JP7647264B2 - Visible light-blocking photosensitive composition, visible light-blocking film, and sensor - Google Patents

Description

The present invention relates to a visible light-blocking photosensitive composition containing an organic pigment. By forming a film of this composition, the visible light-blocking function can be utilized to conceal the base and make it invisible to the human eye, or to be used as a coating material that does not transmit visible light for objects whose base is affected by visible light. The present invention can also be used in sensors, etc., by utilizing the visible light-blocking properties of this composition.

Visible light-blocking photosensitive compositions can obtain light-blocking properties by combining multiple organic pigments. Patent Document 1 discloses an example of a coloring composition using three or four types of organic pigments, in which a dispersant having a base block and an acid group block is used. However, since visible light-blocking photosensitive compositions are made by combining multiple organic pigments to form a dispersion, they have poor dispersion stability and problems with viscosity stability and coating uniformity. In addition, when the pigment concentration is increased to improve visible light-blocking properties, there are problems with reduced developability, and deterioration of pattern resolution and adhesion.

JP 2016-177273 A

The present invention aims to provide a visible light-shielding photosensitive composition that exhibits excellent light-shielding properties in the visible light region with wavelengths of 400 to 700 nm, excellent coating uniformity, high viscosity storage stability, pattern adhesion, and excellent resolution, and a visible light-shielding film using the same.

The visible light-blocking photosensitive composition of the present invention comprises a colorant (A), a resin-type dispersant (B), a polymerizable compound (C) and a photopolymerization initiator (D),
In 100% by mass of the colorant (A), the colorant (A) contains 20 to 50% by mass of copper phthalocyanine blue pigment, 20 to 50% by mass of C.I. Pigment Yellow 139, and 15 to 45% by mass of C.I. Pigment Violet 23;
The present invention relates to a visible light-blocking photosensitive composition, wherein the resin-type dispersant (B) contains two or more kinds of acidic resin-type dispersants (B1) having an acid value of 30 to 80 mgKOH/g.

The present invention also relates to a visible light-blocking photosensitive composition in which the acidic resin-type dispersant (B1) contains an acidic resin-type dispersant (B1-1) whose side chain has a glass transition temperature of -30°C or lower.

The present invention also relates to a visible light-blocking photosensitive composition in which the content of the acidic resin-type dispersant (B1-1) is 2 to 10 mass % of the total solid content of the visible light-blocking photosensitive composition.

The present invention also relates to a visible light-blocking photosensitive composition in which the copper phthalocyanine blue pigment is at least one selected from the group consisting of C.I. Pigment Blue 15:3, 15:4, and 15:6.

The present invention also relates to a visible light-blocking photosensitive composition, wherein the photopolymerization initiator (D) contains a compound represented by the following general formula (1):
General formula (1)


[In the general formula (1), X ¹ , X ³ and X ⁶ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN; X ² represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent; X ⁴ and X ⁵ each independently represent R ¹¹ , OR ¹¹ , SR 11 , COR ¹¹ , CONR ¹² R ¹³ , NR ^{12 COR 11 ,} OCOR ¹¹ , COOR ¹¹ , SCOR 11 , COSR ^{11 , COSR 11 ,} CSOR ¹¹ , CN, a halogen atom, or a hydroxyl group. R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. a and b each independently represent an integer of 0 to 3.]

The present invention also relates to a visible light-shielding film formed from the above-mentioned visible light-shielding photosensitive composition.

The present invention also relates to a sensor equipped with the above-mentioned visible light blocking film.

The present invention can provide a visible light-shielding photosensitive composition that exhibits excellent light-shielding properties in the visible light region with wavelengths of 400 to 700 nm, excellent coating uniformity, high storage stability, pattern adhesion, and excellent resolution, as well as a visible light-shielding film using the same.

First, the terms used in this specification are defined. Unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", and "(meth)acrylate" respectively mean "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", and "acrylate and/or methacrylate". Additionally, "C.I." in this specification means Color Index (C.I.). Light-blocking properties refer to the ability to block visible light. Colorants include pigments and dyes.

<Visible light blocking photosensitive composition>
<Colorant (A)>
The colorant (A) in the present invention contains 20 to 50 mass% copper phthalocyanine blue pigment, 20 to 50 mass% C.I. Pigment Yellow 139, and 15 to 45 mass% C.I. Pigment Violet 23 in a total of 100 mass% of the colorant (A). This provides light-shielding properties. The colorant (A) may contain other organic pigments, dyes, inorganic pigments, etc. other than the organic pigments as necessary. The contents are preferably 30 to 40 mass% copper phthalocyanine blue pigment, 30 to 45 mass% C.I. Pigment Yellow 139, and 20 to 35 mass% C.I. Pigment Violet 23, which is more effective in enhancing light-shielding properties, particularly on the long wavelength side of the visible light region.

(Blue organic pigment: copper phthalocyanine blue pigment)
The copper phthalocyanine blue pigment preferably contains one or more selected from the group consisting of C. I. Pigment Blue 15:3, 15:4 and 15:6, and more preferably C. I. Pigment Blue 15:6.

(yellow organic pigment)
Other yellow pigments that can be used in combination with C.I. Pigment Yellow 139 include, for example, 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, 231 or 233, etc.

(Purple organic pigment)
Other purple pigments that can be used in combination with C.I. Pigment Violet 23 include, for example, C.I. Pigment Violet 1, 19, 27, 29, 30, 32, 37, 40, 42, 50, and the like.

(Other organic pigments)
Other specific examples of organic pigments are shown below by color index numbers.

Red organic pigments include, 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, 21 5, 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, 287, 295, or 296.

Examples of orange organic pigments include C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, and 73.

