JP7512673B2 - Infrared-transmitting coloring composition, infrared filter, infrared camera, and infrared sensor - Google Patents

Description

The present invention relates to an infrared-transmitting coloring composition using an organic dye, an infrared-transmitting filter, an infrared camera, and an infrared sensor. The present invention relates to an infrared-transmitting coloring composition used in the manufacture of an infrared-transmitting filter, and an infrared-transmitting filter formed using the same for use in an infrared-transmitting filter for solid-state imaging devices, a filter for inspection cameras such as near-infrared cameras, surveillance cameras, vehicle-mounted cameras, medical cameras, and inspection/analysis cameras, a temperature sensor, a distance sensor, a medical sensor, a touch sensor for a display, and a sensor using infrared light such as a biometric authentication sensor, which are provided in optical systems.

In various optical devices, a light separation function that selectively transmits light of a specific wavelength is required. One method to achieve this is to use the interference of a dielectric multilayer thin film to transmit only light of a specific wavelength (see Patent Document 1). This method has many advantages such as reliability and freedom of wavelength selection design, but one of its disadvantages is its angle dependency. Since the interference characteristics are determined by the optical film thickness, it is known that if the effective optical path length through which light passes changes due to oblique incidence, the wavelength of the transmitted light changes accordingly, making it impossible to obtain the desired filter characteristics.
In order to solve this problem, a filter using a method of utilizing light absorption has been proposed. For example, colored glass in which a metal ion dye is dispersed in inorganic glass as a light absorbing substance is known (see Patent Document 2 and Patent Document 3). This method is known to have problems such as the harmfulness of the coloring component (cadmium, etc.), thickening of the optical film due to the use of glass, and workability and weight reduction. Therefore, from the viewpoint of solving these problems, a method of forming a light selective filter film using a dye on a substrate such as a resin film is being developed. Among them, there is an increasing need for a filter that blocks light in the visible light region and transmits only light in the near infrared region. As a coloring composition for an infrared transmission filter, a combination of multiple organic pigments is known (for example, Patent Documents 4, 5, 6, and 7), but there is a problem that it is difficult to ensure sufficient quality in characteristics such as the stability of the dispersion because multiple organic pigments are combined.

JP 2001-331965 A JP 2004-250285 A JP 2003-146695 A JP 2013-077009 A JP 2014-130338 A JP 2015-63593 A JP 2016-177273 A

The present invention aims to provide an infrared-transmitting coloring composition and an infrared-transmitting photosensitive coloring composition that have excellent hiding properties in the visible light region with wavelengths of 400 to 700 nm, high transmittance in the near-infrared region with wavelengths of 800 nm or more, and exhibit excellent properties such as low initial viscosity, excellent coatability, high heat resistance, high solvent resistance, low rate of foreign matter generation, high filterability, and high storage stability, as well as an infrared-transmitting filter using the same.

As a result of intensive research conducted by the present inventors to solve the above problems, they discovered that an infrared-transmitting coloring composition containing a colorant (A), a resin-type dispersant (B), and an organic solvent, in which the total of 100% by mass of the colorant (A) contains specific ratios of C.I. Pigment Blue 15:6, C.I. Pigment Yellow 139, and C.I. Pigment Violet 23, exhibits excellent properties, and the present invention was made based on this finding.

That is, the present invention relates to an infrared-transmitting coloring composition that contains a colorant (A), a resin-type dispersant (B), and an organic solvent, and that contains 45 to 60 mass% of C.I. Pigment Blue 15:6, 10 to 30 mass% of C.I. Pigment Yellow 139, and 15 to 35 mass% of C.I. Pigment Violet 23, based on a total of 100 mass% of the colorant (A), and that contains an acidic resin-type dispersant (B1) having an acid value of 30 to 80 mgKOH/g.

The present invention also relates to an infrared transmitting coloring composition comprising an acidic resin-type dispersant (B1) which is a reaction product of polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a polymer having a hydroxyl group at at least one end and a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride and/or a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride.

The present invention also relates to the infrared transmitting coloring composition, in which the acidic resin-type dispersant (B1) contains an acidic resin-type dispersant (B1-1) having an acid value of 30 to 50 mgKOH/g, and an acidic resin-type dispersant (B1-2) having an acid value of 55 to 80 mgKOH/g.

The present invention also relates to the infrared transmitting coloring composition, which further contains a dye derivative (C).

The present invention also relates to the infrared transmitting coloring composition, in which the dye derivative (C) is a phthalocyanine dye derivative.

The present invention also relates to the infrared transmitting coloring composition, which further contains a photopolymerizable monomer and/or a photopolymerization initiator.

The present invention also relates to an infrared filter produced using the infrared-transmitting coloring composition.

The present invention also relates to an infrared camera equipped with the above-mentioned infrared filter.

The present invention also relates to an infrared sensor equipped with the above-mentioned infrared filter.

The present invention can provide an infrared-transmitting coloring composition and an infrared-transmitting photosensitive coloring composition that exhibit excellent properties such as low initial viscosity, excellent coating properties, high heat resistance, high solvent resistance, low rate of foreign matter generation, high filterability, and high storage stability, as well as an infrared-transmitting filter using the same.

The constituent features of the present invention will be described in detail below.
In the present application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", or "(meth)acrylate" refer to "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", or "acrylate and/or methacrylate", respectively. In addition, "C.I." in this specification means Color Index (C.I.).

The infrared-transmitting coloring composition of the present invention is an infrared-transmitting coloring composition containing a colorant (A), a resin-type dispersion resin (B), a dye derivative (C), and an organic solvent, and is characterized in that it contains 45 to 60 mass% of C.I. Pigment Blue 15:6, 10 to 30 mass% of C.I. Pigment Yellow 139, and 15 to 35 mass% of C.I. Pigment Violet 23, out of a total of 100 mass% of the colorant (A).

<Infrared transmitting coloring composition>
<Colorant (A)>
The colorant (A) in the present invention contains 45 to 60% by mass of C.I. Pigment Blue 15:6, 10 to 30% by mass of C.I. Pigment Yellow 139, and 15 to 35% by mass of C.I. Pigment Violet 23. This allows the colorant to exhibit excellent shielding properties without transmitting light in the visible region. In addition, the colorant has low viscosity and exhibits excellent effects in terms of high storage stability, heat resistance, foreign matter resistance, solvent resistance, and filterability. The colorant may also contain other colorants such as organic pigments and dyes.
[Other colorants]
The infrared transmitting coloring composition of the present invention can be used by further adding a pigment. As the pigment, an organic or inorganic pigment can be used alone or in combination of two or more kinds. The pigment is preferably a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the infrared transmitting coloring composition are shown below by color index numbers.

The red coloring material may be, for example, C.I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 97, 122, 123, 146, 149, 150, 168, 169, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215 , 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. As an orange colorant, an orange pigment such as C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 can be used. As a yellow colorant, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126 , 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or 231 can be used.

As the green coloring material, for example, green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 62, and 63 can be used. It is also preferable to use aluminum phthalocyanine pigments, and aluminum phthalocyanine pigments such as those described in JP-A-2004-333817 and Japanese Patent No. 4893859 can also be used.

As the blue colorant, for example, blue pigments such as C.I. Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, and 64 can be used. As the purple colorant, purple pigments such as C.I. Pigment Violet 1, 19, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination. It is also preferable to use aluminum phthalocyanine pigments, such as those described in JP-A-2004-333817 and Japanese Patent No. 4893859.

Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between saturation and brightness.

Other colorants can be used alone or in combination of two or more types.

