JP2023159486A - Photosensitive composition, optical filter, image display device, and solid-state imaging element - Google Patents

Abstract

To provide a photosensitive composition which inhibits water spots on a film after development, has a good film-remaining rate, and can form an excellent pattern.SOLUTION: A photosensitive composition comprises an alkali-soluble resin (A), a polymerizable compound (B), and a photoinitiator (C). The photoinitiator (C) includes an oxime-based photoinitiator (C1) represented by the general formula in the figure and an oxime-based photoinitiator (C2) other than the oxime-based photoinitiator (C1).SELECTED DRAWING: None

Description

The present invention relates to a photosensitive composition and an optical filter using the same.

A color filter is a type of optical filter used in image display devices, solid-state imaging devices, etc. Two or more types of fine band-shaped filter segments of different hues are arranged parallel to each other (in a stripe pattern) on a transparent substrate such as a glass substrate. ) or intersect with each other. Alternatively, two or more types of fine filter segments having different hues are arranged in order in each of the vertical and horizontal directions. These filter segments have small dimensions ranging from several microns to several hundred microns, and are neatly arranged in a predetermined arrangement for each hue.

Currently, the manufacturing method for color filters includes a process of applying a photosensitive composition to a transparent substrate such as glass and removing the solvent from this coating film by drying, and applying this coating film to a photomask having a desired pattern shape. irradiation and curing process (hereinafter referred to as exposure) with radiation through the coating, then a process of cleaning and removing the unexposed areas of this coating film (hereinafter referred to as development), and then, if necessary, sufficiently curing the cured film. In order to achieve this, a filter segment pattern of the first color is obtained through a heat treatment (hereinafter referred to as post-bake) step. Then, by performing a similar operation to this, filter segment patterns of other colors are formed to complete a color filter.

In the development step, an alkaline developer is used as a developer to wash and remove the unexposed areas. At that time, there was a problem in that the exposed portions were chipped or peeled off, resulting in defects in the pattern shape. Further, when the coating film is exposed to an alkaline developer, there is a problem in that the coating film changes color (hereinafter referred to as water stain). Therefore, there is a need for a photosensitive composition that does not cause defective pattern shapes or water stains during the development process. Furthermore, there was also the problem that the film thickness of the coating film changes (hereinafter referred to as residual film ratio) due to elution or vaporization of unreacted substances during the development process and post-baking process.

As an effort to improve water stains, Patent Document 1 discloses a resist composition containing a fluorine-based surfactant with a specific structure. Further, as an effort to improve pattern chipping during development, Patent Document 2 discloses a colored composition containing a polymerizable compound having an alkylene oxide structure. Furthermore, as an effort to improve pattern formation when a high concentration of colorant is included, Patent Document 3 discloses a colored photosensitive resin composition containing a polyfunctional thiol compound and an acetophenone compound.

JP2016-102212A Japanese Patent Application Publication No. 2014-142582 Japanese Patent Application Publication No. 2004-83857

However, none of the compositions disclosed in Patent Documents 1 to 3 were satisfactory in terms of water stains and pattern shapes. Further, the remaining film rate was not taken into consideration, and the results were not satisfactory.

The present invention aims to provide a photosensitive composition that can suppress water stains on a film after development, has a good residual film rate, and can form an excellent pattern.

The present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C),
The photopolymerization initiator (C) is an oxime photopolymerization initiator (C1) represented by the following general formula (1), and an oxime photopolymerization initiator (C2) other than the oxime photopolymerization initiator (C1). ).
General formula (1)

(In the general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents 2 to 20 heterocyclic groups.
R ² represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ³ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ⁴ represents a monovalent substituent. n represents an integer from 0 to 3. )

According to the present invention, it is possible to provide a photosensitive composition that suppresses water stains on a film after development, has a good residual film rate, and can form an excellent pattern. Further, the present invention can provide an optical filter, an image display device, and a solid-state image sensor.

Below, modes for carrying out the photosensitive composition of the present invention will be explained in detail. Note that the present invention is not limited to the following embodiments, and can be modified and implemented within the scope that can solve the problem.

In the present invention, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" are respectively used unless otherwise specified. , means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide" . Further, "C.I." means Color Index (C.I.; published by The Society of Dyers and Colorists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.
In addition, regarding the molecular weight of the compound in the present invention, for low-molecular compounds whose molecular weight can be specified, the value calculated by calculation (formula weight) or the molecular weight measured by ESi-MS (electrospray ionization mass spectrometry), For compounds with a molecular weight distribution, this is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent. The polymerizable compound (B) is a compound that forms a film upon curing. Monomers are compounds that form resins upon polymerization. The monomers are in an unreacted state, and the monomer units are in a state where a resin is formed after the monomers are polymerized.

<Photosensitive composition>
One embodiment of the present invention relates to a photosensitive composition. The photosensitive composition of the present invention is a photosensitive composition containing an alkali-soluble resin (A), a polymerizable compound (B), and a photoinitiator (C),
The photopolymerization initiator (C) is an oxime photopolymerization initiator (C1) represented by the following general formula (1), and an oxime photopolymerization initiator (C2) other than the oxime photopolymerization initiator (C1). )including. The photosensitive composition of the present invention can be patterned, and is preferably used after forming a film and photocuring. The coating is preferably used to be incorporated into an optical device such as an image display device or a solid-state image sensor, for example.
General formula (1)

In the general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 carbon atoms. ~20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents a monovalent substituent. n represents an integer from 0 to 3.

Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

[Photopolymerization initiator (C)]
The photosensitive composition of the present invention uses an oxime-based photoinitiator (C1) represented by general formula (1) as a photoinitiator (C), and an oxime-based photoinitiator other than the oxime-based photoinitiator (C1). Contains a photopolymerization initiator (C2).
It is thought that by using (C1) and (C2) with a different structure, the wavelength range of light that can be used effectively is expanded and the sensitivity is improved, making the film tougher and reducing water stains and film retention.

(Oxime photopolymerization initiator (C1))
The oxime photopolymerization initiator (C1) is a compound represented by the following general formula (1).
General formula (1)

In the general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 carbon atoms. ~20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents any monovalent substituent. n represents an integer from 0 to 3.

In the general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 carbon atoms. ~20 heterocyclic groups.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group. group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group , hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, and the like.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, and the like.
Among the above, from the viewpoint of reactivity, a methyl group, an ethyl group, or a phenyl group is preferable, and a methyl group or an ethyl group is more preferable.

In the general formula (1), R ₂ is an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group.
The alkyl group having 3 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, propyl group, isopropyl group, butyl group, isobutyl group, t -Butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group , cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, and the like.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, and the like.
Among the above, from the viewpoint of pattern shape, alkyl groups having 3 to 20 carbon atoms are preferred, alkyl groups having 3 to 8 carbon atoms are more preferred, and pentyl groups are even more preferred.

In the general formula (1), R ₃ is an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group.
The alkyl group having 3 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, propyl group, isopropyl group, butyl group, isobutyl group, t -Butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group , cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, and the like.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, and the like.
Among the above, from the viewpoint of suppressing water stains, a branched alkyl group having 3 to 15 carbon atoms is preferred, a branched alkyl group having 5 to 12 carbon atoms is more preferred, and a 3-methylbutyl group, a 2- Ethylhexyl group is more preferred.

In general formula (1), R ₄ represents any monovalent substituent.
Monovalent substituents include alkyl groups having 1 to 20 carbon atoms such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms such as methoxy and ethoxy groups; F, Cl, Br, i, etc. halogen atom; acyl group having 1 to 20 carbon atoms; alkyl ester group having 1 to 20 carbon atoms; alkoxycarbonyl group having 1 to 20 carbon atoms; halogenated alkyl group having 1 to 20 carbon atoms, carbon atom Aromatic ring group having 4 to 20 atoms; amino group; aminoalkyl group having 1 to 20 carbon atoms; hydroxyl group; nitro group; cyano group; benzoyl group that may have a substituent; thenoyl group that may have a substituent Examples include groups. Examples of substituents that the benzoyl group or thenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, etc. , in the range of 1 to 3.
Among the above, from the viewpoint of reactivity, a benzoyl group which may have a substituent is preferable, and a benzoyl group whose substituent is an alkoxycarbonyl group is more preferable.

