JP6857296B1 - Near-infrared absorbing pigment and near-infrared absorbing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared absorbing pigment having low absorption in the visible region, excellent near-infrared absorbing ability, high transparency, high dispersibility, thinning, and good dispersibility. A near-infrared absorbing pigment containing a compound represented by the following general formula (1) and an isomer thereof, wherein the average primary particle size of the near-infrared absorbing pigment is 10 to 80 nm, which is the reverse. The results of analysis of near-infrared absorbing pigments using phase-based liquid chromatography show the peaks that appear at the longest retention time under the condition that a mixed solution of acetonitrile and water mixed in a volume ratio of 8: 2 is used as the mobile phase. A near-infrared absorbing pigment in which the ratio of the area is 60 to 78% of the total of the peak areas of all the peaks derived from the near-infrared absorbing pigment. [Selection diagram] None

Description

The present invention relates to a near-infrared absorbing pigment.

Near-infrared absorbing materials include, for example, a near-infrared absorbing film that blocks heat rays, a near-infrared absorbing plate, an agricultural near-infrared absorbing film that selectively uses sunlight, a recording medium that uses the absorbed heat of near-infrared rays, and an electronic device. Used in a wide range of applications such as near-infrared cut filter, 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, laser fusion, etc. ing.

As the near-infrared absorbing material, a phthalocyanine-based material, a cyanine-based material, and a diimonium-based material are known. As the phthalocyanine-based material, a phthalocyanine compound or a naphthalocyanine compound having a substituent (for example, see Patent Document 1), a phthalocyanine compound having an amino group (for example, see Patent Documents 2 to 6), and a phthalocyanine compound having an aryloxy group (for example, see Patent Document 1). , Patent Document 7), fluorine-containing phthalocyanine compounds (see, for example, Patent Documents 8 and 9) and the like are disclosed. However, since these have an absorption band peculiar to phthalocyanine in the visible light region (400 nm to 700 nm), the transparency of visible light is insufficient. In addition, heat resistance and light resistance were also insufficient.

Further, the cyanine-based material and the diimonium-based material are excellent in near-infrared absorbing ability and extremely good in transparency of visible light (see, for example, Patent Documents 10 to 14). These materials have high solubility and compatibility. However, since the stability of the compound itself is extremely low, the heat resistance and light resistance cannot be satisfied.

On the other hand, the squarylium-based material has little absorption in the visible region, has excellent near-infrared absorption ability, and has high durability (see, for example, Patent Documents 15 to 21). However, in order to use it for sensor applications, higher transparency and thinning are required. Therefore, Patent Document 15 discloses a material having high durability, but does not satisfy high transparency, thinning, and high dispersibility at the same time. That is, the near-infrared absorbing pigments disclosed in Patent Documents 15 to 21 did not satisfy all of absorption with a small visible region, excellent near-infrared absorbing ability, transparency, high dispersibility, and thinning.

Japanese Unexamined Patent Publication No. 10-78509 Japanese Unexamined Patent Publication No. 2004-18561 Japanese Unexamined Patent Publication No. 2001-106689 Japanese Unexamined Patent Publication No. 2000-63691 Japanese Unexamined Patent Publication No. 06-025548 Japanese Unexamined Patent Publication No. 2000-026748 Japanese Unexamined Patent Publication No. 2013-241563 Japanese Unexamined Patent Publication No. 05-078364 Japanese Unexamined Patent Publication No. 06-107663 JP-A-2007-219114 Japanese Unexamined Patent Publication No. 2010-072575 Japanese Unexamined Patent Publication No. 05-247437 Japanese Unexamined Patent Publication No. 2005-325292 Japanese Unexamined Patent Publication No. 2003-096040 Japanese Unexamined Patent Publication No. 2011-68847 Japanese Unexamined Patent Publication No. 2011-132361 JP-A-2017-88765 Japanese Unexamined Patent Publication No. 2017-145347 JP-A-2018-87939 JP-A-2018-193516 Japanese Unexamined Patent Publication No. 2019-211764

An object of the present invention is to provide a near-infrared absorbing pigment that absorbs little in the visible region, has excellent near-infrared absorbing ability, has high transparency, can be thinned, and has good dispersibility.

The near-infrared absorbing pigment of the present invention contains a compound represented by the following general formula (1) and an isomer thereof.
The average primary particle size of the near-infrared absorbing pigment is 10 to 80 nm.
The analysis result of the near-infrared absorbing pigment using reverse phase liquid chromatography shows the peak that appears at the longest retention time under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as the mobile phase. The ratio of the peak area is 60 to 78% of the total peak area of all the peaks derived from the near-infrared absorbing pigment.

General formula (1)

(X _{1 to} X ₆ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁ R ₂ ,- COOR ₁ , -CONR ₁ R ₂ , represent a nitro group, a cyano group, and a halogen atom. R ₁ and R ₂ independently represent an alkyl group that may have a hydrogen atom and a substituent. Also, X ₁ In ~ X ₆ , substituents may be bonded to each other to form a ring, _{except for those in which X 1 to} X ₄ are all hydrogen atoms.)

According to the above invention, a near-infrared absorbing pigment, a near-infrared absorbing composition, which absorbs little in the visible region, has excellent near-infrared absorbing ability, has high transparency, can be thinned, and has good dispersibility. A near-infrared cut filter and a near-infrared transmission filter can be provided.

The present invention will be described in detail.
<Near infrared absorbing pigment>
The near-infrared absorbing pigment of the present invention contains a compound represented by the following general formula (1) and an isomer thereof.

General formula (1)

X _{1 to} X ₆ independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁ R ₂ ,- Represents COOR ₁ , -CONR ₁ R ₂ , nitro group, cyano group, halogen atom. R ₁ and R ₂ independently represent a hydrogen atom and an alkyl group which may have a substituent. Further, in X _{1 to} X ₆ , the substituents may be bonded to each other to form a ring. However, those in which X _{1 to} X ₄ are all hydrogen atoms are excluded.

The _{"alkyl groups that may have a substituent" in X 1 to} X ₆ are methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, tert-amyl group, 2-ethylhexyl group and stearyl. Examples thereof include a group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group and a dimethylcyclohexyl group. Among these, a methyl group, an ethyl group, and an n-propyl group, which have good durability and are easy to synthesize, are preferable, and a methyl group is more preferable.

The _{"alkenyl group which may have a substituent" in X 1 to} X ₆ is a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, 1-. Examples thereof include a pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group and the like. Of these, vinyl groups and allyl groups, which have good durability and are easy to synthesize, are preferable.

The _{"aryl groups that may have a substituent" in X 1 to} X ₆ are phenyl group, naphthyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, pentafluorophenyl group, 4-bromophenyl group. , 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like. Among these, a phenyl group and a 4-methylphenyl group, which have good durability and are easy to synthesize, are preferable.

Examples of the "aralkyl group which may have a substituent" in X _{1 to X 6} include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like. Among these, a benzyl group having good durability and easy synthesis is preferable.

In X _{1 to} X ₆ , "alkoxy groups even if they have a substituent" are methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group, 2-ethylhexyloxy group. , Trifluoromethoxy group, cyclohexyloxy group, stearyloxy group and the like. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group, which have good durability and are easy to synthesize, are preferable.

In X _{1 to} X ₆ , the "aryloxy group which may have a substituent" is a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methyl group. Examples thereof include a phenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group and the like. Of these, phenoxy groups and naphthyloxy groups, which have good durability and are easy to synthesize, are preferable.

In X _{1 to} X ₆ , the "substituted amino group" is a methylamino group, an ethylamino group, an isopropylamino group, an n-butylamino group, a cyclohexylamino group, a stearylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, Examples thereof include 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, dimethylamino groups and diethylamino groups, which have good durability and are easy to synthesize, are preferable.

Examples of the "halogen atom" in X _{1 to} X ₆ include fluorine, bromine, chlorine and iodine.

Substituents may be bonded to X _{1 to} X _{6 to form a ring.} Hereinafter, the ring will be illustrated.

The "alkyl group which may have a substituent" in _{R 1} and R ₂ has the same meaning as _{X 1 to} X _6.

X _{1 to} X ₆ preferably contain an unsubstituted alkyl group, more preferably at least one of _{X 3} and X _{4 is an unsubstituted alkyl group, and X 3} is an unsubstituted alkyl group. Is even more preferable. The unsubstituted alkyl group is preferably a methyl group.

Any one of X _{1 to} X ₄ is a functional group other than a hydrogen atom.

In the present invention, when the compound represented by the general formula (1) is synthesized, a near-infrared absorbing pigment containing one or more isomers is produced. In the present invention, the near-infrared absorbing pigment is treated with a solvent after synthesis to adjust the isomer having the lowest solubility in an organic solvent among a plurality of isomers to 60 to 78% of all the isomers. This improves heat resistance. In addition, the dispersibility is improved by appropriately containing the isomer. As described above, the near-infrared absorbing pigment of the present invention can achieve both heat resistance and dispersibility. In addition, about 2 to 4 isomers may be produced.
This is because the analysis result of reverse phase liquid chromatography shows the peak area of the peak that appears at the longest retention time under the condition that a mixed solution of acetonitrile and water mixed in a volume ratio of 8: 2 is used as the mobile phase. It is confirmed that the ratio is 60 to 78% of the total of the peak areas of all the peaks derived from the near-infrared absorbing pigment. In other words, the above-mentioned "60 to 78%" is the peak (latest peak) that appears at the longest retention time in the area obtained by integrating all the peaks derived from the near-infrared absorbing dye with respect to the baseline in the chart curve measured by HLPC. ) Is the area. The analysis method by HPLC is as follows. First, the near-infrared absorbing pigment is dissolved in tetrahydrofuran (THF) to prepare ^{a THF solution of 1 × 10 -4} mol / L or less. As the solvent THF, for example, THF for HPLC is used. Further, in the preparation of the THF solution, for example, the THF solution may be irradiated with ultrasonic waves for 30 minutes so that the near-infrared absorbing pigment is dissolved.

