JP2023159489A - Photosensitive composition, and cured film, optical filter, image display device, solid-state imaging element and infrared sensor which employ that composition - Google Patents

Abstract

To provide a photosensitive composition capable of forming a cured film excellent in the developability, the pattern shape and the heat resistance.SOLUTION: A photosensitive composition comprises a near-infrared absorbing dye (A) having a maximum absorption at a wavelength of 700 to 2,000 nm, an alkali-soluble resin (B), a polymerizable compound (C), and a photoinitiator (D). The alkali-soluble resin (B) includes an alkali-soluble resin (B1) having a glass transition temperature of 10 to 150°C. The photoinitiator (D) includes a photoinitiator (D1) represented by the formula in the figure.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive composition, a cured film using the same, an optical filter, an image display device, a solid-state image sensor, and an infrared sensor.

Video cameras, digital cameras, mobile devices with camera functions, and the like use CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state imaging devices for color images. Since a silicon photodiode sensitive to infrared rays is used in the light receiving section of these solid-state image sensors, it is necessary to perform visibility correction, and an infrared cut filter or the like is arranged. The infrared cut filter is manufactured using, for example, a composition containing a near-infrared absorbing dye.

Conventionally, infrared cut filters have been used as flat films, but in recent years, studies have been made to form patterns on infrared cut filters using photolithography. However, near-infrared absorbing dyes used in infrared cut filters and the like have low heat resistance and have a problem in that near-infrared absorbing ability decreases during heat treatment (post-bake) during pattern formation. On the other hand, films with high heat resistance have problems with poor developability and pattern formation.

Various efforts have been made to solve the above problems. For example, Patent Document 1 describes a thermosetting resin composition containing two types of cyanine compounds, an epoxy resin with a specific structure, and an epoxy resin curing agent as a resin composition that can produce an infrared cut filter with excellent processability and heat resistance. things are disclosed. Furthermore, Patent Document 2 describes a photosensitive resin composition for a near-infrared absorbing material that can obtain a fine pattern, including a phthalocyanine compound having a maximum absorption wavelength in the near-infrared region, a binder resin, a photopolymerizable compound, and a A photosensitive resin composition for a near-infrared absorbing material containing a polymerization initiator and a solvent is disclosed.

Japanese Patent Application Publication No. 2015-34252 Japanese Patent Application Publication No. 2010-160380

However, neither of the compositions described in Patent Documents 1 and 2 satisfies all of developability, pattern formation, and heat resistance.

An object of the present invention is to provide a photosensitive composition that has excellent developability and can form a cured film that is excellent in pattern formation and heat resistance.

The present invention provides a photosensitive composition containing a near-infrared absorbing dye (A) having maximum absorption in the wavelength range of 700 to 2,000 nm, an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). It is a thing,
The alkali-soluble resin (B) includes an alkali-soluble resin (B1) having a glass transition temperature of 10 to 150°C,
The present invention relates to a photosensitive composition in which the photopolymerization initiator (D) includes a photopolymerization initiator (D1) represented by the following general formula (1).
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 any monovalent substituent. n represents an integer from 0 to 3. )

According to the present invention described above, it is possible to provide a photosensitive composition that has excellent developability and can form a cured film that is excellent in pattern formation and heat resistance. Further, the present invention can provide a cured film, an optical filter, an image display device, a solid-state image sensor, and an infrared sensor.

FIG. 1 shows a schematic cross-sectional view of an image display device equipped with the cured film of the present invention. FIG. 2 shows a schematic cross-sectional view of a solid-state imaging device provided with the cured film of the present invention. FIG. 3 shows a schematic cross-sectional view of an infrared sensor equipped with the cured film of the present invention.

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.
Regarding the molecular weight of the compound in the present invention, for low-molecular compounds whose molecular weight can be specified, the molecular weight is the value calculated by calculation or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry). Compounds with a molecular weight distribution is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent.
Monomers are compounds that form resins upon polymerization. The monomers are in an unreacted state, and the monomer units are in a state where the monomers form a resin after polymerization.

<Photosensitive composition>
One embodiment of the present invention relates to a photosensitive composition. The photosensitive composition of the present invention comprises a near-infrared absorbing dye (A) having maximum absorption at a wavelength of 700 to 2,000 nm, an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). A photosensitive composition comprising:
The alkali-soluble resin (B) includes an alkali-soluble resin (B1) having a glass transition temperature of 10 to 150°C,
The photopolymerization initiator (D) is a photosensitive composition containing a photopolymerization initiator (D1) represented by the following general formula (1).
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 any 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.

[Near infrared absorbing dye (A)]
The photosensitive composition of the present invention contains a near-infrared absorbing dye (A).

The near-infrared absorbing dye (A) is a compound having maximum absorption in the wavelength range of 700 to 2,000 nm, and may be a pigment (also referred to as a near-infrared absorbing pigment) or a dye (also referred to as a near-infrared absorbing dye). It's okay. Further, a near-infrared absorbing pigment and a near-infrared absorbing dye may be used together. From the viewpoint of heat resistance, near-infrared absorbing pigments are preferred.
In the present invention, the near-infrared absorbing pigment preferably has a solubility in 100 g of propylene glycol monomethyl ether acetate at 25°C of less than 2 g, more preferably less than 1 g, particularly preferably 0.5 g or less. .

Examples of the near-infrared absorbing dye (A) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds. Among these, from the viewpoint of heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, and squarylium compounds are preferred, and naphthalocyanine compounds and squarylium compounds are more preferred.

Cyanine compounds are disclosed in International Publication No. 2006/006573, International Publication No. 2010/073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; Phthalocyanine compounds are JP-A-4-23868, JP-A-06-192584, JP-A-2000-63691, International Publication No. 2014/208514, etc.; Naphthalocyanine compounds are disclosed in JP-A-11-152414, JP-A-2000-86919, etc. No. 2009-29955, International Publication No. 2018/186490, etc.; indigo compounds, JP2013-230412, etc.; immonium compounds, JP2005-336150, 2007- 197492, JP 2008-88426, etc.; anthraquinone compounds, JP 62-903, JP 1-172458, etc.; pyrrolopyrrole compounds, JP 2009-263614, JP 2010-90313, JP 2011-068731; squarylium compounds are JP 2011-132361, JP 2016-142891, WO 2017/135359, WO 2018/225837, JP2019-001987A, International Publication No. 2020/054718, etc.; Examples of the croconium compound include compounds described in International Publication No. 2019/021767, etc.

(squarylium compound)
The squarylium compound is preferably a compound represented by the following general formula (2).
General formula (2)

(In general formula (2), R ¹ to R ⁴ are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR ¹⁰ , -COR ¹¹ , -COOR ¹² , -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , -NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ¹⁹ R ²⁰ , -NHCOOR ²¹ , -SR ²² , -SO ₂ R ²³ , -SO ₂ OR ²⁴ , -NHSO ₂ R ²⁵ , -SO ₂ NR ²⁶ R ²⁷ , -B(OR ²⁸ ) ₂ , and -NHBR ²⁹ R ³⁰ are represented. R ¹⁰ to R ³⁰ each independently represent a hydrogen atom, a substituted Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group that may have a group.In addition, when R ¹² of -COOR ¹² is hydrogen (that is, a carboxyl group), hydrogen The atom may be dissociated (i.e., carbonate group) or may be in a salt state.Also, when R ²⁴ of -SO ₂ OR ²⁴ is a hydrogen atom (i.e., sulfo group), the hydrogen atom may be dissociated. (i.e., a sulfonate group) or may be in the form of a salt. Also, R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring.)