Dyes can also be used in the present invention. Examples include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, and triphenylmethane dyes. When using dyes, it is effective to incorporate the dye into the resin using the polar group of anionic or cationic dyes to impart solubility in organic solvents.

Specific examples of usable anionic dyes are shown below with their color index numbers.

Red dyes include C.I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 5 6, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131 , 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 2 52, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc.

Also, C.I. Direct Red 1, 2, 2:1, 4, 5, 6, 7, 8, 10, 10:1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26:1, 28, 29, 31, 33, 33:1, 34, 35, 36, 37, 39, 42, 43, 43:1, 44, 46, 49, 52 , 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 11 6, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 16 9, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

Yellow dyes include C.I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68 , 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc.

C.I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc. can also be used.

Examples of orange dyes include C.I. Acid Orange 1, 1:1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20:1, 22, 23, 24, 24:1, 25, 27, 28, 28:1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, and 138.
Also usable are C.I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29:1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102:1, 104, 108, 112, 114, and the like.

Blue dyes include C.I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55 , 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204 , 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, etc.

Also, C.I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98:1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130 :1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158:1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263, etc. can also be used.

Purple dyes include C.I. Acid Violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc.

Also, C.I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc. can be used.

Examples of green dyes include C.I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25:1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, and 95.
Also usable are C.I. Direct Green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, and the like.

Specific examples of cationic dyes that can be used are shown below with their color index numbers.

Examples of triphenylmethane cationic dyes include C.I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 26 (Victoria Blue B conc.), C.I. Basic Green 1 (Brilliant Green GX), and 4 (Malachite Green).

Examples of xanthene cationic dyes include C.I. Basic Red 1 (Rhodamine 6G, 6GCP), 3, and 8 (Rhodamine G). Of these, it is preferable to use C.I. Basic Red 1.

Examples of cyanine cationic dyes include C.I. Basic Yellow 11, 21, and 28.

Anthraquinone cationic dyes include C.I. Basic Blue 72, flavin cationic dyes include C.I. Basic Yellow 1, auramine cationic dyes include C.I. Basic Yellow 2 and 3, safranine cationic dyes include C.I. Basic Red 2, acridine cationic dyes include C.I. Basic Yellow 5, oxazine cationic dyes include C.I. Basic Blue 3, thiazine cationic dyes include C.I. Basic Blue 24, and methylene blue cationic dyes include C.I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), 25 (Basic Blue GO), and 24 (New Methylene Blue NX). Among them, it is preferable to use C.I. Basic Yellow 1, 9, 24, and 25.

Examples of squarylium-based cationic dyes include (SQ-1K) described in JP-A-2017-114956.
<Resin-type dispersant (B)>

The resin-type dispersant (B) in the present invention is characterized by containing an acidic resin-type dispersant (B1) with an acid value of 30 to 80 mgKOH/g. This allows for excellent shielding properties without light transmission in the visible region. In addition, it has low viscosity and produces excellent effects in terms of high storage stability, heat resistance, foreign matter resistance, solvent resistance, and filterability. In addition, the resin-type dispersant may contain other resin-type dispersants, such as acidic resin-type dispersants with an acid value other than 30 to 80 mgKOH/g, and basic resin-type dispersants with an amine value.

Furthermore, in the present invention, it is preferable to use in combination, in the acidic resin-type dispersant (B1), an acidic resin-type dispersant (B1-1) having an acid value of 30 to 50 mgKOH/g and an acidic resin-type dispersant (B1-1) having an acid value of 55 to 80 mgKOH/g. By using these in combination, the adsorption balance of the resin-type dispersant to the pigment, which is the colorant, and the dye derivative is improved, and excellent properties are shown in terms of viscosity stability over time and filterability.

The acidic dispersant will be described in detail below.
[Acidic Resin-Type Dispersant (B1)]
Examples of acidic dispersants include those having a carboxyl group, a sulfone group, a phosphate group, etc. in the resin, but from the viewpoint of viscosity stability and heat resistance, a resin-type dispersant having a carboxyl group is preferred. The shape of the resin-type dispersant having a carboxyl group includes a straight-chain resin-type dispersant and a comb-shaped resin-type dispersant.

Furthermore, the acidic resin-type dispersant (B1) in the present invention is preferably a comb-shaped resin-type dispersant which is a reaction product (S1) between a polymer having a hydroxyl group at at least one terminal and a tetracarboxylic acid dianhydride and/or a reaction product (S2) obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic acid dianhydride.
<Straight-chain acidic resin-type dispersant>
All linear resin-type dispersants having a carboxyl group can be produced using known methods, and can be synthesized using known methods such as those shown in, for example, JP-A-2009-251481, JP-A-2007-23195, and JP-A-1996-143651. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group can be produced by adding a tricarboxylic acid anhydride to the hydroxyl group of a vinyl polymer having one hydroxyl group at one end as a raw material.
<Comb-shaped acidic resin-type dispersant>
The carboxyl group-containing comb-shaped resin-type dispersants (S1) and (S2) are described below.
[Resin-type dispersant (S1)]
The acidic resin-type dispersant (S1) can be produced by known methods such as those described in WO2008/007776, JP2008-029901A, and JP2009-155406A.
Examples of such a resin-type dispersant include a resin-type dispersant which is a reaction product between a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, and a resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride.

[Resin-type dispersant (S2)]
The acidic resin-type dispersant (S2) can be produced by known methods such as those described in WO2008/007776, JP2009-155406A, JP2010-185934A, and JP2011-157416A.
For example, there may be mentioned a resin-type dispersant obtained by reacting, in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, a resin-type dispersant having a side chain formed by polymerizing an ethylenically unsaturated monomer having a thermal crosslinking group such as a hydroxyl group, a t-butyl group or an oxetane skeleton, or a blocked isocyanate, with an ethylenically unsaturated monomer having an isocyanate group at the hydroxyl group on the side chain.

Furthermore, in the present invention, the following dispersants may be used.
[Other resin-type dispersants]
Other resin-type dispersants may be any dispersant that has a colorant affinity site having the property of adsorbing to an added colorant and a site compatible with the colorant carrier, and that functions to adsorb to an added colorant and stabilize the dispersion in the colorant carrier. Specific examples of the dispersant that may be used include polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylates, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylate esters, and the like. Examples of the dispersants that can be used include modified polyacrylates, amides formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group and salts thereof, and other oil-based dispersants; water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphates. These can be used alone or in combination of two or more.
Examples of polymer dispersants having a basic functional group include nitrogen atom-containing graft copolymers, and nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in their side chains.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2156, 2157, 2158, 2159, 2160, 2161, 2162, 2163, 2164, 2165, 2166, 2167, 2168, 2169, 2170, 2171, 2172, 2173, 2174, 2175, 2176, 2177, 2178, 2179, 2180, 2181, 2182, 2183, 2184, 2185, 2186, 2187, 2188, 2189, 2200, 2201, 2202, 2203, 2204, 2205, 2206, 2207, 2208, 2209, 2210, 2211, 2212, 2213, 2214, 2215, 221 163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 2600 manufactured by Nippon Lubrizol Co., Ltd. 0, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 440 manufactured by BASF 1, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajispar PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

The content of the resin-type dispersant (B) is preferably 5 to 200 parts by mass relative to the total amount of the colorant (A), and more preferably 10 to 100 parts by mass from the viewpoint of film-forming properties.