Green organic pigments include, for example, C.I. Pigment Green 7, 10, 36, 37, 58,
59, 62, 63, etc.

Blue organic pigments include, for example, 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, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, 64, etc.
(Inorganic pigments)
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, amber, and synthetic iron black.

(dye)
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are dye derivatives and lake pigments obtained by converting dyes into lakes.

Examples of dyes include salt-forming compounds of acid dyes having an acidic group such as sulfonic acid or carboxylic acid with a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; and salt-forming compounds of resin components having these amino groups with acid dyes. Salt-forming compounds of acid dyes with compounds having an onium base are also preferred because of their excellent fastness. The compound having an onium base is preferably a resin having a cationic group in the side chain.

The chemical structure of dyes includes, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, etc.), dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific structures of dyes are described in "New Edition Dye Handbook" (edited by the Society of Organic Synthesis Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colourists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986), etc.

<Resin-type dispersant (B)>
The resin-type dispersant (B) in the present invention is characterized by containing two or more kinds of acidic resin-type dispersants (B1) having an acid value of 30 to 80 mgKOH/g. This provides an excellent effect in terms of storage stability. In addition, the resin-type dispersant (B1) preferably contains an acidic resin-type dispersant (B1-1) having a polymer moiety in the molecule, the polymer moiety having a glass transition temperature of −30° C. or lower. This provides good coating uniformity. Furthermore, the acidic resin-type dispersant (B1-1) is preferably 2 to 10% by mass in the total solid content of the visible light-blocking photosensitive composition. When it is within this range, the coating uniformity is further improved, and in addition, the balance between the adhesion and the resolution of the pattern is most favorable.
The resin type dispersant may also include other resin type dispersants, such as an acidic resin type dispersant having an acid value other than 30 to 80 mgKOH/g, or a basic resin type dispersant having an amine value.

The glass transition temperature was calculated from the polymer moiety using the following formula.
1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+W _n /Tg _n
( _W1 to _Wn indicate the mass fractions of the n types of monomers used, and _Tg1 to _Tgn indicate the glass transition temperatures (units are absolute temperature "K") of homopolymers (homopolymers of monomers).

The acidic dispersant will be described in detail below.
[Acidic Resin-Type Dispersant (B1)]
The acidic resin-type dispersant (B1) used in the visible light-blocking photosensitive composition of the present invention is preferably an acidic resin-type dispersant represented by any one of the following (b1-1) to (b1-3).
(b1-1): A resin-type dispersant which is a reaction product between a hydroxyl group of a polymer having a hydroxyl group at its terminal and an acid anhydride group of a tetracarboxylic dianhydride or a tricarboxylic anhydride, or a resin-type dispersant which has a polymer portion 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 or a tricarboxylic anhydride.
(b1-2): A resin-type dispersant represented by the following general formula (2):
General formula (2)
(HOOC-) _m -R ¹ -(-COO-[-R ³ -COO-] _n -R ² ) _t
(In the formula, ^R1 represents a residue of a tetravalent tetracarboxylic acid compound, ^R2 represents a monoalcohol residue, ^R3 represents a lactone residue, m represents 2 or 3, n represents an integer of 1 to 50, and t represents (4-m).)

(b1-3): A resin-type dispersant that contains an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group and another ethylenically unsaturated monomer as a copolymer component (polymer portion).

The resin-type dispersants (b1-1) to (b1-3) will be described below.
(Resin-type dispersant (b1-1))
A resin-type dispersant described in WO2008/007776.

(Resin-type dispersant (b1-2))
A resin-type dispersant described in JP 2007-140487 A.

(Resin-type dispersant (b1-3))
Resin-type dispersants described in JP-A-2003-253078 and JP-A-2008-161737.

(Basic resin type dispersant)
The basic resin type dispersant is preferably a dispersant having a functional group including, for example, a primary, secondary, or tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocycle. For example, the basic resin type dispersants described in JP-A-2016-122073 and JP-A-5513691 can be preferably used. In addition, the vinyl resin type dispersant having a hindered amine skeleton described in JP-A-2015-110711 is also preferred, and as described in the same publication, it is preferred to use it in combination with an acidic resin type dispersant, as this may further contribute to dispersion stability.

(Other resin-type dispersants)
In the visible light-shielding photosensitive composition of the present invention, known resin-type dispersants other than those mentioned above may be used. The resin-type dispersant may be any dispersant that has a colorant affinity site having the property of adsorbing to an added colorant and a site compatible with a colorant carrier, and that functions to adsorb to an added colorant and stabilize the dispersion in the colorant carrier. Specifically, examples of the resin-type dispersant include urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylates, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof. Examples of the dispersants that can be used include oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group and salts thereof, 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 alcohols, and polyvinylpyrrolidone, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide/propylene oxide adducts, and phosphate-based compounds, and these can be used alone or in combination of two or more kinds.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, and 215 manufactured by BYK Japan Co., Ltd. 5, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, BYK-LPN21116, BYK-LPN21324, or Lactimon, Lactimon-WS or Bykumen, etc. manufactured by Nippon Lubrizol Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20 000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. manufactured by BASF Corporation; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 40 80, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajispar PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

It is preferable to use about 3 to 200% by weight of the resin-type dispersant based on the total amount of colorant, and from the viewpoint of film-forming properties, it is more preferable to use about 5 to 100% by weight.

<Dye derivatives>
The visible light-blocking photosensitive composition may contain a dye derivative, if necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue.

By adding a dye derivative to the pigment and carrying out a micronization process such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the dye derivative is adsorbed onto the pigment surface, making it possible to make the primary pigment particles finer than when the dye derivative is not added.

Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, as well as amine salts thereof, sulfonamide groups, or compounds having basic substituents such as a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009/081930 B, WO 2011/052617 B, WO 2012/102399 B, and JP 2017-156397 A, phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016/163351 B, JP 2017-165820 B, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are described in 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 disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine dye derivatives are disclosed in JP-A-2011-162662; thiazine indigo dye derivatives are disclosed in JP-A-2007-3147 85, triazine-based dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681, benzoisoindole-based dye derivatives are disclosed in JP-A-2009-57478, quinophthalone-based dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2007-314681. Examples of the naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, examples of the azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092, examples of the acidic substituents include those described in JP-A-2004-307854, and examples of the basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In addition, in these documents, the dye derivative may be described as a derivative, pigment derivative, dispersant, 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 organic dye residue is synonymous with the dye derivative.

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

The amount of the dye derivative used is preferably 1 to 100 parts by weight, more preferably 3 to 70 parts by weight, and even more preferably 5 to 50 parts by weight, per 100 parts by weight of the colorant.

By adding a dye derivative to the colorant (A) and carrying out a dispersion treatment such as wet dispersion using a two-roll mill, a three-roll mill, or beads, the dye derivative is adsorbed to the pigment surface, the pigment surface becomes polar, and the adsorption of the resin-type dispersant is promoted, and the compatibility with the pigment, the dye derivative, the resin-type dispersant, the solvent, and other additives is improved, and the dispersion stability and viscosity stability over time when the light-shielding photosensitive composition is formed are improved. In addition, the improved compatibility provides excellent stability over time of the coating film when the colored curable composition is applied to a glass substrate, etc., and the stability and characteristic dependency of the pattern shape on the waiting time from application to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay) of the visible light-shielding photosensitive composition, as well as line width sensitivity stability, are improved. In addition, by adsorbing and covering the pigment surface with the dye derivative and the resin-type dispersant, the aggregation of the pigment and crystal precipitation due to sublimation can be suppressed when the coating film is heated and baked. It also reduces variations in development time and development residue.

<Fine particle size of colorant (A)>
The colorant (A) is preferably used in a finely divided form in terms of increasing the 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 preferred. 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. A suitable particle size improves dispersibility and the contrast ratio.

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 preferred because it is inexpensive. From the standpoint of both processing efficiency and production efficiency, it is preferable to use 50 to 2,000 parts by weight of the water-soluble inorganic salt per 100 parts by weight of the pigment, and more preferably 300 to 1,000 parts by weight.

The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, 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 mass, more preferably 50 to 500 parts by mass, per 100 parts by mass 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 examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. 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>
The visible light-shielding photosensitive composition of the present invention can contain a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a coating film having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. In terms of curability, examples of the binder resin include thermoplastic resins and active energy ray curable resins. The active energy ray curable resin is a thermoplastic resin having an active energy ray reactive functional group. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. The alkali solubility is for imparting development solubility in the alkali development step during the production of a color filter, and an acidic group is required.

<Thermoplastic resin>
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 the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin/maleic acid (anhydride) copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene/styrenesulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin preferably has a polymerizable unsaturated group. The polymerizable unsaturated group can be introduced, for example, by the following method (i) or (ii). The resin is three-dimensionally crosslinked by the effect of active energy rays, increasing the crosslink density and improving chemical resistance.

[Method (i)]
In the method (i), for example, a carboxyl group of a monocarboxylic acid monomer is added to a side-chain epoxy group of a copolymer obtained by copolymerizing an epoxy group-containing monomer with another monomer, and then a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce a polymerizable unsaturated group and a carboxyl group.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with monocarboxylic acid monomers.

Examples of monocarboxylic acid monomers 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, and cyano at the α-position.

Examples of polybasic acid anhydrides include tricarboxylic acid anhydrides such as tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and trimellitic anhydride, and tetracarboxylic acid dianhydrides such as pyromellitic dianhydride.

Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate;
Alternatively, examples of the vinyl monomer include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of such compounds include N-substituted maleimides such as imidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

A method similar to method (i) is, for example, a method in which a polymerizable unsaturated group and a carboxyl group are introduced by addition reaction of an epoxy group of an epoxy group-containing monomer with some of the side chain carboxyl groups of a copolymer obtained by copolymerizing a monocarboxylic acid monomer with another monomer.

[Method (ii)]
The method (ii) is a method in which a hydroxyl group in a side chain of a copolymer obtained by copolymerizing a hydroxyl group-containing monomer with another monomer is reacted with an isocyanate group of an isocyanate group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and/or poly12-hydroxystearic acid. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use a monomer having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

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

Examples of the other monomer include, in addition to the other monomers already explained, N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate group-containing monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine and the like. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

The monocarboxylic acid monomer can be any of the monomers already described.

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

<Alkali-soluble resin having no polymerizable unsaturated group>
The visible light-blocking photosensitive composition of the present invention can contain, as a binder resin, an alkali-soluble resin having no polymerizable unsaturated group in order to adjust the degree of hardening of the coating.

In terms of solubility in alkaline development, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The Mw/Mn value is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves the adhesion of the coating to the substrate and improves solubility in alkaline development.

In terms of solubility in alkaline development, the acid value of the alkali-soluble resin is preferably 50 to 200 (mg KOH/g), more preferably 70 to 180, and even more preferably 90 to 170. A moderate acid value improves solubility in alkaline development and improves adhesion to the substrate.

Each raw material used in the synthesis of the binder resin can be used alone or in combination of two or more types.

The binder resin can be used alone or in combination of two or more types. In this specification, by using an alkali-soluble resin having a polymerizable unsaturated group in combination with an alkali-soluble resin not having a polymerizable unsaturated group, the degree of photocuring in the coating film is controlled, and the adhesion of the fine line pattern after development is improved.