As the analyzer for reverse phase liquid chromatography, for example, a high performance liquid chromatography device (HPLC device, manufacturer: Shimadzu Corporation, model number: LC-10A) is used.
An octadecylsilyl column (ODS column) is used as the column for HPLC. Specifically, for example, the manufacturer: Kemco, trade name: CHEMCOSORB, product number: 5-ODS-H, particle size: 5 μm, inner diameter: 4.6 mm, Length: 150 mm can be mentioned. Here, the octadecylsilyl column is a column packed with chemically bonded porous spherical silica gel whose surface is modified with an octadecylsilyl group as a stationary phase.
The measurement conditions are, for example, column temperature: 45 ° C., injection volume of measurement sample: 10 μl, flow rate of measurement sample: 1 ml / min, detection wavelength: 254 nm, mobile phase: mixed solution of acetonitrile and water (volume ratio is: The condition of acetonitrile: water = 8: 2) can be mentioned.

The isomer having the lowest solubility in an organic solvent is retained for the longest time in the analysis of reverse phase liquid chromatography under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as a mobile phase. A peak appears in time. This isomer has a strong cohesive force, and it is presumed that the presence of this isomer in a high ratio also strengthens the cohesive force as a crystal and enhances heat resistance and light resistance. When this isomer is present in all isomers in a ratio of less than 60%, high heat resistance and light resistance cannot be obtained.

On the other hand, when this isomer is present in all the isomers at a ratio of more than 78%, the dispersibility described later is deteriorated. In this case, the cohesive force of the crystal becomes excessive and it becomes difficult to disperse.
If the dispersibility deteriorates, the stability of the dispersion liquid at a high pigment concentration cannot be obtained. Therefore, the pigment concentration must be lowered, and it is difficult to design the composition with a high pigment concentration.
In order to make the film thinner, it is necessary to prepare a composition having a higher pigment concentration. If the film thickness is reduced at the same pigment concentration, the absorption of near-infrared rays is also reduced. Therefore, in order to secure the same near-infrared absorption while reducing the film thickness, it is necessary to increase the pigment concentration. As described above, if the ratio of this isomer becomes too large, the dispersibility deteriorates and it becomes difficult to make a thin film.

It is presumed that these isomers actually have two cyclohexane structures in the general formula (1) centered in a trans-type arrangement and a cis-type arrangement. .. In particular, it is presumed that the one in the transformer type arrangement has poor solubility in the organic solvent, and when this is present in a high ratio, the cohesive force of the crystal becomes strong and the heat resistance and light resistance become high. In this trans-type arrangement, in the analysis of reverse phase liquid chromatography, under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as a mobile phase, at the longest holding time. It is speculated that a peak will appear. When _{all of X 1 to} X ₄ are hydrogen atoms, the trans-type arrangement and the cis-type arrangement can be freely changed in structure, and it is presumed that these isomers cannot exist.

The near-infrared absorbing pigment of the present invention has an average primary particle size of 10 to 80 nm. If the average primary particle size exceeds 80 nm, the transparency deteriorates. This is because the larger the pigment particles, the stronger the scattering and the loss of transparency. High transparency is required for sensor applications. On the other hand, if the average primary particle size is smaller than 10 nm, dispersion described later becomes difficult. When the average primary particle size is 10 to 80 nm, high transparency and good dispersibility can be obtained.

(Manufacturing method of near-infrared absorbing pigment)
The method for producing a near-infrared absorbing pigment preferably includes three steps of synthesizing the near-infrared absorbing pigment, treating the synthesized pigment with a solvent, and refining the solvent-treated pigment.
The solvent treatment of the pigment is carried out in order to make 60 to 78% of the isomers of the pigment having the lowest solubility in an organic solvent. Further, the solvent-treated pigment is miniaturized so that the average primary particle size is 10 to 80 nm.

(Synthesis of near-infrared absorbing pigment)
The method for producing a near-infrared absorbing pigment is as follows: For example, 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 the following formula ( The compound represented by the general formula (1) can be synthesized by adding 3,4-dihydroxy-3-cyclobutene-1,2-dione shown in 3) and further heating and refluxing to condense. Needless to say, the synthesis method is not limited.

(Solvent treatment of near-infrared absorbing pigment)
Solvent treatment is an effective means for making 60 to 78% of the isomers of the near-infrared absorbing pigment having the lowest solubility in an organic solvent. The solvent treatment here refers to the action of mixing the synthetically obtained pigment with an organic solvent for a certain period of time and filtering out only the insoluble components. At this time, the highly soluble component is dissolved in the organic solvent, and among the insoluble components taken out, a certain amount of low-soluble isomers are present. Therefore, by performing the above action, the ratio of the isomer having the lowest solubility in the organic solvent can be increased to some extent.

Examples of the organic solvent include N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran and the like. Of these, N-methylpyrrolidone is preferable.

The mixing temperature is preferably 5 to 80 ° C, more preferably 15 to 50 ° C. Mixing at an appropriate temperature makes it easy to increase the ratio of isomers having the lowest solubility in organic solvents.

The mixing time is preferably 1 to 72 hours, more preferably 4 to 48 hours. When mixed for an appropriate period of time, the ratio of the isomer having the lowest solubility in the organic solvent is unlikely to vary.

(Solvent-treated pigment miniaturization)
The solvent-treated pigment is preferably refined by salt milling treatment. In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated while heating using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and it is considered that the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling, which causes an active surface and crystal growth. There is. Therefore, during kneading, crushing of the pigment and crystal growth occur at the same time, and the primary particle size of the pigment obtained differs depending on the kneading conditions.

In order to promote crystal growth by heating, the heating temperature is preferably 40 to 150 ° C. If the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently and the shape of the pigment particles becomes close to amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., the crystal growth progresses too much and the primary particle size of the pigment becomes large, which is not preferable. The kneading time of the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

By optimizing the conditions for salt milling the pigment, the average primary particle size can be adjusted to 10 to 80 nm.

Examples of the water-soluble inorganic salt include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and may be any one that dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety.
Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, and the like. Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Can be mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

Resin can be added to the salt milling treatment as needed. The type of resin is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

The average primary particle size of the near-infrared absorbing pigment can be 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 pigment were measured, and the average was taken as the particle size of the pigment primary particles. Next, for 100 or more pigment particles, the volume (weight) of each particle is obtained by approximating it to a cube having the obtained particle size, and the volume average particle size is defined as the average primary particle size.

The near-infrared absorbing composition preferably contains a near-infrared absorbing pigment and a resin-type dispersant. The near-infrared absorbing pigment can form a fine dispersion by dispersing it using a resin-type dispersant or the like. Applications of the near-infrared absorbing composition include, for example, a coating application for forming a film by coating and a molding application for producing a molded product by kneading with a resin.

<Application for coating>
The materials used for coating purposes will be described.
(Resin type dispersant)
The resin-type dispersant has a pigment-affinity portion having a property of adsorbing to a pigment and a relaxation portion having a high affinity with a component other than the pigment and causing steric repulsion between pigment particles. As the resin type dispersant, a structurally controlled resin such as a graft type (comb type) or a block type is preferably used.

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

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

The basic resin type dispersant has a nitrogen atom-containing graft copolymer and a nitrogen atom-containing acrylic block copolymer having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain. Examples thereof include coalescing and urethane-based polymer dispersants.
The basic resin type dispersant can be used by neutralizing the basic group with phosphoric acid or sulfonic acid.

In the present specification, the resin-type dispersant is preferably a basic resin-type dispersant, and more preferably a resin-type dispersant having a tertiary amino group or a quaternary ammonium salt as a dye adsorbing group.

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

The resin-type dispersant can be used alone or in combination of two or more.

The content of the resin type dispersant is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the pigment. When an appropriate amount is contained, a film is easily formed.

(Photopolymerizable monomer)
The near-infrared absorbing composition can contain a photopolymerizable monomer. This makes it possible to form a coating film that is cured by ultraviolet rays, heat, or the like.
The photopolymerizable monomer is a compound having a polymerizable unsaturated group and includes a monomer and an oligomer. These can be used alone or in combination of two or more.

The monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like. 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 (meth) acrylate ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di ( Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and methacrylate ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether , (Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

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

The content of the photopolymerizable monomer is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the pigment. When an appropriate amount is contained, appropriate photocurability can be obtained.

(Photopolymerization initiator)
When the near-infrared absorbing composition contains a photopolymerizable monomer, the near-infrared absorbing composition may contain a photopolymerization initiator.

Photopolymerization initiators are 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy. Cyclohexylphenyl ketone, 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; benzoin, benzoin methyl ether, benzoin ethyl Benzoyl compounds such as 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-diisopropylthioxanthone, or Thioxanthone compounds such as 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-trichloromethyl- (4) Triazine compounds such as'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N -Oxime ester compounds such as (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2,4 , 6-trimethylbenzoyldiphenylphosphine oxide and other phosphine compounds; 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone and other quinone compounds Compounds; Borate-based compounds; Carbazole-based compounds; Imidazole-based compounds; Alternatively, titanocene-based compounds and the like are used.

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

The content of the photopolymerization initiator is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the pigment.

(Binder resin)
The near-infrared absorbing composition can contain a binder resin.
The binder resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region when a film having a thickness of 2 μm is formed. In terms of curability, the binder resin includes, for example, a thermoplastic resin, an active energy ray-curable resin, and the like. The active energy ray-curable resin is a resin obtained by imparting an active energy ray-reactive functional group to a thermoplastic resin. Further, the binder resin is preferably an alkali-soluble resin in that a film formed from the composition can be patterned by a photolithography method. The alkali-soluble resin is preferably a photosensitive alkali-soluble resin. The alkali-soluble resin requires an acidic group because of its developability.

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

The acid value of the alkali-soluble resin is preferably 20 to 300 mgKOH / g. Developability is improved by an appropriate acid value.