In general formula (1), n represents an integer of 0 to 3. Among these, from the viewpoint of radical generation efficiency, it is preferably 0 or 1, and more preferably 1.

A known method can be used to produce the oxime photopolymerization initiator (C1). For example, methods described in International Publication No. 2008/078678, International Publication No. 2014/050738, Japanese Translation of PCT International Publication No. 2016-519675, etc. can be mentioned.

Specific examples of the compound represented by general formula (1) are shown below. Note that the present invention is not limited to these.

Among the compounds of chemical formulas (2) to (7), the compound of chemical formula (7) is preferred from the viewpoint of water stain suppression, pattern shape, and film remaining rate.

The oxime photopolymerization initiator (C1) can be used alone or in combination of two or more types.

(Oxime-based photopolymerization initiator (C2))
The oxime photopolymerization initiator (C2) is a photopolymerization initiator other than the oxime photopolymerization initiator (C1) represented by general formula (1). Commercial products of the oxime photopolymerization initiator (C2) include, for example, IRGACURE OXE-01, 02, 03, 04 manufactured by BASF Japan, and ADEKA Arkles N-1919, NCi-730, 831, 930 manufactured by ADEKA. , TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 346, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Strong New Materials, OMNIRAD1312, 1314, 1316 manufactured by IGM Resins, Examples include SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, and DFI-020, 306 and EOX-01 manufactured by Daito Chemix.

Specific examples of the oxime photopolymerization initiator (C2) include the following. Note that the present invention is not limited to these.

Chemical formula (12) Chemical formula (13)

Methods for producing compounds of chemical formulas (8) to (16) are described, for example, in Japanese Patent Publication No. 2004-534797, Japanese Patent Application Publication No. 2008-80068, Japanese Patent Application Publication No. 2012-526185, International Publication No. 2015/036910, International Publication No. 2015/036910, Examples include methods described in Publication No. 2015/152153, Japanese Translated Patent Application Publication No. 2016-504270, Japanese Patent Application Publication No. 2017-512886, and the like.

Among the compounds of chemical formulas (8) to (16), the oxime photopolymerization initiator (C2) is preferably a compound of chemical formulas (11) to (16) from the viewpoint of water stain suppression, pattern shape, and film retention rate. One or more types selected from the group consisting of are preferred.

The oxime photopolymerization initiator (C2) can be used alone or in combination of two or more types.

The mass ratio of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) is preferably 90:10 to 10:90 from the viewpoint of water stain suppression, pattern shape, and film remaining rate. The ratio is more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

The total content of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) is 100 mass of the photopolymerization initiator (C) from the viewpoint of water stain suppression, pattern shape, and film remaining rate. %, preferably 50% by mass or more, more preferably 80% by mass or more.

(Photopolymerization initiator (C3) other than (C1) and (C2))
The photosensitive composition of the present invention includes a photopolymerization initiator (C3) other than the oxime photopolymerization initiator (C1) and the oxime photopolymerization initiator (C2) (hereinafter also referred to as other photopolymerization initiator (C3)). ) can be included.

Other photopolymerization initiators (C3) are not particularly limited as long as they are compounds that can initiate polymerization of the polymerizable compound (B) by light, and any known photopolymerization initiators may be used. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl )-1-butanone, or acetophenone compounds such as 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone;
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)-triazine methyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4 , 6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine. system compound;
Acyl phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

Other photopolymerization initiators (C3) can be used alone or in combination of two or more.

From the viewpoint of photocurability, the content of the photopolymerization initiator (C) is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, and 5 to 50 parts by mass, based on 100 parts by mass of the polymerizable compound (B). ˜25 parts by mass is more preferred.

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

The alkali-soluble resin (A) may be any resin that dissolves in an alkaline developer, and any known resin may be used. The alkali-soluble resin (B) can be classified into non-photosensitive alkali-soluble resins and photosensitive alkali-soluble resins. The alkali-soluble resin (A) has an alkali-soluble group such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, or a phenolic hydroxyl group. Among these, carboxyl groups are preferred.
Non-photosensitive alkali-soluble resins include, for example, acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, Alternatively, examples include isobutylene/(anhydrous) maleic acid copolymer. The photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. Moreover, the alkali-soluble resin (A) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

From the viewpoint of developability, the weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably from 2,000 to 40,000, more preferably from 3,000 to 300,00, and from 4,000 to 20,000. More preferred. Moreover, the value of Mw/Mn is preferably 10 or less. A suitable weight average molecular weight (Mw) improves adhesion to the substrate and development solubility.

The acid value of the alkali-soluble resin (A) is preferably 50 to 200 mgKOH/g, more preferably 70 to 180 mgKOH/g, even more preferably 90 to 170 mgKOH/g. A suitable acid value improves adhesion to the substrate and development solubility.

The content of the alkali-soluble resin (A) is preferably 1 to 80% by weight, more preferably 5 to 60% by weight, and even more preferably 10 to 50% by weight based on 100% by weight of nonvolatile content of the photosensitive composition.

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

From the viewpoint of pattern formation, the alkali-soluble resin (A) preferably contains a photosensitive alkali-soluble resin.

(Alkali-soluble resin (A1))
The photosensitive composition of the present invention, as the alkali-soluble resin (A), contains an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit from the viewpoint of suppressing water stains, remaining film rate, and pattern formation. It is preferable to include an alkali-soluble resin (A1) containing a monomer unit (a2).
The alicyclic hydrocarbon structure, which is highly hydrophobic and has both flexibility and rigidity, has a low affinity with developing solutions and is thought to be able to form a tough film, and is expected to suppress water stains, reduce film retention, and improve patterns. Formability is improved. Furthermore, it is presumed that a stronger coating could be formed by combining the highly sensitive oxime photopolymerization initiator (C1) and oxime photopolymerization initiator (C2).

[Alicyclic hydrocarbon-containing monomer unit (a1)]
Alicyclic hydrocarbon-containing monomers include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, ) acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, and the like. Among these, from the viewpoint of pattern formation, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[Carboxyl group-containing monomer unit (a2)]
Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Furthermore, a monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, can also be used in combination. Among these, acrylic acid and methacrylic acid are preferred.

[Other monomer units (a3)]
The alkali-soluble resin (A1) can contain other monomer units (a3) in addition to the alicyclic hydrocarbon-containing monomer (a1) and the carboxyl group-containing monomer unit (a2).

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth) (Meth)acrylates such as acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate;
2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate ) Hydroxyl group-containing (meth)acrylates such as acrylate;
Polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or poly12- Polyester mono(meth)acrylates with added hydroxystearic acid, etc.;
Epoxy groups such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate Contains (meth)acrylates;
(Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine. ;
Styrene or styrenes such as α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4 '-Bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N -(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl -2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6- N-substituted maleimides such as maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine;
2-(meth)acryloyloxyethyl acid phosphate, a compound containing a phosphoric acid ester group, such as a compound obtained by reacting a phosphoric acid esterification agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate. Examples include (meth)acrylates.

The alkali-soluble resin (A1) may contain an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2), and its synthesis method is not limited. Preferred synthesis methods, method (i) and method (ii), will be explained below.

<Method (i)>
In method (i), for example, the alkali-soluble resin (A1) can be synthesized by synthesizing a copolymer of an alicyclic hydrocarbon-containing monomer and a carboxyl group-containing monomer.

<Method (ii)>
In method (ii), for example, a copolymer of an alicyclic hydrocarbon-containing monomer and an epoxy group-containing monomer is synthesized. Next, an alkali-soluble resin (A1) can be synthesized by adding a carboxyl group-containing monomer to the epoxy group of the copolymer and causing an esterification reaction between the generated hydroxyl group and an acid anhydride.

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 is mentioned. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. These can be used alone or in combination of two or more.

The content of the alicyclic hydrocarbon-containing monomer unit (a1) is preferably 5 to 60% by mass based on 100% by mass of the total constituent units of the alkali-soluble resin (A1) from the viewpoint of suppressing water stains and forming a pattern. , more preferably 10 to 50% by mass.

