JP2022026877A - Photosensitive composition for fingerprint authentication sensor, optical filter, fingerprint authentication sensor and image display device - Google Patents

Abstract

To provide a photosensitive composition for fingerprint authentication sensor which enables formation of an optical filter that suppresses transmission of light in the vicinity of a wavelength of 660 nm, transmits the light in a wide wavelength region on a lower wavelength side than a wavelength of 570 nm and has the high transmittance.SOLUTION: There is provided a photosensitive composition for fingerprint authentication sensor which enables formation of coating having 50% or greater of the transmittance in a wavelength of 420-520 nm in a film thickness 1.0 μm. The photosensitive composition for fingerprint authentication sensor comprises: a pigment (A-1) expressed by a following chemical formula (1) as a pigment (A); alkali-soluble resin (B); a polymerizable compound (C); and a photoinitiator (D).SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive composition used in a fingerprint authentication sensor.

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 discloses an optical fingerprint authentication sensor that performs fingerprint authentication by irradiating light having a wavelength of around 570 nm and generating an image captured image based on the light reflected from a finger.

Japanese Unexamined Patent Publication No. 2017-196319

However, since the body tissue has a high transparency to light having a wavelength of around 660 nm, the fingerprint authentication sensor of Patent Document 1 may not be able to correctly recognize the fingerprint because a part of the irradiated light passes through the finger. there were.

The present invention is a photosensitive composition for a fingerprint authentication sensor capable of suppressing the transmission of light in the vicinity of a wavelength of 660 nm, transmitting light in a wide wavelength range on the wavelength side lower than the wavelength of 570 nm, and forming an optical filter having a high transmittance. The purpose is to provide.

The present invention is a photosensitive composition for a fingerprint authentication sensor capable of forming a film having a transmittance of 50% or more at a wavelength of 420 to 520 nm at a film thickness of 1.0 μm.
A fingerprint authentication sensor containing the pigment (A) represented by the following chemical formula (1), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). For photosensitive compositions.

Chemical formula (1)

According to the above invention, for a fingerprint authentication sensor capable of suppressing the transmission of light near a wavelength of 660 nm, transmitting light in a wide wavelength range on the wavelength side lower than the wavelength of 570 nm, and forming an optical filter having a high transmittance. A photosensitive composition, an optical filter, a fingerprint authentication sensor, and an image display device can be provided.

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

Hereinafter, a mode for carrying out the photosensitive composition for a crest authentication sensor of the present invention (hereinafter, also simply referred to as “photosensitive composition”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

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 "acrylic and / or methacryloyl", "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 refers to an ethylenically unsaturated double bond.

<Photosensitive composition for fingerprint authentication sensor>
The present invention is a photosensitive composition for a fingerprint authentication sensor capable of forming a film having a transmittance of 50% or more at a wavelength of 420 to 520 nm at a film thickness of 1.0 μm.
A fingerprint authentication sensor containing the pigment (A) represented by the following chemical formula (1), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). It is a photosensitive composition for use.

Chemical formula (1)

The coating film formed from the composition of the present invention 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. The composition of the present invention contains the pigment (A-1) represented by the chemical formula (1) to suppress the transmission of light in the vicinity of the wavelength of 660 nm, and to emit light in a wide wavelength range on the wavelength side lower than the wavelength of 570 nm. It can be made transparent and can form a film with high transmittance.

[Pigment (A)]
(Pigment (A-1))
The photosensitive composition of the present invention contains the pigment (A-1) represented by the following chemical formula (1) as the pigment (A).

Chemical formula (1)

The pigment (A-1) includes α-type, β-type, γ-type, δ-type, ε-type, π-type and the like depending on the difference in crystal structure. The α type is C.I. I. Pigment Blue 15: 1, 15: 2, β type is C.I. I. Pigment Blue 15: 3, 15: 4, γ type is C.I. I. Pigment blue 15: 5, ε type is C.I. I. Pigment Blue 15: 6. Among these, the pigment (A-1) is selected from the α-type, β-type, and ε-type groups from the viewpoint of transmitting light in a wide wavelength range on the wavelength side lower than the wavelength of 570 nm and achieving high transmittance. It is preferable to contain at least one of the above, more preferably α-type and / or β-type, and even more preferably β-type.

