JP2022054522A - Photosensitive composition, optical filter, fingerprint authentication sensor, and image display device - Google Patents

Abstract

To provide a photosensitive composition which enables formation of an optical filter that suppresses permeation of light in the vicinity of a wavelength of 660 nm, can permeate light on a lower wavelength side than a wavelength of 600 nm in a wide wavelength region and is excellent in fingerprint authentication accuracy, is less likely to generate a foreign matter by solvent shock, and is excellent in development property (pattern shape with less development residue and reduced in chipping).SOLUTION: A photosensitive composition contains a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), in which the pigment (A) contains a zinc halide phthalocyanine pigment (A-1) and a pigment (A-2) represented by general formula (1), and the total content of the zinc halide phthalocyanine pigment (A-1) and the pigment (A-2) represented by general formula (1) is 95 mass% or more in 100 mass% of the pigment (A).SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive composition. In particular, it relates to a photosensitive composition preferably used for manufacturing a fingerprint authentication sensor. Further, the present invention relates to an optical filter using a photosensitive composition, a fingerprint authentication sensor, and an image display device.

In recent years, mainly mobile terminals such as smartphones and tablet terminals have been equipped with a user authentication function using biometric information such as fingerprints, faces, irises, and voices. In particular, fingerprint authentication has the excellent convenience of being able to unlock by simply placing a finger on it, and because it is compact and inexpensive, the use of fingerprint authentication sensors is expanding in smartphones.

In the past, it was common for smartphones to place a capacitive fingerprint authentication sensor on the bezel (outside the image display), but with the trend toward larger displays, the bezel has disappeared and the entire display has become available. It has become mainstream. Therefore, it has become necessary to install the fingerprint authentication sensor inside the display. However, since the capacitance type fingerprint authentication sensor requires the finger to be placed directly on the sensor portion, the capacitance type fingerprint authentication sensor does not operate even if the capacitance type fingerprint authentication sensor is arranged inside the display. Examples of the fingerprint authentication sensor that can be installed inside the display include an optical type and an ultrasonic type, and in particular, an optical type that is inexpensive and easy to arrange is being studied.

Patent Document 1 irradiates green light having a wavelength of around 570 nm or blue light having a wavelength lower than 570 nm, transmits the light reflected from a finger through an optical filter, and generates an image captured image based on the transmitted light. As a result, an optical fingerprint authentication sensor that performs fingerprint authentication is disclosed.

As a method for forming an optical filter used in an optical fingerprint authentication sensor, a dyeing method, a printing method, an electrodeposition method, an inkjet method, a pigment dispersion method and the like are known. Among these methods, the pigment dispersion method is known as a method suitable for high quality and mass productivity because it is based on a photolithography method.

To form a filter by the pigment dispersion method, a photosensitive composition is applied to a substrate using a coating device (for example, spin coating or die coating), the solvent is removed by drying, pattern exposure is performed, and then an unexposed portion is formed. Is removed in the developing process, and if necessary, treatment such as heating is added.

Japanese Unexamined Patent Publication No. 2017-196319

When an optical type fingerprint authentication sensor is installed inside a display such as a smartphone, there is no cover that blocks external light, so light that passes through the body tissue and has a wavelength of around 660 nm causes noise and correctly generates an captured image. There was a problem that the fingerprint authentication accuracy was lowered.

Further, since the coating device for forming the optical filter is washed with an organic solvent or the like after use, the cleaning solvent remains in the piping or the like, and then remains when the photosensitive composition is applied. Mix with organic solvent. For example, when an organic solvent such as cyclohexanone having high detergency is used, so-called solvent shock occurs in which aggregated foreign substances are generated in the photosensitive composition due to the shock. Therefore, when the photosensitive composition is applied, there is a problem that foreign matter or the like is present in the filter and the fingerprint authentication accuracy is lowered.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to form an optical filter having excellent fingerprint authentication accuracy capable of suppressing the transmission of light in the vicinity of a wavelength of 660 nm and transmitting light in a wide wavelength range on the wavelength side lower than 600 nm, and by a solvent shock. It is an object of the present invention to provide a photosensitive composition having less generation of foreign matter and excellent developability (pattern shape with less development residue and suppressed chipping).

The present invention is a photosensitive composition comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
The pigment (A) contains a halogenated zinc phthalocyanine pigment (A-1) and a pigment (A-2) represented by the following general formula (1).
The total content of the halogenated zinc phthalocyanine pigment (A-1) and the pigment (A-2) represented by the following general formula (1) is 95% by mass or more in 100% by mass of the pigment (A). , With respect to the photosensitive composition.

(X in the general formula (1) represents a halogen atom, and n represents 4 to 16).

According to the above invention, it is possible to form an optical filter having excellent fingerprint authentication accuracy, which can suppress the transmission of light near a wavelength of 660 nm and transmit light in a wide wavelength range on the wavelength side lower than 600 nm. It is possible to provide a photosensitive composition, an optical filter, a fingerprint authentication sensor, and an image display device, which generate less foreign matter due to a solve shock and have excellent developability (a pattern shape having a small amount of development residue and suppressed chipping).

FIG. 1 is a schematic cross-sectional view of an image display device.

Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be modified and implemented within a range in which the problem can be solved.

In the present specification, "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are referred to as "(meth) acrylamide" unless otherwise specified. Means "acrylloyl and / or metaacryloyl", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or metaacrylamide", respectively. do. Further, "CI" means a color index (CI; The Society of Dyers and Colorists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.

<Photosensitive composition>
The present invention is a photosensitive composition comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
The pigment (A) contains a halogenated zinc phthalocyanine pigment (A-1) and a pigment (A-2) represented by the following general formula (1).
The total content of the halogenated zinc phthalocyanine pigment (A-1) and the pigment (A-2) represented by the following general formula (1) is 95% by mass or more in 100% by mass of the pigment (A). , A photosensitive composition.
General formula (1)

(X in the general formula (1) represents a halogen atom, and n represents 4 to 16).

The photosensitive composition of the present invention preferably forms a film by coating or the like. The coating is preferably used as a member constituting the fingerprint authentication sensor. Examples of the fingerprint authentication sensor include an optical fingerprint authentication sensor and the like.

[Pigment (A)]
The photosensitive composition of the present invention contains the pigment (A).

The pigment (A) contains a halogenated zinc phthalocyanine pigment (A-1) and a pigment represented by the general formula (1) (A-2), and is a halogenated zinc phthalocyanine pigment (A-1) and a general formula. The total content of the pigment (A-2) represented by (1) is 95% by mass or more in 100% by mass of the pigment (A).

The total content of the halogenated zinc phthalocyanine pigment (A-1) and the pigment (A-2) represented by the general formula (1) is 99% by mass in 100% by mass of the pigment (A) from the viewpoint of fingerprint authentication accuracy. % Or more is preferable, and 100% by mass is more preferable.

(Halogenated zinc phthalocyanine pigment (A-1)
The halogenated zinc phthalocyanine pigment (A-1) is a compound in which a maximum of 16 halogen atoms are bonded to each phthalocyanine molecule whose central metal is zinc.
The halogenated zinc phthalocyanine pigment (A-1) is preferably a compound represented by the following general formula (2).
General formula (2)

In the general formula (2), Y represents a halogen atom, and m represents 4 to 16. When the general formula (2) contains a plurality of compounds represented by Y having different numbers of halogen atoms, m is the average value of the plurality of compounds.

Examples of the halogen atom represented by Y in the general formula (2) include fluorine, bromine, chlorine, and iodine. Of these, bromine and chlorine are preferable. Two or more kinds of halogen atoms can be contained.

The m in the general formula (2) is preferably 6 to 15 and more preferably 7 to 14 from the viewpoint of transmittance at a wavelength of 440 to 590 nm.

The halogenated zinc phthalocyanine pigment (A-1) is described in, for example, C.I. I. Examples thereof include zinc phthalocyanine pigments described in Pigment Green 58,59, JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-070342, and the like. Examples of commercially available products include Fastgen Green A110, A350, and C100 manufactured by DIC Corporation. Among these, from the viewpoint of transmittance at wavelengths of 440 to 590 nm, C.I. I. Pigment Green 58 is preferred.

The halogenated zinc phthalocyanine pigment (A-1) can be used alone or in combination of two or more.

(Pigment represented by the general formula (1) (A-2))
The pigment (A-2) is a compound represented by the following general formula (1).
General formula (1)

In the general formula (1), X represents a halogen atom, and n represents 4 to 16. When the general formula (1) contains a plurality of compounds represented by X having different numbers of halogen atoms, n is an average value of the plurality of compounds.

Examples of the halogen atom represented by X in the general formula (1) include fluorine, bromine, chlorine, and iodine. Among these, bromine and chlorine are preferable, and bromine is more preferable, from the viewpoint of transmittance at a wavelength of 440 to 590 nm. Two or more kinds of halogen atoms can be contained.

The n in the general formula (1) is preferably 6 to 12 and more preferably 7 to 11 from the viewpoint of transmittance at a wavelength of 440 to 590 nm and suppression of solvent shock.

The pigment (A-2) can be used alone or in combination of two or more.

[Method for producing pigment (A-2) represented by general formula (1)]
The method for producing the pigment (A-2) represented by the general formula (1) of the present invention is not particularly limited and can be produced by a known method. For example, the following method can be mentioned.

The compound represented by the following chemical formula (3) is halogenated and then hydrolyzed to obtain the following general formula (4), which is reacted with diphenyl phosphate to obtain the pigment (A) represented by the general formula (1). -2) can be manufactured.

Chemical formula (3)

The halogenation of the compound represented by the chemical formula (3) is carried out by, for example, the chlorosulphonic acid method, the dissolution method or the like described in The Phalocynanines Volume II Manufacture and Applications (CRC Press, Inc., 1983) or the like. Can be synthesized.

Examples of the chlorosulphonic acid method include dissolving the compound represented by the chemical formula (3) in a sulfur oxide-based solvent such as chlorosulphonic acid and sulfuric acid, and adding a halogenating agent to the solution to halogenate the compound. The reaction temperature at this time is preferably 20 to 120 ° C., and the reaction time is preferably about 1 to 10 hours.

Examples of the dissolution method include aluminum chloride, aluminum halide such as aluminum bromide, titanium halide such as titanium tetrachloride, sodium chloride, sodium bromide and the like, as described in Japanese Patent Application Laid-Open No. 51-64534. Such alkali metal halides or alkaline earth metal halides (hereinafter referred to as alkali (earth) metal halides], thionyl chloride, etc., which are composed of one kind or a mixture of two or more kinds of various halogenating agents, about 10 to 170 ° C. A method of halogenating a phthalocyanine compound in the melt of the above can be mentioned.

The halogenating agent means a fluorinating agent, a chlorinating agent, a brominating agent and an iodizing agent. For example, examples of the fluorinating agent include fluoroxitrifluoromethane, cesium sulfate, acetylhypofluorite, N-fluorosulfonamide, diethylaminosulfatrifluoride, N-fluoropyridinium salt and the like.
Examples of the chlorinating agent include chlorine (Cl ₂ ), N-chlorosuccinimide, sulfuryl chloride, trichloroisocyanuric acid, sodium dichloroisocyanuric acid, 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone. , 2,3,4,4,5,6-hexachloro-2,5-cyclohexadienone, N-chlorotriethylammonium chloride, benzeneselenenyl chloride and the like.
Examples of the brominating agent include bromine (Br ₂ ), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexy. Sa-2,5-dieneon, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1,3-dibromo-5,5-dimethylhydantin, etc. Can be mentioned.
Examples of the iodine agent include iodine (I ₂ ), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetylhypoyodite, iodine-periodic acid, ethylene iodochloride, N-iodosuccinimide and the like. ..