The content of the alkali-soluble resin (A1) is preferably 50% by mass or more, and 70% by mass or more in 100% by mass of the alkali-soluble resin (A) from the viewpoint of suppressing water stains, remaining film rate, and pattern formation. More preferred.

(Alkali-soluble resin (A2))
The photosensitive composition of the present invention can contain an alkali-soluble resin (A2) other than the alkali-soluble resin (A1) as the alkali-soluble resin (A).

[Polymerizable compound (B)]
The photosensitive composition of the present invention contains a polymerizable compound (B).

Examples of the polymerizable compound (B) include monomers and oligomers. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Examples of the polymerizable compound (B) include a lactone-modified polymerizable compound (B1), a polymerizable compound having an acid group (B2), a polymerizable compound having a urethane bond (B3), and other polymerizable compounds (B4). etc.

(Lactone-modified polymerizable compound (B1))
The photosensitive composition of the present invention preferably contains a lactone-modified polymerizable compound (B1) from the viewpoint of suppressing water stains.

The lactone-modified polymerizable compound (B1) is a compound having a lactone-modified structure in its molecule. The lactone-modified polymerizable compound (B1) is a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimerolmelamine. It can be obtained by esterifying (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound (B1) is preferably a compound represented by the following general formula (17).

General formula (17)

In general formula (17), all six R's are groups represented by the following general formula (18), or 1 to 5 of the six Rs are groups represented by the following general formula (18). , the remainder is a group represented by the following general formula (19).

General formula (18)

In the general formula (18), R ¹ represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond bonding to the oxygen atom of the general formula (17).

General formula (19)

In the general formula (19), R ¹ represents a hydrogen atom or a methyl group, and * is a bond bonding to the oxygen atom of the general formula (17).

The lactone-modified polymerizable compound (B1) is, for example, KAYARAD manufactured by Nippon Kayaku Co., Ltd.
It is commercially available as the DPCA series, and DPCA-20 (in the above general formulas (17) to (19), m = 1, the number of groups represented by general formula (18) = 2, and R ¹ is all hydrogen atoms) (a certain compound), DPCA-30 (a compound in which in the above general formulas (17) to (19), m = 1, the number of groups represented by general formula (18) = 3, and all R ¹ are hydrogen atoms), DPCA-60 (in the above general formulas (17) to (19), m = 1, the number of groups represented by general formula (18) = 6
, a compound in which R ¹ is all hydrogen atoms), DPCA-120 (in the above general formulas (17) to (19), m = 2, the number of groups represented by general formula (18) = 6, R ¹ is (compounds in which all hydrogen atoms are hydrogen atoms), etc.

From the viewpoint of suppressing water stains, the lactone-modified polymerizable compound (B1) has m=1 in the above general formulas (17) to (19), and the number of groups represented by general formula (18)=2. ~6, compounds in which all R ¹ are hydrogen atoms are preferred; in the above general formulas (17) to (19), m = 1, the number of groups represented by general formula (18) = 2 or 3, R ¹ A compound in which all are hydrogen atoms is more preferred.

From the viewpoint of suppressing water stains, the content of the lactone-modified polymerizable compound (B1) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass based on 100% by mass of the polymerizable compound (B). , more preferably 20 to 60% by mass.

(Polymerizable compound (B2) having an acid group)
The photosensitive composition of the present invention preferably contains a polymerizable compound (B2) having an acid group from the viewpoint of alkali developability and pattern formation. Examples of the acid group of the polymerizable compound (B2) having an acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, carboxyl groups are preferred.

The polymerizable compound (B2) having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid; Examples include esterified products with hydroxyalkyl (meth)acrylates.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.
Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.
Examples of polyhydric carboxylic acids 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 include triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like.

Commercial products of the polymerizable compound (B2) having an acid group include Viscoat #2500P manufactured by Osaka Organic Co., Ltd. and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M manufactured by Toagosei Co., Ltd. -521 etc. are mentioned.

From the viewpoint of alkali developability and pattern formation, the content of the polymerizable compound (B2) having an acid group is preferably 5 to 80% by mass, and 10 to 70 parts by mass based on 100% by mass of the polymerizable compound (B). It is more preferable that the amount is 20 to 60% by mass.

(Polymerizable compound (B3) having a urethane bond)
From the viewpoint of pattern formation, the photosensitive composition of the present invention preferably contains a polymerizable compound (B3) having a urethane bond.

The polymerizable compound (B3) having a urethane bond is, for example, a urethane (meth)acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or a polyfunctional isocyanate obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate. Examples include urethane (meth)acrylate obtained by reacting (meth)acrylate having a hydroxyl group.

The (meth)acrylate having a hydroxyl group is, for example, 2-hydroxyethyl (meth)
Acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene Oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, epoxy Examples include reaction products of group-containing compounds and carboxy (meth)acrylates, hydroxyl group-containing polyol polyacrylates, and the like.

Examples of the polyfunctional isocyanates include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanate such as isophorone diisocyanate. , their burette bodies, isocyanate nurate bodies, trimethylolpropane adducts, and the like.

From the viewpoint of developability, it is also preferable that the polymerizable compound (B3) having a urethane bond further has an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among these, a carboxyl group is preferred.

As a method for introducing an acid group into the polymerizable compound (B3) having a urethane bond, for example, first, the above-mentioned (meth)acrylate having a hydroxyl group and the above-mentioned polyfunctional isocyanate are reacted. Next, it can be synthesized by adding a mercapto compound having a carboxyl group to the product.

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

From the viewpoint of pattern formation, the content of the polymerizable compound (B3) having a urethane bond is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, based on 100 parts by mass of the polymerizable compound (B). More preferably 20 to 60% by mass.

(Other polymerizable compounds (B4))
Other polymerizable compounds (B4) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxylic Ethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate , isocyanuric acid EO modified tri(meth)
Acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di( meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine ( Various acrylic esters and methacrylic esters such as meth)acrylic esters and epoxy(meth)acrylates, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl Examples include (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like.

Other commercially available polymerizable compounds (B4) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, and R-604 manufactured by Nippon Kayaku Co., Ltd. , R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, and Aronix M-303, M-305, M-306, M- manufactured by Toagosei Co., Ltd. 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, #335HP, #700, #295, #330, #360, #GPT manufactured by Osaka Organic Co., Ltd. , #400, #405, AH-600, AT-600 manufactured by Kyoeisha Chemical Co., Ltd., NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd. Examples include EBECRYL40, 130, 140, 145 manufactured by Daicel Allnex Corporation, and OGSOL EA-0200, 0300 manufactured by Osaka Gas Chemical Company.
etc.

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

The polymerizable compound (B) is a lactone-modified polymerizable compound (B1), an acid group-containing polymerizable compound (B2), and a urethane bond and a urethane bond. It is preferable to contain at least one kind selected from the group consisting of polymerizable compounds (B3) having an acid group, and more preferably to contain two or more kinds.

The content of the polymerizable compound (B) is preferably 1 to 60% by weight, more preferably 2 to 50% by weight based on 100% by weight of the nonvolatile content of the photosensitive composition.

[Thiol chain transfer agent (D)]
The photosensitive composition of the present invention preferably contains a thiol chain transfer agent (D) from the viewpoint of suppressing water stains and forming a pattern.

The thiol chain transfer agent (D) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). In addition, 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 photocure from the surface of the film to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercapto Tris(2-hydroxyethyl)propionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- Examples include s-triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent (D) can be used alone or in combination of two or more types.

The content of the thiol-based chain transfer agent (D) is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the nonvolatile content of the photosensitive composition.

[Colorant (E)]
The photosensitive composition of the present invention can contain a colorant (E).

The colorant (E) may be either a pigment or a dye, and they can be used in combination.

(pigment)
Pigments are compounds classified as pigments in the color index.
The red pigment is, for example, C.I. 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: 3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151, 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, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, C. I. Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigment described in JP2014-134712A, the pigment described in Japanese Patent No. 6368844 are preferable, C. I. Pigment Red 177,254,291,295,296, the pigment described in Japanese Patent Application Publication No. 2014-134712, and the pigment described in Japanese Patent No. 6368844 are more preferable.