Further, the pigment (A-1) preferably contains β-type and / or ε-type, and more preferably β-type, from the viewpoint of suppressing the transmission of light having a wavelength of 570 to 730 nm.

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

In the present specification, the crystal structure of the pigment (A-1) is preferably β-type. When the β type is used, it is possible to highly suppress the transmission of light in the vicinity of the wavelength of 660 nm (570 to 730 nm), transmit light in a wide wavelength range on the wavelength side lower than the wavelength of 570 nm, and form a film having high transmittance.

The content of the pigment (A-1) is preferably 95 parts by mass or more, more preferably 99 parts by mass or more, still more preferably 100 parts by mass, based on 100% by mass of the pigment (A). When an appropriate amount is contained, it is possible to transmit light in a wide wavelength range on the wavelength side lower than the wavelength of 570 nm and to form a film having a high transmittance.

The pigment (A-1) preferably contains as little free copper as possible from the viewpoint of improving fingerprint authentication accuracy. Free copper can be reduced, for example, by the method described in JP-A-2008-308605.

The concentration of free copper ions in the photosensitive composition is preferably 500 ppm or less, more preferably 300 ppm or less, still more preferably 200 ppm or less. This can improve the fingerprint authentication accuracy.

(Other pigments (A-2))
The pigment (A) can contain other pigments (A-2) other than the pigment (A-1). The other pigment (A-2) is not particularly limited, and known pigments can be used.

Other pigments (A-2) 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 1,2,4,7,8,10,13,14,15,17,18,19,26,36,37,45,48,50,51,54,55,58,59,62, 63 mag green pigment;
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 is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and 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.

For the salt milling treatment, the resin may be changed if necessary. 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 used 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 can contain known compounds.

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 (E)]
The photosensitive composition of the present invention can contain the dye derivative (E), if necessary.

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

The content of the dye derivative (E) 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 (F)]
The photosensitive composition of the present invention may contain a dispersion resin (F), if necessary.
The dispersed resin (F) 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. Be done.

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

The resin type of the dispersed resin (F) 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 (F) 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 (F) 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, etc. 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Described in JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, etc. Resin is mentioned.

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

The content of the dispersed resin (F) 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, or an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (anhydrous) maleic acid copolymer and the like. 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.

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.

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

Further, as a method similar to the method (i), for example, a carboxyl group-containing monomer and a monomer other than the above are synthesized to prepare a polymer. 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)]
Method (ii) synthesizes, for example, polymers of (meth) acrylic acid esters, hydroxyl group-containing monomers, 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.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl ( Examples thereof include meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and ethoxypolyethylene glycol (meth) acrylate.

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.

Examples of other monomers include N-substituted maleimides, alkyleneoxy group-containing monomers, phosphoric acid ester group-containing ethylenically unsaturated monomers, and carboxyl group-containing monomers.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-. 4-Methyl-3-maleimidecoumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedi maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitro) Phenyl) Maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4- Maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimide acrydin and the like can be mentioned.
Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenylacrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, and paracumylphenol. Examples thereof include EO or propylene oxide (PO) modified (meth) acrylate, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

As the monocarboxyl group-containing monomer, the monomer already described can be used.

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

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 2,000 to 40,000, preferably 3,000 to 3,000, and more preferably 4,000 to 20,000 from the viewpoint of developability. 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 trimer, 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, dipentaerythritol and the like.
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 are Viscoat # 2500P manufactured by Osaka Organic Co., Ltd. and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. , M-521 and the like.

The content of the polymerizable compound (C-1) having an acid group is preferably 5 to 80% by mass, preferably 25 to 60% 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. More preferably, it is by mass%.

(Polymerizable compound having urethane bond and acid group (C-2))
It is more preferable that the photosensitive composition of the present invention contains a polymerizable compound (C-2) having a urethane bond and an acid group represented by the following general formula (2).
General formula (2) (H ₂ C = C (R ¹ ) COO) _m -X- (OCOCH (R ¹ ) CH ₂ S (R ² ) COOH) _n
In the general formula (2), 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 (2), 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, and mercaptosuccinic acid.

