commercially available products are Uniox M-400, M-550, M-2000, Blemmer PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP-. 1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET There are series, 30PPT-800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, 10APB-500B and the like.

Here, the alkylene group of alkylene oxide, constitutes the R ¹⁰² in the repeating unit G ¹ in the general formula (8).

Specific examples of the lactone include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. It is preferable to use δ-valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone from the viewpoint of ring-opening polymerizable property.

In the production method of the present invention, the lactone can be used without being limited to the above examples, and may be used alone or in combination of two or more. When two or more types are used in combination, the crystallinity may decrease and the liquid may become liquid at room temperature, which is preferable in terms of workability and compatibility with other resins.

As the lactide, those represented by the following general formula (9) are preferable (including glycolide).

General formula (9):

[In general formula (9),
R ¹⁰⁹ and R ¹¹⁰ are independently alkyl groups having 1 to 20 carbon atoms of hydrogen atoms, saturated or unsaturated linear or branched carbon atoms.
R ¹¹¹ and R ¹¹² are independently hydrogen atoms, halogen atoms, and saturated or unsaturated linear or branched lower alkyl groups having 1 to 9 carbon atoms. ]

Lactides (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane) are particularly suitable as raw materials for the dispersant having an aromatic carboxyl group of the present invention. -2,5-Zeon). Further, among the lactones or lactides, the lactone is preferably used as a raw material for the dispersant having an aromatic carboxyl group of the present invention.

Ring-opening polymerization of lactone and / or lactide can be carried out in a known method, for example, by charging a reactor to which a dehydration tube and a condenser are connected with an initiator, lactone and / or lactide, and a polymerization catalyst, and under a nitrogen stream. .. When a low boiling point monoalcohol is used, it can be reacted under pressure using an autoclave. When a monoalcohol having an ethylenically unsaturated double bond is used, it is preferable to add a polymerization inhibitor and carry out the reaction under a dry air flow.

The number of moles of polymerization of the lactone and / or lactide with respect to 1 mol of the initiator is preferably in the range of 1 to 60 mol, more preferably 2 to 20 mol, and most preferably 3 to 15 mol.

As the polymerization catalyst of lactone and / or lactide, known ones can be used without limitation, and for example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and tetramethylammonium iodine can be used. , Tetrabutylammonium iodo, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, or quaternary ammonium salts such as benzyltrimethylammonium iodo;
Tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium bromide, tetrabutylphosphonium iodine, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium chloride, tetraphenylphosphonium chloride, A quaternary phosphonium salt such as tetraphenylphosphonium bromide or tetraphenylphosphonium iodo;
Phosphorus compounds such as triphenylphosphine;
Organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, or sodium benzoate;
Alkali metal alcoholates such as sodium alcoholate or potassium alcoholate;
Tertiary amines;
Organometallic compounds such as organotin compounds, organoaluminum compounds, or organotitanate compounds; or
Examples include zinc compounds such as zinc chloride.

The amount of the catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. If the amount of catalyst exceeds 3000 ppm, the resin may be heavily colored. On the contrary, if the amount of the catalyst used is less than 0.1 ppm, the ring-opening polymerization rate of the lactone and / or lactide becomes extremely slow, which is not preferable.

The polymerization temperature of the lactone and / or lactide is 100 ° C. to 220 ° C., preferably 110 ° C. to 210 ° C. If the reaction temperature is less than 100 ° C, the reaction rate is extremely slow, and if it exceeds 220 ° C, side reactions other than the addition reaction of lactone and / or lactide, such as depolymerization of the lactone adduct to the lactone monomer, cyclic lactone dimer or trimmer. Generation etc. is likely to occur.

Here, the portion other than the ester group of the lactone or lactide constitutes R ¹⁰³ in the repeating unit G ² in the general formula (8).

Examples of the dicarboxylic acid anhydride include succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, itaconic acid anhydride, glutaric acid anhydride, dodecenyl succinic acid anhydride, chlorendecic acid anhydride and the like.

Examples of the epoxide include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, phenyl glycidyl ether, p-terriary butyl phenyl glycidyl ether, 2,4-dibromophenyl glycidyl ether, and the like. Examples thereof include 3-methyl-dibromophenyl glycidyl ether (whereever the substitution position of bromo is arbitrary), allyl glycidyl ether, ethoxyphenyl glycidyl ether, glycidyl (meth) acrylate, glycidyl phthalimide, styrene oxide and the like.

Dicarboxylic acid anhydride and epoxide are used simultaneously with the initiator and react alternately. At this time, the acid anhydride group of the dicarboxylic acid anhydride first reacts with the hydroxyl group of the initiator, the primary amino group, the secondary amino group, or the thiol group to generate a carboxyl group, and then the carboxyl group is epoxide. Epoxide groups react to form hydroxyl groups. Further, the same reaction as described above can be sequentially carried out, such that the acid anhydride group of the dicarboxylic acid anhydride reacts with this hydroxyl group. The polymerization moles of the dicarboxylic acid anhydride and the epoxide with respect to 1 mol of the initiator are preferably 0 to 30 mol, respectively. The reaction ratio ([G] / [H]) of the dicarboxylic acid anhydride and the epoxide is
0.8 ≤ [G] / [H] ≤ 1.0
([G] is the number of moles of dicarboxylic acid anhydride and [H] is the number of moles of epoxide)
Is preferable. If it is less than 0.8, epoxide remains unfavorably, and if it exceeds 1.0, a polymer having a hydroxyl group at one end cannot be obtained, and a polymer having a carboxyl group at one end is formed, which is not preferable.

Alternate polymerization of the dicarboxylic acid anhydride and the epoxide is preferably carried out in the range of 50 ° C. to 180 ° C., more preferably 60 ° C. to 150 ° C. When the reaction temperature is less than 50 ° C or higher than 180 ° C, the reaction rate is extremely slow.

Here, constitute the repeating units G ³ in R ¹⁰⁴ in a portion other than the dicarboxylic acid anhydride groups of the dicarboxylic acid anhydride the formula (8), portions other than oxygen atoms forming a cyclic ether epoxide said R ¹⁰⁵ in the repeating unit G ³ in the general formula (8) is configured.

When a monoalcohol having an ethylenically unsaturated double bond, a dicarboxylic acid anhydride, or an epoxide is used in producing the polymer represented by the general formula (8), a polymerization inhibitor may be used. preferable. As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, phenothiazine and the like are preferable, and 0.01% to 6 of these are used alone or in combination. %, preferably in the range of 0.05% to 1.0%.

<< Vinyl-based polymer having a hydroxyl group at one end [E1-2] >>
As the vinyl-based polymer [E1-2] having a hydroxyl group at one end, the polymer represented by the following general formula (10) is preferable.

General formula (10):

[In the general formula (10), Y ² is a polymerization terminating group of the vinyl polymer.
Z ² is -OH or -R ²⁰⁸ (OH) ₂ , and R ²⁰⁸ is a trivalent hydrocarbon group having 1 to 18 carbon atoms.
R ²⁰¹ and R ²⁰² are independently hydrogen atoms or methyl groups, respectively.
In R ²⁰³ and R ²⁰⁴ , one is a hydrogen atom and the other is an aromatic group, or -C (= O) -X ^13- R ²⁰⁵ (where X ¹³ is -O- or -N (R). ²⁰⁶ )-)
R ²⁰⁵ and R ²⁰⁶ are hydrogen atoms, linear or branched alkyl groups having 1 to 18 carbon atoms, or linear or branched alkyl groups having 1 to 18 carbon atoms having an aromatic group as a substituent. Alkyl group
X ¹² is, ^{-O-R 207} -, or ^{-S-R 207} - a and,
R ²⁰⁷ is a direct-bonded or linear or branched alkylene group having 1 to 18 carbon atoms.
n is 2 to 50. ]

The polymer represented by the general formula (10) is a vinyl-based polymer obtained by polymerizing an ethylenically unsaturated monomer.

The repeating unit portions of the polymer represented by the general formula (10), that is, {-[C (R ²⁰¹ ) (R ²⁰³ ) -C (R ²⁰² ) (R ²⁰⁴ )] n-} are identical to each other. It may consist of one (homopolymer) or a different one (copolymer). In the preferred form of the polymer represented by the general formula (10), one of R ²⁰¹ and R ²⁰² is a hydrogen atom, the other is a hydrogen atom or a methyl group, and R ²⁰³ and R ²⁰⁴ are any of them. One is a hydrogen atom and the other is -C (= O) -OR ²⁰⁹ (R ²⁰⁹ is a linear or branched alkyl group having 1 to 8 carbon atoms and has an aromatic group as a substituent. This is the case where -X ^12- Z ² is -S-CH ₂ CH _2- OH or -S-CH ₂ CH (OH) CH _2- OH.