The orange pigment is, for example, C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Yellow pigments include, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 6
3,65,73,74,77,81,83,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, JP Examples include pigments described in 2012-226110. Among these, C. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP 2012-226110 A are preferred.

The green pigment is, for example, C.I. 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 etc. are mentioned. Among these, C. I. Pigment Green 36, 58, 59, 62, and 63 are preferred.

The blue pigment is, for example, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, Examples include 35, 36, 56, 56:1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like. Among these, C. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

The purple pigment is, for example, C.I. 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, 37, 39, 42, 44, 47, 49, 50, etc. Among these, C. I. Pigment Violet 19 and 23 are preferred.

Specifically, the black pigment is C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. Alternatively, at least two or more pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and violet pigments may be used as a black coloring agent.

Among the pigments, inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, deep blue, chromium oxide green, and cobalt. Examples include green, amber, and synthetic iron black.

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

It is preferable that the acidic dye has an acidic group such as sulfonic acid or carboxylic acid. Further, a salt-forming compound which is a salt of an acidic dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. Also preferred are salt-forming compounds that are salts of resin components having these functional groups and acidic dyes. Further, by converting the salt-forming compound into a sulfonamide compound and modifying it into a sulfonic acid amide compound, a photosensitive composition with excellent resistance (light resistance, solvent resistance) can be easily obtained.
Further, a salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent resistance (light resistance, solvent resistance). Note that the compound having an onium base is preferably a resin having a cationic group.

Although the basic dye can be used as it is, it is preferably a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion components that act as counter ions in the salt-forming compounds of basic dyes include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and carbonized halides. Preferred are salt forming compounds obtained by forming salts with an anionic compound having a conjugate base of an organic acid having a hydrogen group and an acidic dye. Note that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples include dye structures derived from dyes selected from dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

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

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

The content of the colorant (E) is preferably 5 to 70% by weight, more preferably 10 to 60% by weight based on 100% by weight of the nonvolatile content of the photosensitive composition.

(Refining of pigment)
It is preferable to use the pigment in a finely divided form. The refinement method is not particularly limited, and, for example, any of wet grinding, dry grinding, and solution precipitation methods can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. Note that from the viewpoint of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

Salt milling is a process in which a mixture of pigments, water-soluble inorganic salts, and water-soluble organic solvents is mechanically heated while being heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attriter, or sand mill. After kneading, water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling pigments, it is possible to obtain pigments with very fine primary particle diameters, narrow distribution widths, and sharp particle size distributions.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. The water-soluble inorganic salt is preferably sodium chloride (salt) from the viewpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by weight, more preferably 300 to 1,000 parts by weight, based on 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is a solvent that dissolves (mixes with) water but does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling point solvent with a boiling point of 120° C. or higher is preferred 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, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

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

[Dye derivative (F)]
The photosensitive composition of the present invention can contain a dye derivative (F).

The dye derivative (F) is a compound having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (F) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, or an amine salt thereof, or a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimido alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzoisomer pigments. Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520 A, WO 2009/081930, WO 2011/052617, WO 2012/102399, JP 2017 -156397, as phthalocyanine dye derivatives, JP 2007-226161, WO 2016/163351, JP 2017-165820, and Japanese Patent No. 5753266, as anthraquinone dye derivatives, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, International Publication No. 2009/025325, Quinacridone series Examples of dye derivatives include JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383, and dioxazine-based dye derivatives include JP-A-2
011-162662, thiazine indigo dye derivatives, JP 2007-314785, triazine dye derivatives, JP 61-246261, JP 11-199796, JP 2003 -165922, JP 2003-168208, JP 2004-217842, JP 2007-314681, as benzisoindole dye derivatives, JP 2009-57478, quinophthalone dye derivatives. As for the naphthol dye derivative, JP 2003-167112, JP 2006-291194, JP 2008-31281, JP 2012-226110, and naphthol dye derivatives include JP 2012-208329, JP 2014-5439, Azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic substituents, JP 2004-307854, basic substituents Examples include known dye derivatives described in JP-A No. 2002-201377, JP-A No. 2003-171594, JP-A No. 2005-181383, and JP-A No. 2005-213404. In addition, in these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. A compound having a substituent such as a neutral group has the same meaning as a dye derivative.

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

The content of the dye derivative (F) is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the colorant (E).

[Dispersion resin (G)]
The photosensitive composition of the present invention can contain a dispersion resin (G).

The dispersion resin (G) is preferably a resin having an adsorption group with high affinity for the colorant (E). It is preferable that the adsorption group has at least one kind of a basic group and an acidic group, and from the viewpoint of developability, it is preferable that the adsorption group has an acidic group.

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonia base, and a nitrogen atom-containing group such as a nitrogen-containing heterocycle.

Examples of acidic groups include carboxyl groups, phosphoric acid groups, and sulfonic acid groups. Among these, carboxyl groups and phosphoric acid groups are preferred from the viewpoint of adsorption to pigments and developability.

The resin species of the dispersion resin (G) include, for example, urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acids. Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups. Water-soluble products such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples include water-soluble resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, and the like.

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

Commercially available products of the dispersion resin (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, manufactured by BYK Chemie Japan Co., Ltd. 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 136 manufactured by Japan Lubrizol Co., Ltd. 50,13940 ,16000,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,38500,41000, 41090, 53095, 55000, 56000, 76500 etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Techno Co., Ltd., JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, International Publication No. 2008/007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007- Examples include resins described in JP-A No. 23195, JP-A No. 1996-143651, and the like.

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

From the viewpoint of dispersion stability, the content of the dispersion resin (G) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the colorant (E).

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

Examples of the sensitizer (H) include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone. Derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrin derivatives Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α- Siloxy ester, acyl oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4
Examples include '-tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Among the sensitizers (H), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. 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 preferred.

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 weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator (C). Containing an appropriate amount improves photocurability and developability.

[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, increasing the crosslinking density and improving heat resistance.

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 epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy compound (I1))
Epoxy compounds (I1) include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene). , alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.). Polymerization of compounds, phenols, and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'- benzene dimethanol, biphenyl dimethanol, α, α, α', α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethyl biphenyl, etc.) etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amines. Examples include glycidyl ester-based epoxy resins and glycidyl ester-based epoxy resins.

Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd. EOCN-102S, 103S, 104S, 1020 Epicote 1004, 1256 manufactured by Japan Epoxy Resin Co., Ltd., JER1032H60, 157S65, 157S70, 152, 154, Celoxide 2021 manufactured by Daicel Chemical Industries, EHPE-3150, Denacol manufactured by Nagase ChemteX EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, TEPIC-L, H, S, etc. manufactured by Nissan Chemical Industries, Ltd. can be mentioned.

From the viewpoint of heat resistance of the cured film, the content of the epoxy compound (I1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

(Oxetane compound (I2))
The oxetane compound (iI2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or more functional oxetane compounds.

Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl-3-yl.
Hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl -3-{[3-(triethoxysilyl)propoxy]methyl}oxetane and the like.

Commercially available products include, for example, OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

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-Oxanonan, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3 -ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3- ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified 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 hydrogenated bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like.

Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

Trifunctional or higher functional oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, oxetane group-containing resin ( Examples include polymers obtained by radical polymerization of (meth)acrylic monomers such as oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462) and the above-mentioned OXE-30.

The content of the oxetane compound (I2) is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight based on 100% by weight of the nonvolatile content of the photosensitive composition.

A 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 per melamine ring of 5.0 or more. Having an appropriate number of methylol groups or ether groups makes it easy to obtain just the right amount of heat resistance.

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, manufactured by Sanwa Chemical Co., Ltd. MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX- 417, MX-410, and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries.

Among these, Nikalac MW-30HM, MW-390, MW-100LM, and MX- manufactured by Sanwa Chemical Co., Ltd. have an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. 750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45, Cymel 232, 235, 236, 238, 300 manufactured by Nihon Cytec Industries, 301, 303, 350, etc. are preferable in that they can increase the crosslinking density.