The content of the binder resin is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant. When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

<Thermosetting Compound>
The light-blocking photosensitive composition may further contain a thermosetting compound, which improves the strength of the coating after post-baking.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

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

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

Examples of acid group-containing monomers include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Urethane bond-containing monomer)
Examples of the urethane bond-containing monomer include polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc.

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine (meth)acrylic acid ester, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

The polymerizable compound (C) may be used alone or in combination of two or more types.

The content of the polymerizable compound (C) is preferably 1 to 50 mass %, and more preferably 2 to 40 mass %, based on 100 mass % of the nonvolatile content of the visible light-blocking photosensitive composition. When an appropriate amount is added, the curability and developability are further improved.

<Photopolymerization initiator (D)>
Examples of the photopolymerization initiator (D) that can be used in the present invention include acetophenone-based compounds 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)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, benzoin methyl ether, etc. benzoin compounds such as benzoin ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone compounds such as benzophenone, 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- Examples of the compounds include triazine-based compounds such as triazine, oxime ester-based compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, or 1-(O-acetyloxime), phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide, quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate-based compounds, carbazole-based compounds, imidazole-based compounds, and titanocene-based compounds. Among these, oxime ester-based compounds are preferred.

(Oxime ester compounds)
In the oxime ester compound, the N-O bond of the oxime is cleaved by absorbing ultraviolet light, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small amount of exposure. When the colorant concentration of the light-blocking photosensitive composition is high, the ultraviolet transmittance of the coating film decreases, and the degree of curing of the coating film may decrease, but oxime ester compounds are preferably used because they have high quantum efficiency.

Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. In particular, it is preferable to contain a compound represented by the following general formula (1) in order to fully exert the effects of the present invention.
General formula (1)

[In the general formula (1), X ¹ , X ³ and X ⁶ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN; X ² represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent; X ⁴ and X ⁵ each independently represent R ¹¹ , OR ¹¹ , SR 11 , COR ¹¹ , CONR ¹² R ¹³ , NR ^{12 COR 11 ,} OCOR ¹¹ , COOR ¹¹ , SCOR 11 , COSR ^{11 , COSR 11 ,} CSOR ¹¹ , CN, a halogen atom, or a hydroxyl group. R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. a and b each independently represent an integer of 0 to 3.]

Examples of compounds represented by general formula (1) include the following compounds:

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

The content of the photopolymerization initiator is preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight, per 100 parts by weight of the colorant. When an appropriate amount is added, the photocuring property and developability are further improved.

<Sensitizer>
The visible light-blocking photosensitive composition can contain a sensitizer.
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, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred, and 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc. are more preferred.

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

The content of the sensitizer is preferably 3 to 60 parts by weight, and more preferably 5 to 50 parts by weight, per 100 parts by weight of the photopolymerization initiator. When an appropriate amount is included, the curing property and developability are further improved.

<Thiol-based chain transfer agent>
The visible light-shielding photosensitive composition may contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, improving the sensitivity of the visible light-shielding photosensitive composition.

The thiol chain transfer agent is preferably a multifunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the coating becomes easier to photocure from the surface to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, 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 tetrakisthioglycolate, Examples of such thiopropionates include erythritol 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, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and 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 0.1 to 10 mass %, and more preferably 0.1 to 3 mass %, based on 100 mass % of the nonvolatile content of the visible light-blocking photosensitive composition. When an appropriate amount is included, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The visible light-blocking photosensitive composition may contain a polymerization inhibitor.
Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl Examples of the alkyl resorcinol compound include alkyl resorcinol compounds such as n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucine.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the non-volatile content of the visible light-blocking photosensitive composition. By including an appropriate amount of polymerization inhibitor, the resolution of the pattern can be further improved.

<Ultraviolet absorbing agent>
The visible light-shielding photosensitive composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. The ultraviolet absorbing agent may be a low molecular weight compound or a polymer.

Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 5% by mass of 2-methoxy-1-methylethyl Benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and linear alkyl esters, 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, methyl 3-(3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and linear alkyl esters, )-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol , 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

The content of the UV absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the UV absorber being 100% by mass. If an appropriate amount is included, the resolution after development will be further improved.

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 visible light-blocking photosensitive composition. When an appropriate amount is included, the adhesion between the substrate and the coating is improved, and good resolution can be obtained.

<Antioxidants>
The visible light-shielding photosensitive composition can contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound from oxidizing and yellowing during the thermal process of post-baking or ITO annealing, and can improve the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component is reduced, and therefore, measures such as using a highly sensitive crosslinking component or increasing the amount of the photopolymerization initiator are taken, resulting in a phenomenon in which yellowing during the thermal process becomes stronger. 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.

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

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

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

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

<Leveling Agent>
The visible light-shielding photosensitive composition of the present invention may contain a leveling agent. This improves the coating properties of the composition and the drying properties of the coating. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants may be used.

The content of the leveling agent is preferably 0.001 to 2.0 mass % of the non-volatile content of the visible light-blocking photosensitive composition, and more preferably 0.005 to 1.0 mass %. Within this range, the balance between the coatability, pattern adhesion, and transmittance of the visible light-blocking photosensitive composition is improved.

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

<Storage stabilizer>
The visible light-blocking photosensitive composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The content of the storage stabilizer is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the colorant.

<Adhesion improver>
The visible light-blocking photosensitive composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to a substrate.

Examples of adhesion improvers include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3 Examples of the silane coupling agent include aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant. This range is more effective and provides better adhesion, making it more preferable.