"Substituents" include halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups,
Alkynyl group, aryl group, heteroaryl group, aralkyl group,
-OR ¹⁰⁰ , -COR ^{101 ,} -COOR ¹⁰² , -OCOR 103, -NR ¹⁰⁴ R ¹⁰⁵ , -NHCOR ¹⁰⁶ , -CONR ¹⁰⁷ R ¹⁰⁸ , -NHCONR ¹⁰⁹ R ¹¹⁰ , -NHCOOR ¹¹¹ , -SR ¹¹² , -SO ₂ R ¹¹³ , -SO ₂ OR ¹¹⁴ , -NHSO ₂ R ¹¹⁵ or -SO ₂ NR ¹¹⁶ R ¹¹⁷ .
R ¹⁰⁰ to R ¹¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. Note that when R ¹⁰² of -COOR ¹⁰² is hydrogen (ie, a carboxyl group), the hydrogen atom may be dissociated (ie, a carbonate group) or may be in a salt state. Furthermore, when R ¹¹⁴ in -SO ₂ OR ¹¹⁴ is a hydrogen atom (ie, a sulfo group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched, or cyclic.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched, or cyclic.
The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkynyl group may be linear, branched, or cyclic.
The number of carbon atoms in the aryl group is preferably 6 to 25, more preferably 6 to 15, particularly preferably 6 to 10.
The alkyl portion of the aralkyl group is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the above aryl group. The aralkyl group preferably has 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, and particularly preferably 7 to 25 carbon atoms.
The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, and particularly preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The heteroaryl group preferably has a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12.
The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, and aralkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned "substituent".

The squarylium compound is more preferably a compound represented by the following general formula (3) from the viewpoint of light resistance and heat resistance.
General formula (3)

(In general formula (3), R ⁵ to R ⁸ are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR ⁵⁰ , -COR ⁵¹ , -COOR ⁵² , -OCOR ⁵³ , -NR ⁵⁴ R ⁵⁵ , -NHCOR ⁵⁶ , -CONR ⁵⁷ R ⁵⁸ , -NHCONR ⁵⁹ R ⁶⁰ , -NHCOOR ⁶¹ , -SR ⁶² , -SO ₂ R ⁶³ , -SO ₂ OR ⁶⁴ , -NHSO ₂ R ⁶⁵ or -SO ₂ NR ⁶⁶ R ⁶⁷ , -B(OR ⁶⁸ ) ₂ , and -NHBR ⁶⁹ R ⁷⁰ are represented. R ⁵⁰ to R ⁷⁰ each independently represent a hydrogen atom, a substituted Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group that may have a group.In addition, when R ⁵² of -COOR ⁵² is hydrogen (that is, a carboxyl group), hydrogen The atom may be dissociated (i.e., carbonate group) or may be in a salt state.Also, when R ⁶⁴ of -SO ₂ OR ⁶⁴ is a hydrogen atom (i.e., sulfo group), the hydrogen atom may be dissociated. (i.e., a sulfonate group) and may be in the form of a salt. Also, R ⁵ and R ⁶ and R ⁷ and R ⁸ may be bonded to each other to form a ring.)

"Substituent" has the same meaning as the above-mentioned "substituent".

Specific examples of squarylium compounds are shown below. Note that the present invention is not limited to these.

(Pyrrolopyrrole compound)
The pyrrolopyrrole compound is preferably a compound represented by the following general formula (4).

General formula (4)

(In general formula (4), R ^1x and R ^1y each independently represent an alkyl group, aryl group, or heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, R ² and R ³ may combine with each other to form a ring, R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4x R ^4y , or a metal atom, and R ⁴ represents , R ^1x , R ^1y and R ³ , and each of R ^{4x and} R ^4y independently represents a substituent. General formula (4) is It is described in JP2009-263614A, JP2011-68731A, and International Publication No. 2015/166873.

R ^1x and R ^1y are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group. Further, the alkyl group, aryl group, and heteroaryl group represented by R ^1x and R ^1y may have a substituent or may be unsubstituted. Examples of the substituent include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR ¹¹ , -SOR ¹² , -SO ₂ R ¹³ and the like. R ¹¹ to R ¹³ each independently represent a hydrocarbon group or a heteroaryl group. Further, examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A No. 2009-263614. Among these, as the substituent, an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR ¹¹ , -SOR ¹² and -SO ₂ R ¹³ are preferable. The groups represented by R ^1x and R ^1y are preferably an alkoxy group having a branched alkyl group or an aryl group having a group represented by -OCOR ¹¹ as a substituent. The number of carbon atoms in the branched alkyl group is preferably 3 to 30, more preferably 3 to 20.

At least one of R ² and R ³ is preferably an electron-withdrawing group, more preferably R ² represents an electron-withdrawing group, and R ³ represents a heteroaryl group. The heteroaryl group preferably has a 5-membered ring or a 6-membered ring. Further, the heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, and more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. It is preferable that the heteroaryl group has one or more nitrogen atoms. Two ^R2s in general formula (4) may be the same or different. Furthermore, two R ^3s in general formula (4) may be the same or different.

R ⁴ is preferably ^{a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR 4x R 4y ;} A group represented by the formula -BR ^4x R ^4y is more preferable, and a group represented by -BR 4x R 4y is particularly preferable. The substituent represented by R ^4x R ^4y is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. Two R ^4s in general formula (4) may be the same or different.

Specific examples of pyrrolopyrrole compounds are shown below. In the following structural formula, Me represents a methyl group and Ph represents a phenyl group. In addition, as pyrrolopyrrole compounds, paragraphs 0016 to 0058 of JP2009-263614A, paragraphs 0037 to 0052 of JP2011-68731A, paragraphs 0014 to 0027 of JP2014-130343A, and International Publication No. Examples include compounds described in paragraphs 0010 to 0033 of No. 2015/166873. Note that the present invention is not limited to these.

(Naphthalocyanine compound)
The naphthalocyanine compound is preferably a compound represented by the following general formula (5).

General formula (5)


(In general formula (5), R ¹ to R ²⁴ are each independently a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group that may have a substituent, and a substituent aryl group which may have a substituent, cycloalkyl group which may have a substituent, alkoxyl group which may have a substituent, aryloxy group which may have a substituent, alkylthio which may have a substituent represents an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, and a sulfamoyl group which may have a substituent.
Z is a polymer site containing a monomer unit represented by general formula (6) or a phosphorus compound site represented by general formula (7), and * is a bond with Al. )
General formula (6)


(In general formula (6), X is -CONH-R ²⁵ -, -COO-R ²⁶ -, -CONH-R ²⁷ -O-, -COO-R ²⁸ -O-, R ²⁵ to R ²⁸ are Represents an alkylene group or arylene group in which carbon atoms may be connected by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-.R ³¹ represents hydrogen or a methyl group.)