The content of the polymerizable compound (C-2) having a urethane bond and an acid group is preferably 5 to 80% by mass, preferably 5 to 80% 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. More preferably, it is ~ 60% by mass.

(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, DAUA-167 manufactured by Kagaku Co., Ltd.

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-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) Methyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine. System compounds;
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;
Examples thereof include quinone compounds such as 9,10-phenanslenquinone, camphor-quinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanosen compounds.

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) -phenylphosphinoxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphinoxide), 1,2-octanedione, 1- [4- (phenylthio) phenyl-, as an oxime compound, 2- (O-benzoyloxime)] (IRGACURE OXE-01), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-yl]-, 1- (O-acetyloxime) ) (IRGACURE OXE 02), IRGACURE OXE 04 (all manufactured by BASF), N-1919, NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR -PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-3054 (all manufactured by Joshu Strong New Materials Co., Ltd.) and the like can be mentioned. 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.

[Near infrared absorber (G)]
The photosensitive composition of the present invention can contain a near-infrared absorber (G). 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 (G) is a compound that absorbs light having a wavelength of 750 to 1200 nm.

From this, examples of the near-infrared absorber (G) include a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, an immonium compound, a pyrolopyrrole compound, a squarylium compound, and a croconium compound. Among these, a cyanine compound, a pyrolopyrrole compound, and a squarylium compound are preferable.

Among the near-infrared absorbers (G), 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; Pyrrolopyrrol 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 (G) can be used alone or in combination of two or more.

[Sensitizer (H)]
The photosensitive composition of the present invention can contain a sensitizer (H).
The sensitizer (H) includes, for example, chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and the like. 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 sensitizers (H), thioxanthone derivatives, Mihira-ketone derivatives, and carbazole derivatives 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 (H) can be used alone or in combination of two or more.

The content of the sensitizer (H) 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 (I)]
The photosensitive composition of the present invention can contain a thermosetting compound (I). As a result, the thermosetting compound (I) 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 (I) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (I) 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 (I-1))
Examples of the epoxy compound include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) and phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted). Dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Phenols and polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, noorbornadiene, vinylnolbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Polycondensates of s and ketones (acetones, methyl ethyl ketones, methylisobutylketones, acetophenones, benzophenones, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α' -Polycondensate with benzenedimethanol, biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethyl, etc.) Polycondensate with biphenyl, etc.), polycondensate of bisphenols and various aldehydes, glycidyl ether-based epoxy resin obtained by glycidylizing alcohols, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidyl Examples thereof include an amine-based epoxy resin and a glycidyl ester-based epoxy resin.

Commercially available products include, for example, Epicoat 807,815,825,827,828,190P, 191P (trade name; manufactured by Yuka Shell Epoxy), Epicoat 1004, 1256 (trade name; manufactured by Japan Epoxy Resin). , TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resin), JER 157S65, 157S70 (trade name; Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, 154 (the above are product names; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, 103S, 104S, 1020 (the above are products). Name; manufactured by Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (trade name; manufactured by Daicel Chemical Industry Co., Ltd.), Denacol EX-21,212,252,313,314,321,411,421,512,5211 611, 612, 614, 614B, 622, 711,721 (the above are trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, H, S (manufactured by Nissan Chemical Industry Co., Ltd.) and the like can be mentioned.

The content of the epoxy compound (I-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 (I-2))
The oxetane compound (I-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.
Specific examples 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.
Specific examples include OXBP, OXTP manufactured by Ube Industries, Ltd., OXT-121,221 manufactured by Toagosei Co., Ltd., and the like.

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 (I-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 it has an appropriate number of methylol groups and ether groups, it is easy to obtain heat resistance that is not excessive or insufficient.

Commercially available products include, for example, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, 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 ( Sanwa Chemical Co., Ltd.), Cymel 223, 235, 236,238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries Co., Ltd.) and the like.

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 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232,235,236,238,300,301,303,350 (Nippon Cytec Industry) -Z) and the like are preferable in terms of increasing the crosslink density.

The thermosetting compound (I) 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.

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

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

The content of the thiol-based chain transfer agent (J) 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 (K)]
The photosensitive composition of the present invention can contain a polymerization inhibitor (K).