<Method of producing visible light-blocking photosensitive composition>
The visible light shielding photosensitive composition of the present invention is prepared by dispersing the colorant (A) and an organic solvent, etc. to prepare a pigment dispersion. When a dye derivative is used in the dispersion, the organic pigment can be dispersed more finely. Also, when the colorant (A) has high solubility in the solvent, the dispersion may not be necessary. A pigment dispersion can be prepared for each colorant (A) and then mixed. Also, a pigment dispersion can be prepared in a lump using a plurality of colorants (A). Next, a polymerizable compound (C) and a photopolymerization initiator (D) are mixed with the pigment dispersion and mixed to obtain a visible light shielding coloring composition. It goes without saying that the timing of mixing each material is arbitrary.

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 the colorant and have a large effect of preventing the colorant from re-aggregating 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 phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, 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 visible light-shielding photosensitive 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 membrane filter, etc. In this way, it is preferable that the visible light-shielding photosensitive composition does not substantially contain particles of 0.5 μm or more, more preferably 0.3 μm or less.

<Visible light shielding film and sensor>
The visible light-shielding film of the present invention is a film that shields visible light, and can be prepared by a method of coating the light-shielding photosensitive composition on various plastic substrates or glass substrates, or by kneading the composition into a plastic material and molding it. As long as a film that shields visible light is formed, it can be prepared by various methods regardless of the method. By combining the films prepared by these methods with a photodiode, they can be used as various sensors such as illuminance sensors, distance sensors, medical sensors, touch sensors for displays, and biometric authentication sensors.

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 particle. Next, the volume (mass) of each particle was calculated for 100 or more pigment particles 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.

(Number average molecular weight (Mn) and weight average molecular weight (Mw) of acidic resin-type dispersant and binder resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the acidic resin-type dispersant and binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and two "TSK-GEL SUPER HZM-N" packings were used as both packings connected in series. The oven temperature was 40°C, a THF solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalent values.

(Number average molecular weight (Mn) and weight average molecular weight (Mw) of basic resin type dispersant)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the basic resin-type dispersant were measured by gel permeation chromatography (GPC) equipped with an RI detector.
The apparatus used was an HLC-8320GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, both of which used "TSKgel SUPER-AW3000" as the packing material, and the measurements were performed at an oven temperature of 40°C, an N,N-dimethylformamide solution of 3 mM triethylamine and 10 mM LiBr as the eluent, and a flow rate of 0.6 ml/min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 10 microliters were injected. All molecular weights are polystyrene equivalent values.

(Acid Value of Acidic Resin-Type Dispersant and Binder Resin)
The acid value of the acidic resin-type dispersant and the binder resin is a value obtained by measuring the acid value (mgKOH/g) according to the potentiometric titration method of JIS K 0070 and converting it into a non-volatile content.

(Amine value of basic resin type dispersant)
The amine value of the basic resin-type dispersant is a value calculated by converting the total amine value (mg KOH/g) measured in accordance with the method of ASTM D 2074 into a solid content value.

(Glass transition temperature of resin-type dispersant)
The glass transition temperature of the side chain portion was calculated using the following formula.
1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+W _n /Tg _n
( _W1 to _Wn indicate the mass fractions of the n types of monomers used, and _Tg1 to _Tgn indicate the glass transition temperatures (units are absolute temperature "K") of homopolymers (homopolymers of monomers).

<Production of finely divided pigment>
(Blue organic pigment (A-1))
100 parts of blue organic pigment C.I. Pigment Blue 15:6 (PB15:6) ("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 a finely divided blue organic pigment (A-1). The average primary particle size of the obtained pigment was 28.3 nm.

(Blue organic pigment (A-2))
A similar treatment to that for the blue organic pigment (A-1) was carried out, except that C.I. Pigment Blue 15:6 ("Leonor Blue ES" manufactured by Toyo Color Co., Ltd.) was replaced with C.I. Pigment Blue 15:3 (PB15:3) ("Leonor Blue FG-7351" manufactured by Toyo Color Co., Ltd.), to obtain a finely divided blue organic pigment (A-2). The average primary particle diameter of the obtained pigment was 30.9 nm.

(Blue organic pigment (A-3))
A similar treatment to that for the blue organic pigment (A-1) was carried out, except that C.I. Pigment Blue 15:6 ("Leonor Blue ES" manufactured by Toyo Color Co., Ltd.) was replaced with C.I. Pigment Blue 15:4 (PB15:4) ("Leonor Blue FG-7400G" manufactured by Toyo Color Co., Ltd.), to obtain a finely divided blue organic pigment (A-3). The average primary particle diameter of the obtained pigment was 32.1 nm.

(Yellow organic pigment (A-4))
Yellow organic pigment C.I. Pigment Yellow 139 (PY139) (Clariant "Novoperm Yellow P-M3R") 100 parts, ground salt 800 parts, and diethylene glycol 100 parts were charged into a stainless steel 1 gallon kneader (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 a finely divided yellow organic pigment (A-4). The average primary particle diameter of the obtained pigment was 41.1 nm.

(Purple organic pigment (A-5))
100 parts of a purple organic pigment C.I. Pigment Violet 23 (PV23) ("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 a finely divided purple organic pigment (A-5). The average primary particle diameter of the obtained pigment was 53.7 nm.

(Other organic pigments (A-6))
C.I. Pigment Yellow 185 (PY185) (BASF Japan "Paliogen Yellow D1155") 95 parts, dye derivative (b-1), 5 parts, rosin maleic acid resin (Arakawa Chemical Industries "Marquid 32") 10 parts, sodium chloride 1200 parts, and diethylene glycol 120 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into 8000 parts of hot water, heated to about 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours to obtain a finely divided organic pigment (A-6). The average primary particle diameter of the obtained pigment was 40.7 nm.