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

[Curing agent (curing accelerator)]
The photosensitive composition of the present invention can be used in combination with a curing agent (curing accelerator) in order to assist in curing the thermosetting compound (I).

Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. 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 (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, -Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.).

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

The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of thermosetting compound (I).

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

Examples of the polymerization inhibitor (J) include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, and 4-ethylcatechol. , 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol , 4-t-butylcatechol, alkylcatechol compounds such as 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 - Alkylresorcinol compounds such as propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri- Examples include phosphine compounds such as benzylphosphine, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, and phloroglucin.

The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

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

The ultraviolet absorber (K) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. Examples include compounds.

The benzotriazole compound is, for example, 2-(5methyl-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-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazole) 2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-( 1,1,3,3-tetramethylbutyl)phenol, methyl 3
-(3-(2H-benzotriazol2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol2-yl)-4-( 1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] , 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5 -di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert- Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H -benzotriazol2-yl)phenyl]propionate.

Commercially available products include, for example, TINUVIN P, PS, 234, 32 manufactured by BASF Japan.
6,329,384-2,900,928,99-2,1130, ADEKA STAB LA-29, LA-31RG, LA-32, LA-36, KEMiSORB71, 73, 74, manufactured by ChemiPro Kasei Co., Ltd. 79,279, RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

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

Commercially available products include, for example, KEMISORB 102 manufactured by ChemiPro Kasei Co., Ltd., and TINUVIN 400, 405, 460, 477, 479, 1577ED, and AD manufactured by BASF Japan.
EKA's ADK STAB LA-46, LA-F70, Sun Chemical's CYASORB
Examples include UV-1164.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3, 2-hydroxy-4-n-oct Xybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octa Desyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like can be mentioned.

Commercially available products include, for example, KEMISORB 10, 11, 11S, and 12 manufactured by ChemiPro Kasei Co., Ltd.
, 111, SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., and the like.

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

The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass out of the total 100% by mass of the photopolymerization initiator (C) and the ultraviolet absorber (K).

[Antioxidant (L)]
The photosensitive composition of the present invention can contain an antioxidant (L).

The antioxidant (L) prevents the photopolymerization initiator (C) and thermosetting compound (i) contained in the photosensitive composition from yellowing due to oxidation during heat curing or the thermal process during iTO annealing. . In particular, when the concentration of the colorant (E) in the photosensitive composition is high, the content of the polymerizable compound (B) is relatively reduced, so it is necessary to increase the amount of the photopolymerization initiator (C) or to increase the amount of the thermosetting compound ( If the formulation i) is used, the cured film tends to yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

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

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

The hindered 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)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2- t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)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-hexamethylenebis (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-hexanedi-rubis[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 the like.

Commercially available products include, for example, Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, and KEMINOX101, 179, 76, 9425 manufactured by Chemipro. , IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, Syanox CY-1790, CY-2777 manufactured by Sun Chemical, etc. Can be mentioned.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 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-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , 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-piperidineethanol and 3, Ester of 5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy) decanedioate) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bis(1, 1dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, 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- Hexamethylene diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. Can be mentioned.

Commercially available products include, for example, ADEKA STAB LA-52, LA-57, LA-6.
3P, 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. , Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan, and Cyasorb UV-3346, UV-3529, UV-3853 manufactured by Sun Chemical.

Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2'-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4' -Isopropylidene diphenyl diphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropylidene 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)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethylbis(2,4-phosphite) -di-t-butyl-6-methylphenyl) and the like.

Commercially available products include, for example, ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. - EPQ etc.

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- Examples include cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, and the like.

Examples of commercially available products include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMiNOXPLS manufactured by ChemiPro Kasei.

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

The content of the antioxidant (L) is preferably 0.5 to 5.0% by weight based on 100% by weight of the nonvolatile content of the photosensitive composition. Containing an appropriate amount improves transmittance, spectral characteristics, and sensitivity.

[Leveling agent (M)]
The photosensitive composition of the present invention can contain a leveling agent (M). This further improves the wettability and drying properties for the substrate during coating.

Examples of the leveling agent (M) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of silicone surfactants include linear polymers comprising siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.

Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, manufactured by BYK Chemie. 378, 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Dow Corning Toray, X-22-4952, X-22-4272, X- manufactured by Shin-Etsu Chemical Co., Ltd. 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Examples of the fluorosurfactant include a surfactant or a leveling agent having a fluorocarbon chain.

Commercially available products include, for example, Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical, and Megafac F-253, 477, 551, 552, 555, 558, 560, 570 manufactured by DIC. , 575, 576, R-40-LM, R-41, RS-72-K, DS-21, FC-4430, 4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. , EF-PP32C1, and Futergent 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 myristele ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan triolate, sorbitan sesquiolate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxytetraoleate Ethylene sorbitol, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl Examples include alkanolamide and alkylimidazoline.

Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 manufactured by Kao Corporation. , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemur PD-420, PD-430, PD-430S, PD-450, Rheodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-iS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amito 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44,61,62,64,71,72,101,121, TR-701,702,704,913R, (meth)acrylic acid-based (co)polymer Polyflo-No. manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 etc. are mentioned.

Examples of the cationic surfactant include alkyl amine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Conc manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyl ether disulfonates, and lauryl sulfate monoethanol. Examples include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Commercially available products include, for example, Ftergent 100 and 150 manufactured by Neos, ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E, and EC-8600 manufactured by ADEKA.

Examples of the amphoteric surfactant include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkyl amine oxides such as lauryl dimethylamine oxide.

Commercially available products include Amhitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

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

The content of the leveling agent (M) is from 0.001 to 100% by mass of the nonvolatile content of the photosensitive composition.
It is preferably 2.0% by weight, more preferably 0.005 to 1.0% by weight. Within this range, the balance between coating properties and adhesion of the photosensitive composition is further improved.

[Storage stabilizer (N)]
The photosensitive composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive composition over time.

Storage stabilizers (N) include, for example, quaternary ammonium chloride such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl. Examples include organic phosphines and phosphites.

Storage stabilizers (N) can be used alone or in combination of two or more.

The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass based on 100% by mass of nonvolatile content of the photosensitive composition.

[Adhesion improver (O)]
The photosensitive composition of the present invention can contain an adhesion improver (O). This improves the adhesion between the coating and the base material. Further, it becomes easier to form a narrow pattern using photolithography.

Examples of the adhesion improver (O) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylic silanes such as 3-methacryloxypropyltriethoxysilane and 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 hydrochloride of dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl Mercapto compounds such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryl compounds such as p-styryltrimethoxysilane, ureido compounds such as 3-ureidopropyltriethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, etc. Examples include silane coupling agents such as sulfides and isocyanates such as 3-isocyanatepropyltriethoxysilane.

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

The content of the adhesion improver (O) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight based on 100% by weight of nonvolatile content of the photosensitive composition.

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

The organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol. Diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone , ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxy Butyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N -Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, Isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , propyl acetate, dibasic acid esters, and the like. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Alcohols such as glycol acetates, benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

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

[Method for manufacturing photosensitive composition]
The photosensitive composition of the present invention is subjected to a dispersion treatment by adding, for example, a colorant (E), an alkali-soluble resin (A), a dispersion resin (G), a dye derivative (F), an organic solvent (P), etc. In this way, a dispersion is produced. Thereafter, the polymerizable compound (B), the photopolymerization initiator (C), etc. are added to the dispersion and mixed. Note that the timing of blending each material is arbitrary. Moreover, the dispersion step can also be performed multiple times.

Examples of the dispersing machine that performs the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

The average dispersed particle size (secondary particle size) of the colorant 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 with high dispersion stability.

The average dispersed particle size (secondary particle size) can be measured using, for example, Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method). D. The particle shape is non-spherical, and the D50 particle diameter is the average diameter. It is preferable to use the organic solvent used for dispersion as the diluting solvent for measurement, and to measure the sample treated with ultrasonic waves immediately after sample preparation, because results with less variation can be easily obtained.