Y ² in the general formula (10) ^in, i.e., the polymerization terminating group of the vinyl polymer may be employed in any known polymerization terminator to be introduced to the polymerization of normal ethylenically unsaturated monomers when carried out in the usual manner It is a basis and is obvious to those skilled in the art. Specifically, it can be, for example, a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Regardless of which of these chemical structures Y ² has, the dispersant of the present invention can exert its effect without being affected by the polymerization terminating group Y ² .

Among the polymers represented by the general formula (10), those having Z ² of −OH can be produced by a known method, for example, a compound having a hydroxyl group and a thiol group and an ethylenically unsaturated monomer. Can be obtained by mixing and heating.

Examples of the compound having a hydroxyl group and a thiol group in the molecule include mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, 2-mercapto-3-butanol and the like. Can be mentioned.

Among the polymers represented by the general formula (10), those having Z ² of −R ²⁰⁸ (OH) ₂ can be produced by a known method, and for example, a compound having two hydroxyl groups and one thiol group. It can be obtained by mixing with an ethylenically unsaturated monomer and heating. In this case, among the polymers [E] having a hydroxyl group at one end, the polymer [E3] having two hydroxyl groups at one end is the most preferable embodiment.

Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1,2-propanediol. (Thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto- Examples thereof include 2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like.

Preferably, bulk polymerization or solution polymerization is carried out using a compound having 1 to 30 parts by weight of a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours. If the compound having a hydroxyl group and a thiol group is less than 1 part by weight, the molecular weight becomes large and the viscosity of the dispersion becomes high, which may not be preferable. If it exceeds 30 parts by weight, the molecular weight becomes small, and the steric repulsion effect due to the solvent-friendly vinyl polymer portion decreases, which may be unfavorable.

Since the thiol group serves as a radical generating group for polymerizing the ethylenically unsaturated monomer, another polymerization initiator is not always required for the polymerization, but it can also be used. When the polymerization initiator is used, it is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.

As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), and 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) , 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2,2'-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like. Examples of organic peroxides are benzoyl peroxide, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxy. Examples thereof include dicarbonate, t-butylperoxyneodecanoate, t-butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like. These polymerization initiators can be used alone or in combination of two or more.

Examples of the ethylenically unsaturated monomer include an acrylic monomer and a monomer other than the acrylic monomer. Examples of the acrylic monomer include 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) ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or (meth) acrylates such as ethoxypolyethylene glycol (meth) acrylate, or ( Meta) acrylamide (Note that when referred to as "(meth) acrylamide", it means acrylamide and / or methacrylamide. The same shall apply hereinafter), N, N-dimethyl (meth) acrylamide, N, N- Examples thereof include (meth) acrylamides such as diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin.

Examples of the monomer other than the acrylic monomer include styrene, styrenes such as α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and the like. Examples thereof include vinyl ethers, vinyl acetate, and fatty acid vinyls such as vinyl propionate. The monomer other than the acrylic monomer can also be used in combination with the acrylic monomer.

Further, the carboxyl group-containing ethylenically unsaturated monomer can be used alone or in combination with the monomer. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-couplerolactone-added acrylic acid, ε-couplerolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, or crotonic acid. Acids and the like can be mentioned, and one type or two or more types can be selected.

In the step of producing the polymer represented by the general formula (10), a solvent-free or optionally a solvent can be used. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene. Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like are used, but are not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used.

The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. After the reaction is completed, the used solvent can be removed by an operation such as distillation, or can be used as it is as a part of the dispersant product.

[Polymer having a hydroxyl group in the side chain [E2]]
The polymer [E2] having a hydroxyl group in the side chain of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a hydroxyl group with another ethylenically unsaturated monomer, if necessary. As an ethylenically unsaturated monomer having a hydroxyl group,
A (meth) acrylate-based monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate. , A hydroxyalkyl (meth) acrylate such as cyclohexanedimethanol mono (meth) acrylate, or an alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate, or
A (meth) acrylamide-based monomer having a hydroxyl group, for example, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, or N- (2-hydroxybutyl) ( N- (hydroxyalkyl) (meth) acrylamide such as meta) acrylamide, or
A vinyl ether-based monomer having a hydroxyl group, for example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, or 2- (or 3- or 4-) hydroxybutyl vinyl ether, or
An allyl ether-based monomer having a hydroxyl group, for example, a hydroxyalkyl such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, or 2- (or 3- or 4-) hydroxybutyl allyl ether Allyl ether and the like can be mentioned.

Further, a monomer having two hydroxyl groups such as glycerol mono (meth) acrylate can also be mentioned. Further, an ethylene-based unsaturated monomer having a cyclic ether group such as an epoxy group is reacted with a carboxyl group-containing ethylenically unsaturated monomer such as (meth) acrylic acid, or (meth) acrylic acid. Examples thereof include those obtained by reacting a carboxyl group-containing ethylenically unsaturated monomer such as the above with a monofunctional cyclic ether compound such as a monofunctional epoxy compound.

In addition, the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether hydroxyalkylallyl ether, or glycerol mono (meth) acrylate, alkylene oxide and / Or an ethylenically unsaturated monomer obtained by adding a lactone can also be used as an ethylenically unsaturated monomer having a hydroxyl group in the method of the present invention. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, or 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide, and a combination system of two or more of these is also used. Can be used. The binding form when two or more kinds of alkylene oxides are used in combination may be either random and / or block. Examples of the lactone to be added include δ-valerolactone, ε-caprolactone, or ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these can also be used. .. Both alkylene oxide and lactone may be added.

The copolymerization ratio of the ethylenically unsaturated monomer having a hydroxyl group to another ethylenically unsaturated monomer is determined so that at least 0.3 to 177 hydroxyl groups are contained in one molecule after polymerization on average. Is preferable.

Examples of other ethylenically unsaturated monomers include the acrylic monomer described in the step of producing the polymer represented by the general formula (10) and a monomer other than the acrylic monomer. , Can be used arbitrarily.

As the polymerization initiator, for example, the azo compound described in the step of producing the polymer represented by the general formula (10) or an organic peroxide can be used. When the polymerization initiator is used, it is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.

As the polymerization solvent, for example, the solvent described in the step of producing the polymer represented by the general formula (10) can be used in the same manner.

<< Reaction of OH resin and acid anhydride >>
Next, a step of reacting the polymer [E1] having a hydroxyl group at one end or the polymer [E2] having a hydroxyl group in the side chain with the tricarboxylic acid anhydride [F] will be described.

By reacting the hydroxyl group of the polymer [E1] having a hydroxyl group at one end or the hydroxyl group [E2] having a hydroxyl group in the side chain with the anhydride group of the aromatic tricarboxylic acid anhydride [F], the present invention The dispersant having the aromatic carboxyl group of the present invention can be obtained.

Examples of the aromatic tricarboxylic acid anhydride [F] include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid anhydride). , Etc.), Naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalentricarboxylic acid anhydride, 1,2,8 -Naphthalene tricarboxylic acid anhydride, etc.), 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2 , 3,2'-biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenylsulfonetricarboxylic acid anhydride and the like.

The aromatic tricarboxylic acid anhydride [F] used in the present invention is not limited to the compounds exemplified above, and may have any structure. These may be used alone or in combination. Trimellitic anhydride is preferable as used in the present invention.

When the number of moles of the hydroxyl group of the polymer [E] is <M> and the number of moles of the carboxylic acid anhydride group of the aromatic tricarboxylic acid anhydride [F] is <N>, the reaction ratio is 0.3 ≦ <M. > / <N> ≦ 3 is preferable, and 0.5 ≦ <M> / <N> ≦ 2 is more preferable. In particular, when the polymer [E1] or the polymer [E3] is used, 1 <<M> / <N> ≦ 2 is preferable. If the reaction is carried out with <M> / <N> <1, the remaining acid anhydride may be hydrolyzed with a required amount of water or alcoholized with a monofunctional alcohol.