Since the compound represented by the general formula (4) has properties as a pigment, a method such as an acid pacing method or a solvent salt milling method is used prior to the reaction in order to improve the reaction efficiency with diphenyl phosphate. It is desirable to use the one that has been miniaturized by. By refining the compound represented by the general formula (4) in advance, it becomes easy to obtain fine pigments (A-2) represented by the general formula (1) produced from the compound. When used as a photosensitive composition, high contrast can be easily obtained.

The reaction between the compound represented by the general formula (4) and diphenyl phosphate can be allowed to proceed, for example, by mixing and stirring in an organic solvent. Then, by removing the organic solvent, the pigment (A-2) represented by the general formula (1) can be obtained.

The organic solvent used in the production of the pigment (A-2) represented by the general formula (1) is, for example, a monovalent alcohol solvent typified by methanol, ethanol, isopropanol and t-butanol, and ethylene. For glycols, propylene glycols, diethylene glycols, polyethylene glycols, thiodiglycols, dithiodiglycols, 2-methyl-1,3-propanediols, 1,2,6-hexanetriols, acetylene glycol derivatives, glycerin, trimethylolpropane, etc. Typical polyhydric alcohol solvents, 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactum, formamide, N-methylformamide, N, N-dimethylformamide , Acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropaneamide, hexamethylphosphoric triamide, urea, or amide-based solvents such as tetramethylurea, and other ethylene glycol monomethyl (or ethyl). ) Lower monoalkyl ether solvents of polyhydric alcohols such as ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglime), or tri. Polyether-based solvents such as ethylene glycol dimethyl ether (triglime), sulfur-containing solvents such as sulfolane, dimethylsulfoxide, or 3-sulfolen, polyfunctional solvents such as diacetone alcohol and diethanolamine, acetic acid, maleic acid, docosahexaenoic acid, and trichloro. Examples thereof include carboxylic acid-based solvents such as acetic acid or trifluoroacetic acid, sulfonic acid-based solvents such as methanesulfonic acid or trifluorosulfonic acid, and aromatic hydrocarbon-based solvents such as benzene, toluene and xylene, but phosphoric acid. Due to the good dissolution of diphenyl, monovalent alcohol solvents such as methanol, ethanol and isopropyl alcohol, and aprotonic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide and 1-methyl-2-pyrrolidinone. It is preferable to use. These organic solvents can be used alone or in combination of two or more.

The method for removing the organic solvent after completion of the reaction is not particularly limited, and a known method can be used, but it is compatible with the organic solvent used after suction filtration or pressure filtration. Moreover, it is desirable to remove it by drying after washing with an organic solvent having a low boiling point. In the case of a water-soluble organic solvent, it is desirable to mix it with water and then remove it by washing with water.

In the photosensitive composition of the present invention, the mass ratio of the halogenated zinc phthalocyanine pigment (A-1) to the pigment (A-2) represented by the general formula (1) is 90:10 to 10:90. Is preferable. From the viewpoint of suppressing solvent shock and fingerprint authentication accuracy, 90:10 to 40:60 is more preferable, and 80:20 to 60:40 is particularly preferable.

(Other pigments (A-3))
The photosensitive composition of the present invention may contain another pigment (A-3) as the pigment (A). The other pigment (A-3) is not particularly limited, and known pigments can be used.

Other pigments (A-3) are, for example, C.I. I. Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 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, 98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,139,147, 150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,1733,174,175,176,177,179,180,1811 182,185,187,188,193,194,198,199,213,214,218,219,220,221, Japanese Patent Application Laid-Open No. 2012-226110, Japanese Patent No. 6432077;
C. I. Pigment Red 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48, 48: 1,48: 2,48: 3,48: 4,49,49: 1,49: 2,50: 1,52: 1,52: 2,53,53: 1,53: 2,53: 3,57,57: 1,57: 2,58: 4,60,63,63: 1,63: 2,64,64: 1,68,69,81,81: 1,81: 2,81: 3,81: 4,83,88,90: 1,101,101: 1,104,108,108: 1,109,112,113,114,122,123,144,146,147,149,1511 166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208, 209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254 255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280, 281,282,283,284,285,286,287,291,295,296, the pigment described in JP-A-2014-134712, the red pigment described in Japanese Patent No. 6368844;
C. I. Pigment Green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,37,45,48,50,51,54,55,62 and other green pigments;
C. I. Pigment Blue 1,1: 2,9,14,16,17,19,25,27,28,29,33,35,36,56,56: 1,60,61,61: 1,62,63, Blue pigments such as 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79;
C. I. Pigment Violet 1,1: 1,2,2: 2,3,3: 1,3: 3,5,5: 1,14,15,16,19,23,25,27,29,31,32, Purple pigments such as 37, 39, 42, 44, 47, 49, 50;
C. I. Pigment Orange 36, 38, 43, 64, 71, 73 and other orange pigments can be mentioned.

The content of the pigment (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

(Miniaturization of pigment (A))
The pigment (A) is preferably used in a finely divided form. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used. Among these, the salt milling treatment by the kneader method, which is one of the wet grinding methods, is preferable. The average primary particle size determined by the TEM (transmission electron microscope) of the finely divided pigment is preferably 5 to 90 nm. From the viewpoint of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

Salt milling treatment is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating it using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the pigment (A) from the viewpoint of both treatment efficiency and production efficiency.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. 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 and the like are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

If necessary, a resin may be added to the salt milling treatment. The type of the resin is not particularly limited, and examples thereof include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. Among these, it is preferable that it is solid at room temperature, is insoluble in water, and is partially soluble in the above organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.

(dye)
The photosensitive composition of the present invention can contain a dye. The dye is not particularly limited, and a known dye can be used.

Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium-dye dyes, building dyes, sulfide dyes and the like. Further, a derivative of a dye and a lake pigment obtained by converting a dye into a lake can also be mentioned.

The dye is preferably used as a salt-forming compound. The salt-forming compound is a salt-forming compound of an acidic dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a resin component having an amino group and a salt-forming compound such as an acidic dye; Salt-forming compounds of acidic dyes and compounds having onium bases; salt-forming compounds of basic dyes with organic acids, perchloric acids, or metal salts thereof. Among these, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments. The compound having an onium base is preferably a resin having a cationic group in the side chain.

The chemical structure of the dye is, for example, azo dye, disazo dye, azomethin dye (Indoaniline dye, Indophenol dye, etc.), Dipyrromethene dye, Kinone dye (Benzoquinone dye, Naftkinone dye, Anthracone). Dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azines. Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, Examples thereof include dye structures derived from dyes selected from perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and their metal complex dyes.

Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthracinone dyes, dipyrromethene dyes from the viewpoint of color characteristics such as hue, color separability, and color unevenness. , Squalylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, and dyes selected from dyes are preferable. A dye structure derived from a dye selected from the dyes and phthalocyanine dyes is more preferable.

[Dye derivative (F)]
The photosensitive composition of the present invention may contain a dye derivative (F), if necessary.

The dye derivative (F) is not particularly limited, and examples thereof include a dye derivative having an acidic group, a basic group, a neutral group, or the like as an organic dye residue. The dye derivative (F) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphate group, an amine salt thereof, or a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal. Examples thereof include compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthracinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, etc. Examples include indol pigments such as benzoisoindole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo, disazo, polyazo and other azo pigments. Be done.

Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-22520, International Publication No. 2009/081930, International Publication No. 2011/0526117, International Publication No. 2012/102399, JP-A-2017 -156397, as phthalocyanine dye derivatives, JP-A-2007-226161, International Publication No. 2016/163351, JP-A-2017-165820, Patent No. 5735266, as anthracinone dye derivatives. , JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265679, JP-A-2007-079094, International Publication No. 2009/025325, As the quinacridone-based dye derivative, JP-A-48-54128, JP-A-03-9961 and JP-A-2000-273383, and as the dioxazine-based dye derivative, JP-A-2011-162662, JP-A-2011-162662, Tiadine indigo. As the dye derivative, JP-A-2007-314785, and as the triazine-based dye derivative, JP-A-61-246261, JP-A-11-19976, JP-A-2003-165922, JP-A-2003- 168208, JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, and JP-A-2003-167112 as a quinophthalone-based dye derivative. JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, and as naphthol-based dye derivatives, JP-A-2012-208329, JP-A-2014-5439, Azo JP-A-2001-172520 and JP-A-2012-1722092 are used as dye derivatives, JP-A-2004-307854 is used as an acidic substituent, and JP-A-2002-201377 is used as a basic substituent. , JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

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

The content of the dye derivative (F) is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the pigment (A).

[Dispersed resin (G)]
The photosensitive composition of the present invention may contain a dispersion resin (G), if necessary.
The dispersed resin (G) has an adsorbing group having a high affinity for the pigment. The adsorbing group is preferably one or more of a cationic group and an anionic group.

Examples of the resin having a cationic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonia base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle as the cationic group. Will be.

Examples of the resin having an anionic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group and the like as anionic groups. Of these, a carboxyl group and a phosphoric acid group are preferable from the viewpoint of adsorptivity to pigments.

The resin type of the dispersed resin (G) is, for example, a urethane resin, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a polycarboxylic acid. Alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters and modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups. Water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples thereof include sex resins, water-soluble polymer compounds, polyester-based materials, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.

Examples of the structure of the dispersed resin (G) include a random structure, a block structure, a graft structure, a comb-shaped structure, and a star-shaped structure. Among these, a block structure or a comb-shaped structure is preferable from the viewpoint of dispersion stability.

Commercially available products of the dispersed resin (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, manufactured by Big Chemie Japan. 166,167,168,170,171,174,180,181,182,183,184,185,190,2000,2001,2009,2010,2020,2025,205,2070,2095,2150,2155,2163 2164, or Anti-Terra-U203,204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykuman, etc. , 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 Etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan Ltd. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. In JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, etc. Examples thereof include the described resins.

The dispersed resin (G) can be used alone or in combination of two or more.

The content of the dispersed resin (G) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the pigment (A) from the viewpoint of dispersion stability.

[Alkali-soluble resin (B)]
The photosensitive composition of the present invention contains an alkali-soluble resin (B).

The alkali-soluble resin (B) is a resin that dissolves in an alkaline developer, and a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm when a film having a thickness of 2 μm is formed is preferable. The transmittance is preferably 95% or more.
The alkali-soluble resin (B) can be classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin. Examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group. Among these, a carboxyl group is preferable. Further, the alkali-soluble resin (B) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

(Non-photosensitive alkali-soluble resin)
The non-photosensitive alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, and the like. Alternatively, isobutylene / (anhydrous) maleic acid copolymer and the like can be mentioned. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable.

(Photosensitive alkali-soluble resin)
The photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. As the photosensitive alkali-soluble resin, for example, a resin synthesized by the method (i) or (ii) shown below is preferable. By curing with active energy rays, the resin is three-dimensionally crosslinked to improve the crosslink density and chemical resistance.

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

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

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-. Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethylene oxide (EO) modified cresol acrylate, n-nonyl Phenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, nonylphenol (Meta) acrylates such as PO-modified (meth) acrylates;
(Meta) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloyl morpholine. ;
Styrene, or styrenes such as α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidecoumarin, 4,4'-Bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedi maleimide, N, N'-1,4-phenylenedi Maleimide, 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-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl N-substituted maleimides such as -6-maleimide hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimide acrydin;
2- (Meta) acryloyloxyethyl acid phosphate, a phosphate ester group-containing compound such as a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer described later with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Ester is mentioned.