(Other organic pigments (A-7))
100 parts of C.I. Pigment Red 177 (PR177) (BASF Japan "Cromophthal Red A2B" (anthraquinone-based red pigment)), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and salt milled. The kneaded product obtained was added to 3 liters of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight to obtain a finely divided organic pigment (A-7). The average primary particle diameter of the obtained pigment was 38.6 nm.

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

<Preparation of Acidic Resin-Type Dispersant (B1) Solution>
(Acidic Resin-Type Dispersant (B1-1-1) Solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecane, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst were charged, and the mixture was replaced with nitrogen gas, and then heated and stirred at 120°C for 4 hours. After confirming that 98% had reacted by solid content measurement, 73.3 parts of pyromellitic anhydride were added and reacted at 120°C for 2 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by acid value measurement. The obtained dispersant was a white solid at room temperature and had an acid value of 51 mgKOH/g. The solution was diluted with PGMAc so that the nonvolatile content was 40% by nonvolatile content measurement, and a dispersant (B1-1-1) solution with an acid value of 51 mgKOH/g was obtained. Table 1-1 shows the glass transition temperature of the polymer portion.

(Acidic Resin-Type Dispersant (B1-1-2) Solution)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 6 parts of methacrylic acid, 6 parts of methyl methacrylate, 100 parts of 2-methoxyethyl methacrylate, 40 parts of ethyl acrylate, 38 parts of n-butyl acrylate, and 10 parts of tert-butyl acrylate, and the inside of the vessel was replaced with nitrogen gas.
The inside of the reaction vessel was heated to 50° C. with stirring, and 12 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.
14 parts of pyromellitic anhydride, 299 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 at 100° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the mixture was diluted with propylene glycol monomethyl ether acetate so that the nonvolatile content was 40% by measuring the nonvolatile content, to obtain an acidic resin-type dispersant (B1-1-2) solution having an acid value of 53 mg KOH/g and a weight average molecular weight of 8470. Table 1-2 shows the glass transition temperature of the polymer portion.

(Acidic Resin-Type Dispersant Solutions (B1-2-1) to (B1-2-3), (BC-1) to (BC-2))
Except for changing the composition as shown in Table 1-2, acidic resin-type dispersant solutions (B1-2-1) to (B1-2-3) and (BC-1) to (BC-2) were prepared in the same manner as in (B1-1-2).

<Preparation of Basic Resin-Type Dispersant Solution>
(Basic resin type dispersant (BC-3) solution)
In a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator and 5.6 parts of cuprous chloride as a catalyst were added.
133 parts of propylene glycol monomethyl ether acetate and 133 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more calculated from the nonvolatile content. Next, 61 parts of propylene glycol monomethyl ether acetate, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reaction apparatus, and the mixture was stirred while maintaining 110° C. and a nitrogen atmosphere to continue the reaction. Two hours after the charging, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization. As a result of GPC measurement, the weight average molecular weight of the polymer was 20000, the molecular weight distribution Mw/Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin type dispersant (BC-3) with an amine value of 169.8 mgKOH/g per nonvolatile content was obtained. After cooling to room temperature, about 2 g of the resin type dispersant solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether acetate was added to the previously synthesized basic resin type dispersant (BC-3) so that the nonvolatile content was 40% in the nonvolatile content measurement to prepare a basic resin type dispersant (BC-3) solution.

<Production example of binder resin (E)>

(Preparation of binder resin (E-1) liquid)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, heated to 80°C, and the flask was replaced with nitrogen. A mixture of 18 parts of dicyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel, and the reaction was continued for 6 hours at 120° C., and the reaction was terminated when the solid acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120° C. to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20 mass% to prepare a binder resin (E-1) liquid. The weight average molecular weight (Mw) was 10,000.

(Preparation of binder resin (E-2) liquid) 160 parts of propylene glycol monomethyl ether acetate was introduced into a separable four-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. The atmosphere inside the flask was then changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution of 2.0 parts of azobisisobutyronitrile added to a mixture of 96.0 parts of benzyl methacrylate, 17.6 parts of methacrylic acid, 22.0 parts of dicyclopentanyl methacrylate and 140 parts of propylene glycol monomethyl ether acetate was dripped into the flask from the dropping funnel over a period of 2 hours. The mixture was then stirred at 100°C for 5 hours to obtain a solution of acrylic resin with an acid value of 85 mg KOH/g and a weight average molecular weight (Mw) of 15,000. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass to prepare a binder resin (E-2) liquid.

<Preparation of colorant liquid>
(Production Example 1)
The following materials were mixed and stirred to be uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a filter having a pore size of 5.0 μm to prepare a colorant liquid (PP-1).
Pigment (A-1): 3.7 parts Pigment (A-4): 3.7 parts Pigment (A-5): 3.2 parts Dye derivative (f-1): 1.5 parts Acidic resin type dispersant ((B1-1-1): 40% non-volatile liquid): 1.3 parts Acidic resin type dispersant ((B1-2-2): 40% non-volatile liquid): 18.7 parts Propylene glycol monomethyl ether acetate (PGMAc): 68.0 parts

(Production Examples 2 to 21: Colorant Liquids (PP-2 to 21))
Colorant liquids (PP-2 to PP-21) were prepared in the same manner as in Production Example 1 (PP-1), except that the combinations were changed as shown in Table 2.

[Synthesis of Photopolymerization Initiators D1-1 and D1-3]
The above photopolymerization initiators D1-1 and D1-3 were synthesized by the following method.

<Synthesis of Photopolymerization Initiator (D1-1)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-ethyl-3-nitro-carbazole were charged into an ice-cooled reaction vessel. While maintaining the reaction temperature at 5°C or less, 64 mmol of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was gradually added dropwise to this mixture. After the addition was completed, the mixture was stirred at 20°C for 4 hours. Thereafter, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. Next, the desiccant was removed from this liquid by filtration, and the solvent was further removed by distillation. In this manner, an acylated product was obtained.