When the polymer [E2] is used, it is preferable to introduce 0.3 to 3 aromatic tricarboxylic acids into one molecule. Specifically, the number average molecular weight of the polymer [E2] is measured, and when the measured value is [X], when the aromatic tricarboxylic acid anhydride [F] is used, it is relative to the resin [X] g. The aromatic tricarboxylic acid anhydride of 0.3 mol or more and 3 mol or less may be reacted.

A catalyst may be used for the reaction between the polymer [E] and the aromatic tricarboxylic acid anhydride [F]. As the catalyst, for example, a tertiary amine compound can be used, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-. Undecene, 1,5-diazabicyclo- [4.3.0] -5-nonen and the like can be mentioned.

The reaction between the polymer [E] and the aromatic tricarboxylic acid anhydride [F] may be carried out without a solvent, or an appropriate dehydrated organic solvent may be used. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the dispersant product. The solvent used is not particularly limited, but the solvent described in the step of producing the polymer represented by the general formula (10) can be used in the same manner.

The reaction temperature of the polymer [E] and the aromatic tricarboxylic acid anhydride [F] is preferably in the range of 50 ° C. to 180 ° C., more preferably 60 ° C. to 160 ° C. If the reaction temperature is less than 50 ° C., the reaction rate is slow, and if it exceeds 180 ° C., the ring-opened acid anhydride may produce cyclic anhydride again, making it difficult to complete the reaction.

The acidic resin-type dispersant [D] of the present invention is an acidic resin-type dispersant [D1], which is a reaction product of a polymer [E1] having a hydroxyl group at one end and an aromatic tricarboxylic acid anhydride [F]. Examples thereof include an acidic resin-type dispersant [D2] which is a reaction product of a polymer [E2] having a hydroxyl group in a chain and an aromatic tricarboxylic acid anhydride [F]. Among them, a weight having two hydroxyl groups at one end. It is more preferable to use an acidic resin type dispersant [D3] which is a reaction product of the coalescence [E3] and the aromatic tricarboxylic acid anhydride [F].

The acidic resin type dispersant [D] of the present invention preferably has a weight average molecular weight (Mw) of 1,000 to 30,000. It is preferable to use the acidic resin type dispersant [D] having an Mw of 1,000 or more and 30,000 or less because the dispersion stability and storage stability of the near-infrared absorbing composition are further improved. Further, the acidic resin type dispersant [D] of the present invention preferably has an acid value of 10 to 200 mgKOH / g.

The acidic resin-type dispersant [D] of the present invention is preferably used together with the basic resin-type dispersant [B1] when dispersing the near-infrared absorbing dye [A].

The content of the acidic resin type dispersant [D] of the present invention can be adjusted as needed, but from the viewpoint of dispersion stability, storage stability and optical properties, the basic resin type dispersant [B] The weight ratio of the / acidic resin type dispersant [D] is preferably adjusted to 95/5 to 60/40, and more preferably 85/15 to 70/30.

<Binder resin>
The near-infrared absorbing composition of the present invention may contain a binder resin in order to more efficiently produce a near-infrared cut filter. The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. When used in the form of an alkali-developable resist material, it is preferable to use an alkali-soluble vinyl-based resin in which an acidic group-containing ethylenically unsaturated monomer is copolymerized. Further, for the purpose of further improving the light sensitivity and the solvent resistance, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for the alkali-developed resist, no foreign matter in the coating film is generated after the near-infrared absorbing composition of the present invention is applied. , The stability of the dye in the resist material is improved, which is preferable. When a linear resin that does not have an ethylenically unsaturated double bond is used in the side chain, the dye is less likely to be trapped by the resin in a liquid in which the resin and the dye are mixed, so that the dye has a degree of freedom. The components are easily aggregated and precipitated, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the dye is easily trapped by the resin in the liquid in which the resin and the dye are mixed. In the solvent resistance test, the dye is hard to elute, the dye component is hard to aggregate and precipitate, and the dye molecule is fixed by three-dimensional cross-linking of the resin when exposed to active energy rays to form a film. It is presumed that even if the solvent is removed in the subsequent development step, the dye components are less likely to aggregate and precipitate.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the Mw / Mn value is preferably 10 or less.

When a binder resin is used as a near-infrared absorbing composition, a fat that acts as an alkali-soluble group during development from the viewpoint of permeability, developability, and heat resistance of the near-infrared absorbing dye [A] of the present invention. The balance of the aliphatic group and the aliphatic group acting as the affinity group for the dye carrier and the solvent is important for the permeability, developability and durability of the near infrared absorbing dye [A] of the present invention. , It is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.

Since the binder resin has good film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 30 parts by weight or more with respect to 100 parts by weight of the total weight of the dye, and the dye concentration is high and good optical characteristics can be exhibited. Therefore, it is preferable to use it in an amount of 500 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with the acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as an aliphatic carboxyl group and a sulfone group. Specifically, as the alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples thereof include isobutylene / (maleic anhydride) copolymer. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (a) and (b) shown below.

[Method (a)]
As the method (a), for example, the side chain epoxy group of the copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other monomers is used. , The carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added and reacted, and the generated hydroxyl group is reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4 epoxybutyl (meth) acrylate. And 3,4 epoxycyclohexyl (meth) acrylates are mentioned, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, α-position haloalkyl of (meth) acrylic acid, monocarboxylic acids such as alkoxyls, halogens, nitros, and cyano-substituted products, and these are used alone. It is also possible to use two or more types in combination.

Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more.

As a method similar to the method (a), for example, the copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an aliphatic carboxyl group with one or more other monomers. There is a method of adding an unsaturated ethylenic monomer having an epoxy group to a part of the side chain aliphatic carboxyl group to introduce an unsaturated ethylenically double bond and an aliphatic carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another aliphatic carboxyl group or another monomer is copolymerized. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited to these. However, two or more types can be used together.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, cardo resin, and phenol resin.

The thermosetting resin may be a low molecular weight compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts when the filter segment is fired, the crosslink density of the coating film is increased, the heat resistance is improved, and the pigment aggregation during the firing of the filter segment is suppressed. Be done.
Among these, epoxy resin, cardo resin, or melamine resin is preferable.

<Photopolymerizable monomer>
The near-infrared absorbing composition of the present invention may contain a photopolymerizable monomer in order to form a filter by curing with ultraviolet rays, heat, or the like. The photopolymerizable monomer that can be used in the present invention contains a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, and these may be used alone or in combination of two or more. Can be done. The blending amount of the monomer is preferably 5 to 400 parts by weight, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability with respect to 100 parts by weight of the dye.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and the like, but the present invention is not limited thereto.

<Photopolymerization initiator>
In the near-infrared absorbing composition of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator or the like is added to color the composition by solvent development or alkali development. It can be adjusted in the form of a resist material. When the photopolymerization initiator is used, the blending amount is preferably 5 to 200 parts by weight, and 10 to 150 parts by weight from the viewpoint of photocurability and developability, based on 100 parts by weight of the total amount of the dye. Is more preferable.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and other acetophenone compounds; benzophenone, benzoin Benzophenones such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -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- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoy) Oxime ester compounds such as luoxime)] or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanosen-based compound or the like is used.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the dye in the near-infrared absorbing composition (100% by weight), and 10 to 10% by weight from the viewpoint of photocurability and developability. More preferably, it is 150% by weight.

<Sensitizer>
Further, the near-infrared absorbing composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives Azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, Biimidazole derivative, α -Acyloxyester, acylphosphine oxide, methylphenylglioxylate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4 , 4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount is preferably 3 to 60 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the total weight of the photopolymerization initiator contained in the near-infrared absorbing composition. From the viewpoint of developability, it is more preferably 5 to 50 parts by weight.

<Multifunctional thiol>
The near-infrared absorbing composition of the present invention can contain a polyfunctional thiol that acts as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanthithioglycolate, trimethylolpropanetristhiopropionate, trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetraxthioglycolate, Pentaerythritol tetraxthiopropionate, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-) Dibutylamino) -4,6-dimercapto-s-triazine and the like can be mentioned. These polyfunctional thiols can be used alone or in admixture of two or more at any ratio as required.

The content of the functional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the weight of the total solid content of the near-infrared absorbing composition (100% by weight). If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The near-infrared absorbing composition of the present invention can contain an antioxidant. The antioxidant is a transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the near-infrared absorbing composition from being oxidized and yellowed by the thermal process at the time of heat curing or ITO annealing. Can be raised. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained. The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical capture function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenolic or hindered amine compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the hindered phenol-based antioxidant, the hindered amine-based antioxidant, the phosphorus-based antioxidant or the sulfur-based antioxidant are preferable. Agents can be mentioned. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant. The antioxidants can be used alone or in admixture of two or more at any ratio, if necessary. The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the near-infrared absorbing composition (100% by weight) because the sensitivity is good.