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. Further, if necessary, a tricarboxylic acid dianhydride such as trimellitic acid anhydride and a tetracarboxylic acid dianhydride such as pyromellitic acid anhydride can be used to hydrolyze the remaining anhydride groups.

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

[Method (ii)]
The method (ii) synthesizes, for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

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

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

As the monocarboxyl group-containing monomer and other monomers, those described above can be used.

The raw materials used for the synthesis of the alkali-soluble resin (B) can be used alone or in combination of two or more.

The alkali-soluble resin (B) can be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 3,000, and 4,000 to 20,000 from the viewpoint of developability. Especially preferable. Further, the value of Mw / Mn is preferably 10 or less. The appropriate weight average molecular weight (Mw) improves the adhesion to the substrate and the alkali development solubility.

The acid value of the alkali-soluble resin (B) is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. Adhesion to the substrate and alkali development solubility are improved by an appropriate acid value.

The content of the alkali-soluble resin (B) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the pigment (A).

[Polymerizable compound (C)]
The photosensitive composition of the present invention contains the polymerizable compound (C). The polymerizable compound (C) is a monomer (monomer) containing a polymerizable unsaturated group, a dimer, a dimer, and an oligomer. Examples of the polymerizable unsaturated group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group and the like. The polymerizable compound (C) is, for example, a polymerizable compound having an acid group (C-1), a polymerizable compound having a urethane bond and an acid group (C-2) (excluding (C-1)), and the like. Other examples include a polymerizable compound (C-3).

(Polymerizable compound having an acid group (C-1))
The photosensitive composition of the present invention preferably contains a polymerizable compound (C-1) having an acid group. As a result, the development residue can be suppressed when forming a pattern by the photolithography method, so that the fingerprint authentication accuracy is improved. Examples of the acid group of the polymerizable compound (C-1) having an acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Of these, a carboxyl group is preferable.

The polymerizable compound (C-1) having an acid group is, for example, an esterified product of a polyhydric alcohol, a free hydroxyl group-containing poly (meth) acrylate of (meth) acrylic acid, and a dicarboxylic acid; , Esterized products with monohydroxyalkyl (meth) acrylates and the like.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, dimethylolpropane, pentaerythritol, and dipentaerythritol.
Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, itaconic phthalate and the like.
Examples of the polyvalent carboxylic acid include trimellitic acid and pyromellitic acid.
Examples of monohydroxyalkyl (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and pentaerythritol. Examples thereof include triacrylate and 2-hydroxy-3-acryloyloxypropyl methacrylate.

Commercially available products of the polymerizable compound (C-1) having an acid group include, for example, Viscoat # 2500P manufactured by Osaka Organic Co., Ltd. and Aronix M-5300, M-5400, M-5700, M-510, M manufactured by Toagosei Co., Ltd. -520, M-521 and the like can be mentioned.

The content of the polymerizable compound (C-1) having an acid group is preferably 5 to 100% by mass, preferably 25 to 100% by mass, based on 100% by mass of the polymerizable compound (C) from the viewpoint of the development residue at the time of pattern formation. % By mass is more preferable. By improving the pattern formation property, the fingerprint authentication accuracy is also improved.

(Polymerizable compound having urethane bond and acid group (C-2))
The photosensitive composition of the present invention more preferably contains a polymerizable compound (C-2) having a urethane bond and an acid group. The polymerizable compound (C-2) is preferably a compound represented by the following general formula (5).

General formula (5) (H ₂ C = C (R ¹ ) COO) _m -X- (OCOCH (R ¹ ) CH ₂ S (R ² ) COOH) _n
In the general formula (5), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and X is an organic having a (m + n) -valent urethane bond having 3 to 60 carbon atoms. The group, m is an integer of 2 to 18, and n is an integer of 1 to 3.

For the compound represented by the general formula (5), for example, first, a polyfunctional isocyanate compound is first reacted with a hydroxyl group-containing (meth) acrylate. Then, it can be synthesized by a method of adding a mercapto compound having a carboxyl group to the product.

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

The (meth) acrylate having a hydroxyl group is, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylol propandi (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol propanthryl (meth). Meta) 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, glycero- Examples thereof include luacrylate methacrylate, glycero-ludimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid and the like.

The content of the polymerizable compound (C-2) having a urethane bond and an acid group is preferably 5 to 100% by mass, preferably 5 to 100% by mass, based on 100% by mass of the polymerizable compound (C) from the viewpoint of the development residue at the time of pattern formation. ~ 100% by mass is more preferable.

(Other polymerizable compounds (C-3))
Other polymerizable compounds (C-3) 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-hexanedioldi (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethyl propantri (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 ) Acrylate, isocyanuric acid EO-modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanedio-ldiglycidyl ether di ( Meta) 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) Various acrylic acid esters such as meth) acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, and methacrylic acid ester, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Examples thereof include pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

Other commercially available products of the polymerizable compound (C-3) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R manufactured by Nippon Kayaku Co., Ltd. -604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Toagosei Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M- 400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat # 310HP manufactured by Osaka Organic Co., Ltd. , # 335HP, # 700, # 295, # 330, # 360, #GPT, # 400, # 405, UV-4108F, UV-4117F, NK Ester A-9300, UA-160TM, Kyoeisha, manufactured by Shin-Nakamura Chemical Co., Ltd. Examples thereof include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Chemical Corporation.

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

The content of the polymerizable compound (C) is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

[Photopolymerization Initiator (D)]
The photosensitive composition of the present invention contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D), the photosensitive composition can be cured by ultraviolet irradiation, and an optical filter can be formed by a photolithography method.

The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2. -Methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1-[ 4- (4-Molholino) phenyl] -2- (phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone and other acetophenone compounds;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal;
Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4, Benzophenone compounds such as 4'-tetra (t-butylperoxycarbonyl) benzophenone;
Thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine. Triazine;
1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)], or ester, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-Il]-, 1- (O-acetyloxime) and other oxime ester compounds;
Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Kinone-based compounds such as 9,10-phenanthrene quinone, camphor-quinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds may be mentioned.

Commercially available products include "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one) and "Omnirad 369E" manufactured by IGM Resins as acetphenone compounds. (2- (Dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone), "Omnirad 379EG" (2- (dimethylamino) -2-[((dimethylamino) -2-[() 4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), as a phosphine compound, manufactured by IGM Resins, "Omnirad 819" (bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphinoxide), as an oxime compound, 1,2-octanedione, 1- [4- (4), manufactured by BASF Japan, Inc. Phenylthio) Phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-yl]-, 1- (O-Acetyl Oxime) (IRGACURE OXE 02), IRGACURE OXE 04), N-1919, NCI-730, NCI-831, NCI-930 manufactured by ADEKA, TRONLY TR-PBG-304 manufactured by Changzhou Strong New Materials Co., Ltd. , TRONLY TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-3054 and the like. Further, the oxime ester-based photopolymerization described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-02998, etc. Initiators can also be mentioned.

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

The content of the photopolymerization initiator (D) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the pigment (A) from the viewpoint of photocurability and developability.

[Triarylsulfonium compound (E)]
The photosensitive composition of the present invention preferably contains the triarylsulfonium compound (E). By using the triarylsulfonium compound (E), the transmittance at a wavelength of 700 to 730 nm can be effectively suppressed.

The triarylsulfonium compound (E) includes a compound represented by the following general formula (6).
General formula (6)

In the general formula (6), R ₁ to R ₃ independently have a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, and an alkoxyl which may have a substituent. The aryl group which may have a group and a substituent is shown. X ^- represents a monovalent counter anion.

R ₁ to R ₃ and X ^- in the general formula (6) will be described.

In the general formula (6), R ₁ to R ₃ independently have a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, and an alkoxyl which may have a substituent. The aryl group which may have a group and a substituent is shown.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The alkyl group which may have a substituent is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, and the like. Linear alkyl groups such as stearyl group and 2-ethylhexyl group, or branched alkyl groups, cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, as well as trichloromethyl group and trifluoromethyl group. , 2,2,2-Trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group , Benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and other alkyl groups having substituents.

The alkoxyl group which may have a substituent is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, a 2,3-dimethyl-. A linear alkoxyl group such as 3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, or a branched alkoxyl group, and cyclopropyloxy group, cyclobutyloxy group, cyclopentyl. In addition to cyclic alkoxyl groups such as oxy group and cyclohexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2, Examples thereof include an alkoxyl group having a substituent such as a 2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group and a benzyloxy group.

The aryl group which may have a substituent includes an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and a p-methoxyphenyl group. , 2,4-Dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5 Examples thereof include an aryl group having a substituent such as a 8-trichloro-2-naphthyl group, an anthraquinonyl group and a 2-aminoanthraquinonyl group.

Above all, from the viewpoint of suppressing the transmittance at a wavelength of 700 to 730 nm, it is preferable that at least one of R ₁ to R ₃ is a hydrogen atom.

In the general formula (6), X ⁻ represents a monovalent counter anion. Examples of X- include F- ^{, Cl- ,} Br- ^, I- ^, compounds represented by the following general formulas (7) to (12), and the like.

General formula (7 ⁾ MY _a-
In the general formula (7), M represents a phosphorus atom, a boron atom, or an antimony atom. Y represents a halogen atom and a represents an integer of 4 to 6.

Examples of the compound represented by the general formula (7) include PF ₆ ⁻ , BF ₆ ⁻ , and SbF ₆ ⁻ . Of these, PF ₆ is preferable.

General formula (8) (Rf) _b PF _6- ^b-
In the general formula (8), Rf represents an alkyl group having 1 to 8 carbon atoms in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. The alkyl group may be linear, branched or cyclic. b represents an integer of 1 to 5.

The compounds represented by the general formula (8) are, for example, (CF ₃ CF ₂ ) ₂ PF ^- ₄ , (CF ₃ CF ₂ ) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₂ PF _4- ^, (((CF 3 CF 2)) CF ₃ ) ₂ CF) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^-and the like.

General formula (9 ⁾ R ⁴ _c LY _c-
In the general formula (9), R ⁴ represents a phenyl group in which at least one hydrogen atom is substituted with a halogen atom. L represents a boron atom and a gallium atom, and c represents an integer of 1 to 4.

The compounds represented by the general formula (9) are, for example, (C ₆ F ₅ ) B- ^, ((CF ₃ ) ₂ C ₆ H ₃ ) B- ^, (CF ₃ C ₆ H ₄ ) ₄ B- ^, (C). ₆ F ₅ ) ₄ Ga-, (C ₆ H ₃ F ₂ ) ₄ Ga ^{- and} the like.

General formula (10 ⁾ R ⁵ SO _3-
In the general formula (10), R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a perfluolalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and represents an alkyl group and a perfluolol group. The alkyl group may be linear, branched or cyclic, and the aryl group may be unsubstituted or having a substituent.

The compound represented by the general formula (10) is, for example, trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nanofluorbutane sulfonic acid anion, pentafluorophenylsulfonic acid anion, p-toluene. Examples thereof include sulfonic acid anion, benzene sulfonic acid anion, camphor sulfonic acid anion, butane sulfonic acid anion.

General formula (11) (R ⁶ SO ₂ ⁾ ₃ C-
In the general formula (11), R ⁶ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and is an alkyl group and a perfluoroalkyl group. May be linear, branched or cyclic, and the aryl group may be unsubstituted or having a substituent.

The compounds represented by the general formula (11) are, for example, (CF ₃ SO ₂ ) ₃ C- ^, (C ₂ F ₅ SO ₂ ) ₃ C- ^, (C ₃ F ₇ SO ₂ ) ₃ C- ^, (C ₄ ). F ₉ SO ₂ ) ₃ C ^- etc.