（一般式（７）中、Ｒ^２９およびＲ^３０は、それぞれ独立に、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基または置換基を有してもよいアリールオキシ基を表し、Ｒ^２９とＲ^３０は、互いに結合して環を形成しても良い。） General formula (7)

(In general formula (7), R ²⁹ and R ³⁰ each independently represent a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, and an aryl group that may have a substituent) It represents an alkoxyl group or an aryloxy group which may have a substituent, and R ²⁹ and R ³⁰ may be bonded to each other to form a ring.)

Specific examples of naphthalocyanine compounds are shown below. Note that the present invention is not limited to these.

The near-infrared absorbing dye (A) can be used alone or in combination of two or more. When two or more kinds of compounds are used in combination, it is preferable to use at least two kinds of compounds having different maximum absorption wavelengths. As a result, compared to the case where one type of near-infrared absorbing dye (A) is used, the waveform of the absorption spectrum is broadened, and near-infrared rays in a wide wavelength range can be absorbed.

From the viewpoint of near-infrared absorption, the content of the near-infrared absorbing dye (A) is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass based on 100% by mass of non-volatile content of the photosensitive composition. .

[Alkali-soluble resin (B)]
The photosensitive composition of the present invention contains, as the alkali-soluble resin (B), an alkali-soluble resin (B1) having a glass transition temperature of 10 to 150°C. Thereby, a cured film with good developability, pattern formation, and heat resistance can be obtained.

(Alkali-soluble resin (B1))
The alkali-soluble resin (B1) may be any resin that has a glass transition temperature of 10 to 150°C and is soluble in an alkaline developer, and any known resin may be used.

The glass transition temperature of the alkali-soluble resin (B1) is preferably 10 to 120°C, more preferably 10 to 80°C, from the viewpoints of developability, pattern formation, and heat resistance.

As the glass transition temperature (hereinafter also referred to as Tg), a measured Tg obtained by actual measurement can be applied. Specifically, for the measured Tg, a value measured by differential scanning calorimetry (DSC) can be used.
However, if measurement is difficult due to decomposition of the resin, etc., the calculated Tg determined by the following formula is applied.
1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+W _n /Tg _n
Here, it is assumed that the resin to be calculated is a copolymerization of n types of monomer components from W ₁ to W _n , where W _n is the weight fraction of the nth monomer, and Tg _n is n It is the glass transition temperature (absolute temperature) of the homopolymer of the th monomer. Note that the value of the glass transition temperature of a homopolymer (hereinafter also referred to as a homopolymer) of each monomer is given by Brandrup, J. Immergut, E. H. The values given in the compilation "Polymer Handbook, Third edition, John Wiley & sons, 1989" are used.

From the viewpoint of pattern formation and heat resistance, the alkali-soluble resin (B1) is an alicyclic hydrocarbon-containing monomer unit (b1) and an aromatic ring-containing monomer unit whose homopolymer glass transition temperature is 80°C or higher. It is preferable to contain (b2).

[Alicyclic hydrocarbon-containing monomer unit (b1) whose homopolymer glass transition temperature is 80°C or higher]
Monomers forming the alicyclic hydrocarbon-containing monomer unit (b1) whose homopolymer has a glass transition temperature of 80° C. or higher include, for example, isobornyl acrylate, isobornyl methacrylate, adamantyl acrylate, and adamantyl methacrylate. , 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, and the like. Among these, isobornyl methacrylate, adamantyl methacrylate, and dicyclopentanyl methacrylate are preferred.

[Aromatic ring-containing monomer unit (b2) whose homopolymer glass transition temperature is 80°C or higher]
Examples of the monomer forming the aromatic ring-containing monomer unit (b2) having a homopolymer glass transition temperature of 80° C. or higher include styrene, α-methylstyrene, vinylnaphthalene, and the like. Among them, styrene and α-methylstyrene are preferred.

The total content of the alicyclic hydrocarbon-containing monomer unit (b1) and the aromatic ring-containing monomer unit (b2) is determined based on the total content of the alkali-soluble resin (B1) from the viewpoint of pattern formation and heat resistance. It is preferably 10 to 70 mol%, more preferably 20 to 60 mol% in the unit.

The ratio of the alicyclic hydrocarbon-containing monomer unit (b1) and the aromatic ring-containing monomer unit (b2) is preferably 40:60 to 90:10 from the viewpoint of pattern formation and heat resistance. The ratio is preferably 50:50 to 80:20.

[Polymerizable unsaturated group-containing monomer unit (b3)]
The alkali-soluble resin (B1) preferably contains a polymerizable unsaturated group-containing monomer unit (b3) from the viewpoints of pattern formation and heat resistance.

Examples of methods for incorporating the polymerizable unsaturated group-containing monomer unit (b3) into the alkali-soluble resin (B1) include methods (i) to (iii) shown below.

<Method (i)>
There is a method (i) in which a carboxyl group of a carboxyl group-containing monomer is added to an epoxy group of an epoxy group-containing monomer unit contained in the alkali-soluble resin (B1).

Monomers forming the epoxy group-containing monomer unit include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, Acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among these, acrylic acid and methacrylic acid are preferred.

From the viewpoint of developability, a product in which a carboxyl group of a carboxyl group-containing monomer is added to the epoxy group of an epoxy group-containing monomer unit and further reacted with an acid anhydride also has a polymerizable unsaturated group. It is useful as the containing monomer unit (b3).

Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

<Method (ii)>
There is a method (ii) in which an epoxy group of an epoxy group-containing monomer is added to a carboxyl group of a carboxyl group-containing monomer unit contained in the alkali-soluble resin (B1).

<Method (iii)>
There is a method (iii) in which the hydroxyl group of the hydroxyl group-containing monomer unit contained in the alkali-soluble resin (B1) is reacted with the isocyanate group of the isocyanate group-containing monomer.

Hydroxyl group-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, Examples include acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate.

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

The content of the polymerizable unsaturated group-containing monomer unit (b3) should be adjusted so that the double bond equivalent of the alkali-soluble resin (B1) is 200 to 1000 from the viewpoint of pattern formation and heat resistance. is preferable, 200 to 800 is more preferable, and 200 to 700 is particularly preferable. The double bond equivalent is the weight per mole of ethylenically unsaturated double bonds in the resin, and can be calculated using the following formula.
Double bond equivalent = weight of resin (g) / amount of ethylenically unsaturated double bonds in resin (mol)

[Other monomer units (b4)]
The alkali-soluble resin (B1) contains other monomer units (b4) other than (b1) to (b3).
can contain.

Other monomers forming the monomer unit (b4) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 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)acrylates such as (meth)acrylate, phenoxydiethylene glycol (meth)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;
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid;
(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. ;
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.

From the viewpoints of pattern formation and heat resistance, the content of the alkali-soluble resin (B1) is preferably 40% by mass or more, more preferably 60% by mass or more, based on 100% by mass of the alkali-soluble resin (B).

The alkali-soluble resin (B1) can be used alone or in combination of two or more types.

From the viewpoint of heat resistance, the weight average molecular weight (Mw) of the alkali-soluble resin (B1) is preferably 5,000 to 40,000, more preferably 5,000 to 30,000.

From the viewpoint of developability, the acid value of the alkali-soluble resin (B1) is preferably 30 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g.

(Alkali-soluble resin (B2))
The photosensitive composition of the present invention may contain, as the alkali-soluble resin (B), an alkali-soluble resin (B2) other than the alkali-soluble resin (B1) within a range that does not impair the effects of the present invention.