The content of the binder resin is preferably 30 to 500 parts by mass with respect to 100 parts by mass of the pigment. When it is contained in an appropriate amount, a film is easily formed.

The thermoplastic resin is, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, etc. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene, polybutadiene, and polyimide resin. Among these, it is preferable to use an acrylic resin.

The alkali-soluble resin is preferably a thermoplastic resin having an acidic group. Examples of the acidic group include a carboxyl group and a sulfone group. The alkali-soluble resin is, for example, 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 an isobutylene /. (Anhydrous) maleic anhydride copolymer and the like can be mentioned. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable in terms of developability, heat resistance, and transparency, and an acrylic resin having an acidic group is more preferable.

As the photosensitive alkali-soluble resin, for example, a resin synthesized by the following methods (i) and (ii) is preferable. As a result, the crosslink density of the film formed from the photosensitive coloring composition by light irradiation is further improved.

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

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

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.

The monomer and the polybasic acid anhydride can be used alone or in combination of two or more.

Further, as a method similar to the method (i), for example, a carboxyl group-containing monomer and a monomer other than the carboxyl group-containing monomer are synthesized to prepare a polymer. Next, a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin can be mentioned.

[Method (ii)]
In method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate. , Or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε- (Poly) ester mono (meth) acrylates to which caprolactone and / or (poly) 12-hydroxystearic acid and the like are added can also be mentioned. Of these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable. Further, glycerol mono (meth) acrylate is preferable in terms of light sensitivity.

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

(Thermosetting compound)
The near-infrared absorption composition can contain a thermosetting compound. Since the crosslink density is improved in the heating process, the heat resistance is improved. The thermosetting compound is a low molecular weight compound or a polymer (thermosetting resin) and is not limited by the molecular weight.
Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferable.

(Organic solvent)
The near-infrared absorbing composition can contain an organic solvent. As a result, the viscosity of the composition can be easily adjusted, so that a film having a smooth surface can be easily formed. The solvent may be appropriately selected according to the purpose of use and may be contained in an appropriate amount.

The organic solvent is, for example, ethyl lactate, benzyl alcohol, 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-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 1,3-Butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m- Diethyl benzene, 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, isophorone, 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, 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 glycol dimethyl ether, Dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, zip Lopyrene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, 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 ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, Examples thereof include n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

Among these, alkyl lactates such as ethyl lactate, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and aromatic alcohols such as benzyl alcohol. And ketones such as cyclohexanone are preferably used.

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

(Sensitizer)
When the near-infrared absorbing composition contains a photopolymerizable initiator, it can contain a sensitizer.
The sensitizer includes, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, 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 Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylglioxylates, benzyls, 9,10-phenanthrene quinones, camphorquinones, ethyl anthraquinones, 4,4'-diethylisophthalofenones, 3,3'or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like can be mentioned.

Among these, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are preferable. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis ( Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4
More preferred are'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole and the like.

Commercially available sensitizers include "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (manufactured by 4,4'-bis (diethylamino) benzophenone Chemical). Can be mentioned.

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

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

(Polyfunctional thiol)
The near-infrared absorbing composition can contain a polyfunctional thiol 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, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (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.

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

The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the non-volatile content of the near-infrared absorbing composition. When an appropriate amount is contained, the light sensitivity and the pattern shape are further improved.

(Antioxidant)
The near-infrared absorbing composition may contain an antioxidant. The antioxidant can increase the transmittance of the coating film because it prevents the photopolymerization initiator and the thermosetting compound contained in the near-infrared absorbing composition from being oxidized and yellowed by the heating step.
Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate ester-based, and triazine-based compounds. Among these, hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based are preferable, and hindered phenol-based, hindered amine-based, and phosphorus-based are more preferable, from the viewpoint of achieving both the transmittance and sensitivity of the coating film.

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

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

<Amine compounds>
The near-infrared absorbing composition can contain an amine compound having a function of reducing dissolved oxygen. Amine compounds include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, Examples thereof include 2-ethylhexyl 4-dimethylaminobenzoate and N, N-dimethylparatoluidine.

<Leveling agent>
The near-infrared absorbing composition can contain a leveling agent. As a result, the wettability to the transparent substrate and the drying property of the coating film at the time of forming the coating film are further improved. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

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

The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the non-volatile content of the near-infrared absorbing composition. Within this range, the balance between the coatability of the photosensitive coloring composition, the pattern adhesion, and the transmittance is further improved.

(Hardener)
When the near-infrared absorbing composition contains a thermosetting compound, a curing agent can be contained to assist the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds.
Amine compounds include (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine). Amines, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2-methylimidazole, etc.) 2-Ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl imidazole, etc. ), Phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-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.) and the like.

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

(Other near-infrared absorbing pigments)
The near-infrared absorbing composition may contain a near-infrared absorbing pigment other than the near-infrared absorbing pigment of the present invention. Near-infrared absorbing pigments other than the near-infrared absorbing pigment that can be used in the near-infrared absorbing composition of the present invention include, for example, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, aminium compounds, diinmonium compounds, croconium compounds, azo compounds, and the like. Examples thereof include quinoid type complex compounds and dithiol metal complex compounds.

(Storage stabilizer)
The near-infrared absorbing composition may contain a storage stabilizer 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 improve the adhesion with the transparent substrate.

Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, organic acids such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples include phosphine and phosphite. The content of the storage stabilizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the pigment.

(Adhesion improver)
The near-infrared absorbing composition can contain an adhesion improver such as a silane coupling agent in order to enhance the adhesion to the substrate.
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) methyl Epoxysilanes such as triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) ) Γ-Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyl Examples thereof include aminosilanes such as trimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the pigment.

(Manufacturing method of near-infrared absorbing composition)
The near-infrared absorbing composition is prepared by dispersing the near-infrared absorbing pigment with a resin-type dispersant. The near-infrared absorbing composition is produced by mixing a near-infrared absorbing pigment, a resin-type dispersant, and if necessary, a binder resin, an organic solvent, and other dispersion aids, and then performing a dispersion treatment. Then, if necessary, it can be prepared by mixing a photopolymerizable compound and a photopolymerizable initiator. Needless to say, the timing of blending each material is arbitrary.

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

(Removal of coarse particles)
The near-infrared absorbing composition for coating of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0. It is preferable to remove coarse particles of 5 μm or more and mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

(Manufacturing method of near-infrared cut filter and near-infrared transmission filter)
The near-infrared cut filter and the near-infrared transmission filter of the present invention can be manufactured by a printing method or a photolithography method. Since the filter segment can be formed by the printing method by printing and drying the near-infrared absorbing composition, the filter manufacturing method is low cost and excellent in mass productivity. Further, with the development of printing technology, it is possible to print a fine pattern 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 a solvent-developed or alkali-developed resist material is applied onto a substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the construction method, coating is performed 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 film may be used without forming a pattern.

The substrate is not particularly limited, but a sheet-shaped, film-shaped, or plate-shaped transparent base material can be used as the shape. Colors are also colorless and colored, and are not particularly limited. The material of the transparent base material is a highly transparent material, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or triacetyl cellulose (TAC). Examples thereof include acrylic resins such as methyl methacrylate-based copolymers, styrene resins, polysulfone resins, polyether sulfone resins, polycarbonate resins, vinyl chloride resins, polymethacrylicimide resins, and glass plates.

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

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

<Molding application>
The materials used for molding purposes will be described. The molding application is an application for producing a film or a three-dimensional body by molding. When the near-infrared absorbing composition is used for molding purposes, it is preferably a melt-kneaded product of a near-infrared absorbing pigment and a thermoplastic resin.

(Thermoplastic resin)
Examples of the thermoplastic resin include polyolefin resin, acrylic resin, polystyrene resin, polyester resin, polyamide resin, polycarbonate resin, cycloolefin resin, polyetherimide resin and the like.

(Polyamide resin)
The polyamide resin is a crystalline resin, and can be synthesized, for example, by subjecting a carboxylic acid component and a compound (Am) having two or more amino groups to a dehydration condensation reaction.

Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, terephthalic acid and the like. As the carboxylic acid component, a compound having 3 or more carboxyl groups can be used.
As the compound (Am) having two or more amino groups, for example, known ones can be used, for example, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylene. Aliphatic polyamines such as tetramine; aliphatic polyamines containing alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; 1,3-diamino-2 -Propanol, 1,4-diamino-2-butanol, 1-amino-3- (aminomethyl) -3,5,5-trimethylcyclohexane-1-ol, 4- (2-aminoethyl) -4,7, Examples thereof include diaminoalcohols such as 10-triazadecane-2-ol, 3- (2-hydroxypropyl) -o-xylene-α and α'-diamine.
Examples of commercially available polyamide resins include 6 nylon (manufactured by Toray Industries, Inc.), 66 nylon (manufactured by Toray Industries, Inc.), 610 nylon and the like.

(Polycarbonate resin)
The polycarbonate resin is an amorphous resin, and is synthesized by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester. In the case of a synthetic reaction using phosgene, for example, an interfacial method is preferable. Further, in the case of a synthetic reaction using a carbonic acid diester, a transesterification method in which the reaction is carried out in a molten state is preferable.

Aromatic dihydroxy compounds include, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3, Bis (hydroxyaryl) alkanes such as 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1, Bis (hydroxyaryl) cycloalkanes such as 1-bis (4-hydroxyphenyl) cyclohexane 4,4'-dihydroxydiphenyl ethers, dihydroxydiaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ethers, 4 , 4'-Dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,3'-Dihydroxydiarylsulfides such as dimethyldiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3 Examples thereof include dihydroxydiaryl sulfoxides such as'-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfone such as 4,4'-dihydroxydiphenyl sulfone, and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. Further, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be mixed and used.

Examples of the carbonate precursor include diaryl carbonates such as phosgene, diphenyl carbonate and ditril carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 30,000, more preferably 16,000 to 27,000. The viscosity average molecular weight in the present specification is a value converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.