The photosensitive composition is prepared by centrifugation, filtration with a sintered filter or membrane filter, etc. to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and contaminants. It is preferable to remove the dust. The photosensitive composition of the present invention preferably does not substantially contain 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 filter segment formed from the photosensitive composition of the present invention. Optical filters can be used for a variety of purposes. In this specification, the optical filter is preferably a color filter.
In the case of a color filter, the filter segment has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (E) used. In place of or in addition to the filter segments, a magenta filter segment, a cyan filter segment, a yellow filter segment, a white filter segment, and a black filter segment may be included. Furthermore, it is possible to have a clear filter that does not use a colorant (E).
Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective base material include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[Optical filter manufacturing method]
The method for manufacturing an optical filter includes, for example, a step (1) of applying a photosensitive composition onto a substrate to form a layer (film) of the composition, and a step (2) of exposing the layer to light in a pattern through a mask. ), step (3) of developing the unexposed portion with alkali to form a patterned cured film, and step (4) of heat-treating the pattern (post-baking).

Hereinafter, a method for manufacturing an optical filter will be explained in detail.
(Step (1))
Step (1) of forming a layer of the composition is to apply the photosensitive composition onto the substrate by a method such as spin coating, roll coating, slit coating, cast coating, or inkjet coating, and apply the photosensitive composition as necessary. Dry (prebake) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, hot plate, etc., depending on the situation.
Examples of the substrate include a glass substrate, a silicon substrate, and the like. For example, an image sensor such as a CCD or CMOS may be formed on the surface of the silicon substrate. Further, an undercoat layer may be provided on the substrate, if necessary, in order to improve adhesion between the upper layer and the layer, to prevent diffusion of substances, and to flatten the surface of the substrate.
The thickness of the layer is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm.

(Step (2))
In the exposure step, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. A cured film is thereby obtained.
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 alkali development treatment, whereby the unexposed portions of the composition layer are eluted into the alkaline aqueous solution, leaving only the cured portions to form a patterned cured film.
Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include alkaline compounds such as pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the developer is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight.
The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed and the residual film rate after development can be improved.

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

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

<Image display device>
The image display device of the present invention includes the optical filter of the present invention. Examples of the image display device include a liquid crystal display and an organic EL display.
The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, Kogyo Chosenkai Co., Ltd., published in 1994) can be mentioned.
For the definition of an image display device and details of each image display device, see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, written by Sangyo Tosho)”. Co., Ltd., published in 1989).

<Solid-state image sensor>
The solid-state image sensor of the present invention includes the optical filter of the present invention.
The form used for the solid-state image sensor is not particularly limited, but for example, a transfer device consisting of a plurality of photodiodes, polysilicon, etc. that constitute the light-receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a base material. It has an electrode, has a light-shielding film on the photodiode and transfer electrode with an opening only at the light-receiving part of the photodiode, and is made of silicon nitride or the like formed 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 and a filter on the device protective film. Furthermore, there may be a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film below the filter (on the side closer to the base material), or a configuration in which the condensing means is provided on the filter. It's okay. Further, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition wall preferably has a low refractive index for each colored pixel.
An imaging device equipped with the solid-state imaging device of the present invention can be used in various applications such as, for example, a digital camera, an electronic device having an imaging function (mobile phone, smart phone, etc.), an in-vehicle camera, a surveillance camera, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to these. Note that "part" means "part by mass" and "%" means "% by mass."
Further, in the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass remaining after standing in an oven at 280°C for 30 minutes.

Prior to Examples, each measurement method will be explained.

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

(Average molecular weight of alkali-soluble resin and dispersed resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alkali-soluble resin and the dispersion resin were measured by gel permeation chromatography (GPC) equipped with an Ri detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters of the solution was injected. The average molecular weight is a polystyrene equivalent value.

(Acid value of alkali-soluble resin and dispersion resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of alkali-soluble resin and dispersed resin solution, stir to dissolve uniformly, and use an automatic titration device (COM -555'' (manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH/g). Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

(Amine value of dispersion resin)
The amine value of the dispersion resin is the value obtained by converting the total amine value (mgKOH/g) measured in accordance with the method of ASTM D 2074 into nonvolatile content.

<Production of colorant (E)>
(Fine red pigment (E-1))
C. i. 100 parts of Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture was poured into hot water, heated to about 80°C and stirred for 1 hour with a high-speed mixer to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and heated to 80°C. A finely divided red pigment (E-1) was obtained by drying the mixture for one day and crushing it.

(Fine red pigment (E-2))
C. i. 100 parts of Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture was poured into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and heated to about 80°C. A finely divided red pigment (E-2) was obtained by drying the mixture for one day and crushing it.

(Finely refined blue pigment (E-3))
C. I. 100 parts of Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 50° C. for 12 hours. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove salt and solvent, the mixture was heated to 80°C. A finely divided blue pigment (E-3) was obtained by drying for 24 hours and pulverizing.

(Finely refined purple pigment (E-4))
C. I. 100 parts of Pigment Violet 23, 1,200 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80° C. for 6 hours. Next, this kneaded material was poured into 8,000 parts of warm water, stirred for 2 hours with a high-speed mixer while heating to 80°C to form a slurry, and filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol. Thereafter, it was dried at 85° C. for 24 hours and pulverized to obtain a finely divided purple pigment (E-4).

(Finely divided green pigment (E-5))
C. I. 100 parts of Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This kneaded material was poured into 3000 parts of warm water, heated to 70°C and stirred for 1 hour with a high-speed mixer to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80°C overnight. A finely divided green pigment (E-5) was obtained by drying and pulverizing.

(Fine green pigment (E-6)
A green pigment (E-6) having the following chemical formula (20) was obtained according to the examples of JP-A-2017-111398. 100 parts of green pigment (E-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded material was poured into 3000 parts of warm water, heated to 70°C and stirred for 1 hour with a high-speed mixer to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80°C overnight. A finely divided green pigment (E-6) was obtained by drying and pulverizing.
Chemical formula (20)

(Fine yellow pigment (E-7))
C. I. 100 parts of Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. This mixture was poured into 2,000 parts of warm water, heated to 80°C and stirred for 1 hour with a high-speed mixer to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80°C overnight. A finely divided yellow pigment (E-7) was obtained by drying and pulverizing.

(Fine yellow pigment (E-8))
C. I. 100 parts of Pigment Yellow 139 ("Novoperm Yellow P-M3R" manufactured by Clariant), 800 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 70°C for 12 hours. . This mixture was poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was kept at 80°C overnight. A finely divided yellow pigment (E-8) was obtained by drying and pulverizing.

(Fine yellow pigment (E-9))
C. I. 100 parts of Pigment Yellow 185 ("Palitol Yellow D1155" manufactured by BASF Japan), 700 parts of crushed sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. . Next, this kneaded material was poured into 8 liters of warm water, stirred for 2 hours with a high-speed mixer while heating to 80°C to form a slurry, and after repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was heated to 85°C. A fine yellow pigment (E-9) was obtained by drying the powder for a day and pulverizing it.

(Fine yellow pigment (E-10)
A yellow pigment (E-10) having the following chemical formula (21) was obtained according to the examples of JP-A-2012-226110. 100 parts of yellow pigment (E-10), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80° C. for 6 hours. Next, this kneaded material was poured into 8 liters of warm water, heated to 80°C and stirred for 2 hours with a high-speed mixer to form a slurry, and after repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80°C. A fine yellow pigment (E-10) was obtained by drying the powder for a day and pulverizing it.
Chemical formula (21)

The average primary particle diameter of the finely divided pigment was within the range of 5 to 120 nm.

(Dye (E-11))
C. by following the steps below. I. A dye (E-11), which is a salt-forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in its side chain, was produced.
67.3 parts of methyl ethyl ketone was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile) ) and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a four-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from nonvolatile components and the weight average molecular weight (Mw) was 6,830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added and reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, a resin 1 was obtained in which the resin component had 47% by mass of ammonium groups and a cationic group in the side chain. The ammonium salt value of the obtained resin was 34 mgKOH/g.
Next, 30 parts (calculated as non-volatile content) of Resin 1 having a cationic group in the side chain was added to 2,000 parts of water, the mixture was sufficiently stirred and mixed, and then heated to 60°C. Meanwhile, 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the resin solution. After the dropwise addition, the mixture was stirred at 60° C. for 120 minutes to fully react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be the end point when there was no bleeding, and it was determined that a salt-forming compound had been obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer, and 32 parts of C.I. i. A dye (E-11) which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in its side chain was obtained. At this time, C.I. in the dye (E-11) I. The content of components derived from Acid Red 52 was 25% by mass.