<Amine compounds>
In addition, the near-infrared absorbing composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the near-infrared absorbing composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on 100% by weight of the total of the near-infrared absorbing composition.

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to a glass plate despite having low surface tension lowering ability, and in an addition amount in which defects of the coating film due to foaming do not appear. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the near-infrared absorbing composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other near-infrared absorbing pigments>
The near-infrared absorbing composition of the present invention may contain a near-infrared absorbing dye in addition to the near-infrared absorbing dye [A] of the present invention. Examples of the near-infrared absorbing dye other than the near-infrared absorbing dye [A] that can be used in the near-infrared absorbing composition of the present invention include a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, an aminium compound, a diimmonium compound and a croconium compound. , Azo compounds, quinoid-type complex compounds, dithiol metal complex compounds and the like, but are not limited thereto.

<Other additive ingredients>
The near-infrared absorbing composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to enhance the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the colorant in the coloring composition.

<Manufacturing method of near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention can be obtained by dispersing the near-infrared absorbing dye [A] with a basic resin type dispersant [B] and an organic solvent [C]. As a specific method for producing the near-infrared absorbing composition of the present invention, the near-infrared absorbing dye [A] is used as a basic resin-type dispersant [B] and an organic solvent [C], and if necessary, an acidic resin. After mixing the type dispersant [D], the binder resin, and other dispersion aids, various dispersions such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor. It can be manufactured by finely dispersing it by means.

<Removal of coarse particles>
The near-infrared absorbing composition of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more of coarse particles by means of centrifugation, sintering filter, membrane filter, or the like. And it is preferable to remove the mixed dust. As described above, it is preferable that the near-infrared absorbing composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Manufacturing method of near infrared cut filter>
The near-infrared cut filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by the printing method can be patterned simply by repeating printing and drying of the near-infrared absorbing composition prepared as a printing ink, so that the filter manufacturing method is low cost and mass-producible. Are better. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When forming a filter segment by a photolithography method, a near-infrared absorbing composition prepared as the above solvent-developed or alkali-developed resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. According to the coating method of, the coating is applied so that the dry film thickness is 0.2 to 5 μm. 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. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a filter. Can be done. Further, in order to promote the polymerization of the resist material, heating can be applied as needed. According to the photolithography method, a filter having higher accuracy than the above printing method can be manufactured.

The transparent substrate is not particularly limited, but a sheet-shaped, film-shaped, or plate-shaped transparent substrate can be used as the shape. Colors are also colorless and colored, and are not particularly limited. Examples of the material of the transparent base material include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and 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.

At the time of 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 ultraviolet exposure sensitivity, the resist material was applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin was applied and dried to form a film for preventing polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

The near-infrared cut filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above methods, but the near-infrared absorbing composition of the present invention can be used in any of the methods. it can.

<Use of near-infrared cut filter>
The near-infrared cut filter of the present invention absorbs little in the visible region (400 nm to 700 nm), has excellent near-infrared absorption ability, and has excellent durability such as heat resistance and light resistance. Therefore, near-infrared absorbing film and near-infrared absorbing plate that block heat rays for energy saving, near-infrared absorbing film for agriculture for selective use of sunlight, near-infrared cut filter for electronic devices, protective glasses, sunglasses, Can be used in a wide range of applications such as heat ray blocking film and laser welding heating material

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. In the examples and comparative examples, "parts" and "%" mean "parts by mass" and "% by mass", respectively. "PGMAc" is propylene glycol monomethyl ether acetate, "CHXA" is cyclohexanol acetate, "Aronix M-402" is dipentaerythritol hexaacrylate, and "OXE-02" is O-acetyl-1- [6. -(2-Methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] means etanone oxime.

(Method for identifying near-infrared absorbing dye [A])
The MALDI TOF-MS spectrum was used to identify the near-infrared absorbing dye [A] used in the present invention. 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 Daltonics. It was.

(Acid value of resin type dispersant and binder resin)
The acid value of the resin-type dispersant and the binder 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 solid content.

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

(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 solid content.

(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 solid content.

<Manufacturing method of near-infrared absorbing dye [A]>
(Manufacturing of near-infrared absorbing dye [A-1])
To 400 parts of toluene, 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed, heated and stirred in an atmosphere of nitrogen gas, and 3 It was refluxed for hours. The water produced during the reaction was removed from the 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 filtered off, washed successively with hexane, ethanol and acetone, dried under reduced pressure, and 61.9 parts of the near-infrared absorbing dye [A-1] (yield: 92%). Got As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-1].

Near infrared absorbing dye [A-1]

(Manufacturing of near-infrared absorbing dye [A-2])
Production of near-infrared absorbing dye [A-1], except that 32.2 parts of 2,6-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 71.9 parts (yield: 97%) of the near-infrared absorbing dye [A-2]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-2].

Near infrared absorbing dye [A-2]

(Manufacture of near-infrared absorbing dye [A-3])
Production of near-infrared absorbing dye [A-1] except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 72.6 parts (yield: 98%) of the near-infrared absorbing dye [A-3]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-3].

Near-infrared absorbing dye [A-3]

(Manufacturing of near-infrared absorbing dye [A-4])
Similar to the production of the near-infrared absorbing dye [A-1], except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. (Yield: 95%) was obtained in 67.2 parts of the near-infrared absorbing dye [A-4]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-4].

Near infrared absorbing dye [A-4]

(Manufacturing of near-infrared absorbing dye [A-5])
Near-infrared absorbing dye [A-1], except that 3,3,5-trimethylcyclohexanone 35.8 parts was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of the above was carried out to obtain 71.3 parts (yield: 92%) of the near-infrared absorbing dye [A-5]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-5].

Near infrared absorbing dye [A-5]

(Manufacturing of near-infrared absorbing dye [A-6])
Production of near-infrared absorbing dye [A-1] except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 76.9 parts (yield: 95%) of the near-infrared absorbing dye [A-6]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-6].

Near infrared absorbing dye [A-6]

(Manufacturing of near-infrared absorbing dye [A-7])
Near-infrared absorbing dye [A-1], except that 39.4 parts of 5-isopropyl-2-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of the above was carried out to obtain 76.9 parts (yield: 95%) of the near-infrared absorbing dye [A-7]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-7].

Near infrared absorbing dye [A-7]

(Manufacturing of near-infrared absorbing dye [A-8])
Similar to the production of the near-infrared absorbing dye [A-1], except that 46.0 parts of 2-cyclohexylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 79.4 parts (yield: 91%) of the near-infrared absorbing dye [A-8]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-8].

Near infrared absorbing dye [A-8]

(Manufacturing of near-infrared absorbing dye [A-9])
Similar to the production of the near-infrared absorbing dye [A-1], except that 28.1 parts of 2-norbornenanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The operation was carried out to obtain 64.6 parts (yield: 92%) of the near-infrared absorbing dye [A-9]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-9].

Near-infrared absorbing dye [A-9]

(Manufacturing of near-infrared absorbing dye [A-10])
Near-infrared absorbing dye [A-1], except that 42.5 parts of spiro [5.5] undecane-1-one was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of -1] was carried out to obtain 78.8 parts (yield: 94%) of the near-infrared absorbing dye [A-10]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-10].

Near infrared absorbing dye [A-10]

(Manufacturing of near-infrared absorbing dye [A-11])
Instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1], 3-methyl-3,4,4a, 5,8,8a-hexahydronaphthalen-1 (2H) -one 41 The same operation as in the production of the near-infrared absorbing dye [A-1] was carried out except that 9 parts were used, and 76.7 parts (yield: 92%) of the near-infrared absorbing dye [A-11] was obtained. .. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-11].

Near-infrared absorbing dye [A-11]

(Manufacturing of near-infrared absorbing dye [A-12])
Near-infrared absorbing dye [A-1], except that 41.0 parts of 3- (2-chloroethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of the above was carried out to obtain 77.5 parts (yield: 94%) of the near-infrared absorbing dye [A-12]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-12].