General formula (12) (R ⁷ SO ₂ ⁾ ₂ N-
In the general formula (12), R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and an alkyl group and a perfluoroalkyl group. May be linear, branched or cyclic, and the aryl group may have a substituent.

The compounds represented by the general formula (12) are, for example, (CF ₃ SO ₂ ) ₂ N- ^, (C ₂ F ₅ SO ₂ ) ₂ N- ^, (C ₃ F ₇ SO ₂ ) ₂ N- ^, (C ₄ ). F ₉ SO ₂ ) ₂ N ^- etc.

In addition to the above anions, ^{perhalochloride} ion (Cl0 _4- , BrO _4- ^, etc.), halogenated sulfonic acid ion (FSO _3- ^, ClSO _3- ^, etc.), sulfate ion (CH ₃ SO _4- ^, CF ₃ SO, etc.) _4- ^, HSO _4- ^, etc.), Carbonate ion (HCO _3- ^, CH ₃ CO _3- ^, etc.), Aluminate ion (AlCl _4- ^, AlF _4- ^, etc.), Carboxylic acid ion (CHCOO- ^, CF ₃ COO- ^, etc.), C ₆ H ₅ COO- ^, CH ₃ C ₆ H ₄ COO- ^, C ₆ F ₅ COO- ^, etc.), Arylborate ion (B (C ₆ H ₅ ) _4- ^, etc.), JP2013-092657, p. Examples thereof include anions described in Japanese Patent Application Laid-Open No. 2013-080245, Japanese Patent Application Laid-Open No. 2013-080240, Japanese Patent Application Laid-Open No. 2013-047211, Japanese Patent Application Laid-Open No. 2013-033161 and the like.

Among them, Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₆ ⁻ , trifluoromethanesulfonate anion, and nonafluorobutane sulfonate anion are preferable as X ⁻ from the viewpoint of suppressing the transmittance at a wavelength of 700 to 730 nm.

Examples of the triarylsulfonium compound (E) represented by the general formula (6) include the following compounds.

Commercially available products of the triarylsulfonium compound (E) are, for example, WPAG-336, 367, 370, 469, 638 manufactured by Fuji Film Wako Pure Chemical Industries, SP-056,066 manufactured by ADEKA, and Sanwa Chemical Co., Ltd. Examples thereof include TS-91 and T1608, 1609 manufactured by Tokyo Chemical Industry Co., Ltd.

The triarylsulfonium compound (E) can be used alone or in combination of two or more.

The content of the triarylsulfonium compound (E) is 0.1 with respect to 100 parts by mass of the pigment (A-2) represented by the general formula (1) from the viewpoint of suppressing the transmittance at a wavelength of 700 to 730 nm. It is preferably up to 15 parts by mass, more preferably 0.2 to 10 parts by mass, still more preferably 0.5 to 5% by mass.

[Near infrared absorber (H)]
The photosensitive composition of the present invention can contain a near-infrared absorber (H). As a result, near-infrared light having high transparency can be blocked from the body tissue, so that the accuracy of fingerprint authentication is improved. The near-infrared absorber (H) is a compound that absorbs light having a wavelength of 750 to 1,200 nm.

Examples of the near-infrared absorber (H) include a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, an immonium compound, a pyrolopyrrole compound, a squarylium compound, a croconium compound and the like. Among these, a cyanine compound, a pyrolopyrrole compound, and a squarylium compound are preferable.

Among the near-infrared absorbers (H), the cyanine compounds are International Publication No. WO2006 / 006573, International Publication No. WO2010 / 073857, JP2013-241598A, JP-A-2016-11351, JP-A-2016-. 113504; The phthalocyanine compound is JP-A-4-23868, JP-A-06-192584, JP-A-2000-63691, International Publication No. WO2014 / 208514; the naphthalocyanine compound is JP-A-11-152414. No., JP-A-2000-86919, JP-A-2009-29955, International Publication No. WO2018 / 186490; For immonium compounds, JP-A-2005-336150, JP-A-2007-197492, JP-A. 2008-88426; Pyrrolopyrrole compounds are JP-A-2009-263614, JP-A-2010-90313, JP-A-2011-066731; for squarylium compounds, JP-A-2011-132361, JP-A. 2016-142891, International Publication No. WO2017 / 135359, International Publication No. WO2018 / 2258337, Japanese Patent Laid-Open No. 2019-001987, International Publication No. WO2020 / 054718; Croconium compounds, International Publication No. WO2019 / 021767, etc. The compounds described in the above are mentioned.

The near-infrared absorber (H) can be used alone or in combination of two or more.

[Sensitizer (I)]
The photosensitive composition of the present invention can contain a sensitizer (I).

The sensitizer (I) may be, for example, a chalcone derivative, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivative typified by benzyl or camphorquinone, a benzoin derivative, a fluorene derivative, etc. Polymethine dyes such as naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridin derivatives, azine derivatives, thiazine derivatives, oxadins. Derivatives, indolin derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triallylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquino Xalilloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyllin derivative, anurene derivative, spiropyran derivative, spiroxazine derivative, thiospiropyrane derivative, metal allene complex, organic ruthenium complex, or Mihira -Ketone derivatives, α-acyloxyesters, acyloxides, methylphenylglycilate, benzyls, 9,10-phenanthrenquinones, kanfa-quinones, ethyl anthracinones, 4,4'-diethylisophthalofenone, Examples thereof include 3,3'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4'-bis (diethylamino) benzophenone.

Among the sensitizer (I), a thioxanthone derivative, a Mihira-ketone derivative, and a carbazole derivative are preferable. Specific compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis. (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-Dibenzoyl-N-ethylcarbazole and the like are preferable.

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

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

[Thermosetting compound (J)]
The photosensitive composition of the present invention can contain a thermosetting compound (J). As a result, the thermosetting compound (J) reacts in the heating step after the film is formed, and the crosslink density is increased, so that the heat resistance is improved.

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

(Epoxy compound (J-1))
The epoxy compound (J-1) includes, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, etc.). Dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) With polycondensates, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, nourbornadiene, vinylnolbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Polymers, polycondensates of phenols and ketones (acetones, methylethylketones, methylisobutylketones, acetophenones, benzophenones, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, etc.) Polycondensate with α', α'-benzenedimethanol, biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, α'-dichloro Polycondensate with xylene, bischloromethylbiphenyl, etc.), polycondensate of bisphenols and various aldehydes, glycidyl ether-based epoxy resin obtained by glycidylating alcohols, alicyclic epoxy resin, heterocyclic epoxy resin, fat Examples thereof include group epoxy resins, glycidylamine-based epoxy resins, and glycidyl ester-based epoxy resins.

Commercially available products include, for example, Epicoat 807,815,825,827,828,190P,191P manufactured by Yuka Shell Epoxy, TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd. EOCN-102S, 103S, 104S, 1020 Epicoat 1004, 1256 manufactured by Japan Epoxy Resin, JER1032H60, 157S65, 157S70, 152, 154, Serokiside 2021 manufactured by Daicel Chemical Industries, EHPE-3150, Denacol manufactured by Nagase Chemtex. EX-21,212,252,313,314,321,411,421,512,521,611,612,614,614B,622,711,721, TEPIC-L, H, S, etc. manufactured by Nissan Chemical Industries, Ltd. Can be mentioned.

The content of the epoxy compound (J-1) is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the pigment (A) from the viewpoint of heat resistance of the coating film. preferable.

(Oxetane compound (J-2))
The oxetane compound (J-2) is a known compound having an oxetane group. Examples of the oxetane compound include a monofunctional oxetane compound, a bifunctional oxetane compound, and a trifunctional or higher functional oxetane compound.

The monofunctional oxetane compound is, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methylmethacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-. (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxy) Cyril) propoxy] methyl} oxetane and the like.

Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101,212 manufactured by Toagosei Co., Ltd., and the like.

Bifunctional oxetane compounds include, for example, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 1,4-Bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl ether 3 -Ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-oxetanyl)- 5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glyco-subis (3-Ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycolbis (3) -Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-) Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like can be mentioned.

Examples of commercially available products include OXBP and OXTP manufactured by Ube Kosan Co., Ltd., and OXT-121,221 manufactured by Toagosei Corporation.

Examples of the trifunctional or higher functional oxetane compound include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl-3). -Oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-) 3-Oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaxe (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing oxetane group (3-ethyl-3-oxetanylmethyl) ether For example, a polymer obtained by radically polymerizing a (meth) acrylic monomer such as the oxetane-modified phenol novolac resin described in Patent No. 3783462 and the above-mentioned OXE-30 can be mentioned.

The content of the oxetane compound (J-2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

The melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol-type or ether-type compound, and more preferably a melamine compound having an average number of methylol groups and / or ether groups of 5.0 or more per melamine ring. If the number of methylol groups and ether groups is appropriate, it is easy to obtain heat resistance that is not excessive or insufficient.

Commercially available products include, for example, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, manufactured by Sanwa Chemical Co., Ltd. MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX- 417, MX-410, Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Cytec Industries Co., Ltd. and the like can be mentioned.

Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW, which have an average number of methylol groups and / or ether groups of 5.0 or more per melamine ring. -30, MW-22, MS-21, MS-11, MW-24X, MX-45 (all manufactured by Sanwa Chemical Co., Ltd.), Cymel 232,235,236,238,300,301,303,350 (all) (Manufactured by Nippon Cytec Industries Co., Ltd.), etc. are preferable in terms of increasing the crosslink density.

The thermosetting compound (J) can be used alone or in combination of two or more.

In the photosensitive composition of the present invention, a curing agent (curing accelerator) can be used in combination to assist the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2). -Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4 -Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- Examples thereof include S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.).

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

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

[Thiol chain transfer agent (K)]
The photosensitive composition of the present invention can contain a thiol-based chain transfer agent (K). When the thiol-based chain transfer agent (K) is used in combination with the photopolymerization initiator (D), chiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the photosensitivity of the photosensitive composition is improved. do.

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

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butandio-rubistiopropionate, 1,4-butandio-rubistioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propanetristhioglycolate, Trimethylol Propantristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Trimercapto Tris (2-hydroxyethyl) propionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto- Examples thereof include s-triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylol propanthithiopropionate, pentaerythritol tetrakisthiopropionate and the like.

The thiol-based chain transfer agent (K) can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent (K) is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, based on 100 parts by mass of the non-volatile content of the photosensitive composition. When an appropriate amount is contained, the light sensitivity is improved and wrinkles are less likely to occur on the surface of the coating film.

[Polymerization inhibitor (L)]
The photosensitive composition of the present invention can contain a polymerization inhibitor (L).

The polymerization inhibitor (L) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol. , 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol , 4-t-butylcatechol, alkylcatechol compounds such as 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorsinol, 4-ethylresorsinol, 2 -Alkylresolsinol compounds such as propylresorsinol, 4-propylresorsinol, 2-n-butylresorsinol, 4-n-butylresorsinol, 2-t-butylresorsinol, 4-t-butylresorsinol, etc. Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenyl Examples thereof include phosphine compounds such as phosphine and tribenzylphosphine, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin. ..

The content of the polymerization inhibitor (L) is preferably 0.01 to 0.4% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[Ultraviolet absorber (M)]
The photosensitive composition of the present invention can contain an ultraviolet absorber (M).

The ultraviolet absorber (M) is an organic compound having an ultraviolet absorbing function, and is a benzotriazole-based organic compound, a triazine-based organic compound, a benzophenone-based organic compound, a salicylic acid ester-based organic compound, a cyanoacrylate-based organic compound, and salicylate. Examples include system organic compounds.