<Dye Derivative (C)>
In the present invention, it is preferable to use a dye derivative from the viewpoint of agglomerated foreign matter. As the dye derivative (C) used in the present invention, a dye derivative having a functional group introduced into a dye matrix skeleton, which is an organic dye residue, can be used. These can be classified into acidic, basic, and neutral depending on the chemical structure of the functional group introduced into the dye matrix skeleton. For example, acidic dye derivatives include compounds having acidic substituents such as sulfo groups, carboxy groups, and phosphate groups, and amine salts thereof. Basic dye derivatives include compounds having basic substituents such as sulfonamide groups and tertiary amino groups at the terminals. Neutral dye derivatives include compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Examples of the dye matrix skeleton that is an organic dye residue include diketopyrrolopyrrole pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. Among these, a phthalocyanine matrix skeleton is more preferable from the viewpoint of suppressing generation of foreign matter over time.
Specifically, diketopyrrolopyrrole dye derivatives are described in JP2001-220520A, WO2009/081930, WO2011/052617, WO2012/102399, and JP2017-156397A. Phthalocyanine dye derivatives are described in JP2007-226161A, W2016/163351A, JP2017-165820A, and Japanese Patent No. 5753266A. Anthraquinone dye derivatives are described in JP2007-226161A, WO2016/163351A, JP2017-165820A, and Japanese Patent No. 5753266A. JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet; quinacridone dye derivatives are shown in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine dye derivatives are shown in JP-A-2011-162662; thiazine indigo dye derivatives are shown in JP-A-2007-314785 As triazine-based dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, as benzisoindole-based dye derivatives, JP-A-2009-57478, as quinophthalone-based dye derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-2 Examples of naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the dye matrix skeleton, which is the above-mentioned organic dye residue, is synonymous with the dye derivative.
These dye derivatives can be used alone or in combination of two or more kinds.

The content of the dye derivative (C) is preferably 1 to 50 parts by mass, more preferably 1 to 45 parts by mass, and even more preferably 1 to 40 parts by mass, per 100 parts by mass of the colorant.

<Minification of pigment>
When the colorant used in the infrared transmitting coloring composition of the present invention is a pigment, it is preferable to use it after it has been finely divided from the viewpoint of transmittance in the infrared region. The method of finely dividing is not particularly limited, and examples thereof include wet grinding, dry grinding, and dissolution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the pigment as determined by TEM (transmission electron microscope) is preferably 5 to 90 nm, and more preferably 10 to 70 nm. If the pigment has an appropriate particle size, dispersibility is improved, and the contrast ratio is also improved.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heating using a batch or continuous mixer such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or planetary mixer, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferable because it is inexpensive. From the viewpoints of both processing efficiency and production efficiency, it is preferable to use 50 to 2,000 parts by mass of water-soluble inorganic salts per 100 parts by mass of pigment, and more preferably 300 to 1,000 parts by mass.

The water-soluble organic solvent is a solvent that moistens the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, 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. may be used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

When the pigment is subjected to salt milling, a resin may be added as necessary. There are no particular limitations on the type of resin used, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. may be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the organic solvents mentioned above. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of the pigment.

<Binder resin>
In the present invention, a binder resin can be used in combination to impart a function such as developability to the dispersion. The binder resin is a compound necessary for film formation. Examples of the binder resin include thermoplastic resins, thermosetting resins, and active energy ray curable resins having ethylenically unsaturated double bonds. It is also preferable that the active energy ray curable resin has thermosetting properties. From the viewpoint of developability, the binder resin is preferably an alkali-soluble resin.

The content of the binder resin in the infrared transmitting coloring composition of the present invention is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of the colorant (A). When an appropriate amount is contained, film formation becomes easy and good color characteristics are easily obtained.

Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

The binder resin should preferably have a spectral transmittance of 80% or more, and more preferably 95% or more, over the entire wavelength range of 400 to 700 nm in the visible light region.

The alkali-soluble resin is a resin having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/maleic acid (anhydride) copolymer. Among these, an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, which have improved heat resistance and transparency, are preferred, and an acrylic resin having an acidic group is more preferred.

To impart photoreactivity to the alkali-soluble resin, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated active double bond. This improves the solvent resistance of the cured coating.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenically double bonds have been introduced by the following methods (a) to (c).

[Method (a)]
Method (a) can be exemplified by a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer, and then a polybasic acid anhydride is reacted with the resulting hydroxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, for example to increase the number of carboxyl groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride, which has an unsaturated ethylenic double bond, is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

[Method (b)]
As a method similar to the method (a), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxyl group.
In this method, a larger amount of hydroxyl groups derived from the unsaturated ethylenic monomer having an epoxy group is generated compared to the method (a). When the resin having a cationic group in the side chain used for obtaining the salt forming compound of the present invention contains an oxetanyl group or a t-butyl group as a thermally crosslinkable functional group, it is preferable to use the resin obtained by the method (b) as the binder resin because it exhibits higher heat resistance.

[Method (c)]
Method (c) includes a method in which an unsaturated ethylenic monomer having a hydroxyl group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxyl group or with another monomer, and the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

The unsaturated ethylenic monomer having a hydroxyl group includes hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid, etc., may also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited to these and two or more types can be used in combination.

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

When the binder resin is used as a photosensitive composition, it is preferable to use a resin with an acid value of 20 to 300 mgKOH/g from the viewpoints of dispersibility, penetration, developability, and heat resistance of the pigment and salt-forming compound. If the acid value is less than 20 mgKOH/g, the solubility in the developer is poor, making it difficult to form a fine pattern. If the acid value exceeds 300 mgKOH/g, the fine pattern may not remain.

The binder resin is preferably used in an amount of 30 parts by mass or more per 100 parts by mass of colorant (A) because of its good film-forming properties and various resistances, and is preferably used in an amount of 500 parts by mass or less because the colorant concentration is high and good color characteristics can be expressed.

(Thermosetting Compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin, which is the binder resin. Examples of the thermosetting compound include epoxy compounds and/or resins, oxetane compounds and/or resins, benzoguanamine compounds and/or resins, rosin-modified maleic acid compounds and/or resins, rosin-modified fumaric acid compounds and/or resins, melamine compounds and/or resins, urea compounds and/or resins, and phenolic compounds and/or resins.

<Organic Solvent>
The organic solvent is used to assist the dispersion of the colorant and to appropriately adjust the viscosity of the coloring composition.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 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-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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 monotertiary 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, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol ethanol, 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

Among these, it is preferable to use glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol, diacetone alcohol, and 3-methoxybutanol, and ketones such as cyclohexanone, because these have good dispersibility and penetration of the colorant and good applicability of the coloring composition.

Organic solvents can be used alone or in combination of two or more types.

The organic solvent is preferably used in an amount of 500 to 4,000 parts by mass per 100 parts by mass of colorant (A), since it adjusts the viscosity of the coloring composition to an appropriate level and enables the formation of a colored film with the desired uniform thickness.

<Photopolymerizable Monomer>
The infrared transmitting coloring composition of the present invention can be used as an infrared transmitting photosensitive coloring composition by further adding a photopolymerizable monomer and/or a photopolymerization initiator. The photopolymerizable monomer that may be added to the infrared transmitting coloring composition of the present invention includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl. Examples of the acrylates include, but are not limited to, ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, urethane acrylate, and various other acrylates and methacrylates, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

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

The content of the photopolymerizable monomer is preferably 5 to 400 parts by mass, and more preferably 10 to 300 parts by mass, per 100 parts by mass of colorant (A). When an appropriate amount is added, the photocurability and developability are further improved.

<Photopolymerization initiator>
The infrared transmitting coloring composition of the present invention can contain a photopolymerization initiator. This facilitates photocuring when forming a filter segment by photolithography. The amount of the photopolymerization initiator is preferably 5 to 200 mass %, more preferably 10 to 150 mass %, based on 100 parts by mass of the coloring agent (A). When an appropriate amount is added, the photocurability and developability are further improved.