The content of the alkali-soluble resin (B) 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.

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

Examples of the polymerizable compound (C) 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 (C) include lactone-modified polymerizable compounds, acid group-containing polymerizable compounds, urethane bond-containing polymerizable compounds, and other polymerizable compounds.

(Lactone-modified polymerizable compound)
The photosensitive composition of the present invention preferably contains a lactone-modified polymerizable compound from the viewpoint of heat resistance.

A lactone-modified polymerizable compound is a compound that has a lactone-modified structure in its molecule. Lactone-modified polymerizable compounds include polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimerolmelamine; It is obtained by esterifying meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound is preferably a compound represented by the following general formula (8).

General formula (8)

In general formula (8), all six R's are groups represented by the following general formula (9), or 1 to 5 of the six Rs are groups represented by the following general formula (9). , the remainder is a group represented by the following general formula (10).

General formula (9)

In the general formula (9), R ¹ represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond bonded to the oxygen atom of the general formula (8).

General formula (10)

In the general formula (10), R ¹ represents a hydrogen atom or a methyl group, and * is a bond bonded to the oxygen atom of the general formula (8).

The lactone-modified polymerizable compound is, for example, commercially available as KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd., and DPCA-20 (in the above general formulas (8) to (10), m=1, general formula (9 ), the number of groups represented by = 2, R ¹ is all hydrogen atoms), DPCA-30 (in the above general formulas (8) to (10), m = 1, a compound represented by general formula (9)) number of groups = 3, R ¹ is all hydrogen atoms), DPCA-60 (in the above general formulas (8) to (10), m = 1, number of groups represented by general formula (9) = 6, compound in which R ¹ is all hydrogen atoms), DPCA-120 (in the above general formulas (8) to (10), m = 2, number of groups represented by general formula (9) = 6, R Compounds in which all ¹ are hydrogen atoms), etc.

From the viewpoint of coating film resistance, the lactone-modified polymerizable compound has m=1 in the above general formulas (8) to (10), the number of groups represented by general formula (9)=2 to 6, and R Compounds in which all ¹ are hydrogen atoms are preferred, and in the above general formulas (8) to (10), m = 1, the number of groups represented by general formula (9) = 2 or 3, and all R ¹ are hydrogen atoms. More preferred are compounds where

From the viewpoint of heat resistance, the content of the lactone-modified polymerizable compound is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and more preferably 20 to 60% by mass based on 100% by mass of the polymerizable compound (C). % is more preferable.

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

Polymerizable compounds having acid groups include, for example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid, and dicarboxylic acids; polyhydric carboxylic acids and monohydroxyalkyl ( Examples include esterification products with 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.

Commercially available polymerizable compounds having acid groups include Viscoat #2500P manufactured by Osaka Organic Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521 manufactured by Toagosei Co., Ltd. can be mentioned.

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

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

Polymerizable compounds having a urethane bond include, for example, urethane (meth)acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a compound obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further having a hydroxyl group. Examples include urethane (meth)acrylate obtained by reacting (meth)acrylate.

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 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.

A method for introducing an acid group into a polymerizable compound having a urethane bond is, for example, by first reacting the above-mentioned (meth)acrylate having a hydroxyl group with the above-mentioned polyfunctional isocyanate. 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.

The number of polymerizable unsaturated groups in the polymerizable compound having a urethane bond is preferably 3 to 15, more preferably 5 to 12, from the viewpoint of pattern formation.

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

(Other polymerizable compounds)
Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and β-carboxyethyl (meth)acrylate. ) 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, phenoxytetra Ethylene 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, methyl - various acrylic esters and methacrylic esters such as (meth)acrylic ester of melamine, epoxy (meth)acrylate, urethane acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, Examples include (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like.

Other commercially available polymerizable compounds include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R- manufactured by Nippon Kayaku Co., Ltd. 684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, and Aronix M-303, M-305, M-306, M-309, M manufactured by Toagosei Co., Ltd. -310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406 , M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP manufactured by Osaka Organic Co., Ltd., #3
35HP, #700, #295, #330, #360, #GPT, #400, #405, NK ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE manufactured by Shin-Nakamura Chemical Co., Ltd. -4, EBECRYL40, 130, 140, 145 manufactured by Daicel Allnex, AH-600, AT-600 manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL EA-0200, 0300 manufactured by Osaka Gas Chemical Company.

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

The polymerizable compound (C) is selected from the group consisting of lactone-modified polymerizable compounds, acid group-containing polymerizable compounds, and urethane bond-containing polymerizable compounds from the viewpoints of developability, pattern formation, and heat resistance. It is preferable to include at least one kind of.

The content of the polymerizable compound (C) 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.

[Photopolymerization initiator (D)]
(Photopolymerization initiator (D1) represented by general formula (1))
The photosensitive composition of the present invention contains a photopolymerization initiator (D1) represented by general formula (1) as a photopolymerization initiator (D). This improves reactivity and improves pattern formation and heat resistance.

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 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,
Examples include cyclohexylmethyl group.
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 formation, 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 particularly 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 pattern formation, branched alkyl groups having 3 to 15 carbon atoms are preferred, branched alkyl groups having 5 to 12 carbon atoms are more preferred, and 3-methylbutyl and 2-ethylhexyl groups are preferred. is particularly preferred.

In general formula (1), R ₄ represents any monovalent substituent.
As arbitrary monovalent substituents, alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group; F, Cl, Br, Halogen atoms such as I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms; Aromatic ring group having 4 to 20 carbon atoms; Amino group; Aminoalkyl group having 1 to 20 carbon atoms; Hydroxyl group; Nitro group; Cyano group; Benzoyl group which may have a substituent; Examples include thenoyl group. 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 and heat resistance, 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.
Note that n is preferably 0 or 1, and more preferably 1, from the viewpoint of radical generation efficiency.

The method for producing the photopolymerization initiator (D1) is not particularly limited, and any known method can be used. For example, it is described in International Publication No. 2008/078678, International Publication No. 2014/050738, Japanese Patent Application Publication No. 2016-519675, etc.

Specific examples of the photopolymerization initiator (D1) represented by general formula (1) are shown below. Note that the present invention is not limited to these.

Among the compounds of chemical formulas (11) to (16), the compound of chemical formula (16) is preferred from the viewpoint of pattern formation and heat resistance.

The photopolymerization initiator (D1) can be used alone or in combination of two or more types.

The content of the photopolymerization initiator (D1) is preferably 10 to 100% by mass, more preferably 30 to 90% by mass based on 100% by mass of the photopolymerization initiator (D).

(Photopolymerization initiator (D2) other than (D1))
From the viewpoint of developability and pattern formation, the photopolymerization initiator (D) is a photopolymerization initiator (D2) other than the photopolymerization initiator (D1) represented by the general formula (1) (hereinafter, other photopolymerization initiators). (also referred to as agent (D2)).

Other photopolymerization initiators (D2) are not particularly limited as long as they are compounds that can initiate polymerization of the polymerizable compound (C) with light, and any known photopolymerization initiators can be used.