Near-infrared absorbing dye [A-12]

(Manufacturing of near-infrared absorbing dye [A-13])
Near-infrared absorbing dye [A-1], except that 59.8 parts of 3,5-di (trifluoromethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of -1] was carried out to obtain 93.3 parts (yield: 93%) of the near-infrared absorbing dye [A-13]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-13].

Near-infrared absorbing dye [A-13]

(Manufacturing of near-infrared absorbing dye [A-14])
Similar to the production of the near-infrared absorbing dye [A-1], except that 44.5 parts of 2-phenylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 78.9 parts (yield: 92%) of the near-infrared absorbing dye [A-14]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-14].

Near-infrared absorbing dye [A-14]

(Manufacturing of near-infrared absorbing dye [A-15])
Production of near-infrared absorbing dye [A-1] except that 48.1 parts of 4-p-tolylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 84.7 parts (yield: 95%) of the near-infrared absorbing dye [A-15]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-15].

Near-infrared absorbing dye [A-15]

(Manufacturing of near-infrared absorbing dye [A-16])
Similar to the production of the near-infrared absorbing dye [A-1], except that 48.1 parts of 4-benzylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 85.6 parts (yield: 96%) of the near-infrared absorbing dye [A-16] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-16].

Near infrared absorbing pigment [A-16]

(Manufacturing of near-infrared absorbing dye [A-17])
Similar to the production of the near-infrared absorbing dye [A-1], except that 36.3 parts of 4-ethoxycyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 71.0 parts (yield: 91%) of the near-infrared absorbing dye [A-17] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-17].

Near-infrared absorbing dye [A-17]

(Manufacturing of near-infrared absorbing dye [A-18])
Near-infrared absorbing dye [A-1] except that 68.0 parts of 2,6-di (trifluoromethoxy) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of -1] was carried out to obtain 100.5 parts (yield: 93%) of the near-infrared absorbing dye [A-18]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-18].

Near-infrared absorbing dye [A-18]

(Manufacturing of near-infrared absorbing dye [A-19])
Similar to the production of the near-infrared absorbing dye [A-1], except that 48.6 parts of 4-phenoxycyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 82.5 parts (yield: 92%) of the near-infrared absorbing dye [A-19] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-19].

Near-infrared absorbing dye [A-19]

(Manufacturing of near-infrared absorbing dye [A-20])
Near-infrared absorbing dye [A-1] except that 51.1 parts of 3-oxo-cyclohexanesulfonic acid sodium salt was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-20] to obtain 83.3 parts (yield: 96%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-20].

Near infrared absorbing pigment [A-20]

(Manufacturing of near-infrared absorbing dye [A-21])
Near-infrared absorbing dye [A-1] except that 52.4 parts of N-ethyl-3-oxocyclohexane-1-sulfoamide was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of A-1] was carried out to obtain 87.7 parts (yield: 94%) of the near-infrared absorbing dye [A-21]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-21].

Near-infrared absorbing dye [A-21]

(Manufacturing of near-infrared absorbing dye [A-22])
Production of near-infrared absorbing dye [A-1] except that 36.3 parts of 4-oxocyclohexanecarboxylic acid was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 71.0 parts (yield: 91%) of the near-infrared absorbing dye [A-22]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-22].

Near-infrared absorbing dye [A-22]

(Manufacturing of near-infrared absorbing dye [A-23])
Of the near-infrared absorbing dye [A-1], except that 43.5 parts of ethyl 2-oxocyclohexanecarboxylic acid was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production was carried out to obtain 78.9 parts (yield: 93%) of the near-infrared absorbing dye [A-23]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-23].

Near-infrared absorbing dye [A-23]

(Manufacturing of near-infrared absorbing dye [A-24])
Near-infrared absorbing dye [A-] except that 46.8 parts of 4-oxo-N-propylcyclohexanecarboxyamide was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of 1] was carried out to obtain 87.1 parts (yield: 99%) of the near-infrared absorbing dye [A-24]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-24].

Near infrared absorbing pigment [A-24]

(Manufacturing of near-infrared absorbing dye [A-25])
Similar to the production of the near-infrared absorbing dye [A-1], except that 28.9 parts of 4-aminocyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 68.1 parts (yield: 96%) of the near-infrared absorbing dye [A-25]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-25].

Near infrared absorbing dye [A-25]

(Manufacturing of near-infrared absorbing dye [A-26])
Of the near-infrared absorbing dye [A-1], except that 36.1 parts of 4- (dimethylamino) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production was carried out to obtain 73.9 parts (yield: 95%) of the near-infrared absorbing dye [A-26]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-26].

Near infrared absorbing dye [A-26]

(Manufacturing of near-infrared absorbing dye [A-27])
Production of near-infrared absorbing dye [A-1] except that 31.4 parts of 4-oxocyclohexanecarbonitrile was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 67.5 parts (yield: 92%) of the near-infrared absorbing dye [A-27]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-27].

Near infrared absorbing dye [A-27]

(Manufacturing of near-infrared absorbing dye [A-28])
Similar to the production of the near-infrared absorbing dye [A-1], except that 36.6 parts of 4-nitrocyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 72.0 parts (yield: 92%) of the near-infrared absorbing dye [A-28] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-28].

Near infrared absorbing dye [A-28]

(Manufacturing of near-infrared absorbing dye [A-29])
Production of near-infrared absorbing dye [A-1] except that 34.3 parts of 3,5-difluorocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 70.7 parts (yield: 93%) of the near-infrared absorbing dye [A-29]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-29].

Near infrared absorbing dye [A-29]

(Manufacturing of near-infrared absorbing dye [A-30])
Similar to the production of the near-infrared absorbing dye [A-1], except that 33.9 parts of 2-chlorocyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 71.1 parts (yield: 94%) of the near-infrared absorbing dye [A-30] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-30].

Near infrared absorbing dye [A-30]

(Manufacturing of near-infrared absorbing dye [A-31])
Production of near-infrared absorbing dye [A-1] except that 65.4 parts of 3,3-dibromocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 99.3 parts (yield: 94%) of the near-infrared absorbing dye [A-31]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-31].

Near-infrared absorbing dye [A-31]

(Manufacture of near-infrared absorbing dye [AA-1])
The following near-infrared absorbing dye [AA-1] was synthesized with reference to Japanese Patent No. 3590694.

Near-infrared absorbing dye [AA-1]

Et represents an ethyl group.

<Manufacturing method of basic resin type dispersant [B]>
(Preparation of basic resin type dispersant [B1-1])
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 44.7 parts of methyl methacrylate, 14.9 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and 50 parts were flowed with nitrogen. The mixture was stirred at ° C. for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) were charged, and the temperature was raised to 110 ° C. under a nitrogen stream for the first block. The polymerization of was started. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 33.6 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reaction vessel, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. to continue the reaction. .. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content.
Further, 6.8 parts of benzyl chloride was added to this reactor, stirred for 3 hours while maintaining a nitrogen atmosphere at 110 ° C., and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. In this way, a resin-type dispersant having an amine value of 90 mgKOH / g per solid content, a quaternary ammonium salt value of 30 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by weight [B1- 1] A solution was obtained.

(Preparation of basic resin type dispersant [B1-2])
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 47.8 parts of methyl methacrylate, 15.9 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and 50 parts while flowing nitrogen. The mixture was stirred at ° C. for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc, 25.2 parts of DM as a second block monomer, and 13.8 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride (“Acryester DMC80” manufactured by Mitsubishi Rayon, 80% non-volatile content) were added to this reaction vessel. Then, the mixture was stirred while maintaining the atmosphere of 110 ° C. and nitrogen, and the reaction was continued. After 2 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. did.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. In this way, a resin-type dispersant having an amine value of 90 mgKOH / g per solid content, a quaternary ammonium salt value of 30 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by weight [B1- 2] A solution was obtained.

(Preparation of basic resin type dispersants [B1-3 to 13, B2-1 to 6])
Except for changing to the monomer composition conditions shown in Table 1, the same operation as the preparation of the basic resin type dispersant [B1-2] was carried out, and the basic resin type dispersants [B1-3 to 13, B2-1] were performed. ~ 6] A solution was obtained.

In Table 1, "MMA" is methyl methacrylate, "n-BMA" is n-butyl methacrylate, "DM" is dimethylaminoethyl methacrylate, and "DMC80 aqueous solution" is methacryloyloxyethyl trimethylammonium chloride aqueous solution. ("Acryester DMC80" manufactured by Mitsubishi Rayon, 80% non-volatile content).