Commercially available polycarbonate resin products include, for example, Iupiron H-4000 (manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 16,000), Iupiron S-3000 (manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 23,000), and Iupiron E-2000. (Manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 27,000) and the like.

(Cycloolefin resin)
The cycloolefin resin is an amorphous resin having an alicyclic structure in the main chain and / or the side chain. Examples of the type of alicyclic structure include norbornene polymer, monocyclic cyclic olefin polymer, cyclic conjugated diene polymer, vinyl alicyclic hydrocarbon polymer, and hydrides thereof. Among these, the norbornene polymer is preferable because it is excellent in moldability and transparency. Norbornene monomers include, for example, bicyclo [2.2.1] hept-2-ene (trivial name: norbornene), tricyclo [4.3.0.12.5] deca-3,7-diene (common name: norbornene). Trivial name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.12.5] deca-3-ene (trivial name: metanotetrahydrofluorene), tetracyclo [4.4.0.12 5.17, 10] Dodeca-3-ene (trivial name: tetracyclopentadiene) and the like can be mentioned.
Examples of commercially available cycloolefin resins include Topas (manufactured by Polyplastics) and Appel (manufactured by Mitsui Chemicals).

(Polyetherimide resin)
The polyetherimide resin is an amorphous resin having a glass transition temperature of more than 180 ° C., has good transparency, high strength, high heat resistance, high elastic modulus, and a wide range of chemical resistance. Therefore, it is widely used in various applications such as automobiles, telecommunications, aerospace, electrical / electronic, transportation and healthcare.
One of the processes for producing a polyetherimide resin is a polymerization of an alkali metal salt of a dihydroxyaromatic compound such as _{bisphenol A disodium salt (BPA · Na 2) and bis (halophthalimide).} The molecular weight of the obtained polyetherimide resin can be controlled by two methods. The first method is to use a molar excess of bis (halophthalimide) with respect to the alkali metal salt of the dihydroxyaromatic compound. The second method is to prepare bis (phthalic anhydride) in the presence of a monofunctional compound such as phthalic anhydride that forms the terminal capping agent. Phthalic anhydride reacts with some of the organic diamines to form monohalo-bis (phthalimide). Monohalo-bis (phthalimide) acts as a terminal capping agent in the polymerization step by reaction with phenoxide end groups in the growing polymer chain.
Examples of commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industry Corporation).

The thermoplastic resin is preferably a crystalline resin having a melting point of 100 to 500 ° C. or an amorphous resin having a glass transition temperature of 60 to 300 ° C. Both the melting point and the glass transition temperature can be measured with a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

The near-infrared absorbing composition may contain additives in addition to the near-infrared absorbing pigment and the thermoplastic resin. Examples of the additive include an ultraviolet absorber, a light stabilizer, an antioxidant, a colorant, a dispersant and the like. These additives are compounds known in molded article applications.

UV absorbers are used to impart UV resistance to articles. Examples of the ultraviolet absorber include benzophenone type, benzotriazole type, triazine type, salicylic acid ester type and the like. The content of the ultraviolet absorber is preferably 0.01 to 5% by mass in 100% by mass of the composition.

The light stabilizer is used to impart UV resistance to the molded product, and is preferably used in combination with the UV absorber. As the light stabilizer, for example, a hindered amine light stabilizer is preferable. The content of the light stabilizer is preferably 0.01 to 5% by mass in 100% by mass of the composition.

Antioxidants are used to reduce the deterioration of an article when the article is exposed to natural light or an artificial light source and becomes hot. As the antioxidant, for example, monophenol type, bisphenol type, polymer type phenol type, sulfur type, phosphoric acid type and the like are preferable. The content of the antioxidant is preferably 0.01 to 5% by mass in 100% by mass of the composition.

Dispersants are used to more evenly disperse the near-infrared absorbing pigment in the molded article. As the dispersant, for example, polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, saponified fatty acid wax and the like are preferable. The content of the dispersant is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.

(Preparation of near-infrared absorbing composition)
The near-infrared absorbing composition can be produced by melt-kneading a near-infrared absorbing pigment and a thermoplastic resin. The melt-kneading temperature varies depending on the resin, but is preferably 230 ° C. or higher, more preferably 270 ° C. or higher. It is preferable to cool after melt-kneading. The upper limit of the melt kneading temperature is not limited because it differs depending on the type of the thermoplastic resin. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower. Further, the upper limit needs to be lower than the sublimation temperature or the decomposition temperature of the near-infrared absorbing pigment of the present invention.

Examples of the melt kneading apparatus include a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, and the like.

The resin composition is preferably prepared as a so-called masterbatch. When a masterbatch is produced and then melt-kneaded together with a diluted resin (thermoplastic resin) to produce a molded product, the near-infrared absorbing pigment of the present invention is molded as compared with a molded product produced without undergoing a masterbatch. It is easy to disperse uniformly throughout the body and can suppress the aggregation of the near-infrared absorbing pigment. This improves the transparency of the molded product. The masterbatch is preferably formed into pellets using a pelletizer after the melt kneading.
When produced as a masterbatch, the content of the near-infrared absorbing pigment is preferably 0.01 to 20% by mass, more preferably 0.05 to 2% by mass in 100% by mass of the composition.

The molded product of the present specification is produced by molding a near-infrared absorbing composition. The near-infrared absorbing composition can be molded as it is to prepare a molded product. When the near-infrared absorbing composition is a masterbatch, a molded product can be produced by melt-kneading with a diluted resin (thermoplastic resin) and then molding. The mass ratio of the masterbatch (X) to the diluted resin (Y) is preferably X / Y = 1/5 to 1/500. Within this range, the molded product can easily obtain good optical characteristics.

<Use of near-infrared absorbing composition>
Near-infrared absorbing compositions for coating and molding applications can be used, for example, for the following applications.
(Heat ray absorber)
The near-infrared absorbing composition can be used as a heat ray absorbing material. Sunlight contains near-infrared rays having a wavelength of 700 to 2000 nm, and among them, the intensity of near-infrared rays having a wavelength of 700 to 1000 nm is particularly strong. Near infrared rays have the property of raising the temperature of a substance and are called heat rays. Among them, by absorbing and blocking near infrared rays having a particularly strong intensity of 700 to 1000 nm, it is possible to suppress an increase in the temperature of the substance.
Placing a film or film formed from a near-infrared absorbing composition on the windows of a building or car has the effect of suppressing the temperature rise inside the room or car due to sunlight. In addition, the above film can be used in agricultural greenhouses and the like, and has the effect of suppressing the temperature rise inside the greenhouse. The same applies to protective goggles, eyeglasses, and sunglasses, which can be used to block heat rays.

(Optical recording medium)
The near-infrared absorbing composition can be used as an optical recording medium. When the film or molded body formed from the near-infrared absorbing composition is irradiated with near-infrared rays, the crystal state of the dye changes and the refractive index of the film or molded body changes. This principle is used in recording media such as optical discs.

(Laser welding material / laser marking material)
The near-infrared absorbing composition can be used as a laser welding material or a laser marking material.
When a film or molded body formed from a near-infrared absorbing composition is irradiated with a laser having a wavelength absorbed by a near-infrared absorbing pigment, the dye absorbs the laser beam and generates heat, so that the thermoplastic resin melts and carbonizes. When it melts, it can be welded to other resins, and laser welding uses this principle. Laser marking uses carbonization to turn black.
In the case of laser welding, carbon or the like is usually included in the welding, but in the case of a near-infrared absorbing pigment, the near-infrared absorbing pigment generates heat and the thermoplastic resins are welded to each other by irradiating the near-infrared laser. .. Similarly, laser marking can be performed by generating heat from the near-infrared absorbing pigment and melting and carbonizing the thermoplastic resin.

(Optical filter)
The near-infrared absorbing composition can be used as an optical filter. For example, a digital camera recognizes colors by decomposing the light received during imaging with red, green, and blue filters and sending it to a photodiode that converts the light into an electrical signal. However, the photodiode also reacts with near infrared rays and converts it into an electric signal, so a filter that blocks this is required. A coating or molded product formed from the near-infrared absorbing composition can be used as a filter that blocks the near-infrared rays. It is important that the filter that blocks near infrared rays absorbs little in the visible region. If there is a lot of absorption in the visible region, the received light will be colored, which will adversely affect the color recognition of the photodiode. Since the near-infrared absorbing pigment of the present invention absorbs little in the visible region and has high invisibility, it has little adverse effect on the color recognition of the photodiode.

(Biometric sensor)
The near-infrared absorbing composition can be used for a sensor for biometric authentication (fingerprint authentication or vein authentication), or a touch sensor or touch panel incorporating the sensor.
For example, smartphones, tablet PCs, etc., as well as bank ATMs, multimedia terminals, etc., are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication for security protection. In particular, the development of fingerprint authentication technology used for smartphones and tablet PCs is rapid, and as photodiodes change from inorganic to organic, the authentication range has increased to screen size (full screen), and organic EL displays, liquid crystal displays, etc. A fingerprint authentication sensor with a built-in display has been developed.
However, since many fingerprint sensors with a built-in display irradiate the fingerprint with various light sources installed in the display and sense the reflected light, illegal external light (such as sunlight or LED lighting) is used. When the sensor has a wide range of wavelengths and strong light) is incident on the sensor, there is a problem that it becomes noise at the time of imaging, and there remains some concern in terms of accuracy when using it outdoors. The same applies to finger vein recognition for bank ATMs and multimedia terminals, and measures such as covering the stores with strong lighting and sunny stores to block outside light are taken.
The coating film or molded product using the near-infrared absorbing composition of the present invention is effective in solving these problems by absorbing and preventing the incident of illegal external light on the sensor.
For example, when used for smartphones and tablet PCs, when set on the front surface of the panel, it is necessary to have designability as well, but a material using the near-infrared absorbing composition for coating of the present invention, a coating obtained by coating. A molded product obtained by using a film or a near-infrared absorbing composition for molding has an advantage that it can be suitably used because it has no absorption in the visible region and is invisible, that is, has high transparency. Further, since the near-infrared absorbing composition of the present invention has excellent heat resistance, it can be preferably used in terms of a process for manufacturing a sensor, a touch sensor incorporating the sensor, and a touch panel.
Further, the external light that becomes noise in biometric authentication applications is light of 650 nm to 1000 nm that passes through the living body, and in particular, light of 650 nm to 800 nm overflows in the living space, so that light in this wavelength region can be cut. Increase the accuracy of biometric authentication. Blue pigments and green pigments often absorb in the visible light region of 650 nm to 700 nm, and by combining blue pigments and green pigments with near-infrared absorbing pigments, invisibility is reduced, but the accuracy of biometric authentication is improved. Can be enhanced.