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

[Ultraviolet absorber (L)]
The photosensitive composition of the present invention can contain an ultraviolet absorber (L). The ultraviolet absorber (L) 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 are BASF Japan's TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130, ADEKA's ADEKA STAB LA-29, LA-31RG, LA-32, LA. -36, KEMIROSB71, 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.

Examples of commercially available products include KEMIPROB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, ADEKA Adecaster LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd. Be done.

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 KEMIPROB 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.

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

[Antioxidant (M)]
The photosensitive composition of the present invention may contain an antioxidant (M). As the antioxidant (M), the photopolymerization initiator and the thermosetting compound contained in the photosensitive composition prevent yellowing due to oxidation by the thermosetting and the thermal process at the time of ITO annealing, and the transmittance of the film is increased. The decrease 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 added, 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 (M) 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 are ADEKA's ADEKA STUB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, Chemipro's KEMINOX 101, 179, 76, 9425, BASF Japan. Examples thereof include IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, and Sianox CY-1790 and CY-2777 manufactured by Sun Chemical.

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 are ADEKA's ADEKA STAB 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., Tinuvin249 manufactured by BASF Japan, TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3546 manufactured by Sun Chemical Co., Ltd., UV -3853 and the like can be mentioned.

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.

Examples of commercially available products include ADEKA's ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, BASF Japan's IRGAFOS168, and Clariant Chemicals' HostanoxP-EPQ. Be done.

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 (M) can be used alone or in combination of two or more.

The content of the antioxidant (M) 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 (N)]
The photosensitive composition of the present invention can contain a leveling agent (N). 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 (N) include a silicone-based surfactant, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant and the like.

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 are BYK-300, 306, 310, 313,315N, 320,322,323,330,331,333,342,345,346,347,348,349,370,377,378,3455 manufactured by Big Chemie. , UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609, manufactured by Toray Industries, Inc., X-22-4952, X-22-4272, X-22-6266, KF manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include -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 are AGC Seimi Chemical's Surflon S-242, S-243, S-420, S-611, S-651, S-386, DIC's Megafuck F-253, F-477, F-551. , F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo Examples thereof include FC-4430 and FC-4432 manufactured by 3M, EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronics Chemicals, and Futagent 602A manufactured by Neos.

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 are Emargen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, manufactured by Kao. 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, Emmanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA ADEKA PLRONIC® L-23, 31, 44, 61, 62,64,71,72,101,121, TR-701,702,704,913R, Kyoeisha Chemical Co., Ltd. (meth) acrylic acid-based (co) polymer polyflo-No. 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 piercing 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, and 20N manufactured by Kao Corporation.

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

The content of the leveling agent (N) 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 (O)]
The photosensitive composition of the present invention can contain a storage stabilizer (O). This stabilizes the viscosity of the photosensitive composition over time. The storage stabilizer (O) 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, tetraethylphosphin and tetraphenyl. Examples thereof include organic phosphine and phosphite.

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

[Adhesion improver (P)]
The photosensitive composition of the present invention can contain an adhesion improver (P). 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 (P) 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 (P) can be used alone or in combination of two or more.

The content of the adhesion improver (P) 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 (Q)]
The photosensitive composition of the present invention can contain an organic solvent (Q).

The organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanjiol, 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-ethoxypropionate ethyl, 3-methyl-1,3-butanjiol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 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-propylacetate, 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 monother-shari-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol Monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetylate 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 (Q) can be used alone or in combination of two or more.

<Manufacturing method of photosensitive composition for fingerprint authentication sensor>
To the photosensitive composition of the present invention, for example, a pigment (A), an alkali-soluble resin (B), and if necessary, a dye derivative (E), a dispersed resin (F), an organic solvent (Q) 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 for a fingerprint authentication sensor. 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 the step (3) of forming a pattern.
Further, if necessary, a step of drying the coating film (pre-baking step) and a step of thermosetting the pattern (post-baking step) can be performed.

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 a method such as rotary coating, roll coating, slit coating, cast coating, or inkjet coating, and if necessary, an oven. Using a hot plate or the like, 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.

After drying, the developed film is preferably heat-treated (post-baked) in order to sufficiently cure the film. The heating temperature of the postbake 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.