<Manufacturing method of acidic resin type dispersant [D]>
(Preparation of acidic resin type dispersant [D1-1])
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacement with nitrogen gas, the mixture was heated at 120 ° C. for 4 hours and stirred. After confirming that 98% had reacted by solid content measurement, 64.5 parts of trimellitic anhydride was added thereto, and the mixture was reacted at 120 ° C. for 2 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 to obtain a dispersant. In this way, an acidic resin-type dispersant [D1-1] having an acid value of 91 mgKOH / g per solid content and an aromatic carboxyl group having a weight average molecular weight (Mw) of 1,200 was obtained.

(Preparation of acidic resin type dispersant [D2-1])
60 parts of PGMAc was charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, the temperature was raised to 110 ° C., nitrogen was substituted in the reaction vessel, and then 40 parts of methyl methacrylate and benzyl methacrylate were added from the dropping tank. A mixed solution prepared by uniformly mixing 28 parts, 20 parts of butyl acrylate, 12 parts of 2-hydroxyethyl methacrylate, 40 parts of PGMAc, and 6 parts of dimethyl-2,2'-azobisdiisobutyrate was added dropwise over 2 hours. After that, stirring was continued at the same temperature for 3 hours to complete the reaction. In this way, an intermediate having a number average molecular weight of 3,800 and an average number of hydroxyl groups in one molecule of 3.5 was obtained. The intermediate was charged with 100 parts of solid content, 5.1 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine, and reacted at 100 ° C. for 6 hours. PGMAc was added to the obtained copolymer solution so that the non-volatile content was 40% by weight. In this way, an aromatic carboxyl having an average number of trimellitic acids per molecule, an acid value of 30 mgKOH / g per solid content, a weight average molecular weight (Mw) of 2,000, and a non-volatile content of 40% by weight. Dispersant having a group Acid resin type dispersant [D2-1] was obtained.

(Preparation of acidic resin type dispersant [D3-1])
80 parts of methyl methacrylate, 120 parts of ethyl acrylate, and 40 parts of PGMAc were charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., 4.4 parts of 3-mercapto-1,2-propanediol is added, and then 0.2 parts of 2,2'-azobisisobutyronitrile is divided into 20 portions. It was added every 30 minutes and reacted at 80 ° C. for 12 hours, and it was confirmed by solid content measurement that 95% had reacted. Next, 12 parts of trimellitic anhydride, 190 parts of PGMAc, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and at 120 ° C. for 2 hours at 80 ° C. It was reacted for 5 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, PGMAc was added to the obtained copolymer solution so that the non-volatile content was 40% by weight, and the acid value per solid content was 44 mgKOH. An acidic resin-type dispersant [D3-1] having an aromatic carboxyl group having / g, a weight average molecular weight (Mw) of 2,600, and a non-volatile content of 40% by weight was obtained.

<Manufacturing method of binder resin solution>
(Preparation of binder resin solution)
70.0 parts of PGMAc was charged into a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then n-butyl methacrylate was removed from the dropping tank. 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Synthetic Co., Ltd.) 7.4 parts, 2,2'- A mixed solution in which 0.4 part of azobisisobutyronitrile was uniformly mixed in advance was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having an acid value of 94 mgKOH / g and a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating 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. Prepared a binder resin solution.

<Manufacturing of near-infrared absorbing composition>
[Example 1]
(Near infrared absorbing composition (P-1))
The mixture is uniformly stirred and mixed as described below, dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter of 0.5 μm to obtain a near-infrared absorbing composition (P-). 1) was prepared.
Near-infrared absorbing dye [A-1]: 8.33 parts Basic resin type dispersant [B1-2] solution: 16.67 parts Ethyl lactate: 42.50 parts Propylene glycol monomethyl ether acetate: 32.50 parts

[Examples 2-52, Comparative Examples 1-10]
(Near-infrared absorbing composition (P-2 to 52, P-85-92))
Hereinafter, the near-infrared absorbing composition except that the near-infrared absorbing dye [A], the basic resin type dispersant [B], and the organic solvent [C] are changed to have the compositions and amounts shown in Tables 2 and 3. Near-infrared absorbing compositions (P-2 to 52, P-85-92) were prepared in the same manner as in (P-1).

[Example 53]
(Near infrared absorbing composition (P-53))
The mixture is uniformly stirred and mixed so as to have the following composition, then dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a 0.5 μm filter to obtain a near-infrared absorbing composition. (P-53) was prepared.
Near-infrared absorbing dye [A-3]: 8.33 parts Basic resin type dispersant [B1-2] solution: 16.67 parts Ethyl lactate: 75.00 parts

Since the basic resin type dispersant [B1-2] is a propylene glycol monomethyl ether acetate solution, stripping is performed under reduced pressure to remove the propylene glycol monomethyl ether acetate, and the non-volatile content is reduced to 40% by weight with ethyl lactate. The solution was prepared so as to have the above composition.

[Example 54]
(Near infrared absorbing composition (P-54))
The mixture is uniformly stirred and mixed as described below, dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter of 0.5 μm to obtain a near-infrared absorbing composition (P-). 54) was produced.
Near-infrared absorbing dye [A-3]: 8.15 parts Basic resin type dispersant [B1-2] solution: 16.28 parts Acid resin type dispersant [D3-1] solution: 0.86 parts Ethyl lactate: 42.50 parts Propylene glycol monomethyl ether acetate: 32.21 parts

[Examples 55 to 84, Comparative Examples 9 to 14]
(Near-infrared absorbing composition (P-55-84, P-93-98))
Hereinafter, the near-infrared absorbing dye [A], the basic resin type dispersant [B], the organic solvent [C], and the acidic resin type dispersant [D] are changed so as to have the compositions and amounts shown in Tables 2 and 3. The near-infrared absorbing composition (P-55-84, P-93-98) was prepared in the same manner as the near-infrared absorbing composition (P-54) except for the above.

The composition of the obtained near-infrared absorbing composition is shown below. The resin-type dispersant [B] and the resin-type dispersant [D] indicate the amounts as solids. The [C1] ratio represents the ratio of the organic solvent [C1] in the total organic solvent [C].

The organic solvents used in the above examples were ethyl lactate (154 / 10.0), cyclohexanol acetate (173 / 9.2), cyclohexanone (156 / 9.9), and 3-methoxybutanol (158/10). .9) and propylene glycol monomethyl ether acetate (146 / 8.7) (boiling point (° C.) / SP value (cal / cm ³ ) ^{1/2, respectively} ).

<Evaluation of near-infrared absorbing composition>
The near-infrared absorbing compositions (P-1 to 98) obtained in Examples and Comparative Examples were tested for average primary particle size, spectral characteristics, light resistance, heat resistance, dispersion stability, and storage stability as follows. Got the way. ⊚ 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 Tables 4 and 5.

(Average primary particle size when the near-infrared absorbing dye [A] is dispersed)
The average primary particle size of the near-infrared absorbing dye [A] was measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each dye were measured, and the average was taken as the particle size of the dye primary particles. Next, for 100 or more dye particles, the volume (weight) of each particle was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was defined as the average primary particle size.

(Evaluation of spectral characteristics)
The obtained near-infrared absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so as to have a film thickness of 1.0 μm, dried at 60 ° C. for 5 minutes, and then at 230 ° C. The substrate was prepared by heating for 5 minutes. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 300 to 1000 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 near-infrared absorbing dye [A] coating film of the present invention exists in the near-infrared region (700 to 1000 nm). When this absorbance is 1, it can be said that the smaller the absorbance at 400 to 700 nm, the better the absorption capacity in the near infrared region, the higher the coloring power, and the steeper spectroscopy.
⊚: less than 0.025 ○: 0.025 or more and less than 0.75 Δ: 0.75 or more and less than 0.15 ×: 0.15 or more

(Light resistance test)
A test substrate was prepared by the same procedure as the spectral characterization, placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), and left to stand for 24 hours. The absorbance of the near-infrared absorbing film at the spectral maximum absorption wavelength was measured, the residual ratio to that before light irradiation was determined, and the light resistance in the near-infrared region 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 92.5% or more and less than 95% Δ: Residual rate is 90% or more and less than 92.5% ×: Residual rate is less than 90%