The blue pigment is, for example, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment blue 15: 1 and the like. The green pigment is, for example, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63 can be mentioned. In addition, C.I. I. Means the color index (CI).

(display)
A coating or molded product formed from the near-infrared absorbing composition can also be incorporated into the display. Specifically, a liquid crystal display with a touch panel function such as an electronic blackboard can be mentioned. This liquid crystal display with a touch panel function has three functions of display, writing, and saving, and the built-in touch panel also employs optical methods such as infrared scanning method and infrared projection method. The above-mentioned noise due to external light was a problem. Liquid crystal displays with a touch panel function are often used in schools, etc., so accuracy and good response to touch are important. By incorporating a coating film obtained by coating the near-infrared absorbing composition for coating of the present invention or a molded product obtained by using the near-infrared absorbing composition for molding into a display, external light that becomes noise is emitted. It is preferable because it can be cut.
Further, the coating film or the molded product can be preferably used as an antireflection film for various displays using a liquid crystal, an organic EL, a Mini-LED, or a Micro-LED. By suppressing the reflection of not only visible light but also light in the near infrared region, there is an advantage that the black display on the display can be made blacker. Since the near-infrared absorbing composition of the present invention has excellent heat resistance, it can also be preferably used for resistance to processes required in display manufacturing.

(Near infrared transmission filter)
LEDs with wavelengths of 850 nm, 870 nm, 900 nm, 940 nm, etc. have become widespread, and in various sensors such as distance measurement and biometric authentication (fingerprint authentication, iris recognition, face recognition, vein recognition, etc., or a combination thereof) in automatic driving. Used for light detection. However, since light rays of all wavelengths such as ultraviolet rays, visible light, and near infrared rays exist in the atmosphere, a filter that blocks light other than the light of the wavelength to be detected is required. Therefore, by combining a near-infrared absorbing pigment that absorbs light of 700 to 1000 nm with a dye that absorbs visible light, an ultraviolet absorber, etc., only light having a wavelength longer than the absorption wavelength of the near-infrared absorbing pigment is transmitted, and a wavelength shorter than that is transmitted. Light can be blocked. Specifically, it is preferable to combine the near-infrared absorbing pigment with a blue pigment, a yellow pigment, and a red or purple pigment. For coating applications, the blue pigment is C.I. I. Pigment Blue 15: 3 or C.I. I. Pigment blue 15: 6, yellow pigment is C.I. I. Pigment Yellow 139, red pigment is C.I. I. Pigment Red 254, C.I. I. Acid Red 5
2 or C.I. I. Acid Red 289, purple pigment is C.I. I. Pigment Violet 23 is preferably used. For molding applications, the blue pigment is C.I. I. Pigment Blue 15: 3 or C.I. I. Pigment blue 15: 6, yellow pigment is C.I. I. Pigment Yellow 147, red pigment is C.I. I. Solvent red 52 is preferred.

As described above, the optical filter using the near-infrared absorbing composition includes a near-infrared cut filter and a near-infrared transmitting filter. The near-infrared cut filter is mainly composed of a near-infrared absorbing dye, and has a role of blocking near-infrared rays and transmitting visible light. On the other hand, the near-infrared transmitting filter is composed of dyes such as blue, red, and yellow that absorb visible light in addition to the near-infrared absorbing dye, and blocks visible light and near-infrared rays in the wavelength range absorbed by the near-infrared absorbing dye. In addition, it has the role of transmitting near-infrared rays with longer wavelengths.

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. In addition, "part" means "part by mass", and "%" means "mass%". The blending amount in the table is a mass part.

In the examples, "PGMAc" is propylene glycol monomethyl ether acetate, "Aronix M-402") is dipentaerythritol hexaacrylate, "OXE-02") is etanone, 1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime).

(Method of identifying near-infrared absorbing pigment)
The MALDI TOF-MS spectrum was used to identify the near-infrared absorbing pigment 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 non-volatile component.

(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 TSKgel column (manufactured by Tosoh Corporation), a GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120 GPC), 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 the potentiometric titration method using a 0.1 N aqueous hydrochloric acid solution, and then converted to the equivalent of potassium hydroxide. The amine value of the resin type dispersant indicates the amine value of the non-volatile component.

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

<Manufacturing method of near-infrared absorbing pigment>
The near-infrared absorbing pigment of the present invention is obtained by synthesizing a pigment, treating the synthetically obtained pigment with a solvent, and refining the solvent-treated pigment.

(Synthesis of near-infrared absorbing pigment (A-1))
400 parts of toluene is mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 2,6-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate in an atmosphere of nitrogen gas. The mixture was heated and stirred and refluxed for 3 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. Heat and stir in
The reflux reaction was carried out 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 71.9 parts of near-infrared absorbing pigment (A-1) (yield: 97%). Got As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing pigment (A-1).

Near infrared absorbing pigment (A-1)

(Synthesis of near-infrared absorbing pigment (A-2))
Near-infrared absorbing pigment (A) except that 3,5-dimethylcyclohexanone 32.2 parts was used instead of 2,6-dimethylcyclohexanone 32.2 parts used in the synthesis of the near-infrared absorbing pigment (A-1). The same operation as in the synthesis of -1) was carried out to obtain 72.6 parts (yield: 98%) of the near-infrared absorbing pigment (A-2). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing pigment (A-2).

Near infrared absorbing pigment (A-2)

(Synthesis of near-infrared absorbing pigment (A-3))
Near-infrared absorbing pigment (A) except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 32.2 parts of 2,6-dimethylcyclohexanone used in the synthesis of the near-infrared absorbing pigment (A-1). The same operation as in the synthesis of -1) was carried out to obtain 76.9 parts (yield: 95%) of the near-infrared absorbing pigment (A-3). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing pigment (A-3).

Near infrared absorbing pigment (A-3)

(Synthesis of near-infrared absorbing pigment (A-4))
Near-infrared absorbing pigment (A-1), except that 59.8 parts of 3,5-di (trifluoromethyl) cyclohexanone was used instead of 32.2 parts of 2,6-dimethylcyclohexanone used in the synthesis. The same operation as the synthesis of the infrared absorbing pigment (A-1) was carried out to obtain 93.3 parts (yield: 93%) of the near infrared absorbing pigment (A-4). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing pigment (A-4).

Near infrared absorbing pigment (A-4)

(Synthesis of near-infrared absorbing pigment (A-5))
Near infrared absorbing pigment (A-1), except that 68.0 parts of 2,6-di (trifluoromethoxy) cyclohexanone was used instead of 32.2 parts of 2,6-dimethylcyclohexanone used in the synthesis. The same operation as the synthesis of the infrared absorbing pigment (A-1) was carried out to obtain 100.5 parts (yield: 93%) of the near infrared absorbing pigment (A-5). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing pigment (A-5).

Near infrared absorbing pigment (A-5)

(Synthesis of near-infrared absorbing pigment (A-6))
Near-infrared absorbing pigment (A) except that 34.3 parts of 3,5-difluorocyclohexanone was used instead of 32.2 parts of 2,6-dimethylcyclohexanone used in the synthesis of near-infrared absorbing pigment (A-1). The same operation as in the synthesis of -1) was carried out to obtain 70.7 parts (yield: 93%) of the near-infrared absorbing pigment (A-6). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing pigment (A-6).

Near infrared absorbing pigment (A-6)

<Manufacturing of near-infrared absorbing pigment>
(Example 1)
(Solvent treatment process)
50 parts of the near-infrared absorbing pigment (A-1) was mixed with 250 parts of N-methylpyrrolidone, and the mixture was stirred at 23 ° C. for 24 hours. Then, the mixture was filtered, washed with 150 parts of methanol, taken out, and dried at 80 ° C. for 24 hours to obtain 25 parts of powder.
(Miniaturization process)
10 parts of the obtained powder, 100 parts of sodium chloride, and 12.5 parts of ethylene glycol were charged in a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 12 hours. Next, the kneaded mixture is put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. for 24 hours and pulverized. As a result, 9.4 parts of the near-infrared absorbing pigment 1 was obtained.
(Average particle size)
The average primary particle size of the pigment was measured by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle (
Weight) was calculated by approximating a cube with the obtained particle size, and the volume average particle size was taken as the average primary particle size. A transmission type (TEM) was used as the electron microscope.
As a result of measurement by this method, the average primary particle size was 50 nm.
(Component ratio)
5.0 mg of near-infrared absorbing pigment 1 was placed in a 100 ml volumetric flask, THF for HPLC was added, and ultrasonic waves were irradiated for 30 minutes to dissolve the solution, and a 100 ml THF solution was prepared. Using this solution, HPLC measurement of the near-infrared absorbing pigment 1 was carried out by the above-mentioned apparatus and the above-mentioned conditions.
The HPLC measurement was analyzed by reverse phase liquid chromatography under the condition that a mixed solution of acetonitrile and water in a volume ratio of 8: 2 was used as the mobile phase.
As a result, multiple peaks were shown.
Specifically, a peak with a retention time of 12 ± 1 minute (peak 1), a peak with a retention time of 42 ± 1 minute (peak 2), and a peak with a retention time of 46 ± 2 minutes (peak 3). It is composed of a peak with a retention time of 50 ± 2 minutes (peak 4) and a peak with a retention time of 57 ± 2 minutes (peak 5).
The area of peak 5 was 70% of the total area of peaks 1-5.