[Wavelength with transmittance of 50% or more]
The photosensitive composition of the present invention has a transmittance of 50% or more at a wavelength of 420 to 520 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 420 to 530 nm is preferably 50% or more, and more preferably 50% or more at a wavelength of 420 to 540 nm. Fingerprint authentication accuracy is improved by transmitting light in a wide wavelength range on the wavelength side lower than the wavelength of 570 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 in a clean oven at 230 ° C. for 30 minutes to form a square on the substrate. Formed a pattern. 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).

[Wavelength with transmittance of 80% or more]
From the viewpoint of fingerprint authentication accuracy, the photosensitive composition of the present invention preferably has a transmittance of 80% or more at a wavelength of 450 to 490 nm and a wavelength of 450 to 500 nm when a film having a film thickness of 1.0 μm is formed. It is more preferable that the transmittance in the above is 80% or more, and it is further preferable that the transmittance at a wavelength of 450 to 510 nm is 80% or more. Fingerprint authentication accuracy is improved by transmitting light in a wide wavelength range on the wavelength side lower than the wavelength of 570 nm and increasing the transmittance.

[Transmittance with wavelength of 570 to 730 nm]
It is preferable that the photosensitive composition of the present invention does not transmit light having a wavelength of 570 to 730 nm when a film having a film thickness of 1.0 μm is formed. 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 in the wavelength region longer than the wavelength of 730 nm]
The photosensitive composition of the present invention preferably blocks light in a wavelength region longer than the wavelength of 730 nm when a film having a film thickness of 1.0 μm is formed. By blocking near-infrared light with high transparency to body tissues, the generation of noise is suppressed and the accuracy of fingerprint authentication is improved.
Blocking light in a wavelength region longer than 730 nm can be achieved by using the above-mentioned near-infrared absorber.

<Fingerprint authentication sensor>
The fingerprint authentication sensor of the present invention 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, Japanese Patent Application Laid-Open No. 2015-196465, Japanese Patent Application Laid-Open No. 2017-194676, and Japanese Patent Application Laid-Open No. 2019-512762 can be referred to.

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 an inorganic material plays a role of taking out an electric signal to the outside, and in principle, the aperture ratio can be set to 100% with respect to 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 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, Japanese Patent Application Laid-Open No. 2015-196465, Japanese Patent Application Laid-Open No. 2020-35527, and Japanese Patent Application Laid-Open No. 2020-92080 can be referred to. FIG. 1 is a schematic cross-sectional view of an image display device provided with the fingerprint authentication sensor of the present invention 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.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine 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 in 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.

<Production example of pigment (A-1) represented by chemical formula (1)>
(Miniaturized pigment (A-1-1))
The crystal structure represented by the chemical formula (1) is α-type C.I. I. 100 parts of Pigment Blue 15: 2 (Toyo Color Co., Ltd. "Rionol Blue 7255-PS"), 1,000 parts of crushed sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and 50 parts were charged. Kneaded at ° 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-1-1).

(Miniaturized pigment (A-1-2))
The crystal structure represented by the chemical formula (1) is β-type C.I. I. Pigment Blue 15: 3 (“Rionol Blue FG7351” manufactured by Toyo Color Co., Ltd.), 1,000 parts of crushed sodium chloride, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 50 ° C. Kneaded 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-1-2).

(Miniaturized pigment (A-1-3))
The crystal structure represented by the chemical formula (1) is β-type C.I. I. Pigment Blue 15: 4 ("Rionol Blue FG-7400-G" manufactured by Toyo Color Co., Ltd.), 1,000 parts of crushed sodium chloride, and 100 parts of diethylene glycol in a 1-gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). It was charged 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-1-3).

(Miniaturized pigment (A-1-4))
C.I., whose crystal structure represented by the chemical formula (1) is ε-type. I. Pigment Blue 15: 6 (“Rionol Blue ES” 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) at 50 ° C. Kneaded 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-1-4).

<Production example of other pigment (A-2)>
(Miniaturized pigment (A-2-1))
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-2-1).

(Miniaturized pigment (A-2-2))
C. I. 100 parts of Pigment Red 177 (Synic's "Sinic Thread SR3C"), 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-2-2).

(Miniaturized pigment (A-2-3))
C. I. 100 parts of Pigment Green7 (“Rionol Green 8390” 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) and 12 at 50 ° C. Time 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-2-3).