<Production of alkali-soluble resin (A)>
(Alkali-soluble resin (A1-1) solution)
333 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere inside the flask was changed from air to nitrogen. , after heating to 100°C, 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate.
, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc, and 3.6 parts of azobisisobutyronitrile were added to the flask from the dropping funnel over 2 hours. The mixture was added dropwise, and stirring was continued at 100° C. for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol, (100 mol% based on the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0 .9 parts and 0.145 parts of hydroquinone were put into the flask, and the reaction was continued at 110° C. for 6 hours, and the reaction was terminated when the nonvolatile 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 resin solution with an acid value of 80 mgKOH/g. . After cooling to room temperature, approximately 2 parts of the photosensitive resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to prepare a photosensitive alkali-soluble resin (A1-1) solution containing an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2). Prepared. The weight average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (A1-2) solution)
182 parts of PGMAc was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C, and benzyl methacrylate was added. 70.5 parts (0.40 mol) of methacrylic acid, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 136 parts of PGMAc were mixed with azobisisobutylene. A solution containing 3.6 parts of lonitrile was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100° C. for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol % based on the carboxyl group of methacrylic acid used in this reaction)] and 0 parts of trisdimethylaminomethylphenol were added. .9 parts and 0.145 parts of hydroquinone were put into the flask, and the reaction was continued at 110° C. for 6 hours to obtain a photosensitive resin solution with an acid value of 79 mgKOH/g. After cooling to room temperature, approximately 2 parts of the photosensitive resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. A photosensitive alkali-soluble resin (A1-2) solution containing an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2) by adding PGMAc so that was prepared. The weight average molecular weight (Mw) was 13,000.

(Alkali-soluble resin (A2-1) solution)
196 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device. 196 parts of cyclohexanone was then heated to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A non-photosensitive alkali-soluble resin (A2-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin (A2-2) solution)
207 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 stirring device. 207 parts of cyclohexanone was heated to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 20 parts of methacrylic acid, 20 parts of benzyl methacrylate, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110, manufactured by Toagosei Co., Ltd.), 25 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, A mixture of 1.33 parts of 2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while stopping nitrogen gas and injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karens A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour, and cyclohexanone was added so that the nonvolatile content of the resin solution was 20% by mass to prepare a photosensitive alkali-soluble resin (A2-2) solution. The weight average molecular weight (Mw) was 18,000, and the nonvolatile acid value was 130 mgKOH/g.

<Manufacture of dispersed resin (G)>
(Dispersion resin (G-1) solution)
A reaction vessel equipped with a gas inlet tube, temperature, condenser, and 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 the mixture was purged 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 a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by non-volatile content measurement that 95% had reacted. 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 as a catalyst were added and 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 the mixture was diluted with PGMAc 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 (G-1) solution having a weight average molecular weight of 8,500 was obtained.

(Dispersion resin (G-2) solution)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and the mixture was heated with nitrogen gas. After the substitution, the mixture was reacted at 120° C. for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of nonvolatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, and 200 parts of methyl acrylate. 1 part, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80°C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by non-volatile content measurement that 95% had reacted. Finally, 500 parts of a PGMAc diluted solution of the compound obtained in the second step with a non-volatile content of 50%, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOi), and 0.1 part of hydroquinone were added, and the isocyanate was prepared using IR. The reaction was continued until the disappearance of the peak at 2270 cm ⁻¹ based on the group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the nonvolatile content was adjusted with PGMAc to obtain a dispersion resin (G-2) solution with a nonvolatile content of 30%. The resulting dispersed resin (G-2) had an acid value of 68 mgKOH/g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

(Dispersion resin (G-3) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer, and the mixture was flushed with nitrogen. The mixture was stirred at 50° C. for 1 hour while the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to start polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) were added to this reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. and nitrogen atmosphere. Two hours after adding 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured, and the polymerization conversion rate of the second block (A block) was 98 in terms of non-volatile content. % or more, the reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added and diluted so that the nonvolatile content was 30% as determined by nonvolatile content measurement, to obtain a dispersion resin (G-3) solution with an amine value per nonvolatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn). .

(Dispersion resin (G-4) solution)
In a 500 mL round-bottomed 4-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts of dimethylketenemethyltrimethylsilyl acetal as an initiator were added. Parts by mass were added via the addition funnel, and the mixture was sufficiently purged with nitrogen. Using a syringe, 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, a blocking monomer having solvent affinity, was added. , 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate were added using an addition funnel for 60 minutes. It dripped. The temperature was kept below 40°C by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, which is a monomer for a colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying.
Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round bottom flask, and 1.1 parts by mass of phenylphosphinic acid (dimethylaminopropyl methacrylamide), which is a salt forming component, was dissolved in 35 parts by mass of PGMAc. The mixture was stirred at a reaction temperature of 30° C. for 20 hours, and adjusted by adding PGMAc to obtain a dispersion resin (G-4) solution with a nonvolatile content of 30%.

<Production of polymerizable compound (B)>
(Polymerizable compound (B3-1) solution having urethane bond)
Into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged. The temperature was raised to .degree. C., and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from a dropping tube over 2 hours. After the dropwise addition, the mixture was reacted for 8 hours at a temperature of 50 to 70°C, and the disappearance of isocyanate absorption at 2180 cm ^-1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged, and the mixture was reacted at a temperature of 50 to 60°C for 6 hours. The nonvolatile content was adjusted to 50% by mass to obtain a solution of a polymerizable compound (B3-1) having a urethane bond.

<Production of dispersion>
(Dispersion 1)
After stirring and mixing the following raw materials so that they were uniform, they were dispersed for 3 hours using an Eiger mill (“Mini Model M-250 MKii” manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. The mixture was filtered through a 1.0 μm filter to produce Dispersion 1. The organic solvent (P-1) is PGMAc.
Fine blue pigment (E-3): 9.05 parts by mass Fine purple pigment (E-4): 0.31 parts by mass Dye (E-11): 4.16 parts by mass Pigment derivative (F-1) ): 1.04 parts by mass Dispersion resin (G-1) solution: 3.47 parts by mass Alkali-soluble resin (A2-1) solution: 2.00 parts by mass Organic solvent (P-1): 79.97 parts by mass

ｐｃは、フタロシアニン骨格を表す。 Pigment derivative (F-1): structure below

pc represents a phthalocyanine skeleton.

Dispersions 2 to 9 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts listed in Table 1 were changed.

Dye derivative (F-2) in Table 1: structure below

Dye derivative (F-3) in Table 1: Structure below

<Manufacture of photosensitive composition>
[Example 1]
(Photosensitive composition 1)
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive coloring composition 1.
Dispersion 1: 28.85 parts by mass Alkali-soluble resin (A1-1) solution: 10.00 parts by mass Polymerizable compound (B1-1): 3.00 parts by mass Polymerizable compound (B2-1): 3.00 Parts by mass Polymerizable compound (B3-1) solution: 2.00 parts by mass Oxime photoinitiator (C1-1): 0.50 parts by mass Oxime photoinitiator (C2-6): 0.50 parts by mass Thiol chain transfer agent (D): 0.35 parts by mass Thermosetting compound (i): 0.50 parts by mass
Polymerization inhibitor (J): 0.01 parts by mass Leveling agent (M): 1.00 parts by mass Organic solvent (P): 50.29 parts by mass

[Examples 2 to 35, Comparative Examples 1 to 3]
(Photosensitive compositions 2 to 38)
Photosensitive compositions 2 to 38 were prepared in the same manner as in Example 1, except that the raw materials and amounts of Photosensitive composition 1 in Example 1 were changed to those listed in Tables 2-1 to 2-4.

The raw materials listed in Tables 2-1 to 2-4 are as follows.