(Step 2)
In a nitrogen stream, 20 mmol of the above acylated product, 2.1 g (30 mmol) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reaction vessel. The mixture was stirred at 80° C. for 1 hour, then cooled to room temperature to separate into an oily phase and an aqueous phase. The solvent was removed from the liquid constituting the oily phase by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90° C. for 1 hour, then cooled to room temperature, and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, the mixture was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and further recrystallization was performed using ethyl acetate as a solvent. In this manner, a photopolymerization initiator (D1-1) was obtained.

<Synthesis of Photopolymerization Initiator (D1-3)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-ethyl-3-nitrocarbazole compound were charged into an ice-cooled reaction vessel. While maintaining the reaction temperature at 5°C or less, 64 mmol of 4-(ethoxymethyl)-2-methyl-benzoyl chloride was gradually added dropwise to this mixture. After the addition was completed, the mixture was stirred at 20°C for 4 hours. Thereafter, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The desiccant was removed from this liquid by filtration, and the solvent was further removed by distillation. In this manner, an acylated product was obtained.

(Step 2)
In a nitrogen stream, 20 mmol of the above acylated product, 2.1 g (30 mmol) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reaction vessel. The mixture was stirred at 80° C. for 1 hour, then cooled to room temperature to separate into an oily phase and an aqueous phase. The solvent was removed from the liquid constituting the oily phase by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90° C. for 1 hour, then cooled to room temperature, and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, the mixture was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and further recrystallization was performed using ethyl acetate as a solvent. In this manner, a photopolymerization initiator (D1-3) was obtained.

<Method of producing visible light-blocking photosensitive composition>
[Example 1]
(Preparation of Visible Light-Shielding Photosensitive Composition (R-1))
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a visible light-blocking photosensitive composition (R-1).
Colorant liquid (PP-1: non-volatile content 20%): 67.5 parts Binder resin liquid (E-1: non-volatile content 20%): 6.6 parts Polymerizable compound (C-1): 2.7 parts Dipentaerythritol penta- and hexaacrylate ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (D1-1): 0.5 parts Propylene glycol monomethyl ether acetate (PGMAc): 22.7 parts

[Examples 2 to 19, Comparative Examples 1 to 4]
(Preparation of Light-Blocking Photosensitive Compositions (R-2 to R-23))
The same procedure as in Example 1 was carried out to prepare a visible light-blocking photosensitive composition (
R-2 to R-23) were prepared, respectively.
However, Examples 2 and 8 are reference examples.

The ingredients for each are as follows:

<Photopolymerization initiator (D)>
(D-3) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02
(Manufactured by BASF Japan)]

Example 20: Preparation of visible light-blocking photosensitive composition (R-24)
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a visible light-blocking photosensitive composition (R-24).
Colorant liquid (PP-1: non-volatile content 20%): 67.5 parts Binder resin liquid (E-1: non-volatile content 20%): 2.6 parts Binder resin liquid (E-2: non-volatile content 20%): 4.0 parts Polymerizable compound (C-1): 2.7 parts Dipentaerythritol penta- and hexaacrylate (Toagosei Co., Ltd. "Aronix M402")
Photopolymerization initiator (D1-1): 0.5 parts Propylene glycol monomethyl ether acetate (PGMAc): 22.7 parts

Example 21 (Preparation of visible light-blocking photosensitive composition (R-25))
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a visible light-blocking photosensitive composition (R-25).
Colorant liquid (PP-1: non-volatile content 20%): 67.5 parts Binder resin liquid (E-1: non-volatile content 20%): 2.5 parts Binder resin liquid (E-2: non-volatile content 20%): 4.0 parts Polymerizable compound (C-1): 2.7 parts Dipentaerythritol penta- and hexaacrylate ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (D1-1): 0.5 parts Methylhydroquinone 1% solution: 0.5 parts (a solution of "MH" manufactured by Seiko Chemical Co., Ltd. adjusted with PGMAc so that the nonvolatile content is 1% by mass)
Propylene glycol monomethyl ether acetate (PGMAc): 22.3 parts

<Evaluation of Visible Light-Shielding Photosensitive Composition>
The obtained visible light-shielding photosensitive compositions were evaluated for storage stability (viscosity), adhesion, coating uniformity, resolution, and light-shielding properties as described below, where ⊚ indicates a very good level, ◯ indicates a good level, △ indicates a practically acceptable level, and × indicates a level not suitable for practical use.

(Evaluation of storage stability (viscosity evaluation))
The viscosity of the obtained visible light-blocking photosensitive composition was measured using an E-type viscometer immediately after preparation and after storage for one month at 10° C. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria.
◎: 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 Adhesion)
(Evaluation of Adhesion to Substrate)
The obtained visible light shielding photosensitive composition was applied to a 10 cm x 10 cm square glass substrate using a spin coater, and then prebaked at 90 ° C for 120 seconds to form a coating film with a thickness of 2.0 μm. Next, the substrate was exposed to light at an exposure dose of 100 mJ / cm ² using a high pressure mercury lamp. After that, the substrate was spray-developed using a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C, washed with ion-exchanged water, air-dried, and heated at 230 ° C for 30 minutes in a clean oven to prepare a sample substrate. In accordance with JIS K5400, a checkerboard test was carried out on 100 1 mm square checkerboards of the coating film on each sample substrate, and the peeling state was observed using cellophane tape. The number of adhesions (the number of checkerboards remaining without peeling) among the 100 checkerboards was counted to evaluate the adhesion to the substrate.
〇: 90 or more △: 80 to 89
×: 79 or less