Further, the rate of change of "average absorbance AA _{2 at} 400 to 700 nm" after light irradiation was obtained from "average absorbance AA _{1 at} 400 to 700 nm" when the absorbance at the maximum absorption wavelength before light irradiation was 1. The light resistance in the visible light region was evaluated according to the following criteria. The rate of change was calculated using the following formula.
Rate of change = (AA _2- AA ₁ ) ÷ (AA ₁ ) × 100
◎: Change rate is less than ± 2.5% ○: Change rate is ± 2.5% or more and less than 5% △: Change rate is ± 5% or more and less than 7.5% ×: Change rate is 7.5% or more

(Heat resistance test)
A test 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 near-infrared absorbing 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 92.5% or more and less than 95% Δ: Residual rate is 90% or more and less than 92.5% ×: Residual rate is less than 90%

Further, the rate of change of "average absorbance AA _{4 at} 400 to 700 nm" after the heat resistance test was obtained from "average absorbance AA _{3 at} 400 to 700 nm" when the absorbance at the maximum absorption wavelength before the heat resistance test was 1. , The heat resistance in the visible light region was evaluated according to the following criteria. The rate of change was calculated using the following formula.
Rate of change = (AA _4- AA ₃ ) ÷ (AA ₃ ) × 100
◎: Change rate is less than ± 2.5% ○: Change rate is ± 2.5% or more and less than 5% △: Change rate is ± 5% or more and less than 7.5% ×: Change rate is 7.5% or more

(Dispersion stability test)
The dispersion stability of the obtained near-infrared absorbing composition was evaluated by obtaining the thixotropy index (= TI value) by measuring the viscosity as follows. The viscosity of the near-infrared absorbing composition was determined by using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C., initial viscosity Iη _{50 at 50} rpm and initial viscosity Iη _{20 at 20} rpm. Was measured, and the dispersion stability was evaluated according to the following criteria. The TI value was calculated using the following formula.
TI value = (Iη ₂₀ ) ÷ (Iη ₅₀ )
⊚: TI value is less than 1.05 ○: TI value is 1.05 or more and less than 1.10 Δ: TI value is 1.10 or more and less than 1.15 ×: TI value is 1.15 or more

(Storage stability test)
The storage stability of the obtained near-infrared absorbing composition was evaluated by measuring the viscosity as follows. For the viscosity of the near-infrared absorbing composition, the initial viscosity η ₁ at 50 rpm at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the near-infrared absorbing composition was allowed to stand at 40 ° C. for 120 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the viscosity over time η ₂ to obtain storage stability. It was evaluated according to the following criteria. The viscosity change rate was calculated using the following formula.
Viscosity change rate = (η ₂ -η ₁ ) ÷ (η ₁ )
⊚: When the viscosity change rate is less than ± 5% and no sediment is formed.
◯: When the viscosity change rate is ± 5% or more and less than 10%, and no sediment is formed.
Δ: When the viscosity change rate is ± 10% or more and less than 20% and no sediment is formed.
X: When the viscosity change rate is ± 20% or more, or when the sediment is formed even if the viscosity change rate is less than ± 20%.

The near-infrared absorbing dye [A] is a block copolymer composed of an A block having a tertiary amino group and a quaternary ammonium base in the side chain and a B block having no tertiary amino group and a quaternary ammonium base. Nearly produced by dispersing with a basic resin type dispersant [B1] and an organic solvent [C1] having a boiling point of 120 to 210 ° C. at 760 mmHg and a solubility parameter of 9.0 to 13.0. The infrared-absorbing composition has good spectral characteristics because it absorbs little in the visible region (400 nm to 700 nm) and has excellent near-infrared absorbing ability, and has excellent light resistance and heat resistance, dispersion stability, and storage stability. It was also excellent in properties (Examples 1 to 50). As the near-infrared absorbing dye [A], a near-infrared absorbing composition in which a near-infrared absorbing dye [A-3, A-5] having a methyl group is dispersed has better spectral characteristics, light resistance, and heat resistance. It was a result (Examples 3 and 5).

In the basic resin type dispersant [B1], the near-infrared absorbing composition dispersed using an amine value of 20 or more and 160 or less (mgKOH / g) has better spectral characteristics and storage stability. There were (Examples 3, 38, 39). Further, in the basic resin type dispersant [B1], a near-infrared absorbing composition dispersed by using a quaternary ammonium salt value of 30 or more and 70 or less (mgKOH / g) has spectral characteristics and heat resistance in the visible range. The results were better in terms of property, dispersion stability, and storage stability (Examples 3 and 42). Further, the content of the basic resin type dispersant [B1] is such that the near-infrared absorbing composition dispersed using 50% or more based on the total basic resin type dispersant (100% by weight) has spectral characteristics. , Light resistance, heat resistance, dispersion stability, storage stability are good, and the near-infrared absorbing composition dispersed using 80% or more has better spectral characteristics, heat resistance in the visible range, and storage stability. The near-infrared absorbing composition dispersed using 100% had even better dispersion stability and storage stability (Examples 3, 47, 48). Further, as for the organic solvent [C1], a near-infrared absorbing composition containing 20% or more of the total organic solvent [C] as a reference (100% by weight) and dispersed has better storage stability. The near-infrared absorbing composition containing 50% and dispersed had even better dispersion stability (Examples 3, 45 and 46).

In addition, the near-infrared absorbing composition dispersed in combination with the acidic resin type dispersant [D] had better results in light resistance, heat resistance, dispersion stability, and storage stability (Examples 54 to 54). 75). Among them, a near-infrared absorbing composition dispersed by using an acidic resin-type dispersant [D3] which is a reaction product of a polymer [E3] having two hydroxyl groups at one end and an aromatic tricarboxylic acid anhydride [F]. However, the storage stability was better (Example 56). Further, the weight ratio ([B] / [D]) of the basic resin type dispersant [B] and the acidic resin type dispersant [D] was dispersed using the range of 85/15 to 70/30. The near-infrared absorbing composition had better storage stability (Examples 55-57).

On the other hand, the near-infrared absorbing composition dispersed by using the near-infrared absorbing dye [AA-1] other than the near-infrared absorbing dye [A] of the present invention has spectral characteristics, light resistance, heat resistance, dispersion stability, and storage. The stability was significantly deteriorated (Comparative Example 1). Further, the near-infrared absorbing composition dispersed by using a basic resin type dispersant having an amine value of less than 10 or a quaternary ammonium salt value of less than 10 has light resistance in the visible region and heat resistance in the visible region. It deteriorated, and the dispersion stability and storage stability deteriorated remarkably (Comparative Examples 2 and 4). Further, the near-infrared absorbing composition dispersed by using a basic resin-type dispersant having an amine value of more than 200 or a quaternary ammonium salt value of more than 90 has light resistance in the visible region and heat resistance in the visible region. Dispersion stability and storage stability were significantly deteriorated (Comparative Examples 3 and 5). Further, the near-infrared absorbing composition dispersed by using a basic resin-type dispersant having only one of a tertiary amino group or a quaternary ammonium base in the A block is particularly light-resistant and visible in the visible range. The heat resistance, dispersion stability, and storage stability of the region were significantly deteriorated (Comparative Examples 6 and 7). In addition, the near-infrared absorbing composition dispersed without using the organic solvent [C1] of the present invention significantly deteriorated the light resistance in the visible region, the heat resistance in the visible region, the dispersion stability, and the storage stability (Comparative Example). 8).

<Manufacturing of photosensitive near-infrared absorbing composition and near-infrared cut filter>
[Example 85]
(Near infrared cut filter (Q-1))
Prior to the manufacture of the near-infrared cut filter, the following mixture is stirred and mixed so as to be uniform, and then 1. Filtration with a 0 μm filter gave a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorbing composition (P-1): 50.0 parts Binder resin solution: 7.5 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toa Synthetic Co., Ltd.): 2.0 parts Photopolymerization started Agent (BASF "OXE-02"): 1.5 parts Ethyl lactate: 7.0 parts Propylene glycol monomethyl ether acetate: 32.0 parts

The obtained photosensitive near-infrared absorbing composition (R-1) was applied on a glass substrate having a thickness of 1.1 mm with a spin coater, and was heat-treated on a hot plate at 100 ° C. for 1 minute as a prebake. Next, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio, Inc.), pattern exposure was performed with an exposure amount of 1000 mJ / cm ² through a photomask to form a 100 μm square near-infrared absorption cut filter. .. The exposed coating film was used as a developer using a 0.2 wt% sodium carbonate aqueous solution, and the uncured portion of the coating film was removed by a shower development method at a developer pressure of 0.1 mPa to form a pattern of 400 μm × 400 μm. It was. Then, it was post-baked at 100 ° C. for 120 minutes. The film thickness of the near-infrared absorption cut filter (Q-1) after the heat treatment was 1.0 μm.