[Polymerizable compound (B)]
(Lactone-modified polymerizable compound (B1))
B1-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)

(Polymerizable compound (B2) having an acid group)
B2-1: Aronix M-520 (manufactured by Toagosei Co., Ltd.)

(Other polymerizable compounds (B4))
B4-1: Aronix M-420 (manufactured by Toagosei Co., Ltd.)

[Photopolymerization initiator (C)]
(Oxime photopolymerization initiator (C1))
C1-1: Compound of the above chemical formula (2) C1-2: Compound of the above chemical formula (3) C1-3: Compound of the above chemical formula (4) C1-4: Compound of the above chemical formula (5) C1- 5: Compound of the above chemical formula (6) C1-6: Compound of the above chemical formula (7)

(Oxime-based photopolymerization initiator (C2))
C2-1: Compound of the above chemical formula (8) C2-2: Compound of the above chemical formula (9) C2-3: Compound of the above chemical formula (10) C2-4: Compound of the above chemical formula (11) C2- 5: Compound of the above chemical formula (12) C2-6: Compound of the above chemical formula (13) C2-7: Compound of the above chemical formula (14) C2-8: Compound of the above chemical formula (15) C2-9: Compound of the above chemical formula (16)

(Other photopolymerization initiators (C3))
C3-1: Omnirad 907 (manufactured by IGM Resins, acetophenone photopolymerization initiator)

[Thiol chain transfer agent (D)]
D-1: Trimethylolpropane tris (3-mercaptobutyrate)
D-2: Pentaerythritol tetrakis (3-mercaptopropionate)
As described above, (D-1) and (D-2) were mixed in the same amount to prepare a thiol-based chain transfer agent (D).

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

[Thermosetting compound (I)]
(Epoxy compound (I1))
I1-1: EHPE-3150 (manufactured by Daicel)
I1-2: Denacol EX611 (manufactured by Nagase ChemteX)
I1-3: Triglycidyl Isocyanurate The above (I1-1) to (I1-3) were mixed in equal amounts to prepare a thermosetting compound (I).

[Polymerization inhibitor (J)]
J-1: 4-methylcatechol J-2: Methylhydroquinone J-3: t-butylhydroquinone The above (J-1) to (J-3) were mixed in the same amount, and polymerization inhibitor (J) was added. And so.

[Leveling agent (M)]
M-1: BYK-330 (manufactured by BYK Chemie)
M-2: Megafac F-551 (manufactured by DIC)
A mixed solution in which 1 part each of (M-1) and (M-2) were mixed and dissolved in 98 parts of PGMAc was used as a leveling agent (M).

[Organic solvent (P)]
P-1: Propylene glycol monomethyl ether acetate 30 parts P-2: Cyclohexanone 30 parts P-3: Ethyl 3-ethoxypropionate 10 parts P-4: Propylene glycol monomethyl ether 10 parts P-5: Cyclohexanol acetate 10 parts P -6: Dipropylene glycol methyl ether acetate 10 parts Above, (P-1) to (P-6) were mixed in the above mass parts, respectively, to obtain an organic solvent (P).

<Evaluation of photosensitive composition>
The obtained photosensitive compositions 1 to 38 (Examples 1 to 35, Comparative Examples 1 to 3) were evaluated for water stains, pattern forming properties (adhesion, linearity), and residual film rate using the following methods. went. The evaluation results are shown in Table 3.

[Water stain evaluation]
The obtained photosensitive composition was coated on a 0.7 mm glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm x width of 100 mm so that the film thickness after drying was 3.0 μm, and the film was heated at 70°C. It was dried on a hot plate for 1 minute. Next, a high-pressure mercury lamp was used to pass through a mask having a stripe pattern of 100 μm width at an illuminance of 30 mW/cm ² and 40 mJ/cm.
Ultraviolet light exposure was performed under ^{the following} conditions. Thereafter, the film was developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23° C. for 40 seconds, and was washed with pure water. The surface of the obtained pattern was observed using an optical microscope ECLIPSE LV100POL Model manufactured by Nikon, and the degree of discoloration of the portion was evaluated. The evaluation criteria are as follows, and scores of 3 or higher are considered practical.
5: There was no water stain.
4: Water stains accounted for less than 10% of the total.
3: Water stains accounted for 10% or more and less than 20% of the total.
2: Water stains accounted for 20% or more and less than 30% of the total.
1: Water stains accounted for 30% or more of the whole.

<Preparation of substrate for pattern formability evaluation>
The obtained photosensitive composition was applied to a 100 mm long x 100 mm wide, 0.7 mm thick glass substrate (Eagle 2000 manufactured by Corning) by a spin coating method so that the film thickness after drying was 3.0 μm. and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, it was exposed to light using a high-pressure mercury lamp at an illuminance of 30 mW/cm ² and 40 mJ/cm ² through a photomask having a stripe pattern with a width of 5 μm. Thereafter, this substrate was spray developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, then washed with ion-exchanged water, and air-dried. The substrate was heated at 230° C. for 30 minutes in a clean oven to obtain a substrate for evaluating pattern formability. Spray development was carried out for the coating film of each photosensitive composition for the shortest time possible to form a pattern without any development residue.

[Pattern formation evaluation (1): Adhesion]
Among the substrates for evaluating pattern formability created by the above method, patterns with widths of 5, 10, 15, 20, and 25 μm were observed with an optical microscope to confirm the minimum line width of the remaining patterns. The evaluation criteria are as follows, and scores of 3 or higher are considered practical.
5: Fine lines of 10 μm or less remain.
4: Fine lines of 15 μm or less remain.
3: Fine lines of 20 μm or less remain.
2: Fine lines of 25 μm or less remain.
1: No fine lines remain.

[Pattern formation evaluation (2): linearity]
The substrate prepared in pattern formability evaluation (1) was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. Ta. The evaluation criteria are as follows, and scores of 3 or higher are considered practical.
5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths The difference is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[Residual film rate evaluation]
When creating the above-mentioned substrate for evaluating pattern formability, spray development was performed, and the film thickness of the coating film after washing with ion-exchanged water and air drying was measured. This film thickness is defined as the film thickness after development. Thereafter, the film was heated in a clean oven at 230° C. for 30 minutes, and the film thickness was measured at the same location where the film thickness was measured after development. This film thickness is defined as the film thickness after baking. The remaining film rate was calculated from the two film thicknesses using the following formula. The evaluation criteria are as follows, and scores of 3 or higher are considered practical. Note that the film thickness was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).
Formula: Remaining film rate (%) = Film thickness after baking ÷ Film thickness after development x 100
5: Remaining film rate 85% or more 4: Remaining film rate 80% or more and less than 85% 3: Remaining film rate 75% or more and less than 80% 2: Remaining film rate 70% or more and less than 75% 1: Remaining film rate less than 70%

[Examples 2 to 35, Comparative Examples 1 to 3]
(Photosensitive compositions 2 to 38)
Photosensitive compositions 2 to 38 were prepared in the same manner as in Example 1, except that the raw materials and amounts of Photosensitive composition 1 in Example 1 were changed to those listed in Tables 2-1 to 2-4. In addition
Example 1 herein is a reference example.

Claims (7)

A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photoinitiator (C),
The photopolymerization initiator (C) is an oxime photopolymerization initiator (C1) represented by the following general formula (1), and an oxime photopolymerization initiator (C2) other than the oxime photopolymerization initiator (C1). ).
General formula (1)


(In general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents 2 to 20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents a monovalent substituent. n represents an integer from 0 to 3. ) Claim 1, wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A1) containing an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2). The photosensitive composition described. The alkali-soluble resin (A1) contains the alicyclic hydrocarbon-containing monomer unit (a1) in an amount of 5 to 60% by mass based on 100% by mass of the total constituent units of the alkali-soluble resin (A1). 2. The photosensitive composition according to 2. The photosensitive composition according to any one of claims 1 to 3, further comprising a thiol chain transfer agent (D). An optical filter comprising a substrate and a filter segment formed from the photosensitive composition according to any one of claims 1 to 4. An image display device comprising the optical filter according to claim 5. A solid-state imaging device comprising the optical filter according to claim 5.