(Miniaturized pigment (A-2-4))
C. I. 100 parts of Pigmen 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) and 12 at 50 ° C. Time 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-2-4).

(Miniaturized pigment (A-2-5))
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-2-5) was obtained.

(Miniaturized pigment (A-2-6))
C. I. 100 parts of Pigmen Green 59 (manufactured by DIC), 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-2-6) was obtained.

(Miniaturized pigment (A-2-7))
A finely divided pigment (A-2-7) represented by the following chemical formula (2) was produced by the method described in Examples of JP-A-2017-1111398.

Chemical formula (2)

(Miniaturized pigment (A-2-8))
A finely divided pigment (A-2-8) represented by the following chemical formula (3) was produced by the method described in Examples of JP-A-2017-1111398.

Chemical formula (3)

<Production example of alkali-soluble resin (B)>
(Alkali-soluble resin (B-1) solution)
196 parts of cyclohexanone was placed 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-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. , 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) 20. A mixture of 7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of 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 PGMAc is added to the previously synthesized resin solution so that the non-volatile content becomes 20%. Prepared 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 an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution is sampled, heated and dried 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. in the reaction vessel. 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 part of triethylamine were charged in the reaction vessel, and the reaction was carried out at 110 ° C. for 12 hours. I let you. 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 polymerizable compound (C-2)>
(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 following chemical formula (4) was used as the polymerizable compound represented by the general formula (1). ) Was obtained as a polymerizable compound (C-2-1).

Chemical formula (4)

<Production example of dispersed resin (F)>
(Dispersed resin (F-1) solution)
A reaction vessel equipped with a gas introduction tube, a temperature, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2'-azobisisobutyronitrile was added to 90 parts of PGMAc. It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene were added as a catalyst, and the mixture was reacted at 100 ° C. for 7 hours. .. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and PGMAc was added and diluted so that the non-volatile content was 30% by measuring the non-volatile content, and the acid value was 70 mgKOH / g. , A dispersion resin (F-1) solution having a weight average molecular weight of 8,500 was obtained.

<Manufacturing of dispersion>
(Dispersion 1)
The following raw materials are stirred and mixed so as to be uniform, and then dispersed 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 for 3 hours, and then the pore diameter is changed. The dispersion 1 was prepared by filtering with a 1.0 μm filter.
Finely divided pigment (A-1-1): 12.0 parts Dye derivative (E-1): 1.0 part Dispersed resin (F-1) solution: 2.0 parts Alkaline-soluble resin (B-1) Solution: 20.0 parts Organic solvent (Q-1): 65.0 parts

ｐｃは、フタロシアニン骨格を表す。
有機溶剤（Ｑ－１）は、ＰＧＭＡｃ Dye derivative (E-1): The following structure

pc represents the phthalocyanine skeleton.
The organic solvent (Q-1) is PGMAc.

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

<Manufacturing of photosensitive compositions for fingerprint authentication sensors>
[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: 27.0 parts Alkali-soluble resin (B) solution: 25.0 parts Polymerizable compound (C-2-1): 3.15 parts Polymerizable compound (C-3-1): 2.15 parts Photopolymerization Initiator (D-1): 0.5 Part Photopolymerization Initiator (D-2): 0.5 Part Sensitizer (H): 0.2 Part Epoxy Compound (I-1): 1.0 Part Oxetane compound (I-2): 1.0 part Thiol-based chain transfer agent (J): 0.4 part Polymerization initiator (K): 0.01 part UV absorber (L): 0.1 part Oxidation Initiator (M): 0.1 part Leveling agent (N): 1.0 part Storage stabilizer (O): 0.2 part Organic solvent (Q-1): 36.69 parts

[Examples 2 to 23, Comparative Examples 1 to 3]
(Photosensitive Compositions 2-26)
Photosensitive compositions 2 to 26 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 are as follows.

[Alkali-soluble resin (B) solution]
Alkali-soluble resin (B-2) to (B-6) solutions were mixed in equal amounts to obtain 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: The compound of the above chemical formula (4) (other polymerizable compound (C-3))
C-3-1: Aronix M-402 (manufactured by Toagosei Co., Ltd.)