Specifically, the photoinitiator (D2) is 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane. -1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-( 4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] -Acetophenone photopolymerization initiator such as 1-butanone;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl -A benzophenone photopolymerization initiator such as 4'-methyldiphenyl sulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone;
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. photopolymerizable initiator;
Initiation of photopolymerization of acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide agent;
1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole Oxime-based photopolymerization initiators such as [3-yl]-,1-(O-acetyloxime) (excluding photopolymerization initiator (D1));
2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4' , 5,5'-tetra(m-methoxyphenyl)biididazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'- Bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2
, 2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5' -Imidazole photopolymerization initiators such as tetraphenylbiimidazole and the like can be mentioned.
Among these, from the viewpoint of developability and pattern formation, acetophenone-based photopolymerization initiators, acylphosphine oxide-based polymerization initiators, and oxime-based photopolymerization initiators (excluding photopolymerization initiator (D1)) are recommended. preferable.

Commercially available acetophenone photopolymerization initiators include Omnirad 907, 369, and 379EG manufactured by IGM Resins.
Commercially available acylphosphine oxide polymerization initiators include Omnirad 819 and TPO manufactured by IGM Resins.
Commercial products of oxime-based photopolymerization initiators (excluding photopolymerization initiator (D1)) include IRGACURE OXE-01, 02, 03, 04 manufactured by BASF Japan, and ADEKA ARCURE N- manufactured by ADEKA. 1919, NCI-730, 831, 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057, manufactured by IGM Resins OMNIRAD1312, 1314, and 1316 from Samyang Corporation, SPI-02, 03, 04, 05, 06, and 07 from Samyang Corporation, and DFI-020, 306 and EOX-01 from Daito Chemix.

Other photopolymerization initiators (D2) can be used alone or in combination of two or more.

The content of the photopolymerization initiator (D) is preferably 2 to 50 parts by mass, and preferably 2 to 30 parts by mass, from the viewpoint of photocurability and developability, based on 100 parts by mass of the near-infrared absorbing dye (A). More preferably, it is parts by mass.

[Sensitizer (E)]
The photosensitive composition of the present invention can contain a sensitizer (E) from the viewpoint of pattern formation.

Examples of the sensitizer (E) include chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzyl and camphorquinone, benzoin compounds, and fluorenes. Polymethine compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonol compounds, etc. Pigments, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, Tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, and benzophenone compounds. Among these, from the viewpoint of pattern formation, thioxanthone compounds (E1) or benzophenone compounds (E2) are preferred, and benzophenone compounds (E2) are more preferred.

(Thioxanthone compound (E1))
Examples of the thioxanthone compound (E1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. It will be done. Among these, 2,4-diethylthioxanthone is preferred.

(Benzophenone compound (E2))
Examples of the benzophenone compound (E2) include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

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

From the viewpoint of pattern formation, the content of the sensitizer (E) is preferably 150 to 400 parts by weight, more preferably 150 to 300 parts by weight, based on 100 parts by weight of the photopolymerization initiator (D).

[Colorant (F)]
The photosensitive composition of the present invention can contain a colorant (F). Thereby, the transmittance of each wavelength region of the color filter can be controlled, and color separation performance is improved.

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

(pigment)
The pigment is preferably a compound classified as a pigment 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, 63, 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, and pigments described in JP-A-2012-226110. Among these, C. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A No. 2012-226110 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 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,
Examples include cobalt green, amber, and synthetic iron black.

(dye)
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, 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 (F) can be used alone or in combination of two or more types.

The content of the colorant (F) 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, sodium sulfate, etc., and sodium chloride (salt) is preferred 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 not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent 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.

[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 near-infrared absorbing dye (A). It is preferable that the adsorption group has one or more types of basic groups and acidic groups.

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.

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 resins 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 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-23195, JP-A-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 near-infrared absorbing dye (A).

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

The dye derivative (H) is not particularly limited, and includes dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (H) 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 compound having 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 a diketopyrrolopyrrole dye derivative, JP-A No. 2001-22052
0 Publication, International Publication No. 2009/081930, International Publication No. 2011/052617, International Publication No. 2012/102399, Japanese Patent Application Publication No. 2017-156397, and as a phthalocyanine dye derivative, Japanese Patent Application Publication No. 2007-226161. , International Publication No. 2016/163351, JP 2017-165820, JP 5753266, as anthraquinone dye derivatives, JP 63-264674, JP 09-272812, JP 10 H. -245501, JP 10-265697, JP 2007-079094, WO 2009/025325, and as quinacridone dye derivatives, JP 48-54128, JP 03-9961. JP-A-2000-273383; as a dioxazine dye derivative, JP-A 2011-162662; as a thiazine indigo dye derivative, JP 2007-314785; as a triazine dye derivative, JP 61-246261, JP 11-199796, JP 2003-165922, JP 2003-168208, JP 2004-217842, JP 2007-314681, Benzo Isoindole dye derivatives include JP-A No. 2009-57478, and quinophthalone-based dye derivatives include JP-A Nos. 2003-167112, 2006-291194, 2008-31281, and 2012. -226110, as naphthol dye derivatives, JP 2012-208329, JP 2014-5439, as azo dye derivatives, JP 2001-172520, JP 2012-172092 , as the acidic substituent, JP 2004-307854, and as the basic substituent, JP 2002-201377, JP 2003-171594, JP 2005-181383, JP 2005- Known dye derivatives described in JP-A No. 213404 and the like can be mentioned. 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 (H) can be used alone or in combination of two or more types.

The content of the dye derivative (H) is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the near-infrared absorbing dye (A).

[Thermosetting compound (I)]
The photosensitive composition of the present invention can contain a thermosetting compound (I). Thereby, the thermosetting compound (I) reacts in the heating step, and the crosslinking density increases, so that the heat resistance improves.

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'- benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, 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))
Oxetane compound (I2) 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.

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

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, Nikarak 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 Nippon Cytec Industries, Ltd. , 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 the curing of 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).

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

The thiol chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably a polyfunctional thiol having four or more. 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 (J) can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent (J) 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. When contained in an appropriate amount, photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

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

Examples of the polymerization inhibitor (K) 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, tribenzylphosphine, etc. , phosphine compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, and phloroglucin.

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

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

The ultraviolet absorber (L) is an organic compound having an ultraviolet 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.

Examples of benzotriazole compounds include 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-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 95% with 5% 2-methoxy-1-methylethyl acetate
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, 326 manufactured by BASF Japan.
, 329, 384-2, 900, 928, 99-2, 1130, ADEKA STAB LA-29, LA-31RG, LA-32, LA-36, KEMISORB71, 73, 74, 79 manufactured by ChemiPro Kasei Co., Ltd. , 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.
Examples include ADK STAB LA-46 and LA-F70 manufactured by EKA, and CYASORB UV-1164 manufactured by Sun Chemical.

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, etc. .

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

[Antioxidant (M)]
The photosensitive composition of the present invention can contain an antioxidant (M). The antioxidant (M) prevents the photopolymerization initiator (D) and thermosetting compound (I) in the photosensitive coloring composition from oxidizing and yellowing due to heat curing or the thermal process during ITO annealing. . In particular, when the concentration of the near-infrared absorbing dye (A) in the photosensitive composition is high, the content of the polymerizable compound (C) is relatively reduced, so it is necessary to increase the amount of the photopolymerization initiator (D) or If the compound is mixed, 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. The antioxidant (M) is preferably a compound that does not contain a halogen atom.