Benzotriazole compounds include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3. , 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole 2-yl)-(1,1- Dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester mixture, 2- (2H-benzotriazole 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole 2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H) -Reaction product of -benzotriazole 2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole 2-yl) -4- (1,1,3) 3-Tetramethylbutyl) Phenol, 2,2'-Methylenebis [6- (2H-benzotriazole2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2H-) Benzotriazole 2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole 2-yl) -6-t-butyl-4-methylphenol, 2- (3,5-di-t-amyl) -2-Hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy- 5- (5-Chloro-2H-benzotriazole2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole2-yl) ) Phenol] propionate.

Commercially available products include, for example, TINUVIN P, PS, 234,326,329,384-2,900, 928,99-2,1130 manufactured by BASF Japan, and ADEKA STAB LA-29, LA-31RG, LA manufactured by ADEKA. -23, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

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

Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, ADEKA STAB LA-46, LA-F70 manufactured by ADEKA, and CYASORB manufactured by Sun Chemical Co., Ltd. UV-1164 and the like can be mentioned.

Examples of the benzophenone compound include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 2 -Hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-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'-tetrahydroxybenzopheno , 2-Hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of commercially available products include KEMIROSB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Sipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., and the like. Be done.

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

The content of the ultraviolet absorber (M) is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (M).

[Antioxidant (N)]
The photosensitive composition of the present invention may contain an antioxidant (N). As the antioxidant (N), the photopolymerization initiator (D) and the thermosetting compound (J) contained in the photosensitive composition prevent yellowing due to oxidation by heat curing or a thermal process during ITO annealing. , The decrease in the transmittance of the film can be suppressed. In particular, when the pigment concentration of the photosensitive composition is high, the content of the photopolymerizable compound decreases relatively, so if the amount of the photopolymerization initiator is increased or the thermosetting compound is blended, the film will turn yellow. easy. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and suppress a decrease in the transmittance of the coating film.

Examples of the antioxidant (N) include hydride-based phenol-based, hydride-based amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound containing no halogen atom.

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

The hydride phenolic antioxidant is, for example, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trion, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 4,4'-butylidene-bis- (2' -T-butyl-5-methylphenol), 3- (3,5-di-t-butyl-4-hydroxyphenyl) stearyl propionate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-) 4-Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4 8,10-Tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1, 3,5-Tris (3-hydroxy-4-t-butyl-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2 '-Methylenebis (6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylene Bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6- Bis (dodecylthiomethyl) -o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis (octylthiomethyl) -o-cresol, bis [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2'-thio -Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis -(4) , 6-dimethyl-phenol), 2,2'-methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol And so on.

Commercially available products include, for example, ADEKA tabs AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, and KEMINOX 101, 179, 76, 9425 manufactured by Chemipro. , BASF Japan's IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sun Chemical's Sianox CY-1790, CY-2777, etc. Can be mentioned.

Examples of the hindered amine antioxidants include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and tetrakis (2,2,6). , 6-Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6) , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-yl Weights of piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidylmethacrylate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine Condensate, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4) -Piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol Ester of 3,5,5-trimethylhexanoic acid, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-) Piperidine) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine, bisdecanediate (2,2,6,6-tetramethyl-1- (octyl) Oxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (3,5-bis (3,5-bis) 1,1 dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate methyl 1,2,2,6,6-pentamethyl-4-piperidylsevakate, poly [[6-morpholino-s-triazine-2 , 4-Diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1, 6-Hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide And so on.

Commercially available products include, for example, ADEKA tab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87. , LA-402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan, and Siasorb UV-3346 manufactured by Sun Chemical Co., Ltd. , UV-3259, UV-3853 and the like.

Phylline antioxidants include, for example, di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis (4,6). -Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4' -Isopropyridene diphenyl diphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisodecylphosphite, tris (isodecyl) phosphite, triphenylphosphite, tetrakis (2,4-di-t-butylphenyl)- 4,4-Biphenyldiphoshonito, Tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropyridene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (biphenyl) phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (Nonylphenyl) Pentaerythritol diphosphite, Phenylbisphenol A Pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodiumbis (4-t-butylphenyl) phos Fight, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2,4) -Dit-butyl-6-methylphenyl) and the like.

Commercially available products include, for example, ADEKA tab PEP-36, PEP-8, HP-10, 211, 1178, 1500, C, 135A, 3010, TPP, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. -EPQ and the like can be mentioned.

Sulfur-based antioxidants include, for example, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate], 3,3'-. Ditridecyl thiobispropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o- Cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like can be mentioned.

Examples of commercially available products include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

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

The content of the antioxidant (N) is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive composition. Appropriate amounts improve transmittance, spectral characteristics, and sensitivity.

[Leveling agent (O)]
The photosensitive composition of the present invention can contain a leveling agent (O). As a result, the wettability to the substrate and the dryness of the film at the time of film formation are further improved. Examples of the leveling agent (O) include a silicone-based surfactant, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.

Commercially available products include, for example, BYK-300, 306, 310, 313,315N, 320,322,323,330,331,333,342,345,346,347,348,349,370,377, manufactured by Big Chemie. 378,3455, UV3510,3570, FZ-7002,2110,2122,212,2191,5609, manufactured by Toray Industries, Inc., X-22-4952, X-22-4272, X-, manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain or a leveling agent.

Commercially available products include, for example, AGC Seimi Chemical's Surflon S-242,243,420,611,651,386 and DIC's Megafuck F-253,477,551,552,555,558,560,570. , 575,576, R-40-LM, R-41, RS-72-K, DS-21, FC-4430, 4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1 manufactured by Mitsubishi Materials Electronics Chemical Corporation. , EF-PP32C1, Neos Co., Ltd. Futergent 602A and the like.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristel ether, and polyoxyethylene octyl. Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrene phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monoolate, sorbitan triolate, sorbitan sesquiolate, polyoxyethylene sorbitan mono Laurate, Polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan monoolate, Polyoxyethylene sorbitan triisostearate, Polyoxytetraoleate Ethylene sorbit, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monostearate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl Examples thereof include alkanolamide and alkylimidazolin.

Commercially available products include, for example, Emargen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 manufactured by Kao Corporation. , 705,707,709,1108,1118S-70,1135S-70,1150S-60,2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Polymer 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Adecapluronic® L-23, 31, 44,61,62,64,71,72,101,121, TR-701,702,704,913R, (meth) acrylic acid-based (co) polymer polyflo-No. manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 and the like can be mentioned.

Examples of the cationic surfactant include alkylquaternary ammonium salts such as alkylamine salts, lauryltrimethylammonium chlorides, stearyltrimethylammonium chlorides, and cetyltrimethylammonium chlorides, and ethylene oxide adducts thereof.

Examples of commercially available products include acetamine 24, coatamine 24P, 60W, 86P conch manufactured by Kao Corporation.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanol lauryl sulfate. Examples thereof include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and the like.

Examples of commercially available products include Futergent 100 and 150 manufactured by Neos, Adeka Hope YES-25 manufactured by ADEKA, and Adecacol TS-230E, PS-440E, and EC-8600.

Examples of the amphoteric tenside include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Examples of commercially available products include Anhitor 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation.

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

The content of the leveling agent (O) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition. Within this range, the balance between the coatability of the photosensitive composition, the pattern adhesion, and the transmittance is further improved.

[Storage stabilizer (P)]
The photosensitive composition of the present invention can contain a storage stabilizer (P). This stabilizes the viscosity of the photosensitive composition over time. The storage stabilizer (P) includes, for example, quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenyl and the like. Examples thereof include organic phosphine and phosphite.

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

[Adhesion improver (Q)]
The photosensitive composition of the present invention can contain an adhesion improver (Q). This improves the adhesion between the coating and the base material. In addition, the photolithography method facilitates the formation of narrow patterns.

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

The adhesion improver (Q) can be used alone or in combination of two or more.

The content of the adhesion improver (Q) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the pigment (A).

[Organic solvent (R)]
The photosensitive composition of the present invention can contain an organic solvent (R).

The organic solvent (R) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butandiole, 1,3-butylene glycol, 1,3-butylene glycol. Diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone , 3-Ethylene Propionate Ethyl, 3-Methyl-1,3-Butandiol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl Acetate, 3-methoxybutanol, 3-methoxy Butyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N -Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, Isophoron, Ethylene Glycol Diethyl Ether, Ethylene Glycol Dibutyl Ether, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monoethyl Ether Acetate, Ethylene Glycol Monotershary Butyl Ether, Ethylene Glycol Monobutyl Ether, Ethylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Monopropyl Ether, Ethylene Glycol Monohexyl Ether, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monomethyl Ether Acetate, Diisobutyl Ketone, Diethylene Glycol Diethyl Ether, Diethylene Glycol Diethyl Ether, Diethylene Glycol Monoisopropyl Ether, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether, Diethylene Glycol Monobutyl Ether Acetate, Diethylene Glycol Monomethyl Ether, Cyclohexanol, Cyclohexanol Acetate, Cyclohexanone, Dipropylene Glycol Dimethyl Ether, Dipropylene Glycol Methyl Ether Acetate G, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monomethyl Ether, Diacetone Alcohol, Triacetin, Tripropylene Glycol Monobutyl Ether, Tripropylene Glycol Monomethyl Ether, Propylene Glycol Diacetate , Propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl Examples thereof include alcohol, methylisobutylketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. Among these, from the viewpoint of dispersibility of pigments and solubility of alkali-soluble resins, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like Alcohols such as glycol acetates, benzyl alcohols and diacetone alcohols and ketones such as cyclohexanone are preferable.

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

<Manufacturing method of photosensitive composition>
To the photosensitive composition of the present invention, for example, a pigment (A), an alkali-soluble resin (B), and if necessary, a dye derivative (F), a dispersed resin (G), an organic solvent (R) and the like are added. A dispersion is produced by performing a dispersion treatment. Then, it can be produced by blending the polymerizable compound (C) and the photopolymerization initiator (D) with the dispersion and mixing them. The timing of blending each material is arbitrary. Further, the dispersion step can be performed a plurality of times.

Examples of the disperser for performing the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, and an attritor.

The average dispersed particle size (secondary particle size) of the pigment (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. When the particle size is appropriate, it is easy to obtain a photosensitive composition having high dispersion stability.

As a method for measuring the average dispersed particle size (secondary particle size), for example, Nikkiso's Microtrack UPA-EX150, which employs a dynamic light scattering method (FFT power-spector method), is used to absorb particle permeability. The particle shape is non-spherical, and the D50 particle diameter is the average diameter. As the diluting solvent for measurement, the organic solvent used for dispersion is used, and it is preferable to measure the sample treated by ultrasonic waves immediately after sample preparation because it is easy to obtain results with little variation.

The photosensitive composition is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the dust. The photosensitive composition for a crest authentication sensor of the present invention preferably contains substantially no particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<Optical filter>
The optical filter of the present invention includes a substrate and a coating formed by using a photosensitive composition. It is preferable that the film is patterned by a photolithography method.

[Manufacturing method of optical filter]
The optical filter is, for example, a step of applying a photosensitive composition on a substrate to form a film (1), a step of exposing the film in a pattern through a mask (2), and developing and removing an unexposed portion. It can be produced by performing a step of forming a pattern (3) and a step of heat-treating the pattern (4).