(Examples 2 to 12, Comparative Examples 1 to 11)
Based on the production of the near-infrared absorbing pigment 1, the near-infrared absorbing pigments 2 to 11 and the comparative near-infrared absorbing pigments 1 to 11 were produced under the conditions shown in Table 1. In Comparative Examples 1 and 8 to 11, no solvent treatment was performed.

<Manufacturing method of binder resin solution>
(Adjustment of binder resin solution): 70.0 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a random copolymer separable 4-neck flask, and the temperature was raised to 80 ° C. After substituting nitrogen in the reaction vessel, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (Toa Synthetic Co., Ltd.) A mixture of 7.4 parts of "Aronix M110" manufactured by the company and 0.4 parts of 2,2'-azobisisobutyronitrile 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 a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Ether acetate was added to prepare a binder resin solution.

<Manufacturing method of resin type dispersant>
(Resin-type dispersant 1 solution): Block copolymer [Synthesis of ethylenically unsaturated monomer (b-5)]
60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3- (dimethylamino) propylamine, and 120 parts of THF were charged in a reaction vessel equipped with a stirrer and a thermometer, and the mixture was stirred at room temperature for 5 hours. After confirming that the reaction was completed by FT-IR, the solvent was distilled off by a rotary evaporator to obtain 73 parts of the following ethylenically unsaturated monomer (b-5) as a pale yellow transparent liquid. (Yield 82%). Identification of the obtained compound was carried out by 1H-NMR.

Ethylene unsaturated monomer (b-5)

[Synthesis of ethylenically unsaturated monomer (b-9)]
In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of the ethylenically unsaturated monomer (b-5) obtained by the synthesis of the above ethylenically unsaturated monomer (b-5), ion exchange. After charging 5 parts of water and stirring at room temperature, 8 parts of a 35% aqueous hydrochloric acid solution was added dropwise. It was confirmed by the amine value measurement that the reaction was completed, and 20 parts of an aqueous ethylenically unsaturated monomer (b-9) solution was obtained as a pale yellow transparent liquid. Identification of the obtained compound was carried out by 1H-NMR.

Ethylene unsaturated monomer (b-9)

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 17.7 parts of methyl methacrylate, 53.2 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 100 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 non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, in this reaction vessel, 20 parts of PGMAc, 21.2 parts of an ethylenically unsaturated monomer (b-5) as a second block monomer, and 27 parts of an aqueous solution of an ethylenically unsaturated monomer (b-9) (nonvolatile). 38%) was added, and the mixture was stirred while maintaining an atmosphere of 110 ° C. and a nitrogen, and the reaction was continued. After 2 hours, the polymerization solution was sampled and the non-volatile 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 mass. In this way, one solution of a resin-type dispersant having an amine value of 50 mgKOH / g per non-volatile content, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass is prepared. Obtained.

(Resin-type dispersant 2 solution): 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine in a reaction device equipped with a block copolymer gas introduction tube, a condenser, a stirring blade, and a thermometer. The part was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to replace the inside of the system with nitrogen. Next, 9.3 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 non-volatile 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 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reactor, 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 non-volatile content was measured. 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 brought to room temperature. It was cooled to stop the polymerization.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, it is a poly (meth) acrylate skeleton having an amine value per non-volatile content of 71.4 mgKOH / g, a weight average molecular weight of 9900 (Mw), and a non-volatile content of 40% by mass, and is a resin type having a tertiary amino group. Two dispersant solutions were obtained.

(Resin-type dispersant 3 solution): 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine in a reaction apparatus equipped with a block copolymer gas introduction tube, a condenser, a stirring blade, and a thermometer. The part was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to replace the inside of the system with nitrogen. Next, 9.3 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 non-volatile 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 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride as a second block monomer (“Acryester DMC78” manufactured by Mitsubishi Rayon Co., Ltd.) were added to this reactor, and the temperature was maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled and the non-volatile content was measured. 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 prepared. The polymerization was stopped by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, a resin type having a poly (meth) acrylate skeleton having an amine value per non-volatile content of 29.4 mgKOH / g, a weight average molecular weight of 9800 (Mw), and a non-volatile content of 40% by mass and having a quaternary ammonium base. A dispersant 3 solution was obtained.

(Resin type dispersant 4 solution): Block copolymer
55 parts of 4-dimethylamino-1,2-epoxybutane and 120 parts of tetrahydrofuran (THF) were charged in a reaction vessel equipped with a stirrer and a thermometer, heated and stirred at 70 ° C., and 35 parts of methacrylic acid was added over 60 minutes. Dropped. After the dropping was completed, the mixture was further heated and stirred at 70 ° C. for 2 hours ^{, and after confirming that the reaction was completed by 1 1} H-NMR, the mixture was allowed to cool to room temperature. The reaction solution was washed successively with 300 parts of ion-exchanged water, 200 parts of saturated sodium hydrogen carbonate, and 200 parts of saturated brine, 20 g of magnesium sulfate was added to the organic layer, and the mixture was stirred and then filtered. The solvent of the obtained solution was distilled off with a rotary evaporator to obtain 31 parts of an ethylenically unsaturated monomer (b-1) having the following structure as a pale yellow transparent liquid (yield 42%). The identified compounds were identified by ¹ H-NMR.

Ethylene unsaturated monomer (b-1)

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 17.6 parts of methyl methacrylate, 52.8 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 100 parts of propylene glycol monomethyl ether acetate 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 non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 25 parts of PGMAc and 25.1 parts of an ethylenically unsaturated monomer (b-1) as a second block monomer were added to this reaction vessel, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. The reaction was continued. Two hours after the addition of the ethylenically unsaturated monomer (b-1), the polymerization solution was sampled and the non-volatile content was measured. confirmed.
Further, 4.5 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 mass. In this way, four solutions of resin-type dispersants having an amine value of 50 mgKOH / g per non-volatile content, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass are prepared. Obtained.

(5 solutions of resin type dispersant)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 parts of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added, and the temperature was 120 ° C. Was reacted for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 50%. In this way, a resin-type dispersant 5 solution having an acid value of 43, a weight average molecular weight of 9000, a poly (meth) acrylate skeleton, and an aromatic carboxyl group was obtained.

(6 solutions of resin type dispersant)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, 0.01 parts of monobutyltin oxide, and PGMAc88. Nine parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and hydroxymethyl. 20 parts of methacrylate was charged, 0.12 part of AIBN and 26.8 parts of PGMAc were added, and the reaction was carried out for 10 hours. The reaction was terminated after confirming that the polymerization had proceeded by 95% by measuring the non-volatile content. PGMAc was added to adjust the non-volatile content to 50% to obtain 6 solutions of a resin-type dispersant having an acid value of 43, a weight average molecular weight of 9000, a poly (meth) acrylate skeleton, and an aromatic carboxyl group.

(7 solutions of resin type dispersant)
BYK-P104 (manufactured by Big Chemie Japan: 50% non-volatile content)

(8 solutions of resin type dispersant)
Disperbyk-171 (manufactured by Big Chemie Japan: non-volatile content 39.5%)

(9 solutions of resin type dispersant)
Disperbyk-142 (manufactured by Big Chemie Japan: 60% non-volatile content)

(10 solutions of resin type dispersant)
Non-volatile content 20% PGMAc solution of the following copolymer

<Manufacturing of near-infrared absorbing composition for coating>
(Example 13)
The mixture having the following composition was uniformly stirred and mixed, 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 prepare a near-infrared absorbing composition. ..
Near-infrared absorbing pigment 1: 10.0 parts Resin type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Examples 14 to 41, Comparative Examples 12 to 22)
Hereinafter, near-infrared absorbing pigment, resin-type dispersant solution, binder resin solution, and solvent are absorbed in the same manner as the near-infrared absorbing composition (D-1) except that the composition and amount shown in Table 2 are changed. The sex compositions (D-2) to (D-40) were prepared.
As a blue pigment, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 1, as a green pigment, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63 was used.

<Evaluation of near-infrared absorbing composition for coating>
The near-infrared absorbing compositions (D-1 to 40) obtained in Examples and Comparative Examples were tested for dispersion stability, spectral characteristics, and resistance (light resistance, heat resistance) by the following methods. ⊚ is a very good level, 〇 + and ◯ are good levels, Δ is a practical level, and × is a level unsuitable for practical use. The results are shown in Table 3.

(Evaluation of dispersion stability)
The viscosity of the obtained near-infrared absorbing composition was measured and used as the initial viscosity. Further, an accelerated test was conducted at 40 ° C. for 7 days, and the accelerated viscosity with time was measured.
As a rate of change due to promotion
The accelerated aging viscosity / initial viscosity was calculated and evaluated according to the following criteria.
⊚: less than 1.05 ○: 1.05 or more, less than 1.10 Δ: 1.10 or more, less than 1.3 ×: 1.3 or more

(Evaluation of spectral characteristics 1)
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 dried 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 900 nm. The "average absorbance at 400 to 700 nm" when the absorbance at the maximum absorption wavelength was set to 1 was evaluated according to the following criteria. The maximum absorption wavelength of the near-infrared absorbing pigment [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 and the steeper the spectroscopy.
⊚: 0.05 or less ○ +: 0.05 or more and less than 0.075 〇: 0.075 or more and less than 0.1 Δ: 0.1 or more and less than 0.4 ×: 0.4 or more

(Spectroscopic evaluation 2)
With respect to the substrate obtained above, the minimum value of the absorbance at 400 nm to 650 nm was evaluated according to the following criteria when the minimum value of the absorbance at 650 nm to 800 nm was 1.
It should be noted that 650 nm to 800 nm is a wavelength region of light transmitted through a living body, which causes noise in biometric authentication and overflows in the living space. Therefore, the wavelength at which the absorbance is minimized in this region is the most transmitted wavelength of light that becomes noise. It becomes the wavelength to be used. The light used for sensing is in the wavelength region of 400 nm to 650 nm, and the wavelength at which the absorbance is minimized in this region is the wavelength at which the light used for sensing is most transmitted. Therefore, the above standard is an index of how to transmit the light to be sensed and cut noise.
⊚: 0.05 or less ○: 0.05 or more and less than 0.1 Δ: 0.1 or more and less than 0.4 ×: 0.4 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 90% or more and less than 95% ×: Residual rate is less than 90%

(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 90% or more and less than 95% ×: Residual rate is less than 90%

When the average primary particle size of the near-infrared absorbing pigment was 10 to 80 nm, the balance between dispersion stability, light resistance, and heat resistance was good. Moreover, even when an appropriate solvent treatment was performed, the balance between dispersion stability, light resistance, and heat resistance was good. With proper solvent treatment, the results of reverse phase liquid chromatography show that in the longest retention time under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as the mobile phase. The ratio of the peak area of the appearing peak is 60 to 7 of the sum of the peak areas of all the peaks derived from the near-infrared absorbing pigment.
It will be 8%.
When the average primary particle size is 10 to 80 nm and the analysis result of the reverse phase liquid chromatography is satisfied, the dispersion stability, the spectral characteristics, the light resistance, and the heat resistance are all good.
It was also confirmed that when the near-infrared absorbing pigment and the blue dye or the green dye are used in combination, the light of 650 nm to 800 nm, which is a noise in biometric authentication, is more blocked, and the light of 400 nm to 650 nm used for sensing is more transmitted. It was.