[Photopolymerization Initiator (D)]
D-1: Irga Cure 907 (manufactured by BASF Japan Ltd.)
D-2: Irga Cure 379 (manufactured by BASF Japan Ltd.)
D-3: Irga Cure OXE01 (manufactured by BASF Japan)
D-4: Irga Cure OXE02 (manufactured by BASF Japan)
D-5: Irga Cure OXE04 (manufactured by BASF Japan)

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

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

[Oxetane compound (I-2)]
I-2-1: Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)

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

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

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

[Antioxidant (M)]
M-1: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate M-2: 3,3'-dioctadecylthiodipropanoate M-3: Tris [2,4- Di- (t) -Butylphenyl] Phenyl M-4: Bis (2,2,6,6-Tetramethyl-4-piperidyl) Sevacate M-5: P-octylphenyl salicylate or higher, (M-1) to ( M-5) was mixed in the same amount to prepare an antioxidant (M).

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

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

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

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

[Evaluation of development residue]
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 area and there was no pattern chipping. 2: At the development time of 70 seconds, the development residue was generated or the pattern was chipped in the unexposed area 1: Development time was 40 seconds. In the unexposed area, a development residue was generated or a pattern was chipped.

<Manufacturing of substrate for spectral characterization>
The obtained photosensitive composition was placed on a glass substrate (Eagle 2000 manufactured by Conning 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, a substrate was prepared by exposing to 50 mJ / cm ² through a 100 μm square square pattern photomask using an ultrahigh pressure mercury lamp. 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, and two or more are practical.
4: Transmittance is 50% or more at a wavelength of 420 to 540 nm 3: Transmittance is 50% or more at a wavelength of 420 to 530 nm 2: Transmittance is 50% or more at a wavelength of 420 to 520 nm 1: Wavelength 420 to There is a portion where the transmittance is less than 50% at 520 nm.

[Measurement of wavelength range where transmittance is 80% or more]
Using OSP-SP100 (manufactured by Olympus Corporation), the obtained spectral characteristic evaluation substrate was measured at a wavelength having a transmittance of 80% or more in the thickness direction of the coating film. The evaluation criteria are as follows.
4: Transmittance is 80% or more at a wavelength of 450 to 510 nm 3: Transmittance is 80% or more at a wavelength of 450 to 500 nm 2: Transmittance is 80% or more at a wavelength of 450 to 490 nm 1: Wavelength 450 to There is a portion where the transmittance is less than 80% at 490 nm.

[Measurement of maximum transmittance at wavelengths of 570 to 730 nm]
The obtained spectral characteristic evaluation substrate was measured for maximum transmittance at a wavelength of 570 to 730 nm in the thickness direction of the coating film using OSP-SP100 (manufactured by Olympus Corporation).

<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 irradiated with light having an emission wavelength of 470 nm to capture a fingerprint image, and the image performance was evaluated. The evaluation criteria are as follows, and two or more are practical.
3: Fingerprints can be clearly recognized.
2: Fingerprints can be recognized.
1: Fingerprint cannot be recognized.

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 50 Finger 100 Display panel

Claims (7)

A photosensitive composition for a fingerprint authentication sensor capable of forming a film having a transmittance of 50% or more at a wavelength of 420 to 520 nm at a film thickness of 1.0 μm.
A fingerprint authentication sensor containing the pigment (A) represented by the following chemical formula (1), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). Photosensitive composition for use.
Chemical formula (1)

The photosensitive composition for a fingerprint authentication sensor according to claim 1, wherein the content of the pigment (A-1) is 95% by mass or more in 100% by mass of the pigment (A). The photosensitive composition for a fingerprint authentication sensor according to claim 1 or 2, wherein the crystal structure of the pigment (A-1) is β-type. The photosensitive composition for a fingerprint authentication sensor according to any one of claims 1 to 3, wherein the polymerizable compound (C) contains a polymerizable compound (C-1) having an acid group. An optical filter comprising a substrate and a coating formed by using the photosensitive composition for a fingerprint authentication sensor according to any one of claims 1 to 4. A fingerprint authentication sensor comprising the optical filter according to claim 5. An image display device including the fingerprint authentication sensor according to claim 6 inside an image display display.

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