Examples of the antioxidant (M) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. 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-4 manufactured by ADEKA.
0, AO-50, AO-60, AO-80, AO-330, KEMINOX101, 179, 76, 9425 manufactured by Chemipro, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL manufactured by BASF Japan , 1520L, 245, 259, 3114, 5057, 565, and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

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-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87. , LA-402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Co., Ltd., Siasorb UV-3346 manufactured by Sun Chemical Co., Ltd. , UV-3529, UV-3853, etc.

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

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

[Leveling agent (N)]
The photosensitive composition of the present invention can contain a leveling agent (N). This further improves the wettability and drying properties for the substrate during coating. Examples of the leveling agent (N) 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 Polyflow-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 (N) can be used alone or in combination of two or more types.

The content of the leveling agent (N) is preferably 0.001 to 2.0% by weight, more preferably 0.005 to 1.0% by weight based on 100% by weight of nonvolatile content of the photosensitive composition. When contained in an appropriate amount, the balance between coating properties and adhesion of the photosensitive composition is further improved.

[Storage stabilizer (O)]
The photosensitive composition of the present invention can contain a storage stabilizer (O). This stabilizes the viscosity of the photosensitive composition over time. Storage stabilizers (O) include, for example, quaternary ammonium chlorides 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.

The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the near-infrared absorbing dye (A).

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

Examples of the adhesion improver (P) 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 (P) can be used alone or in combination of two or more types.

The content of the adhesion improver (P) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the near-infrared absorbing dye (A).

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

The organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-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 (Q) can be used alone or in combination of two or more.

[Method for manufacturing photosensitive composition]
The photosensitive composition of the present invention is produced into a dispersion by, for example, adding a near-infrared absorbing dye (A), a dispersion resin (G), an organic solvent (Q), etc., and performing a dispersion treatment. Thereafter, the alkali-soluble resin (B), the polymerizable compound (C), the photopolymerization initiator (D), and the like 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 near-infrared absorbing dye (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. When the particle size is appropriate, it is easy to obtain a photosensitive composition 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.

<Cured film>
The cured film of the present invention is obtained by curing a film formed using the photosensitive composition of the present invention by a treatment such as exposure.

[Method for manufacturing cured film]
The method for producing the cured film is not particularly limited, and includes, for example, a step (1) of applying a photosensitive composition onto a substrate to form a layer of the composition, and a step of exposing the layer to light in a pattern through a mask. (2), step (3) of developing an unexposed portion with alkali to form a patterned cured film, and step (4) of heat-treating the pattern (post-baking).

The method for manufacturing the cured film will be described in detail below.
(Step (1))
In the step (1) of forming a layer of the composition, the photosensitive composition is applied onto the substrate by a method such as spin coating, roll coating, slit coating, cast coating, or inkjet coating, and 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, prevent diffusion of substances, and flatten the surface of the substrate.
The thickness of the layer after drying 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.

<Optical filter>
The cured film of the present invention can be used for optical filters. Among these, it can be preferably used as an infrared cut filter. It can also be used as an infrared transmission filter. The optical filter of the present invention can be manufactured by the same method as the above-mentioned cured film.

<Image display device>
The cured film of the present invention can be used in image display devices. The form used in the image display device is not particularly limited, but it can be used as a color filter or a black matrix.
The black matrix is a black edge provided at the periphery of an image display device such as a solid-state image sensor or a liquid crystal display device, or a grid-like and/or stripe-like black part between red, blue, and green pixels, Examples include dotted and/or linear black patterns for TFT light shielding.

An example of an image display device of the present invention will be described. The image display device includes the cured film of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because the red reproduction area is expanded. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an image display device equipped with the cured film of the present invention. The image display device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are spaced apart and facing each other, and a liquid crystal LC is sealed between them.

A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22 , a transparent electrode layer 23 made of ITO, for example, is formed thereon, and an alignment layer 24 is formed to cover the transparent electrode layer 23 . is provided.

Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

The liquid crystal LC is TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Optically Compensated).
The orientation is determined according to the drive mode such as birefringence. First transparent substrate 1
A TFT (thin film transistor) array 12 is formed on the inner surface of the substrate 1, and a transparent electrode layer 13 made of ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22 , a transparent electrode layer 23 made of ITO, for example, is formed thereon, and an alignment layer 24 is formed to cover the transparent electrode layer 23 . is provided.

Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a blue LED resin package contains a phosphor. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range from 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I5 at wavelength λ5 is ) is 0.1 or more and 1.3 or less, or a white LED light source (LED1) that has a wavelength (λ1) with maximum emission intensity in the range of 430nm to 485nm and in the range of 530nm to 580nm. spectral characteristics having a second peak wavelength of emission intensity (λ2) within the range, and a ratio (I2/I1) of emission intensity I1 at wavelength λ1 to emission intensity I2 at wavelength λ2 of 0.2 or more and 0.7 or less. It is preferable to use a white LED light source (LED2).

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals) and NSSW304D-HG-V1 (manufactured by Nichia Chemicals).

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemicals) and NSSW304D (manufactured by Nichia Chemicals).

<Solid-state imaging device>
The cured film of the present invention can be used for solid-state imaging devices. The form used for the solid-state image sensor is not particularly limited, but for example, a plurality of photodiodes constituting the light receiving area of the solid-state image sensor (such as a CCD image sensor, a CMOS image sensor, or an organic CMOS image sensor) on a substrate; Examples include a configuration in which a light receiving element made of polysilicon or the like is provided, and the cured film of the present invention is provided on the surface on which the light receiving element is formed or on the opposite side to the surface where the light receiving element is formed. FIG. 2 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device including a cured film of the present invention.

As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging device 201 and a transparent cover glass 203 that is held above the solid-state imaging device 201 and seals the solid-state imaging device 201. There is. Furthermore, a lens layer 211 is provided on top of the cover glass 203 with a spacer 104 interposed therebetween. The lens layer 211 is composed of a support 213 and a lens material 212. When stray light enters the peripheral region of the lens layer 211, the light is diffused, which weakens the light condensing effect of the lens material 212, reducing the amount of light that reaches the imaging unit 202. Further, noise is also generated due to stray light. Therefore, the peripheral area of this lens layer 211 is provided with the cured film 214 of the present invention to shield it from light.

The solid-state image sensor 201 photoelectrically converts an optical image formed by the image sensor 202 serving as its light-receiving surface and outputs it as an image signal. This solid-state image sensor 201 includes a laminated substrate 205 in which two substrates are laminated. The laminated board 205 consists of a rectangular chip board 206 and a circuit board 207 of the same size, and the circuit board 207 is laminated on the back surface of the chip board 206.

An imaging section 202 is provided at the center of the surface of the chip substrate 206. Furthermore, when stray light enters the peripheral area of the imaging unit 202, dark current (noise) is generated from circuits in this peripheral area, so this peripheral area is provided with the cured film (light shielding) 215 of the present invention to shield it from light. has been done.

A plurality of electrode pads 208 are provided on the edge of the surface of the chip substrate 206. The electrode pad 208 is electrically connected to the imaging section 202 via a signal line (not shown) provided on the surface of the chip substrate 206.