The photopolymerization initiator is, for example, an acetophenone-based compound such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin compounds such as benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 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-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; triazine-based compounds such as 1-(N-4-benzoylphenyl-carbazol-3-yl)- Oxime ester compounds such as butane-1,2-dione-2-oxime-O-acetate, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; Borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds, etc., are used.

Photopolymerization initiators can be used alone or in combination of two or more types.

The content of the photopolymerization initiator is preferably 5 to 200% by mass, and more preferably 10 to 150% by mass, relative to 100 parts by mass of colorant (A). When an appropriate amount is used, the photocuring property and developability are further improved.

<Sensitizer>
In the infrared transmitting coloring composition of the present invention, a photopolymerization initiator and a sensitizer can be used in combination.
Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triphenylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of such compounds include compounds having the formula (I), a phthalocyanine derivative, a tetraazaporphyrazine derivative, a tetraquinoxalylporphyrazine derivative, a naphthalocyanine derivative, a subphthalocyanine derivative, a pyrylium derivative, a thiopyrylium derivative, a tetraphylline derivative, an annulene derivative, a spiropyran derivative, a spirooxazine derivative, a thiospiropyran derivative, a metal arene complex, an organic ruthenium complex, or a Michler's ketone derivative, an α-acyloxy ester, an acylphosphine oxide, a methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.

Further examples include sensitizers described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), and "Special Functional Materials" edited by Chuzo Ikemori et al. (CMC, 1986).

Sensitizers can be used alone or in combination of two or more types.

The amount of sensitizer used is preferably 3 to 60% by weight, more preferably 5 to 50% by weight, based on 100 parts by weight of the photopolymerization initiator. Using an appropriate amount will further improve photocurability and developability.

<Amine compounds>
The infrared transmitting coloring composition of the present invention may contain an amine compound, which is capable of reducing dissolved oxygen.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<Leveling Agent>
The infrared transmitting coloring composition of the present invention may contain a leveling agent, which improves the coatability and the surface smoothness of the coating film.
Examples of the leveling agent include, in addition to dimethylsiloxane, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.
The dimethylsiloxane is preferably a dimethylsiloxane having a polyether structure and/or a polyester structure in the main chain. Commercially available products of dimethylsiloxane having a polyether structure in the main chain include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207 manufactured by Dow Corning Toray Co., Ltd., and BYK-333 manufactured by BYK-Chemie Co., Ltd. Commercially available products of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd.

Anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphate esters, etc.

Cationic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants that are added supplementarily to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

Leveling agents can be used alone or in combination of two or more types.

The content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the coloring composition.

<Epoxy Compound>
The infrared transmitting coloring composition of the present invention can contain an epoxy compound.

Examples of epoxy compounds include phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

Commercially available phenol novolac epoxy resins include, for example, Epicron N-740, Epicron N-770, and Epicron N-775 manufactured by DIC Corporation, D.E. N438 manufactured by Dow Chemical Company, RE-306 manufactured by Nippon Kayaku Co., Ltd., and jER152 and jER154 manufactured by Mitsubishi Chemical Corporation.

Commercially available cresol novolac epoxy resins include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, Epicron N-665-EXP, and Epicron N-672-EXP manufactured by DIC Corporation, EOCN-102S, EOCN-103S, and EOCN-104S manufactured by Nippon Kayaku Co., Ltd., UVR-6650 manufactured by Union Carbide Corporation, and ESCN-195 manufactured by Sumitomo Chemical Co., Ltd.

Commercially available trishydroxyphenylmethane epoxy resins include EPPN-503, EPPN-502H, and EPPN-501H manufactured by Nippon Kayaku Co., Ltd., TACTIX-742 manufactured by Dow Chemical Co., and jER E1032H60 manufactured by Mitsubishi Chemical Corporation.

Commercially available dicyclopentadiene phenol type epoxy resins include Epicron EXA-7200 manufactured by DIC Corporation and TACTIX-556 manufactured by Dow Chemical Company.

Commercially available bisphenol-type epoxy resins include bisphenol-A type epoxy resins such as jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Corporation, D.E.R-331 manufactured by Dow Chemical Company, and YD-8125 manufactured by Shin-Nihon Kagaku Epoxy Manufacturing Co., Ltd., and bisphenol-F type epoxy resins such as UVR-6490 manufactured by Union Carbide Corporation and YDF-8170 manufactured by Shin-Nihon Kagaku Epoxy Manufacturing Co., Ltd.

Commercially available biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and bixylenol-type epoxy resins such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation.

Commercially available bisphenol A novolac epoxy resins include Epicron N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

Commercially available naphthalene skeleton-containing epoxy resins include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., and EXA-4750 manufactured by DIC Corporation.

Commercially available alicyclic epoxy resins include Seikicide 2021P, 2081, 2000, Epolead PB3600, PB4700, GT401, EHPE-3150, and Cyclomer M100 manufactured by Daicel Corporation.

Commercially available heterocyclic epoxy resins include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

Epoxy compounds can be used alone or in combination of two or more types.

The content of the epoxy compound is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the infrared transmitting coloring composition. When an appropriate amount is contained, heat resistance is further improved.

<Oxetane Compound>
The infrared transmitting coloring composition of the present invention may contain an oxetane compound. The oxetane compound may be a compound having an oxetane group that is monofunctional, bifunctional, or trifunctional or higher.

Examples of compounds with a monofunctional oxetane group include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane. Commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Examples of compounds with bifunctional oxetane groups include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, and di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane. , 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl 1,4-bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO) modified Examples of such products include bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether. Commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and OXT-221 manufactured by Toagosei.

Examples of compounds having three or more functional oxetane groups include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples include taerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

Oxetane compounds can be used alone or in combination of two or more types.

The content of the oxetane compound is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the coloring composition. When an appropriate amount is contained, heat resistance is further improved.

<Curing agent, curing accelerator>
The infrared transmitting coloring composition of the present invention may contain a curing agent and a curing accelerator to assist the curing of the thermosetting resin.
Examples of the curing agent include phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred.
Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, etc.), and the like. imidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 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.).

The hardener and hardening accelerator can be used alone or in combination of two or more types.

The amount of the curing agent and curing accelerator used is preferably 0.01 to 15 mass% per 100 mass parts of the thermosetting resin.

<Ultraviolet absorbing agent>
The infrared transmitting coloring composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

The content of the ultraviolet absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the ultraviolet absorber being 100% by mass. This allows a high degree of compatibility between photosensitivity and resolution. Note that when the coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

The total content of the photopolymerization initiator and the UV absorber is preferably 1 to 20% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the UV absorber is less than the above, adhesion may weaken and pixel peeling may occur, and if it is more than the above, the sensitivity may be too high, resulting in poor resolution.

Examples of benzotriazole-based organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, a mixture of octyl-3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and straight chain alkyl ester compound, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

Commercially available products include BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", "TINUVIN 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", and "TINUVIN 1130", ADEKA's "ADEKA STAB LA-29", and Otsuka Chemical's "RUNA-93".

Examples of triazine-based organic compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine, etc.

Commercially available products include "KEMISORB 102" manufactured by Chemipro Chemicals, "TINUVIN 400", "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", and "TINUVIN 1577" manufactured by BASF, "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" manufactured by ADEKA, and "CYASORB UV-1164" manufactured by Sun Chemical.

Examples of benzophenone-based organic compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3H2O, 2-hydroxy-4-n-octoxybenzophenone, and 2,2-dihydroxy-4-methoxybenzophenone.