<Manufacturing of photosensitive near-infrared absorbing composition>
(Example 42)
After stirring and mixing the following mixture so as to be uniform, 1. Filtration with a 0 μm filter gave a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorbing composition (D-4): 50.0 parts binder resin solution: 7.5 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization started Agent (BASF Japan "OXE-02"): 1.5 parts PGMAc: 39.0 parts

(Examples 43 to 47 and Comparative Examples 23 to 25)
Hereinafter, the photosensitive near-infrared absorbing composition is the same as that of the photosensitive near-infrared absorbing composition (R-1) except that the near-infrared absorbing composition is changed to the type of the near-infrared absorbing composition shown in Table 3. Objects (R-2) to (R-9) were obtained.

<Evaluation of photosensitive near-infrared absorbing composition>
The photosensitive near-infrared absorbing compositions (R-1 to 8) obtained in Examples and Comparative Examples were tested for dispersion stability, spectral characteristics, and resistance (heat resistance, light resistance) by the following methods. It was. ⊚ is a very good level, 〇 + and ◯ are good levels, Δ is a practical level, and × is a level unsuitable for practical use. The results are shown in Table 4.

(Evaluation of dispersion stability)
The viscosity of the obtained photosensitive near-infrared absorbing composition was measured and used as the initial viscosity. Further, an accelerated test was conducted at 40 ° C. for 7 days, and the accelerated viscosity with time was measured.
As the rate of change due to acceleration, the viscosity with time for acceleration / initial viscosity was calculated and evaluated according to the following criteria. ⊚: less than 1.05 ○: 1.05 or more, less than 1.10 Δ: 1.10 or more, less than 1.3 ×: 1.3 or more

(Spectroscopic characterization 1)
The obtained photosensitive near-infrared absorbing composition was coated on a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater so as to have a thickness of 1.0 μm, and then 20 at 70 ° C. It was dried for a minute, exposed to ultraviolet rays with an integrated light amount of 150 mJ / cm2 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 300-900 nm. The "average absorbance at 400 to 700 nm" when the absorbance at the maximum absorption wavelength was set to 1 was evaluated according to the following criteria. The maximum absorption wavelength of the near-infrared absorbing pigment [A] coating film of the present invention exists in the near-infrared region (700 to 1000 nm). When this absorbance is 1, the smaller the absorbance at 400 to 700 nm, the better the absorption capacity in the near infrared region, and the steeper the spectrum.
⊚: 0.05 or less ○ +: 0.05 or more and less than 0.075 〇: 0.075 or more and less than 0.1 Δ: 0.1 or more and less than 0.4 ×: 0.4 or more

(Spectroscopic characterization 2)
With respect to the substrate obtained above, the minimum value of the absorbance at 400 nm to 650 nm was evaluated according to the following criteria when the minimum value of the absorbance at 650 nm to 800 nm was 1.
It should be noted that 650 nm to 800 nm is a wavelength region of light transmitted through a living body, which causes noise in biometric authentication and overflows in the living space. Therefore, the wavelength at which the absorbance is minimized in this region is the most transmitted wavelength of light that becomes noise. It becomes the wavelength to be used. The light used for sensing is in the wavelength region of 400 nm to 650 nm, and the wavelength at which the absorbance is minimized in this region is the wavelength at which the light used for sensing is most transmitted. Therefore, the above standard is an index of how to transmit the light to be sensed and cut noise.
⊚: 0.05 or less ○: 0.05 or more and less than 0.1 Δ: 0.1 or more and less than 0.4 ×: 0.4 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 90% or more and less than 95% ×: Residual rate is less than 90%

(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 90% or more and less than 95% ×: Residual rate is less than 90%

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 pigment is prepared by dispersing the near-infrared absorbing pigment using a resin-type dispersant having a dye-adsorbing group. The infrared absorbing composition was very excellent in spectral characteristics. In particular, it absorbs little in the visible region (400 nm to 700 nm), has excellent near-infrared absorption ability, has good spectral characteristics, and is also excellent in light resistance and heat resistance.
The average primary particle size of the near-infrared absorbing pigment is 10 to 80 nm, and by applying an appropriate solvent treatment, the analysis result of the reverse phase liquid chromatography shows that acetonitrile and water are used as mobile phases in a volume of 8: 2. When the ratio of the peak area of the peak appearing at the longest retention time is 60 to 78% of the total peak area of all the peaks derived from the near-infrared absorbing pigment under the condition of using the mixed solution mixed by the ratio, the dispersion is stable. The properties, spectral characteristics, light resistance, and heat resistance were all good.
It was also confirmed that when the near-infrared absorbing pigment and the blue dye or the green dye are used in combination, the light of 650 nm to 800 nm, which is a noise in biometric authentication, is more blocked, and the light of 400 nm to 650 nm used for sensing is more transmitted. It was.

<Manufacturing of near infrared cut filter>
[Examples 48 to 51]
The photosensitive near-infrared absorbing composition (R-1) of the present invention was coated on a glass substrate having a thickness of 1.1 mm with a spin coater, and heat-treated on a hot plate at 100 ° C. for 1 minute as a prebake.
Then, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio, Inc.), 100 μ
In order to form an m-square near-infrared absorption cut filter, pattern exposure was performed with an ^{exposure amount of 1000 mJ / cm 2 through a photomask.}
The exposed coating film was used as a developer using a 0.2 mass% 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 (F-1) after the heat treatment was 1.0 μm.
The photosensitive near-infrared absorbing composition (R-2, 3, 6) of the present invention is also a near-infrared cut filter (F-2, 3, 6) in the same manner as the near-infrared absorbing cut filter (F-1). ) Was obtained.

<Evaluation of near infrared cut filter>
The near-infrared cut filters (F-1 to 4) were tested for spectral characteristics and durability (heat resistance, light resistance) in the same manner as in the evaluation of the photosensitive near-infrared absorbing composition. The results are shown in Table 5.

The near-infrared cut filter produced in this way was extremely excellent in spectral characteristics. In particular, there was little absorption in the visible region (400 nm to 700 nm), the near-infrared absorbing ability was excellent, and the spectral characteristics were good. Furthermore, it is excellent in light resistance and heat resistance, and therefore, it can be said that it has excellent performance as a near-infrared cut filter.
Further, when the near-infrared absorbing pigment and the blue pigment or the green pigment are used in combination, the light of 650 nm to 800 nm, which becomes noise in biometric authentication, is further blocked and used for sensing 40.
It has been confirmed that light of 0 nm to 650 nm is more transmitted, and it can be said that it has excellent performance as a near-infrared cut filter for biometric authentication.

<Manufacturing of photosensitive near-infrared transmissive composition>
(Blue coloring composition)
The mixture having the following composition was uniformly stirred and mixed, 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 prepare a blue coloring composition.
C. I. Pigment Blue PB15: 6: 10.0 parts Resin-type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Purple coloring composition)
The mixture having the following composition was uniformly stirred and mixed, 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 prepare a purple colored composition.
C. I. Pigment Violet PV23: 10.0 parts Resin type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Yellow coloring composition)
The mixture having the following composition was uniformly stirred and mixed, 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 prepare a yellow colored composition.
C. I. Pigment Yellow PY139: 10.0 parts Resin type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Example 52)
After stirring and mixing the following mixture so as to be uniform, 1. Filtration with a 0 μm filter gave a photosensitive near-infrared transmissive composition (P-1).
Near-infrared absorbing composition (D-4): 10.0 parts blue pigment composition: 20.0 parts purple pigment composition: 10.0 parts yellow pigment composition: 10.0 parts binder resin solution: 7.5 parts Part photopolymerizable monomer (“Aronix M-402” manufactured by Toa Synthetic Co., Ltd.): 2.0 parts Photopolymerization initiator (“OXE-02” manufactured by BASF Japan): 1.5 parts PGMAc: 39.0 parts

(Examples 53 to 56 and Comparative Examples 26 to 28)
Hereinafter, the photosensitive near-infrared transmissive composition is changed to the type of the photosensitive near-infrared transmissive composition shown in Table 6, and the same as that of the photosensitive near-infrared transmissive composition (P-1) is obtained. Infrared transmissive compositions (P-2) to (P-8) were obtained.

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 2.0 μm, dried at 60 ° C. for 5 minutes, and then dried at 230 ° C. The substrate was prepared by heating for 5 minutes.
The function of the filter is, for example, whether or not near-infrared rays can be transmitted and whether or not light rays in other wavelength regions can be cut.
Hereinafter, the transmittance at 900 nm and 940 nm and the absorbency in the wavelength range of 400 to 800 nm were evaluated.