Hereinafter, a method for manufacturing an optical filter will be described in detail.
(Step (1))
In the step (1) of forming the film, the photosensitive composition is applied onto the substrate by, for example, rotary coating, roll coating, slit coating, cast coating, inkjet coating, or the like, and if necessary. Using an oven, a hot plate, etc., dry (pre-bake) at a temperature of 50 to 120 ° C. for 10 to 120 seconds.
Examples of the substrate include a glass substrate and a silicon substrate. For example, an image pickup element such as a CCD or CMOS may be formed on the surface of the silicon substrate. Further, if necessary, an undercoat layer may be provided on the substrate for improving the adhesion with the layer from the upper part, preventing the diffusion of substances, and flattening the surface of the substrate.
It is preferable to apply the film so that the film thickness is 0.05 to 2.0 μm after drying.

(Step (2))
In the exposure step, the film obtained in the step (1) is exposed to a specific pattern via a mask using, for example, an exposure device such as a stepper. This gives a cured film.
Examples of the radiation used for exposure include ultraviolet rays such as g-line, h-line, and i-line.

(Step (3))
The cured film obtained in step (2) is subjected to an alkaline development treatment, so that the film in the unexposed portion is eluted in the alkaline aqueous solution, and only the cured portion remains.
The developing solution is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc. Pyrrol, piperidine, 1,8-diazabicyclo- [5. 4. 0] -7-Alkaline compounds such as undecene can be mentioned.
The concentration of the developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughening and peeling of the pattern are suppressed, and the residual film ratio after development is improved.

Examples of the developing method include a dip method, a spray method, a paddle method and the like. The development temperature is preferably 15 to 40 ° C. After alkaline development, it is preferable to wash with pure water.

(Step (4))
In the heat treatment, the pattern obtained in the step (3) is sufficiently cured by heat treatment (post-baking). The heating temperature of the post bake is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

Next, the transmittance in each wavelength region of the coating film formed by the photosensitive composition of the present invention will be described.

[Transmittance at wavelengths of 440 to 590 nm]
The photosensitive composition of the present invention preferably has a transmittance of 50% or more at a wavelength of 440 to 590 nm when a film having a film thickness of 1.0 μm is formed from the viewpoint of fingerprint authentication accuracy. The transmittance at a wavelength of 435 to 600 nm is more preferably 50% or more, and the transmittance at a wavelength of 430 to 600 nm is particularly preferably 50% or more. Fingerprint authentication accuracy is improved by transmitting light in a wide wavelength range on the wavelength side lower than the wavelength of 600 nm.

The spectral characteristics of the coating and the method for measuring the film thickness are shown below.

(Measurement of film thickness)
The photosensitive composition of the present invention was applied onto a glass substrate by a spin coating method so that the film thickness after drying was 1.0 μm, dried on a hot plate at 90 ° C. for 2 minutes, and then used with an ultrahigh pressure mercury lamp. Substrates with different exposures of 50 mJ / cm ² were prepared through a photomask having a square pattern of 100 μm square. Then, this substrate was spray-developed with a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated (post-baked) at 230 ° C. in a clean oven for 30 minutes. A square pattern was formed on top. The spray development was performed on the coating film of each photosensitive composition in the shortest time during which a pattern could be formed with no development residue. Then, using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.), 5 points at arbitrary locations were measured, and the average value was taken as the film thickness.
The film thickness of 1.0 μm includes a range of errors allowed in the technical field to which the present invention belongs. Specifically, it means that the film thickness is in the range of 1.0 μm ± 0.1 μm.

(Measurement of transmittance)
For the film whose film thickness was measured, the transmittance in the thickness direction of the film at each wavelength was measured using OSP-SP100 (manufactured by Olympus Corporation).

[Transmittance with wavelength of 630 to 690 nm]
The photosensitive composition of the present invention preferably has a transmittance of 20% or less at a wavelength of 630 to 690 nm from the viewpoint of fingerprint authentication accuracy when a film having a film thickness of 1.0 μm is formed.
More preferably, the transmittance at a wavelength of 620 to 700 nm is 20% or less. The accuracy of fingerprint authentication is improved by suppressing the transmission of light having a wavelength of around 660 nm, which has a high transparency to some extent, to the body tissue.

[Transmittance with wavelength of 700 to 730 nm]
The photosensitive composition of the present invention preferably has a transmittance of 50% or less at a wavelength of 700 to 730 nm from the viewpoint of fingerprint authentication accuracy when a film having a film thickness of 1.0 μm is formed.
More preferably, the transmittance at a wavelength of 700 to 730 nm is 40% or less.

<Fingerprint authentication sensor>
The fingerprint authentication sensor of the present invention preferably includes the optical filter of the present invention.
The configuration of the fingerprint authentication sensor of the present invention is not particularly limited as long as it is a configuration provided with the optical filter of the present invention and functions as a fingerprint authentication sensor. For example, the following configuration can be mentioned.

The substrate has a plurality of photodiodes constituting a light receiving area such as a CCD image sensor, a CMOS image sensor, or an organic CMOS image sensor, and a transfer electrode made of polysilicon or the like. A light-shielding film made of tungsten or the like with only the light-receiving part of the photodiode opened on the transfer electrode, and nitrided on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a device protective film made of silicon or the like, and has an optical filter of the present invention on the device protective film.
Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective layer under the optical filter (the side closer to the substrate), or a configuration having a condensing means on the optical filter. And so on. Further, it is described in JP-A-2015-196465, JP-A-2017-194676, and JP-A-2019-512762.

The organic CMOS image sensor includes a thin-film panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and the organic material plays a role of capturing light and converting it into an electric signal. It is a two-layer hybrid structure in which the inorganic material plays the role of taking out the electric signal to the outside, and in principle, the aperture ratio can be set to 100% with respect to the incident light. Since the organic photoelectric conversion film is a continuous film of structural free and can be laid on a CMOS signal readout substrate, it does not require expensive microfabrication and is suitable for pixel miniaturization.

<Image display device>
The image display device of the present invention preferably includes the fingerprint authentication sensor of the present invention inside the image display display.
The configuration of the image display device of the present invention is not particularly limited as long as fingerprint authentication can be performed on the image display display. For example, it is described in JP-A-2015-196465, JP-A-2020-35527, and JP-A-2020-92080. FIG. 1 is a schematic cross-sectional view of an image display device, and the fingerprint authentication sensor of the present invention is provided inside an image display display. The display panel 100 includes a substrate 11, a drive layer 10, a fingerprint authentication sensor layer 20, an OLED (organic light emitting diode) light emitting layer 30, and a cover glass layer 40.

Examples of the substrate 11 include glass and plastic.

The drive layer 10 is provided between the substrate 11 and the fingerprint authentication sensor layer 20 so as not to impair the light emitting and light receiving functions of the OLED light emitting layer 30 and the fingerprint authentication sensor layer 20, and the fingerprint authentication sensor layer 20 and the OLED light emitting layer are provided. Includes a versatile transistor array for inputting and receiving 30 electrical signals and an interlayer insulating film provided with multilayer wiring.

The OLED light emitting layer 30 includes one or more OLEDs 31 that emit light 33, and is a region for displaying an image and at the same time a region for emitting light for fingerprint authentication. The OLED 31 has an organic light emitting portion and electrodes on the upper and lower portions thereof, respectively.

The fingerprint authentication sensor layer 20 includes at least one fingerprint authentication sensor 21, and the fingerprint authentication sensor 21 includes at least a part of the light 33 emitted by the OLED 31 and reflected by a finger which is an authentication target. Detect a part.

A cover glass layer 40 is arranged on the upper surface of the OLED light emitting layer 30 to protect the lower structure and form a display surface.

The image display device of the present invention can be used without limitation for devices that require fingerprint authentication, such as smartphones, tablet terminals, and notebook PCs.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these. In addition, "part" is "mass part", and "%" is "mass%".

Prior to the embodiment, each measurement method will be described.

(Identification of pigment (A-2))
The identification of the pigment (A-2) in the present invention is obtained by calculation and the molecular ion peak of the mass spectrum obtained by using a time-of-flight mass spectrometer (autoflexIII (TOF-MS), manufactured by Bruker Daltonix). It was performed by matching with the mass number to be obtained, and by matching the ratio of carbon, hydrogen and nitrogen obtained by using an elemental analyzer (2400CHN elemental spectrometer, manufactured by Perkin-Elmer) with the theoretical value. The number of halogen atom substitutions is determined by the amount of halogen in the liquid obtained by burning the pigment by the oxygen combustion flask method and absorbing the combustible in water by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX). Was quantified and converted into the number of halogen atom substitutions.

The weight average molecular weight (Mw), number average molecular weight (Mn), and acid value (mgKOH / g) of the resin are as follows.

(Average molecular weight of alkali-soluble resin and dispersed resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alkali-soluble resin and the dispersed resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Co., Ltd.) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40 ° C. , Tetrahydrofuran (THF) solution was used as an 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 injected with 20 microliters. The molecular weight is a polystyrene-equivalent value.

(Acid value of alkali-soluble resin and dispersed resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of an alkali-soluble resin and a dispersed resin solution, and the mixture is stirred to uniformly dissolve the solution. -555 ”manufactured by Hiranuma Sangyo Co., Ltd.) was used for titration, and the acid value (mgKOH / g) was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

(Amine value of dispersed resin)
The amine value of the dispersed resin is a value obtained by converting the measured total amine value (mgKOH / g) into a solid content according to the method of ASTM D 2074.

<Manufacturing of Halogenated Phthalocyanine Pigment (A-1)>
(Miniaturized pigment (A-1-1))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product was put into 3,000 parts of warm water, stirred for 1 hour while heating at 70 ° C. 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. , A finely divided pigment (A-1-1) was obtained.

(Miniaturized pigment (A-1-2))
C. I. 100 parts of Pigment Green 59 (“FASTGEN GREEN C100” manufactured by DIC Corporation), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product was put into 3,000 parts of warm water, stirred for 1 hour while heating at 70 ° C. 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. , A finely divided pigment (A-1-2) was obtained.

<Manufacturing of pigment (A-2) represented by general formula (1)>
(Miniaturized pigment (A-2-1))
In the reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1,500 parts of concentrated sulfuric acid under an ice bath. Then, 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 20 ° C. for 8 hours. Subsequently, this sulfuric acid solution was poured into 9,000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to 159 parts. The compound (a-2-1) represented by the general formula (4) of the above was obtained.
Next, 1,000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the compound (a-2-1) represented by the general formula (4), and 32 parts of diphenyl phosphate were added to the reaction vessel. After reacting at 85 ° C. for 3 hours, this solution was poured into 8,000 parts of water. The reaction product was filtered, washed with 16,000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 112 parts of the product. Then, the obtained product was added to 600 parts of propylene glycol monomethyl ether acetate, and the mixture was heated at 120 ° C. for 2 hours. The product was filtered and dried under reduced pressure at 60 ° C. for 24 hours to give the pigment (A-2-1). The obtained pigment (A-2-1) was X = bromine and n = 10.
Then, 100 parts of the pigment (A-2-1), 1,000 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. This mixture is poured into 3,000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating to about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80 ° C. The mixture was dried for 24 hours to obtain a finely divided pigment (A-2-1).

(Miniaturized pigment (A-2-2))
Similar to the synthesis of the pigment (A-2-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 175 parts in the synthesis of the pigment (A-2-1). A pigment (A-2-2) was obtained. The obtained pigment (A-2-2) was X = bromine and n = 6. Then, the finely divided pigment (A-2-2) was obtained in the same manner as the finely divided pigment (A-2-1).

(Miniaturized pigment (A-2-3)
Similar to the synthesis of the pigment (A-2-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 215 parts in the synthesis of the pigment (A-2-1). The pigment (A-2-3) was obtained. The obtained pigment (A-2-3) was X = bromine and n = 8. Then, the finely divided pigment (A-2-3) was obtained in the same manner as the finely divided pigment (A-2-1).