Commercially available products include "KEMISORB 10," "KEMISORB 11," "KEMISORB 11S," "KEMISORB 12," and "KEMISORB 111" manufactured by Chemipro Chemicals, "SEESORB 101" and "SEESORB 107" manufactured by Shipro Chemicals, and "ADEKA STAB 1413" manufactured by ADEKA Corporation.

<Thiol-based chain transfer agent>
The infrared transmitting coloring composition can contain a thiol chain transfer agent. When the thiol chain transfer agent is used together with a photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates thiyl radicals that are not easily inhibited by oxygen, improving the photosensitivity. This improves the photocurability from the surface of the coating to the depth of the coating.

Multifunctional thiols include, for example, hexanedithiol and decanedithiol. , 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. are included, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent is preferably 1 to 10%, and more preferably 2 to 8%, based on 100% by mass of the non-volatile content of the infrared transmitting coloring composition. When used in an appropriate amount, the photosensitivity is improved and a coating with a good shape can be obtained.

<Antioxidants>
The infrared transmitting coloring composition of the present invention can contain an antioxidant. The antioxidant can suppress the coating film formed from the infrared transmitting coloring composition from oxidizing and yellowing due to a heating process such as thermal curing, and can maintain the transmittance of the coating film. In particular, when the colorant concentration of the photosensitive coloring composition is high, the crosslinking component is relatively reduced, so that yellowing during the thermal process becomes stronger when a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be any compound that has an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specific examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, etc. can be used. In addition, it is preferable that the antioxidant used in the present invention does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, preferred ones include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

Examples of hindered phenol-based antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butyl- Examples of the phenolic compounds include 2,2'-thiodiethyl bis-(2-t-butyl-5-methylphenol), 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and N,N-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide). In addition, oligomer and polymer type compounds having a hindered phenol structure can also be used.
Commercially available products include Adeka STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, and AO320 manufactured by ADEKA CORPORATION; KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Corporation; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

Examples of the hindered amine antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino. -N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, etc. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.
Commercially available products include Adeka STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, 29, and 94 manufactured by Chemipro Chemicals; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF Corporation; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

Examples of phosphorus-based antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl)phosphite, 4,4'isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol Examples of such phosphite include tetratridecyl 4,4'-butylidene bis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-ditert-butyl-6-methylphenyl) phosphite. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.
Commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, Adeka STAB 2112, 1178, 1500, C, 3013, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Corporation, and HostanoxP-EPQ manufactured by Clariant Chemicals.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.
Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOX PLS manufactured by Chemipro Chemicals Co., Ltd.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.
Commercially available products include Adeka STAB LA-29, LA-31RG, LA-32, LA-36, -412S manufactured by ADEKA CORPORATION, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Chemicals Co., Ltd., and TINUVIN PS, 99-2, 384-2, 900, 928, 1130 manufactured by BASF Corporation.

Benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.
Examples of commercially available products include Adeka STAB 1413 manufactured by ADEKA CORPORATION, KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals Co., Ltd., and UV-12 and UV-329 manufactured by Sun Chemical Co., Ltd.

Examples of triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine, etc. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Examples of commercially available products include Adeka STAB LA-46 and F70 manufactured by ADEKA CORPORATION, KEMISORB102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, and 479 manufactured by BASF Corporation, and Cyasorb UV-1164 manufactured by Sun Chemical Company.

Examples of salicylic acid ester antioxidants include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

These antioxidants can be used alone or in a mixture of two or more in any ratio as needed.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the coloring composition, since this provides good spectral characteristics and sensitivity.

<Other additives>
The infrared transmitting coloring composition of the present invention may contain, as other additives, a storage stabilizer for stabilizing the viscosity of the composition over time, and an adhesion improver such as a silane coupling agent for improving adhesion to a transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The amount of storage stabilizer used is preferably 0.1 to 10 parts by mass per 100 parts by mass of colorant.

Adhesion improvers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The amount of the adhesion improver used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5% by mass, relative to 100 parts by mass of the colorant.

<Method of producing infrared transmitting coloring composition>
The infrared transmitting coloring composition of the present invention is preferably produced by finely dispersing a mixture containing a colorant (A), a resin-type dispersant (B), and an organic solvent using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The infrared transmitting coloring composition of the present invention can also be produced by dispersing the colorant (A) separately and then mixing them. When the solubility of the colorant, such as a dye, is high, specifically, when the solubility in the solvent used is high and the colorant is dissolved by stirring and no foreign matter is confirmed, the above-mentioned fine dispersion step does not need to be performed. In addition, when the mixture contains a pigment, it is preferable to use a dispersing aid such as a dye derivative in combination.

When used as an infrared-transmitting photosensitive coloring composition, it is preferable to prepare it as a solvent-developable or alkali-developable composition. The infrared-transmitting photosensitive coloring composition can be prepared by mixing the infrared-transmitting coloring composition with a photopolymerizable monomer and/or a photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, and additives. The photopolymerization initiator may be added at the stage of preparing the infrared-transmitting coloring composition, or may be added later to the prepared infrared-transmitting coloring composition.

When dispersing the colorant (A), a dispersing aid (e.g., a surfactant) or the like can be used as appropriate. Dispersing aids are excellent at dispersing colorants and have a large effect of preventing re-aggregation of the colorant after dispersion, so that a high spectral transmittance in the infrared region can be obtained.

<Dispersion Aid>
(Surfactant)
Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyl dimethylaminoacetate betaine, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in a mixture of two or more, but are not necessarily limited to these.

Dispersing agents can be used alone or in combination of two or more types.

The amount of dispersing aid used is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, per 100 parts by weight of colorant. Using an appropriate amount will further improve dispersibility.

<Removal of coarse particles>
The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or a membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

<Infrared transmission filter>
Next, the infrared transmission filter of the present invention will be described.
<Method of manufacturing infrared transmission filter>
The infrared transmission filter can be produced by a method of coating the infrared transmission type coloring composition of the present invention on various plastic substrates or glass substrates, a method of kneading the composition into a plastic material and molding the composition, or the like. As long as a film that transmits infrared rays is formed, the filter can be produced by various methods regardless of the method. By combining a film produced by these methods with a photodiode, the filter can be used as various sensors such as an illuminance sensor, a distance sensor, a medical sensor, a touch sensor for a display, and a biometric authentication sensor. Furthermore, the infrared transmission type photosensitive coloring composition of the present invention can be used as an infrared transmission filter for a solid-state imaging device by patterning the photodiode using a photolithography method. The solid-state imaging device in which an infrared transmission filter is produced by a photolithography method will be described in detail below.

<Solid-state imaging device having an infrared transmission filter layer>
A solid-state imaging element having an infrared transmission filter layer will be described. A typical infrared sensor has a structure in which an infrared transmission filter layer is provided on a photodiode, and there is no particular limitation as long as the structure functions as a solid-state imaging element. For example, the following structure can be mentioned.

The substrate has a plurality of photodiodes constituting the light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like, a light shielding film made of tungsten or the like with only the light receiving parts of the photodiodes open on the photodiodes and transfer electrodes, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving parts of the photodiodes, and an infrared transmission filter of the present invention on the device protection film.

Furthermore, the device may have a focusing means (e.g., a microlens, etc.; the same applies below) on the device protection layer and below the infrared transmission filter (on the side closer to the substrate), or may have a focusing means on the infrared transmission filter.

The organic CMOS sensor is composed of a thin panchromatic organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material captures light and converts it into an electrical signal, while the inorganic material takes on the role of extracting the electrical signal to the outside. In principle, the aperture ratio for incident light can be 100%. The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication processes and is suitable for pixel miniaturization.