External connection terminals 209 are provided on the back surface of the circuit board 207 at positions substantially below each electrode pad 208 . Each external connection terminal 209 is connected to an electrode pad 208 via a through electrode 210 that vertically penetrates the laminated substrate 205. In addition, each external connection terminal 209 is connected to a control circuit that controls driving of the solid-state image sensor 201, an image processing circuit that performs image processing on an image signal output from the solid-state image sensor 201, etc. via wiring (not shown). It is connected.

<Infrared sensor>
The cured film of the present invention can be used for infrared sensors. FIG. 3 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor including the cured film of the present invention. The infrared sensor 300 shown in FIG. 3 includes a solid-state image sensor 310.

The imaging area provided on the solid-state imaging device 310 is configured by combining an infrared cut filter 311 and a color filter 312.
The infrared cut filter 311 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm).
The color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed, and for example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used.

A resin film 314 is arranged between the infrared transmission filter 313 and the solid-state image sensor 310 and is capable of transmitting light having a wavelength that has passed through the infrared transmission filter 313.
The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and the cured film of the present invention containing the above-mentioned near-infrared absorbing dye (A) can be used. For example, the infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm.

A microlens 315 is arranged on the incident light side of the color filter 312 and the infrared transmission filter 313. A flattening film 316 is formed to cover the microlens 315.

In the form shown in FIG. 3, a resin film 314 is disposed, but an infrared transmission filter 313 may be formed instead of the resin film 314.

The cured film of the present invention can be used as a light shielding film on the edge and/or side surface of the surface of the infrared cut filter 311, and can also be used on the inner wall of an infrared sensor to prevent internal reflection and/or unnecessary light to the light receiving part. can be prevented from entering and improve sensitivity.

According to this infrared sensor, image information can be captured at the same time, so motion sensing and the like that recognize the target whose movement is to be detected are possible. Further, since distance information can be acquired using this infrared sensor, it is also possible to take images including 3D information. Furthermore, this infrared sensor can also be used as a biometric sensor.

Furthermore, the cured film of the present invention can also be used as a colored spacer. For example, when a spacer is used in a TFT type LCD, the TFT as a switching element may malfunction due to light incident on the TFT, and colored spacers are used to prevent this. The colored spacers can be formed in the same manner as the black matrix described above, except for using a mask for colored spacers.

Moreover, the cured film of the present invention can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, it is suitably used for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members that provide light shielding and antireflection properties.
Examples of micro LEDs and micro OLEDs include those described in Japanese Translation of PCT Publication No. 2015-500562 and Japanese Translation of PCT Publication No. 2014-533890.

Moreover, the cured film of the present invention can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for optical filters and optical films used in quantum dot displays, as well as members that provide light-shielding and antireflection properties.

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."
Furthermore, 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), acid value (mgKOH/g), amine value (mgKOH/g), and glass transition temperature (Tg) of the resin were measured 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 wt % of the above eluent, and 20 microliters of the solution was injected. The 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.

(Glass-transition temperature)
The glass transition temperature of the alkali-soluble resin was measured using a differential scanning calorimeter by weighing 5 mg of the sample into a sample pan and measuring the temperature from −20 to 200° C. at a heating rate of 10° C./min under a nitrogen stream.

<Production of near-infrared absorbing dye (A)>
(Near infrared absorbing dye (A-1))
40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate were mixed with 400 parts of toluene, and the mixture was mixed in a nitrogen gas atmosphere. The mixture was heated and stirred and refluxed for 3 hours. Water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was placed in a nitrogen gas atmosphere. The mixture was heated and stirred for 8 hours under reflux. Water produced during the reaction was removed from the reaction system by azeotropic distillation.
After the reaction was completed, the solvent was distilled off, and 200 parts of hexane was added to the resulting reaction mixture while stirring. After filtering the obtained blackish brown precipitate, it was sequentially washed with hexane, ethanol and acetone, and dried under reduced pressure to obtain a near-infrared absorbing dye (A-1) represented by the following chemical formula (17). Ta. 50 parts of the obtained near-infrared absorbing dye (A-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 12 hours. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and pulverized. By doing so, a finely divided near-infrared absorbing dye (A-1) was obtained.

Chemical formula (17)

(Near infrared absorbing dye (A-2))
40.0 parts of 1,8-diaminonaphthalene, 50.1 parts of 2-hydroxy-9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate were mixed in 400 parts of toluene in an atmosphere of nitrogen gas. The mixture was heated with stirring and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was placed in a nitrogen gas atmosphere. The mixture was heated and stirred for 8 hours under reflux. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the solvent was distilled off, and 200 parts of hexane was added to the resulting reaction mixture while stirring. After filtering the obtained black brown precipitate, it was washed sequentially with hexane, ethanol and acetone, and dried under reduced pressure to obtain a near-infrared absorbing dye (A-2) represented by the following chemical formula (18). Ta.
A near-infrared absorbing dye (A-2) was obtained by pulverizing the near-infrared absorbing dye (A-1) in a similar manner.

Chemical formula (18)

(Near infrared absorbing dye (A-3))
In a reaction vessel, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0] undec-7-ene), 178 parts of 2,3-dicyanonaphthalene, and 40 parts of aluminum chloride anhydride. The mixture was mixed and stirred, and after raising the temperature, the mixture was refluxed at 136°C for 5 hours. The reaction solution, which had been cooled to 30° C. while being stirred, was poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of water, with stirring, to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain a compound of the following chemical formula (19).
5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, thoroughly stirred and mixed, and then heated to 50°C. To this solution, 10 parts of a compound represented by the following chemical formula (19) was added little by little, and then stirred at 90° C. for 120 minutes. Thereafter, this reaction solution was poured into 2000 parts of water, and the generated precipitate was filtered and washed with water in that order, dried, and a near-infrared absorbing dye (A-3) represented by the following chemical formula (20) was obtained. I got it.
A near-infrared absorbing dye (A-3) was obtained by pulverizing the near-infrared absorbing dye (A-1) in a similar manner.

(Near infrared absorbing dye (A-4))
In accordance with the description in International Publication No. 2019/058882, a near-infrared absorbing dye (A-4) represented by the following chemical formula (21) was obtained.
A near-infrared absorbing dye (A-4) was obtained by pulverizing the near-infrared absorbing dye (A-1) in a similar manner.

化学式（２１）

Chemical formula (21)

<Production of alkali-soluble resin (B)>
(Alkali-soluble resin (B1-1) solution)
100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 120°C while nitrogen gas was injected into the vessel. Heat and add 5.2 parts of styrene (hereinafter referred to as St), 35.5 parts of glycidyl methacrylate (hereinafter referred to as GMA), 41.0 parts of dicyclopentanyl methacrylate (hereinafter referred to as DCPMA) from a dropping tube at the same temperature, and start polymerization. A mixture of 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air, and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 17.0 parts of acrylic acid (hereinafter referred to as AA), and the mixture was reacted at 120° C. for 5 hours. Thereby, the epoxy group of GMA and the carboxyl group of AA were reacted, and a polymerizable unsaturated group-containing monomer unit (b3) (hereinafter referred to as GMA+AA) was introduced.
Furthermore, 30.4 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours. Thereby, the hydroxyl group of GMA+AA and TPHA were subjected to an esterification reaction, and a fatty acid anhydride-modified polymerizable unsaturated group-containing monomer unit (b3) (hereinafter referred to as GMA+AA+TPHA) was introduced. Thereafter, PGMAc was added so that the nonvolatile content was 20% to prepare an alkali-soluble resin (B1-1) solution.