(Miniaturized pigment (A-2-4)
Similar to the synthesis of the pigment (A-2-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 358 parts in the synthesis of the pigment (A-2-1). A pigment (A-2-4) was obtained. The obtained pigment (A-2-4) was X = bromine and n = 12. Then, the finely divided pigment (A-2-4) was obtained in the same manner as the finely divided pigment (A-2-1).

(Miniaturized pigment (A-2-5)
Of the pigment (A-2-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 152 parts of trichloroisocyanuric acid in the synthesis of the pigment (A-2-1). Pigment (A-2-5) was obtained in the same manner as in the synthesis. The obtained pigment (A-2-5) had X = chlorine and n = 10. Then, the finely divided pigment (A-2-5) was obtained in the same manner as the finely divided pigment (A-2-1).

(Miniaturized pigment (A-2-6)
In the reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1,500 parts of concentrated sulfuric acid under an ice bath. Then, 75 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 20 ° C. for 3 hours. Subsequently, 170 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 4 hours. Subsequently, this sulfuric acid solution was poured into 9,000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to 159 parts. The compound (a-2-6) represented by the general formula (4) of the above was obtained.
Next, 1,000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the compound (a-2-6) represented by the general formula (4), and 32 parts of diphenyl phosphate were added to the reaction vessel. After reacting at 85 ° C. for 3 hours, this solution was poured into 8,000 parts of water. The reaction product was filtered, washed with 16,000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 112 parts of the product. Then, the obtained product was added to 600 parts of propylene glycol monomethyl ether acetate, and the mixture was heated at 120 ° C. for 2 hours. The product was filtered and dried under reduced pressure at 60 ° C. for 24 hours to give the pigment (A-2-6). The obtained pigments (A-2-6) were X = bromine and chlorine, n = 10 (5 for bromine and 5 for chlorine).
Then, the finely divided pigment (A-2-6) was obtained in the same manner as the finely divided pigment (A-2-1).

<Manufacturing of other pigments (A-3)>
(Miniaturized pigment (A-3-1))
C. I. 100 parts of Pigment Green7 (Toyo Color Co., Ltd. "Rionol Green 8390"), 1,000 parts of crushed sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 12 hours at 50 ° C. Kneaded. This mixture is poured into 3,000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating to about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80 ° C. The mixture was dried for 24 hours to obtain a finely divided pigment (A-3-1).

(Miniaturized pigment (A-3-2))
C. I. 100 parts of Pigment Green36 ("Rionol Green 6YK" manufactured by Toyo Color Co., Ltd.), 1,000 parts of crushed sodium chloride, and 100 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 12 hours at 50 ° C. Kneaded. This mixture is poured into 3,000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating to about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80 ° C. The mixture was dried for 24 hours to obtain a finely divided pigment (A-3-2).

(Miniaturized pigment (A-3-3))
In the reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1,500 parts of concentrated sulfuric acid under an ice bath. Then, 225 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 20 ° C. for 8 hours. Subsequently, this sulfuric acid solution was poured into 9,000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to 159 parts. Pigment (A-3-3) was obtained.
100 parts of the pigment (A-3-3), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is put into 3,000 parts of warm water, stirred for 1 hour while heating at 70 ° C. 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. , A finely divided pigment (A-3-3) was prepared.

(Miniaturized pigment (A-3-4))
C. I. 100 parts of Pigment Yellow 150 (“Yellou Pigment E4GN” manufactured by LANXESS), 1,000 parts of crushed sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. .. This mixture is poured into 3,000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating to about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80 ° C. The mixture was dried for 24 hours to obtain a finely divided pigment (A-3-4).

<Production example of alkali-soluble resin (B)>
(Alkali-soluble resin (B-1) solution)
196 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) , 2,2'-Azobisisobutyronitrile 1.1 parts mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content is 20% in the previously synthesized resin solution. Acetate (hereinafter, PGMAc) was added to prepare an alkali-soluble resin (B-1) solution. The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin (B-2) solution)
207 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Showa Denko's Karenz). A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content becomes 20%. Prepared an alkali-soluble resin (B-2) solution. The weight average molecular weight (Mw) was 18,000.

(Alkali-soluble resin (B-3) solution)
370 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C. 18 parts of Milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-azobisisobutyronitrile 2.0. The mixture of parts was added dropwise over 2 hours. After the dropping, the reaction was further carried out at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of air crilic acid (100% of glycidyl group) into the above container, and the temperature was 120 ° C. The reaction was continued for 6 hours, and when the non-volatile acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGM Ac is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. Prepared an alkali-soluble resin (B-3) solution. The weight average molecular weight (Mw) was 19,000.

(Alkali-soluble resin (B-4) solution)
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Fats), and 40 parts of PGMAc. Eight parts and 32 parts of PGMAc were well mixed and mixed.
After charging 395 parts of PGMAc in the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 parts of triethylamine were charged in the reaction vessel, and the reaction was carried out at 110 ° C. for 12 hours. rice field. After that, 150 parts of PGMAc is added and cooled to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized resin solution. As described above, PGMAc was added to obtain an alkali-soluble resin (B-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile component was 2 mgKOH / g.

(Alkali-soluble resin (B-5) solution)
Introduce 333 parts of PGMAc into a flask equipped with a stirrer, thermometer, reflux condenser, dropping rotor and nitrogen introduction tube, change the atmosphere inside the flask from air to nitrogen, raise the temperature to 100 ° C, and then benzyl methacrylate. 70.5 parts (0.40 mol), 71.1 parts (0.50 mol) of glycidyl methacrylate, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 parts (0.10 mol) A solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 164 parts of PGMAc was added dropwise to the flask over 2 hours from the dropping rotor, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0. 9. 9 parts and 0.145 parts of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the non-volatile acid value reached 1 mgKOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution having an acid value of 80 mgKOH / g. .. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. PGMAc was added so as to prepare an alkali-soluble resin (B-5) solution. The mass average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (B-6) solution)
Introduce 182 parts of PGMAc into a flask equipped with a stirrer, thermometer, reflux condenser, dropping rotor and nitrogen introduction tube, change the atmosphere inside the flask from air to nitrogen, raise the temperature to 100 ° C, and then benzyl methacrylate. 70.5 parts (0.40 mol), 43.0 parts of methacrylic acid (0.5 mol), monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 parts (0.10 mol) A solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 136 parts of PGMac was added dropwise to the flask over 2 hours from the dropping rotor, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9. 9 parts and 0.145 parts of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a photosensitive transparent resin solution having an acid value of 79 mgKOH / g. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. PGMAc was added so as to prepare an alkali-soluble resin (B-6) solution. The mass average molecular weight (Mw) was 13,000.

<Production example of a polymerizable compound (C-2) having a urethane bond and an acid group>
(Polymerizable compound (C-2-1))
In a four-necked flask, 210 parts of dipentaerythritol pentaacrylate, 34 parts of hexamethylene diisocyanate, and 0.5 part of N, N-dimethylbenzylamine were charged, reacted at a temperature of 50 to 70 ° C. for 8 hours, and 2180 cm by IR. It was confirmed that the absorption of isocyanate of ^-1 disappeared. Then, 21 parts of mercaptopropionic acid and 0.6 part of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60 ° C. for 6 hours, and the compound represented by the general formula (5) was represented by the following chemical formula (13). The represented polymerizable compound (C-2-1) was obtained.

Chemical formula (13)

<Production example of dispersed resin (G)>
(Dispersed resin (G-1) solution)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 part of dimethylbenzylamine were added. I prepared it. After replacement with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted at 120 ° C. for 4 hours, and then reacted at 80 ° C. for 2 hours. Further, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA (methacrylic acid (3-ethyloxetane-3-yl) methyl, manufactured by Ube Kosan Co., Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc are charged, and a reaction vessel is charged. While keeping the inside at 80 ° C., 0.2 part of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. The non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomers reacted. PGMAc was added and diluted so as to have a non-volatile content of 30% in the non-volatile content measurement to obtain a dispersed resin (G-1) solution having an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000.

(Dispersed resin (G-2) solution)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and nitrogen was poured. While stirring at 50 ° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidylmethacrylate (manufactured by Hitachi Kasei Kogyo Co., Ltd., Funkryl FA-711MM) as a second block (A block) monomer were added to this reactor. The mixture was charged and stirred while maintaining the atmosphere of 110 ° C. and nitrogen, and the reaction was continued. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidylmethacrylate, the polymerization solution was sampled to measure the non-volatile content, and the polymerization conversion rate of the second block (A block) was 98 when converted from the non-volatile content. % Or more, and the reaction solution was cooled to room temperature to terminate the polymerization. A dispersion resin (G-2) having a piperidine skeleton having an amine value of 57 mgKOH / g and a number average molecular weight of 4,500 (Mn), diluted by adding PGMAc so as to have a non-volatile content of 30% in the non-volatile content measurement. A solution was obtained.

<Manufacturing of dispersion>
(Dispersion 1)
The following raw materials are stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using a zirconia bead having a diameter of 0.5 mm, and then the pore diameter. The dispersion 1 was prepared by filtering with a 1.0 μm filter. The organic solvent (R-1) is PGMAc.
Finely divided pigment (A-1-1): 12.0 parts Dispersed resin (G-1) solution: 13.3 parts Dispersed resin (G-2) solution: 6.7 parts Alkaline-soluble resin (B-1) ) Solution: 10.0 parts Organic solvent (R-1): 58.0 parts

(Dispersions 2-18)
Dispersions 2 to 15 were prepared in the same manner as in Dispersion 1 except that the raw materials and amounts shown in Table 1 were changed.

The raw materials listed in Table 1 are as follows.

[Triarylsulfonium compound (E)]
E-1: SP-066 (manufactured by ADEKA: triphenylsulfonium trifluoromethanesulfonate)
E-2: SP-056 (manufactured by ADEKA: triphenylsulfonium nonaflate butanesulfonate)
E-3: TS-91 (Sanwa Chemical Co., Ltd .: Tris (4-methylphenyl) Sulfonium Hexafluorophosphate)

<Manufacturing of photosensitive composition>
[Example 1]
(Photosensitive composition 1)
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive composition 1.
Dispersion 1: 17.5 parts Dispersion 3: 7.5 parts Alkaline-soluble resin (B) solution: 12.5 parts Polymerizable compound (C-2-1): 2.5 parts polymerizable compound (C-3) -1): 2.5 parts photopolymerization initiator (D-1): 0.5 part photopolymerization initiator (D-2): 0.5 part sensitizer (I): 0.17 part epoxy compound ( J-1): 1.0 part thiol-based chain transfer agent (K): 0.1 part polymerizable inhibitor (L): 0.01 part ultraviolet absorber (M): 0.1 part antioxidant (N) ): 0.1 part Leveling agent (O): 1.0 part Storage stabilizer (P): 0.2 part Organic solvent (R): 53.82 parts

[Examples 2 to 24, Comparative Examples 1 to 9]
(Photosensitive Compositions 2-33)
Photosensitive compositions 2-33 were prepared in the same manner as in Example 1 except that the photosensitive composition 1 of Example 1 was changed to the raw materials and amounts shown in Table 2-1 and Table 2-2.

The raw materials listed in the table are as follows.

[Alkali-soluble resin (B) solution]
Alkali-soluble resin (B-2) to (B-6) solutions were mixed in equal amounts to prepare an alkali-soluble resin (B) solution.