The infrared transmission filter segment for a solid-state imaging element according to the present invention can be formed by any known method without any particular limitation. However, since the filter segments of the imaging element are very fine, ranging from submicrons to about 10-odd microns, it is preferable to use optical lithography.
When the infrared transmission filter segments are formed on corresponding photoelectric conversion elements, they are formed from a negative type photosensitive green composition, and in this case, the thickness of the negative type infrared transmission resist layer is set in the range of 0.1 to 3.0 μm.

The surface of the negative infrared-transmitting resist layer formed from the negative colored film is exposed to a pattern using a photomask in multiple areas that correspond to the multiple photoelectric conversion elements to be formed. Note that the photomask usually has dimensions 4 to 5 times larger than the dimensions of the pattern to be actually formed, and is reduced to 1/4 to 1/5 during pattern exposure.

A typical photomask is a 4-5x reticle, which has a pattern that is 4-5 times larger than the size of the pattern to be exposed on the surface of the negative infrared-transparent resist layer. Then, using a stepper exposure device (not shown), the photomask pattern is reduced to 1/4 to 1/5 and exposed on the surface of the negative infrared-transparent resist layer.

Following the exposure step, an alkaline development process (development step) is performed, which dissolves the uncured parts after exposure into the developer, leaving only the photocured parts. This development step allows the formation of a patterned coating made of infrared transmission filter segments.

The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and these may be combined with a swing method, a spin method, an ultrasonic method, etc.
It is also possible to prevent uneven development by pre-wetting the surface to be developed with water or the like before contacting the developing solution. As the developing solution, an organic alkaline developing solution that does not cause damage to the underlying circuitry is preferable. The developing temperature is usually 20 to 30°C, and the developing time is 20 to 90 seconds.

Examples of alkaline agents contained in the developer include organic alkaline compounds such as aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, and piperidine, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate.

As the developer, an alkaline aqueous solution in which these alkaline agents are diluted with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used. When using a developer consisting of such an alkaline aqueous solution, after development, the substrate is generally washed with pure water to remove excess developer, and then dried.

Finally, the filter segment thus formed is subjected to a hardening treatment.
In the manufacturing method of the present invention, after carrying out the above-mentioned colored layer forming step, exposure step, and development step, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure may be included as necessary. Post-baking is a heat treatment after development to complete the curing, and is usually a thermal curing treatment at 100 to 270° C. When light is used, it can be performed by g-rays, h-rays, i-rays, excimer lasers such as KrF and ArF, electron beams, X-rays, etc., but it is preferable to perform it at a low temperature of about 20 to 50° C. using an existing high-pressure mercury lamp, and the irradiation time is 10 to 180 seconds, preferably 30 to 60 seconds.
In the case where post-exposure and post-heating are used in combination, it is preferable to carry out post-exposure first.

The infrared transmission filter is produced by the infrared transmission layer formation process, exposure process, and development process (and, if necessary, a curing process) described above.

<Infrared camera, infrared sensor>
The infrared camera and infrared sensor of the present invention have the infrared transmission filter of the present invention. Types of infrared cameras include near-infrared cameras, surveillance cameras, vehicle-mounted cameras, medical cameras, inspection and analysis cameras, and the like, and types of infrared sensors include temperature sensors, distance sensors, medical sensors, touch sensors such as displays, biometric authentication sensors, and the like. The configuration of the infrared camera and infrared sensor is not particularly limited as long as it has the infrared transmission filter of the present invention and functions as an infrared camera and infrared sensor.

The present invention will be described below based on examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by a method in which a transmission electron microscope (TEM) was used to directly measure the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each pigment primary particle were measured, and the average was taken as the particle size of the pigment primary particles. Next, the volume (mass) of each of 100 or more pigment particles was calculated by approximating it to a cube of the calculated particle size, and the volume average particle size was taken as the average primary particle size.

(Mass average molecular weight of resin-type dispersion resin (B) and binder resin)
The mass average molecular weight (Mw) of the resin is the polystyrene-equivalent mass average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as a developing solvent.

(Acid value of resin-type dispersion resin (B) and binder resin)
The resin acid value is the acid value (mgKOH/g) measured according to the potentiometric titration method of JIS K 0070 and converted into the non-volatile content.

<Production of resin-type dispersant>
(Acidic Resin-Type Dispersant (BC-1))
DISPER BYK-110 (non-volatile component=51%, amine value=0, acid value=53) manufactured by BYK Chemical Co., Ltd. was used.
(Acidic Resin-Type Dispersant (BC-2))
DISPER BYK-111 (non-volatile component=95%, amine value=0, acid value=129) manufactured by BYK Chemical Co., Ltd. was used.
(Acidic Resin-Type Dispersant (BC-3))
DISPER BYK-111 (non-volatile component=53%, amine value=0, acid value=22) manufactured by BYK was used.
(Acidic resin type dispersant (B1-1-1))
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 6 parts of methacrylic acid, 134 parts of methyl methacrylate, and 60 parts of t-butyl methacrylate, and the atmosphere was replaced with nitrogen gas.
The inside of the reaction vessel was heated to 50° C. with stirring, and 4 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and a solution of 0.1 parts of 2,2′-azobisisobutyronitrile in 90 parts of propylene glycol monomethyl ether acetate was added thereto while reacting for 7 hours. It was confirmed by measuring the solid content that 95% had reacted.
6 parts of pyromellitic dianhydride, 315 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted for 7 hours at 100° C. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the mixture was diluted with propylene glycol monomethyl ether acetate to a solid content of 40% by measuring the solid content, to obtain an acidic resin-type dispersant (B1-1-1) having an acid value of 31 mgKOH/g and a weight average molecular weight of 20,000.

＜バインダー樹脂溶液の製造＞
（バインダー樹脂溶液：Ｊ－１）
セパラブル４口フラスコに温度計、冷却管、窒素ガス導入管、撹拌装置を取り付けた反応容器にメトキシプロピルアセテート７０．０部を仕込み、８０℃に昇温し、反応容器内を窒素置換した後、滴下管よりｎ－ブチルメタクリレート１３．３部、２－ヒドロキシエチルメタクリレート４．６部、メタクリル酸４．３部、パラクミルフェノールエチレンオキサイド変性アクリレート（東亞合成社製「アロニックスＭ１１０」）７．４部、２，２'－アゾビスイソブチロニトリル０．４部の混合物を２時間かけて滴下した。滴下終了後、更に３時間反応を継続し、質量平均分子量２６，０００のアクリル樹脂の溶液を得た。室温まで冷却した後、樹脂溶液約２ｇをサンプリングして１８０℃、２０分加熱乾燥して不揮発分を測定し、先に合成した樹脂溶液に不揮発分が２０％になるようにメトキシプロピルアセテートを添加してバインダー樹脂溶液（Ｊ－１）を調製した。 (Acidic resin-type dispersants (B1-1-2) to (B1-1-3), (B1-2-1) to (B1-2-4), (BC-4) to (BC-5))
Except for changing the composition as shown in Table 1, acidic resin-type dispersants (B1-1-2) to (B1-1-3), (B1-2-1) to (B1-2-4), (BC-4) to (BC-5) were prepared in the same manner as (B1-1-1).

<Preparation of binder resin solution>
(Binder resin solution: J-1)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 parts of methoxypropyl acetate was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. A mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a mass average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content became 20%, to prepare a binder resin solution (J-1).