(Absorbability of 400 to 800 nm)
A transmission spectrum in the wavelength range of 400 to 800 nm was measured on the obtained substrate using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire region of 400 to 800 nm

(900nm transparency)
The transmittance of 900 nm was measured on the obtained substrate using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

(940 nm transparency)
The transmittance of the obtained substrate was measured at 940 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

(Light resistance test)
The obtained substrate was used as a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI).
") And left for 24 hours. At this time, the test was carried out with a wide band light having an irradiance of 47 mW / cm2 and 300 to 800 nm. Then, a transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire region of 400 to 800 nm (heat resistance) test)
The obtained substrate was additionally heated at 210 ° C. for 20 minutes as a heat resistance test. Then, a transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire region of 400 to 800 nm

It was confirmed that by containing both the near-infrared absorbing pigment and the dye that absorbs visible light of 400 to 700 nm, the light in the entire region of 400 to 800 nm is absorbed and the near infrared rays of 900 nm and 940 nm are transmitted.
In particular, the average primary particle size of the near-infrared absorbing pigment is 10 to 80 nm, and by appropriately treating with a solvent, the analysis result of the reverse phase liquid chromatography shows that acetonitrile and water are used as mobile phases at 8: 2. When the ratio of the peak area of the peak appearing in the longest holding time is 60 to 78% of the total peak area of all the peaks derived from the near-infrared absorbing pigment under the condition of using the mixed solution mixed in the volume ratio of. Absorption at 400 to 800 nm, transparency at 900 nm and 940 nm, light resistance, and heat resistance were all good.

<Manufacturing of near-infrared absorbing composition for molding>
<Thermoplastic resin (B)>
(B-1) Polyester MA-2101M (polyester resin, manufactured by Unitika Ltd., crystalline resin, melting point 264 ° C.)
(B-2) Amylan CM3001-N (polyamide resin, manufactured by Toray Industries, Inc., crystalline resin, melting point 265 ° C.)
(B-3) Iupiron S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics, amorphous resin, glass transition temperature 145 ° C)
(B-4) Topas (cycloolefin resin, manufactured by Polyplastics, amorphous resin, glass transition temperature 78 ° C)
(B-5) Apel (cycloolefin resin, manufactured by Mitsui Chemicals, amorphous resin, glass transition temperature 135 ° C)
(B-6) ULTEM (polyetherimide resin, manufactured by Saudi Basic Industry Corporation, amorphous resin, glass transition temperature 217 ° C)

(Example 57)
<Manufacturing of masterbatch>
One part of the near-infrared absorbing pigment 1 and 99 parts of the thermoplastic resin (B-3) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port, and melt-mixed at 300 ° C. After smelting, it was cut into pellets using a pelletizer to prepare a master batch (D-1).

<Film molding>
5 parts of the obtained masterbatch (D-1) was mixed with 95 parts of the thermoplastic resin (B-3) of the diluted resin, and the temperature was 300 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A film (X-1) having a thickness of 250 μm was formed by melting and mixing with.

(Examples 58 to 73, Comparative Examples 29 to 31)
Similar to Example 57, films (X-2) to (X-17) and (XY-1) to (XY-3) having a thickness of 250 μm were molded using the materials shown in Table 7. The following compounds were used.

(Near infrared absorption)
For the obtained film, the absorption spectrum in the wavelength range of 400 to 1000 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), and near-infrared absorption was performed by the absorbance at the maximum absorption wavelength of 700 to 1000 nm. The ability was evaluated according to the following criteria.
◯: Absorbance at maximum absorption wavelength is 1.0 or more Good Δ: Absorbance at maximum absorption wavelength is 0.5 or more and less than 1.0 Practical range ×: Absorbance at maximum absorption wavelength is less than 0.5, 0.1 or more Practical use Impossible XX: Absorbance at the maximum absorption wavelength is less than 0.1 Practical impracticality The above judgments in the practical range and impracticality for the results of 〇 to XX are applied in the same manner below.

(Invisibility)
"Average absorbance at 400 to 700 nm" when the absorbance at the maximum absorption wavelength of 700 to 1000 nm is standardized to 1 using the absorption spectrum in the wavelength range of 400 to 1000 nm obtained in the near infrared absorption test. Invisibility was evaluated according to the following criteria.
◯: Less than 0.05 Δ: 0.05 or more, less than 0.1 ×: 0.1 or more

<Transparency>
The transparency of the obtained film was visually evaluated.
〇: No turbidity is observed.
Δ: Some turbidity is observed.
X: Clearly turbidity is observed.

<Light resistance>
A test film was prepared by the same procedure as the near-infrared absorption evaluation, placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), and the irradiance was 47 mW / cm ² , 30.
It was irradiated with a wide band of light of 0 to 800 nm and left for 24 hours. Next, the test film was taken out, the absorbance of the test film at the maximum absorption wavelength was measured, the residual ratio to the absorbance 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 90% or more Δ: Residual rate is 85% or more and less than 90% ×: Residual rate is less than 85%,

The average primary particle size of the near-infrared absorbing pigment is 10 to 80 nm, and by applying an appropriate solvent treatment, the analysis result of the reverse phase liquid chromatography shows that acetonitrile and water are used as mobile phases in a volume of 8: 2. When the ratio of the peak area of the peak appearing in the longest holding time is 60 to 78% of the total peak area of all the peaks derived from the near-infrared absorbing pigment under the condition of using the mixed solution mixed by the ratio, the near-infrared ray is used. Absorption, invisibility, transparency, and light resistance were all good.

<Manufacturing of near-infrared transmissive composition for molding>
(Example 74)
<Manufacturing of masterbatch>
1 part of near-infrared absorbing pigment 2, 1 part of pigment blue 15: 3, 1 part of pigment yellow 147, 1 part of solvent red 52, 96 parts of thermoplastic resin (B-1) from the same supply port screw diameter It was put into a 30 mm twin-screw extruder (manufactured by Japan Steel Works, Ltd.), melt-kneaded at 300 ° C., and then cut into pellets using a pelletizer to prepare a master batch (DD-1).

<Film molding>
5 parts of the obtained masterbatch (DD-1) was mixed with 95 parts of the thermoplastic resin (B-1) of the diluted resin, and the temperature was 300 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A film (XX-1) having a thickness of 250 μm was formed by melting and mixing with.

(Examples 75 to 79, Comparative Examples 32 to 34)
In the same manner as in Example 74, films (XX-2) to (XX-6) and (XXX-1) to (XXY-3) having a thickness of 250 μm were formed using the materials shown in Table 7.

The suitability of the near-infrared filter was evaluated for the obtained film. The function of the filter is, for example, whether or not near-infrared rays can be transmitted and whether or not light rays in other wavelength regions can be cut.
Hereinafter, the transmittance at 900 nm and 940 nm and the absorbency in the wavelength range of 400 to 800 nm were evaluated.

(Absorbability of 400 to 800 nm)
The transmission spectrum of the obtained film in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire region of 400 to 800 nm

(900nm transparency)
The transmittance of the obtained film was measured at 900 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

(940 nm transparency)
The transmittance of the obtained film was measured at 940 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

(transparency)
The transparency of the obtained film was visually evaluated.
〇: No turbidity is observed.
Δ: Some turbidity is observed.
X: Clearly turbidity is observed.

(Light resistance)
The obtained film is used as a light resistance tester (“SUNTEST CP” manufactured by TOYOSEIKI).
It was placed in S + ”) and left for 24 hours. At this time, the test was carried out with a wide band light having an irradiance of 47 mW / cm2 and 300 to 800 nm. Then, a transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire region of 400 to 800 nm

From the results in Table 8, it was confirmed that by containing both the near-infrared absorbing pigment and the dye that absorbs visible light at 400 to 700 nm, it absorbs light in the entire 400 to 800 nm region and transmits near infrared rays at 900 nm and 940 nm. Was done.
The average primary particle size of the near-infrared absorbing pigment is 10 to 80 nm, and by applying an appropriate solvent treatment, the analysis result of the reverse phase liquid chromatography shows that acetonitrile and water are used as mobile phases in a volume of 8: 2. When the ratio of the peak area of the peak appearing in the longest holding time is 60 to 78% of the total peak area of all the peaks derived from the near-infrared absorbing pigment under the condition of using the mixed solution mixed by the ratio, the near-infrared ray is used. Absorption, invisibility, transparency, and light resistance were all good.

Claims (6)

A near-infrared absorbing pigment containing a compound represented by the following general formula (1) and an isomer thereof.
The average primary particle size of the near-infrared absorbing pigment is 10 to 80 nm.
The analysis result of the near-infrared absorbing pigment using reverse phase liquid chromatography shows the peak that appears at the longest retention time under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as the mobile phase. A near-infrared absorbing pigment in which the ratio of the peak area is 60 to 78% of the total of the peak areas of all the peaks derived from the near-infrared absorbing pigment.
General formula (1)

(X _{1 to} X ₆ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁ R ₂ ,- COOR ₁ , -CONR ₁ R ₂ , represent a nitro group, a cyano group, and a halogen atom. R ₁ and R ₂ independently represent an alkyl group that may have a hydrogen atom and a substituent. Also, X ₁ In ~ X ₆ , substituents may be bonded to each other to form a ring, _{except for those in which X 1 to} X ₄ are all hydrogen atoms.) A near-infrared absorbing composition comprising the near-infrared absorbing pigment according to claim 1 and a resin-type dispersant. The near-infrared absorbing composition according to claim 2, further comprising a photopolymerizable monomer. A near-infrared absorbing composition according to claim 1, which is a melt-kneaded product of the near-infrared absorbing pigment and a thermoplastic resin. A near-infrared cut filter formed from the near-infrared absorbing composition according to any one of claims 2 to 4. A near-infrared ray transmitting filter formed from the near-infrared ray absorbing composition according to any one of claims 2 to 4.