[Polymerizable compound (C)]
(Polymerizable compound having an acid group (C-1))
C-1-1: Aronix M-510 (manufactured by Toagosei Co., Ltd.)
C-1-2: Aronix M-520 (manufactured by Toagosei Co., Ltd.)
C-1-3: Aronix M-521 (manufactured by Toagosei Co., Ltd.)
(Polymerizable compound having urethane bond and acid group (C-2))
C-2-1: Polymerizable compound represented by the chemical formula (13) (other polymerizable compound (C-3))
C-3-1: Aronix M-402 (manufactured by Toagosei Co., Ltd.)

[Photopolymerization Initiator (D)]
D-1: Irgacure 907 (manufactured by BASF Japan Ltd.)
D-2: Irgacure 379 (manufactured by BASF Japan)
D-3: Irga Cure OXE02 (manufactured by BASF Japan)
D-4: Irgacure OXE04 (manufactured by BASF Japan)

[Sensitizer (I)]
I-1: Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)
I-2: 4,4 CHEMARK DEABP (manufactured by Chemark Chemical)
As described above, (I-1) and (I-2) were mixed in the same amount to obtain a sensitizer (I).

[Epoxy compound (J-1)]
J-1-1: EHPE-3150 (manufactured by Daicel)
J-1-2: Denacol EX611 (manufactured by Nagase Chemtex)
J-1-3: Triglycidyl isocyanurate The above and above, (J-1-1) to (J-1-3) were mixed in the same amount to prepare an epoxy compound (J-1).

[Thiol chain transfer agent (K)]
K-1: Trimethylol etanthris (3-mercaptobutyrate)
K-2: Trimethylol Propantris (3-mercaptobutyrate)
K-3: Pentaerythritol tetrakis (3-mercaptopropionate)
K-4: Trimethylol propanthris (3-mercaptopropionate)
K-5: Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate or more, (K-1) to (K-5) are mixed in the same amount, respectively, and combined with the thiol chain transfer agent (K). bottom.

[Polymerization inhibitor (L)]
L-1: 4-Methylcatechol L-2: Methylhydroquinone L-3: t-butylhydroquinone The above, (L-1) to (L-3) are mixed in the same amount, and the polymerization inhibitor (L) is mixed. And said.

[Ultraviolet absorber (M)]
M-1: TINUVIN400 (manufactured by BASF Japan)
M-2: TINUVIN900 (manufactured by BASF Japan)
As described above, (M-1) and (M-2) were mixed in the same amount to obtain an ultraviolet absorber (M).

[Antioxidant (N)]
N-1: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate N-2: 3,3'-dioctadecylthiodipropanoate N-3: Tris [2,4- Di- (t) -Butylphenyl] Phosphine N-4: Bis (2,2,6,6-tetramethyl-4-piperidyl) Sevacate N-5: salicylic acid p-octylphenyl or higher, (N-1) to ( N-5) were mixed in the same amount to prepare an antioxidant (N).

[Leveling agent (O)]
O-1: BYK-330 (manufactured by Big Chemie)
O-2: Megafuck F-551 (manufactured by DIC Corporation)
As described above, 1 part each of (O-1) and (O-2) was mixed, and the mixed solution dissolved in 98 parts of PGMAc was used as the leveling agent (O).

[Storage stabilizer (P)]
P-1: 2,6-bis (1,1-dimethylethyl) -4-methylphenol P-2: triphenylphosphine The above, (P-1) and (P-2) are mixed in the same amount. , Storage stabilizer (P).

[Organic solvent (R)]
R-1: Propylene glycol monomethyl ether acetate 30 parts R-2: Cyclohexanol 30 parts R-3: Ethyl 3-ethoxypropionate 10 parts R-4: Propylene glycol monomethyl ether 10 parts R-5: Cyclohexanol acetate 10 parts R -6: 10 parts or more of diproprene glycol methyl ether acetate and (R-1) to (R-6) were mixed in the above parts by mass to prepare an organic solvent (R).

<Evaluation of photosensitive composition>
The obtained photosensitive composition was evaluated for solvent shock, development residue, spectral characteristics, and fingerprint authentication by the following methods. The evaluation results are shown in Table 3.

[Solvent shock evaluation]
The obtained photosensitive composition and cyclohexanone were mixed at a ratio of 1: 100 and allowed to stand at room temperature for 24 hours. Then, it was filtered with a 0.8 μm membrane filter, and the aggregated foreign matter trapped on the membrane filter was observed with an optical microscope (250 times), and the number of aggregated foreign matter was counted. 3 or more is practical.
5: The number of aggregated foreign substances is less than 5 4: The number of aggregated foreign substances is 5 or more and less than 10 3: The number of aggregated foreign substances is 10 or more and less than 50 2: The number of aggregated foreign substances is 50 or more and 100 Less than 1: 100 or more aggregated foreign substances

[Developability evaluation]
The obtained photosensitive composition was coated on a TFT liquid crystal display driving substrate having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm using a spin coater so that the dry film thickness was 2.0 μm, and the temperature was 90 ° C. Was prebaked for 120 seconds. Next, using an ultra-high pressure mercury lamp, ultraviolet exposure was performed with an integrated light intensity of 30 mJ / cm ² , and ultraviolet rays were exposed through a photomask having a 100 μm wide stripe pattern. Further, after cooling the substrate to room temperature, the substrate was spray-developed with a 0.04% potassium hydroxide aqueous solution at 23 ° C. for a development time of 2 levels (40 seconds, 70 seconds), washed with ion-exchanged water, and air-dried. The obtained substrate was post-baked at 230 ° C. for 30 minutes in a clean oven to form a striped pattern on the substrate. The pattern was observed with an optical microscope, and the presence or absence of development residue and chipping in the unexposed portion was evaluated. It is as follows, and two or more are practical.
3: At the development time of 70 seconds, there was no development residue in the unexposed portion, and there was no pattern chipping.
2: At the development time of 70 seconds, a development residue was generated or a pattern was chipped in the unexposed portion.
1: At the development time of 40 seconds, a development residue was generated or a pattern was chipped in the unexposed area.

<Creation of optical filter for fingerprint authentication evaluation>
A resist solution for a flattening film (“HL-18s” manufactured by Nippon Steel Chemical Co., Ltd. “” is applied on a 6-inch silicon wafer by the spin coating method, heated on a hot plate at 100 ° C for 6 minutes, and then placed in an oven at 230 ° C for 1 hour. The coating film was cured by heating to obtain a silicon wafer with a flat film.
Next, the obtained photosensitive composition was applied onto the flattening film by a spin coating method so that the film thickness after drying was 1.0 μm, prebaked on a hot plate at 100 ° C. for 1 minute, and i-ray. Using a stepper-exposure device FPA-3000i5 + (manufactured by Canon), pattern exposure was performed at an exposure rate of 150 mJ / cm ² through a photomask for forming a 1.0 μm square pattern at a wavelength of 365 nm. The coating film after exposure was paddle-developed with an organic alkaline developer. After the paddle was developed, it was washed with pure water using a spin shower for 20 seconds, and the water droplets remaining on the wafer were blown off with high-pressure air.
Further, heat treatment (post-baking) was performed on a hot plate at 200 ° C. for 5 minutes to obtain a silicon wafer having a pattern as an optical filter.

[Fingerprint authentication evaluation]
The obtained optical filter was incorporated into a fingerprint authentication sensor in accordance with Japanese Patent Application Laid-Open No. 2020-92080. The obtained fingerprint authentication sensor was used to irradiate light with an emission wavelength of 470 nm to capture a fingerprint image, and the image performance was evaluated. The evaluation criteria are as follows, and 2 or more are practical.
3: Fingerprints can be clearly recognized.
2: Fingerprints can be recognized.
1: Fingerprint cannot be recognized.

<Manufacturing of substrate for spectral characterization>
The obtained photosensitive composition was placed on a glass substrate (Eagle 2000 manufactured by Corning Co., Ltd.) having a thickness of 100 mm in length × 100 mm in width and 0.7 mm in thickness by a spin coating method to obtain a film thickness after post-baking. It was applied so as to be 0 μm. Next, after drying on a hot plate at 90 ° C. for 2 minutes, pattern exposure was performed using an ultrahigh pressure mercury lamp with an exposure amount of 50 mJ / cm ² through a photomask having a square pattern of 100 μm square. Then, this substrate was spray-developed with a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 30 minutes. The spray development was performed in the shortest time during which a pattern could be formed with no development residue.

[Measurement of wavelength range where transmittance is 50% or more]
Using OSP-SP100 (manufactured by Olympus Corporation), the obtained spectral characteristic evaluation substrate was measured at a wavelength having a transmittance of 50% or more in the thickness direction of the coating film. The evaluation criteria are as follows.
4: The transmittance is 50% or more at a wavelength of 430 to 600 nm.
3: The transmittance is 50% or more at a wavelength of 435 to 600 nm.
2: The transmittance is 50% or more at a wavelength of 440 to 590 nm.
1: There is a portion where the transmittance is less than 50% at a wavelength of 440 to 590 nm.

[Measurement of wavelength range where transmittance is 20% or less]
Using OSP-SP100 (manufactured by Olympus Corporation) for the obtained spectral characteristic evaluation substrate, the wavelength at which the transmittance was 20% or less was measured in the thickness direction of the coating film. The evaluation criteria are as follows.
3: The transmittance is 20% or less at a wavelength of 620 to 700 nm.
2: The transmittance is 20% or less at a wavelength of 630 to 690 nm.
1: There is a part where the transmittance exceeds 20% at a wavelength of 630 to 690 nm.

[Measurement of maximum transmittance at wavelengths of 700 to 730 nm]
The obtained spectral characteristic evaluation substrate was measured for maximum transmittance at a wavelength of 700 to 730 nm in the thickness direction of the coating film using OSP-SP100 (manufactured by Olympus Corporation).

10 Drive layer 11 Substrate 20 Fingerprint authentication sensor layer 21 Fingerprint authentication sensor 23 Reflected light 30 OLED light emitting layer 31 OLED
33 Light 40 Cover glass layer 50 Finger 100 Display panel

Claims (8)

A photosensitive composition comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
The pigment (A) contains a halogenated zinc phthalocyanine pigment (A-1) and a pigment represented by the following general formula (1) (A-2).
The total content of the halogenated zinc phthalocyanine pigment (A-1) and the pigment (A-2) represented by the following general formula (1) is 95% by mass or more in 100% by mass of the pigment (A). , Photosensitive composition.
Chemical formula (1)

(X in the general formula (1) represents a halogen atom, and n represents 4 to 16). The photosensitive according to claim 1, wherein the mass ratio of the halogenated zinc phthalocyanine pigment (A-1) to the pigment (A-2) represented by the general formula (1) is 90:10 to 10:90. Sex composition. The photosensitive composition according to claim 1 or 2, wherein the polymerizable compound (C) contains a polymerizable compound (C-1) having an acid group. The photosensitive composition according to any one of claims 1 to 3, further comprising a triarylsulfonium compound (E). A photosensitive composition used to form a filter for a fingerprint authentication sensor.
It contains a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
The pigment (A) contains a halogenated zinc phthalocyanine pigment (A-1) and a pigment represented by the following general formula (1) (A-2).
The total content of the halogenated zinc phthalocyanine pigment (A-1) and the pigment (A-2) represented by the following general formula (1) is 95% by mass or more in 100% by mass of the pigment (A). , Photosensitive composition. An optical filter comprising a substrate and a coating formed by using the photosensitive composition according to any one of claims 1 to 5. A fingerprint authentication sensor comprising the optical filter according to claim 6. An image display device including the fingerprint authentication sensor according to claim 7 inside an image display display.

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