[Examples 86 to 147 and Comparative Examples 15 to 28]
(Photosensitive near-infrared absorbing composition (R-2 to 8))
Hereinafter, except that the near-infrared absorbing composition is changed to the type of the near-infrared absorbing composition shown in Table 6, the photosensitive near-infrared absorbing composition (R-1) and the near-infrared cut filter (Q-1) are used. Similarly, photosensitive near-infrared absorbing compositions (R-2 to 77) and near-infrared cut filters (Q-2 to 77) were obtained.

In Table 6, the C1 ratio represents the ratio of the organic solvent [C1] in the total organic solvent [C] in the photosensitive near-infrared absorbing composition.

<Evaluation of photosensitive near-infrared absorbing composition>
The photosensitive near-infrared absorbing compositions (R-1 to 77) obtained in Examples and Comparative Examples were tested for dispersion stability and storage stability by the following methods. ⊚ 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 7.

(Dispersion stability test)
The dispersion stability of the obtained photosensitive near-infrared absorbing composition was evaluated by obtaining the thixotropy index (= TI value) by measuring the viscosity as follows. The viscosity of the photosensitive near-infrared absorbing composition is determined by using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C., initial viscosity at ₅₀ rpm Iη initial viscosity at ₅₀ and 20 rpm. Iη ₂₀ was measured and the dispersion stability was evaluated according to the following criteria. The TI value was calculated using the following formula.
TI value = (Iη ₂₀ ) ÷ (Iη ₅₀ )
⊚: TI value is less than 1.02 ○: TI value is 1.02 or more and less than 1.04 Δ: TI value is 1.04 or more and less than 1.06 ×: TI value is 1.06 or more

(Storage stability test)
The obtained photosensitive near-infrared absorbing composition was evaluated by measuring the viscosity as follows. For the viscosity of the photosensitive near-infrared absorbing composition, the initial viscosity η ₁ at 50 rpm at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the photosensitive near-infrared absorbing composition was allowed to stand at 40 ° C. for 120 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as above to obtain a viscosity η ₂ over time and storage stability. The sex was evaluated according to the following criteria. The viscosity change rate was calculated using the following formula.
Viscosity change rate = (η ₂ -η ₁ ) ÷ (η ₁ )
⊚: When the viscosity change rate is less than ± 3% and no sediment is formed.
◯: When the viscosity change rate is ± 3% or more and less than 5%, and no sediment is formed.
Δ: When the viscosity change rate is ± 5% or more and less than 10% and no sediment is formed.
X: When the viscosity change rate is ± 10% or more, or when the sediment is formed even if the viscosity change rate is less than ± 10%.

The results of the photosensitive near-infrared absorbing composition are the same as those of the near-infrared absorbing composition, and the photosensitive near-infrared absorbing composition containing the near-infrared absorbing composition of the present invention has dispersion stability and storage stability. It was excellent in sex.

<Evaluation of near infrared cut filter>
The near-infrared cut filters (Q-1 to 77) obtained in Examples and Comparative Examples were tested for spectral characteristics, light resistance, and heat resistance by the following methods. ⊚ 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 8.

(Evaluation of spectral characteristics)
The obtained photosensitive near-infrared absorbing composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to a thickness of 1.0 μm, and then at 70 ° C. for 20 minutes. It was dried, exposed to ultraviolet rays with an integrated light amount of 150 mJ / cm ² using an ultra-high pressure mercury lamp, and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating and allowing to cool at 210 ° C. for 5 minutes, the absorption spectrum of the obtained substrate was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) in the wavelength range of 300 to 1000 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 near-infrared absorbing dye [A] coating film of the present invention exists in the near-infrared region (700 to 1000 nm). When this absorbance is 1, it can be said that the smaller the absorbance at 400 to 700 nm, the better the absorption capacity in the near infrared region, the higher the coloring power, and the steeper spectroscopy.
⊚: less than 0.025 ○: 0.025 or more and less than 0.75 Δ: 0.75 or more and less than 0.15 ×: 0.15 or more

(Light resistance test)
A test substrate was prepared by the same procedure as the spectral characterization, placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), and left to stand for 24 hours. The absorbance of the near-infrared absorbing 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 92.5% or more and less than 95% Δ: Residual rate is 90% or more and less than 92.5% ×: Residual rate is less than 90%

Further, the rate of change of "average absorbance AA _{2 at} 400 to 700 nm" after light irradiation was obtained from "average absorbance AA _{1 at} 400 to 700 nm" when the absorbance at the maximum absorption wavelength before light irradiation was 1. The light resistance in the visible light region was evaluated according to the following criteria. The rate of change was calculated using the following formula.
Rate of change = (AA _2- AA ₁ ) ÷ (AA ₁ ) × 100
◎: Change rate is less than ± 2.5% ○: Change rate is ± 2.5% or more and less than 5% △: Change rate is ± 5% or more and less than 7.5% ×: Change rate is 7.5% or more

(Heat resistance test)
A test 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 near-infrared absorbing 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 92.5% or more and less than 95% Δ: Residual rate is 90% or more and less than 92.5% ×: Residual rate is less than 90%

Further, the rate of change of "average absorbance AA _{4 at} 400 to 700 nm" after the heat resistance test was obtained from "average absorbance AA _{3 at} 400 to 700 nm" when the absorbance at the maximum absorption wavelength before the heat resistance test was 1. , The heat resistance in the visible light region was evaluated according to the following criteria. The rate of change was calculated using the following formula.
Rate of change = (AA _4- AA ₃ ) ÷ (AA ₃ ) × 100
◎: Change rate is less than ± 2.5% ○: Change rate is ± 2.5% or more and less than 5% △: Change rate is ± 5% or more and less than 7.5% ×: Change rate is 7.5% or more

The near-infrared cut filter produced in this way has excellent spectral characteristics. In particular, it absorbs little in the visible region (400 nm to 700 nm) and has excellent near-infrared absorption ability and good spectral characteristics. Furthermore, it is excellent in light resistance and heat resistance, particularly light resistance and heat resistance in the visible region, and therefore, it can be said that it has excellent performance as a near-infrared cut filter.

Claims (5)

A near-infrared absorbing composition comprising a near-infrared absorbing dye [A] represented by the following general formula (1), a basic resin type dispersant [B], and an organic solvent [C].
The basic resin type dispersant [B] is a block copolymer composed of an A block having a tertiary amino group and a quaternary ammonium base in the side chain and a B block having no tertiary amino group and a quaternary ammonium base. Contains the basic resin-type dispersant [B1], which is
The amine value of the basic resin type dispersant [B1] in the solid content is 10 to 200 mgKOH / g, and the quaternary ammonium salt value is 10 to 90 mgKOH / g.
The organic solvent [C] has a boiling point of 120 to 210 ° C. at 760 mmHg and a solubility parameter of 9.0 (cal / cm ³ ) ^1/2 or more and less than 13.0 (cal / cm ³ ) ^1/2. A near-infrared absorbing composition comprising a solvent [C1].
General formula (1)


[In the general formula (1), X _{1 to} X ₁₀ 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. 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, − Represents SO ₂ NR ₁ R ₂ , -COOR ₁ , -CONR ₁ R ₂ , nitro group, cyano group or halogen atom. R ₁ and R ₂ each independently represent a hydrogen atom and an alkyl group which may have a substituent. In X _{1 to} X ₁₀ , the substituents may be bonded to each other to form a ring. ] The near-infrared absorbing composition according to claim 1, wherein the content of the organic solvent [C1] is 10 to 100% by mass with respect to the total amount of the organic solvent [C]. The near-infrared absorbing composition according to claim 1 or 2, wherein the organic solvent [C1] contains at least one selected from the group consisting of cyclohexanol acetate, cyclohexanone, ethyl lactate and 3-methoxybutanol. Further, a claim comprising an acidic resin type dispersant [D] having an aromatic carboxyl group, which is a reaction product of a polymer [E] having a hydroxyl group at one end or a side chain and an aromatic tricarboxylic acid anhydride [F]. Item 3. The near-infrared absorbing composition according to any one of Items 1 to 3. A near-infrared cut filter comprising the near-infrared absorbing composition according to any one of claims 1 to 4.