<Production of finely divided pigment>
(Blue Micronized Pigment (P-1))
100 parts of blue pigment C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 12 hours. This mixture was added to 3000 parts of hot water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80°C for 24 hours to obtain 98 parts of blue fine pigment (P-1). The average primary particle size of the obtained pigment was 28.3 nm.

The average primary particle diameter of the pigment was determined by measuring the primary particle diameters of all pigment particles in a sample observed at 50,000 magnification using a transmission electron microscope (JEM-1200EX manufactured by JEOL Ltd.) and averaging the results. If the particle shape was not spherical, the major and minor axes were measured and the particle diameter was calculated by (major axis + minor axis)/2.

(Yellow Micronized Pigment (P-2))
100 parts of yellow pigment C.I. Pigment Yellow 139 (Clariant "Novoperm Yellow P-M3R"), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C for 12 hours. This mixture was added to 3000 parts of hot water, heated to about 70 ° C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C for 24 hours to obtain 97 parts of yellow fine pigment (P-2). The average primary particle diameter of the obtained pigment was 41.1 nm.

(Purple Micronized Pigment (P-3))
100 parts of purple pigment C.I. Pigment Violet 23 ("LIONOGEN VIOLET FG-6140" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 12 hours. This mixture was added to 3000 parts of hot water, heated to about 70 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of purple fine pigment (P-3). The average primary particle diameter of the obtained pigment was 53.7 nm.

<Production of dye derivative>
(Dye Derivatives (C-1) to (C-2))
The dye derivative having the structure shown below was prepared with reference to the literature mentioned in the description of the dye derivative above.

(C-1)

(C-2)

<Production of infrared transmitting coloring composition>
[Example 1]
(Preparation of infrared transmitting colored composition (PP-1))
The mixture below was stirred and mixed to be homogeneous, and then dispersed for 5 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to prepare an infrared transmitting coloring composition (PP-1).
Blue fine pigment (P-1): 5.5 parts Yellow fine pigment (P-2): 2.0 parts Purple fine pigment (P-3): 2.5 parts Resin type dispersant (B-1): 7.7 parts Binder resin solution (J-1): 30.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 52.3 parts
However, Example 1 is a reference example.

[Examples 2 to 36]
(Infrared Transmitting Colored Compositions (PP-2) to (PP-36))

Except for changing the composition to that shown in Table 2, the same procedure as in Example 1 was followed to prepare infrared transmitting colored compositions (PP-2 to PP-36).
However, Examples 2 to 12 are reference examples.

[Comparative Examples 1 to 11]
(Infrared Transmitting Colored Compositions (PP-37) to (PP-47))
Except for changing the composition to that shown in Table 3, the same procedure as in Example 1 was followed to prepare infrared transmitting colored compositions (PP-37 to PP-47).

<Evaluation of infrared transmitting coloring composition>
The obtained colored composition was evaluated for initial viscosity, storage stability (viscosity), foreign matter, storage stability (foreign matter), filterability, and shielding property as described below.

(Evaluation of initial viscosity)
The viscosity of the obtained infrared transmitting coloring composition immediately after preparation was measured using an E-type viscometer and evaluated according to the following criteria: ⊚ is a very good level, ◯ is a good level, Δ is a practically usable level, and × is a level not suitable for practical use.

◎: Viscosity is 5.00 or more and less than 8.00. ◯: Viscosity is 8.00 or more and less than 10.00. △: Viscosity is 10.00 or more and less than 15.00. ×: Viscosity is 15.00 or more.

(Evaluation of storage stability (viscosity evaluation))
The viscosity of the obtained infrared transmitting coloring composition was measured immediately after preparation and after storage at 10° C. for one month using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. ⊚ indicates a very good level, ◯ indicates a good level, △ indicates a practically usable level, and × indicates a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02. ○: Viscosity ratio is 1.02 or more and less than 1.05. △: Viscosity ratio is 1.05 or more and less than 1.10. ×: Viscosity ratio is 1.10 or more.

(Evaluation of aggregated foreign matter)
The obtained infrared transmission type coloring composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thick using a spin coater, and baked in an oven at 230 ° C for 30 minutes, and the transmittance of the coating film at 800 nm after heat treatment was measured using an ultraviolet-visible near-infrared spectrophotometer to produce a coated substrate so that T = 20%. The obtained substrate was then heated at 250 ° C for 1 hour and the surface was observed. For evaluation, a metal microscope "BX60" manufactured by Olympus Systems Co., Ltd. was used. The magnification was set to 500 times, and the number of particles observable in any 5 fields of view in transmission was counted and evaluated. In addition, ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use.
◎: The number of foreign objects is less than 5. ○: The number of foreign objects is 5 or more and less than 10. △: The number of foreign objects is 10 or more and less than 60. ×: The number of foreign objects is 60 or more.

(Storage stability (evaluation of aggregated foreign matter))
The infrared transmitting coloring composition thus obtained was evaluated for foreign matter immediately after preparation and after storage at 10° C. for one month in the same manner as in the above “Evaluation of foreign matter”.

(Evaluation of filterability)
10 g of the obtained infrared transmitting coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), the amount of the composition that passed through the filter was measured, and the result was evaluated according to the following criteria: ◎ is a very good level, ○ is a good level, △ is a practically usable level, and × is a level not suitable for practical use.
◎: Filtration amount is 8.0 g or more. ○: Filtration amount is 5.0 g or more and less than 8.0 g. △: Filtration amount is 3.0 g or more and less than 5.0 g. ×: Filtration amount is 3.0 g or less.

(Evaluation of Concealment)
The obtained infrared transmitting coloring composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, and baked in an oven at 230°C for 30 minutes to prepare a coated substrate such that the transmittance (T) of the coating film at 800 nm after heat treatment was T = 20% as measured using an ultraviolet-visible-near infrared spectrophotometer. The maximum transmittance of the prepared substrate in the 400-700 nm region was measured to evaluate the concealment ability in the visible region. ◎ indicates a very good level, ○ indicates a good level, △ indicates a practically usable level, and × indicates a level not suitable for practical use.
◎: Maximum transmittance is less than 3.0%. ○: Maximum transmittance is 3.0% or more and less than 5.0%. △: Maximum transmittance is 5.0% or more and less than 7.0%. ×: Maximum transmittance is 7.0% or more.

The results of the evaluation using the above methods are shown in Tables 4 and 5.

As shown in Examples 1 to 36, by including any dye derivative, 45 to 60% by mass of C.I. Pigment Blue 15:6, 10 to 30% by mass of C.I. Pigment Yellow 139, and 15 to 35% by mass of C.I. Pigment Violet 23 in a total of 100% by mass of colorant, and including an acidic resin-type dispersant with an acid value of 30 to 80 mgKOH/g, excellent characteristics were shown in all evaluation items.

Furthermore, since the acidic resin-type dispersant is a reaction product obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a polymer having a hydroxyl group at one end and a tetracarboxylic dianhydride and/or a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride or a tetracarboxylic dianhydride, the dispersion state is improved, and a dispersion with excellent initial viscosity characteristics and excellent coatability can be obtained. Furthermore, the filterability is also excellent.

Furthermore, by including an acidic resin-type dispersant (B1) with an acid value of 30 to 50 mgKOH/g (B1-1) and an acidic resin-type dispersant (B1-2) with an acid value of 55 to 80 mgKOH/g, the dispersion state was improved and the product showed excellent viscosity storage stability and filterability.

Furthermore, the use of the dye derivative showed excellent properties in terms of suppressing the generation of foreign matter.
Furthermore, by selecting a phthalocyanine skeleton for the dye derivative, the product showed excellent properties in terms of suppressing the generation of foreign matter even after long-term storage.