(Evaluation of fine line adhesion after development) The obtained visible light-shielding photosensitive composition was applied onto a 10 cm x 10 cm square glass substrate using a spin coater, and then prebaked at 90°C for 120 seconds to form a coating film with a thickness of 2.0 μm. Next, using an ultra-high pressure mercury lamp, the substrate was exposed through a photomask with a stripe pattern of 6 to 25 μm at an illuminance of 30 mW/cm ² and an exposure amount of 100 mJ/cm ^2. Thereafter, the substrate was spray-developed using a 0.04 mass% potassium hydroxide aqueous solution at 23°C, washed with ion-exchanged water, and air-dried. The obtained pattern was observed with an optical microscope to confirm the minimum line width of the remaining fine line pattern.
⊚: Fine lines of 10 μm or less remain.
◯: Fine lines of 15 μm or less remain.
Δ: Fine lines of 20 μm or less remain.
×: Fine lines thicker than 20 μm remain, or fine lines do not remain.

(Evaluation of Coating Uniformity)
The obtained visible light-blocking photosensitive composition was spin-coated onto a 360 mm × 465 mm substrate with a plate thickness of 0.7 mm so that the film thickness at the center (referred to as A) was 2.0 μm, and the coating was dried at 70° C. for 30 minutes. After that, the film thickness at the center and the average film thickness at four points diagonally 200 mm from the center (referred to as B) were measured, and the coating uniformity of the film thickness was evaluated according to the following formula.
(A-B)×100/{(A+B)/2} [%]
◎: Less than 1% ○: 1% to less than 2% △: 2% to less than 5% ×: 5% or more

(Resolution Evaluation)
The obtained visible light-shielding photosensitive composition was applied onto a 10 cm x 10 cm square glass substrate using a spin coater, and then prebaked at 90°C for 120 seconds to form a coating film with a thickness of 2.0 µm. Next, the substrate was exposed to light at an exposure dose of 100 mJ/ ^cm2 through a 30 µm regular hexagonal photomask using an ultra-high pressure mercury lamp. Thereafter, the substrate was exposed to light at 0.04% by mass at 23°C.
After spray development using an aqueous potassium hydroxide solution, the substrate was washed with ion-exchanged water, air-dried, and heated in a clean oven for 30 minutes at 230° C. The spray development was carried out for the shortest time possible for forming a pattern with no residual development in the coating of the light-blocking photosensitive composition, and this was defined as the appropriate development time.
The cross section of the pattern in the 30 μm regular hexagonal portion of the obtained filter segment was observed using an electron microscope and evaluated. The evaluation criteria were as follows:
⊚: The pattern edges are smooth and there is no development residue. The hole size is 28 μm or more.
◯: The pattern edges are smooth and there is no development residue. The hole size is less than 28 μm.
△: Edges of the pattern are rough or have development residues. ×: Edges of the pattern are rough and have development residues. (Evaluation of light-shielding ability)
The obtained visible light-blocking photosensitive composition was applied onto a 100 mm × 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 coating film had a thickness of 2.0 µm after heat treatment.
The maximum transmittance of the prepared substrate in the 400 to 700 nm region was measured to evaluate the light blocking ability in the visible region.
◎: 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 Table 4.

As shown in the results in Table 4, the visible light-blocking photosensitive compositions of Examples 1 to 21 have excellent storage stability, adhesion, coating uniformity, and resolution, and can form coatings with good light-blocking properties.

Claims (7)

A visible light-blocking photosensitive composition comprising a colorant (A), a binder resin, a resin-type dispersant (B), a polymerizable compound (C) and a photopolymerization initiator (D),
In 100% by mass of the colorant (A), the colorant (A) contains 20 to 50% by mass of copper phthalocyanine blue pigment, 20 to 35% by mass of C.I. Pigment Yellow 139, and 15 to 45% by mass of C.I. Pigment Violet 23;
A visible light-blocking photosensitive composition, wherein the resin-type dispersant (B) contains two or more acidic resin-type dispersants (B1) having an acid value of 30 to 80 mgKOH/g, and the acidic resin-type dispersant (B1) contains an acidic resin-type dispersant (B1-1) having a polymer moiety having a glass transition temperature of -30°C or lower in the molecule (however, excluding a visible light-blocking photosensitive composition containing 15% by mass or more of a red organic pigment relative to 100% by mass of the colorant (A). 2. The visible light-blocking photosensitive composition according to claim 1, wherein the content of the acidic resin-type dispersant (B1-1) is from 2 to 10% by mass based on the total solid content of the visible light-blocking photosensitive composition. The binder resin according to claim 1 or
3. The visible light-blocking photosensitive composition according to claim 2 . The visible light-blocking photosensitive composition according to any one of claims 1 to 3, wherein the copper phthalocyanine blue pigment is at least one selected from the group consisting of C.I. Pigment Blue 15:3, 15:4, and 15:6. 5. The visible light-blocking photosensitive composition according to claim 1, wherein the photopolymerization initiator (D) comprises a compound represented by the following general formula (1):
General formula (1)

[In the general formula (1), X ¹ , X ³ and X ⁶ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN; X ² represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent; X ⁴ and X ⁵ each independently represent R ¹¹ , OR ¹¹ , SR 11 , COR ¹¹ , CONR ¹² R ¹³ , NR ^{12 COR 11 ,} OCOR ¹¹ , COOR ¹¹ , SCOR 11 , COSR ^{11 , COSR 11 ,} CSOR ¹¹ , CN, a halogen atom, or a hydroxyl group. R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. a and b each independently represent an integer of 0 to 3.] A visible light-shielding film formed from the visible light-shielding photosensitive composition according to any one of claims 1 to 5. A sensor comprising the visible light blocking film according to claim 6.