In the comparative examples, results that satisfied all items were not obtained, proving the effectiveness of the present invention.

<Production of infrared transmitting photosensitive coloring composition>
[Example 37]
(Infrared-transmitting photosensitive coloring composition (PR-1))
The following mixture was stirred and mixed to a uniform consistency, and then filtered through a 1.0 μm filter to prepare an infrared-sensitive transmitting photosensitive coloring composition (PR-1).

Infrared transmitting coloring composition (PP-1): 60.0 parts Binder resin solution (J-1): 11.0 parts Photopolymerizable monomer 1: 3.6 parts Dipentaerythritol penta- and hexaacrylate ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerizable monomer 2: 1.0 part trimethylolpropane PO modified triacrylate ("Aronix M310" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator 1: 0.6 parts ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime)
("Irgacure OXE02" manufactured by BASF Japan)
Photopolymerization initiator 2: 0.6 parts 1-(N-4-benzoylphenyl-carbazol-3-yl)-butane-1,2-dione-2-oxime-O-acetate Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts
However, Example 37 is a reference example.

[Examples 38 to 72, Comparative Examples 12 to 22]
(Infrared-transmitting photosensitive coloring compositions (PR-2 to PR-36, PR-37 to PR-47))
Infrared transmitting coloring compositions were changed to the infrared transmitting coloring compositions shown in Tables 6 and 7 in the same manner as in Example 29, and infrared transmitting photosensitive coloring compositions (PR-2 to PR-28, PR-29 to PR-38) were prepared.
However, Examples 38 to 48 are for reference only.

<Evaluation of infrared transmitting photosensitive coloring composition>
The obtained infrared transmitting photosensitive coloring composition was evaluated for initial viscosity, storage stability (viscosity), foreign matter, storage stability (foreign matter), filterability, and shielding property as described below.

(Evaluation of initial viscosity)
The viscosity of the obtained infrared transmitting photosensitive coloring composition immediately after preparation was measured using an E-type viscometer and evaluated according to the following criteria: ⊚ is a very good level, ◯ is a good level, Δ is a practically usable level, and × is a level not suitable for practical use.
◎: Viscosity is 3.00 or more and less than 4.00. ◯: Viscosity is 4.00 or more and less than 8.00. △: Viscosity is 8.00 or more and less than 10.00. ×: Viscosity is 10.00 or more.

(Evaluation of storage stability (viscosity evaluation))
The viscosities of the obtained infrared transmitting photosensitive coloring composition immediately after preparation and after storage at 10° C. for one month were measured using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. ⊚ indicates a very good level, ◯ indicates a good level, △ indicates a practical level, and × indicates a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02. ○: Viscosity ratio is 1.02 or more and less than 1.05. △: Viscosity ratio is 1.05 or more and less than 1.10. ×: Viscosity ratio is 1.10 or more.

(Evaluation of aggregated foreign matter)
The obtained infrared transmission type photosensitive coloring composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thick using a spin coater, and after drying at 70 ° C for 20 minutes, the entire substrate was exposed to ultraviolet light with an integrated light amount of 150 mJ / cm ² using an ultra-high pressure mercury lamp to photocure the coating film. Then, the substrate was heated at 230 ° C for 20 minutes and allowed to cool, and the transmittance (T) of the coating film at 800 nm after heat treatment was measured using an ultraviolet-visible near-infrared spectrophotometer to be T = 20%. The obtained substrate was then heated at 250 ° C for 1 hour and the surface was observed. For evaluation, a metal microscope "BX60" manufactured by Olympus Systems Co., Ltd. was used. The magnification was set to 500 times, and the number of particles observable in any 5 fields of view was counted and evaluated in transmission. In addition, ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use.
◎: The number of foreign objects is less than 5. ○: The number of foreign objects is 5 or more and less than 10. △: The number of foreign objects is 10 or more and less than 60. ×: The number of foreign objects is 60 or more.

(Evaluation of storage stability (evaluation of aggregated foreign matter))
The infrared transmitting photosensitive coloring composition thus obtained was evaluated for foreign matter immediately after preparation and after storage at 10° C. for one month in the same manner as in the above “Evaluation of foreign matter”.

(Evaluation of filterability)
10 g of the obtained infrared transmitting photosensitive coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), the amount of the composition that passed through the filter was measured, and the composition was evaluated according to the following criteria: ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use.

◎: Filtration amount is 8.0 g or more. ○: Filtration amount is 5.0 g or more and less than 8.0 g. △: Filtration amount is 3.0 g or more and less than 5.0 g. ×: Filtration amount is 3.0 g or less.

(Evaluation of Concealment)
The obtained infrared transmission type photosensitive coloring composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thick using a spin coater, and after drying at 70 ° C for 20 minutes, the entire surface of the substrate was exposed to ultraviolet light with an integrated light amount of 150 mJ / cm ² using an ultra-high pressure mercury lamp to photocure the coating film. Then, the substrate was heated at 230 ° C for 20 minutes and allowed to cool, and the transmittance (T) of the coating film at 800 nm after heat treatment was measured using an ultraviolet-visible near-infrared spectrophotometer to be T = 20%, so that the coated substrate was prepared. The maximum transmittance of the substrate in the 400-700 nm region was measured to evaluate the concealment ability in the visible region. In addition, ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use.
◎: Maximum transmittance is less than 3.0%. ○: Maximum transmittance is 3.0% or more and less than 5.0%. △: Maximum transmittance is 5.0% or more and less than 7.0%. ×: Maximum transmittance is 7.0% or more.

The results of the evaluation using the above methods are shown in Tables 8 and 9.

The photosensitive coloring composition also gave results similar to those of the coloring compositions shown in Examples 37 to 72 and Comparative Examples 12 to 22.

<Film production for various purposes>
From the above results, it is expected that the optical films prepared in the examples, due to their excellent properties, can be suitably used in near-infrared cameras, surveillance cameras, vehicle-mounted cameras, medical cameras, inspection and analysis cameras, temperature sensors, distance sensors, medical sensors, touch sensors for displays, biometric authentication sensors, and the like.

Claims (8)

An infrared-transmitting coloring composition comprising a colorant (A), a resin-type dispersant (B), and an organic solvent, wherein the colorant (A) comprises 45 to 60% by mass of C.I. Pigment Blue 15:6, 10 to 30% by mass of C.I. Pigment Yellow 139, and 15 to 35% by mass of C.I. Pigment Violet 23, in a total of 100% by mass of the colorant (A), the resin-type dispersant (B) comprises an acidic resin-type dispersant (B1) having an acid value of 30 to 80 mgKOH/g, and the acidic resin-type dispersant (B1) comprises an acidic resin-type dispersant (B1-1) having an acid value of 30 to 50 mgKOH/g, and an acidic resin-type dispersant (B1-2) having an acid value of 55 to 80 mgKOH/g . The infrared transmitting coloring composition according to claim 1, characterized in that the acidic resin-type dispersant (B1) contains a resin-type dispersant which is a reaction product of polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a polymer having a hydroxyl group at at least one end and a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride and/or a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. 3. The infrared transmitting coloring composition according to claim 1 , further comprising a dye derivative (C). 4. The infrared transmitting coloring composition according to claim 3 , wherein the dye derivative (C) is a phthalocyanine dye derivative. The infrared transmitting coloring composition according to any one of claims 1 to 4 , further comprising a photopolymerizable monomer and/or a photopolymerization initiator. An infrared filter having a filter segment produced by using the infrared transmitting colored composition according to any one of claims 1 to 5 . An infrared camera comprising the infrared filter according to claim 6 . An infrared sensor comprising the infrared filter according to claim 6 .