(Alkali-soluble resin (B1-2) to (B1-13) and (B2-1) to (B2-3) solutions))
Alkali-soluble resins (B1-2) to (B1-13) and alkali-soluble resins (B2-1) to (B2- 3) was synthesized, and PGMAc was added to make the nonvolatile content 20%.

MAA+GMA listed in Table 1 is a polymerizable unsaturated group-containing monomer unit in which an epoxy group of glycidyl methacrylate is added to the carboxyl group of methacrylic acid (MAA), which is a monomer unit contained in an alkali-soluble resin. (b3) is represented.

The Tg ranges of the alkali-soluble resins listed in Table 1 are as follows.
A: 10°C or more and 80°C or less B: More than 80°C and 120°C or less C: More than 120°C and 150°C or less D: Less than 10°C or more than 150°C

The range of double bond equivalents of the alkali-soluble resins listed in Table 1 is as follows.
A: 200 or more and 700 or less B: More than 700 and less than 800 C: More than 800 and less than 1000 D: Less than 200 or more than 1000

<Production of polymerizable compound (C)>
(Polymerizable compound (C-1) having a 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 dropping, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, 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 (C-1) having a urethane bond with an average number of polymerizable unsaturated groups of 9.

<Production of colorant (F)>
(Fine green pigment (F-1))
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 (F-1) was obtained by drying and pulverizing.

(Fine red pigment (F-2))
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 (F-2) was obtained by drying the mixture for one day and crushing it.

(Fine blue pigment (F-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 (F-3) was obtained by drying for 24 hours and pulverizing.

(Fine yellow pigment (F-4))
C. I. 100 parts of Pigment Yellow 138, 800 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a 1-gallon stainless steel 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 fine yellow pigment (F-4) was obtained by drying and pulverizing.

(Finely refined purple pigment (F-5))
C. I. 100 parts of Pigment Violet 23, 800 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a 1-gallon stainless steel 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 purple pigment (F-5) was obtained by drying and pulverizing.

<Manufacture of dispersed resin (G)>
(Dispersion resin (G-1) solution)
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C while flowing nitrogen. The mixture was stirred for 1 hour, and the atmosphere in the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to form the first block (B block). Polymerization started. 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, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or more in terms of nonvolatile content, and the reaction solution was heated to room temperature. Polymerization was stopped by cooling. As a result of GPC measurement, the mass average molecular weight of the polymer was 20,000, the molecular weight distribution Mw/Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a dispersion resin (G-1) having an amine value per nonvolatile content of 169.8 mgKOH/g was obtained. After cooling to room temperature, approximately 2 g was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. PGMAc was added so that the non-volatile content was 30% by mass to form a dispersion resin (G-1) solution. was prepared.

(Dispersion resin (G-2) 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 purging the system 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, and 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-2) 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-3) 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-3) solution having a weight average molecular weight of 8,500 was obtained.

<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, and then the pore size was Dispersion 1 was prepared by filtration with a 1.0 μm filter. The organic solvent (Q-1) is PGMAc.
Near-infrared absorption dye (A-1): 15.0 parts Dispersion resin (G-1): 20.0 parts Organic solvent (Q-1): 65.0 parts

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

<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 composition 1.
Dispersion 1: 35.0 parts Alkali-soluble resin (B1-1) solution: 30.0 parts Polymerizable compound (C): 7.0 parts Photopolymerization initiator (D1-1) represented by general formula (1) ): 0.5 parts Benzophenone compound (E2-1): 0.75 parts Leveling agent (N): 1.0 parts Organic solvent (Q): 25.75 parts

[Examples 2 to 35, Comparative Examples 1 to 5]
(Photosensitive compositions 2 to 40)
Photosensitive compositions 2 to 40 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 3-1 to 3-3.

The raw materials listed in Tables 3-1 to 3-4 are as follows.

[Polymerizable compound (C)]
C-1: Polymerizable compound having the above-mentioned urethane bond C-2: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd., lactone-modified polymerizable compound)
C-3: Aronix M-521 (manufactured by Toagosei Co., Ltd., polymerizable compound having an acid group)
C-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
The same amounts of (C-1) to (C-4) were mixed together to form a polymerizable compound (C).

[Photopolymerization initiator (D)]
(Oxime photopolymerization initiator (D1))
D1-1: Photopolymerization initiator of the above chemical formula (11) D1-2: Photopolymerization initiator of the above chemical formula (12) D1-3: Photopolymerization initiator of the above chemical formula (13) D1-4: Above Photopolymerization initiator of chemical formula (14) D1-5: Photopolymerization initiator of chemical formula (15) above D1-6: Photopolymerization initiator of chemical formula (16) above

(Other photopolymerization initiators (D2))
D2-1: Omnirad 369 (manufactured by IGM Resins, acetophenone photopolymerization initiator)
D2-2: Omnirad 907 (manufactured by IGM Resins, acetophenone photopolymerization initiator)
D2-3: Omnirad TPO (manufactured by IGM Resins, acylphosphine oxide photopolymerization initiator)
D2-4: IRGACURE OXE-04 (manufactured by BASF Japan, oxime photoinitiator)

[Sensitizer (E)]
(Thioxanthone compound (E1))
E1-1: 2,4-diethylthioxanthone (benzophenone compound (E2))
E2-1: 4,4'-bis(diethylamino)benzophenone

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

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

<Evaluation of photosensitive composition>
Regarding the obtained photosensitive compositions 1 to 41 (Examples 1 to 36, Comparative Examples 1 to 5), developability,
Pattern formation and heat resistance evaluation were performed using the following methods. The evaluation results are shown in Table 4.

[Developability evaluation]
The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm x width of 100 mm and a thickness of 0.7 mm using a spin coater so that the dry film thickness was 2.0 μm. It was dried on a hot plate at 70°C for 1 minute. Next, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet rays at an illuminance of 30 mW/cm ² and 40 mJ/cm ² through a photomask with a 100 μm wide stripe pattern. Furthermore, after cooling this substrate to room temperature, spray development was performed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C for two levels of development time (40 seconds and 70 seconds), and ion-exchanged water was used. It was washed and air dried. The obtained substrate was post-baked at 230° C. for 30 minutes in a clean oven to form a striped pattern on the substrate. The pattern was observed with an optical microscope, and the presence or absence of development residue and chipping in unexposed areas was evaluated. The evaluation criteria are as follows, and 2 or more is practical.
3: At a development time of 70 seconds, there was no development residue in the unexposed area, and there was no pattern chipping.
2: At a development time of 70 seconds, development residue or pattern chipping occurred in unexposed areas.
1: At a development time of 40 seconds, development residue or pattern chipping occurred in unexposed areas.

[Pattern formation evaluation (1): Adhesion]
The obtained photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm long x 100 mm wide and 0.7 mm thick using a spin coating method so that the film thickness after drying was 2.0 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. After that, this substrate was spray developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes to adhere. A substrate for performance evaluation was obtained. Spray development was performed for the coating film of each photosensitive composition for the shortest time possible to form a pattern without any development residue, and this was defined as the appropriate development time.
Among the patterns of the substrate for adhesion evaluation, a fine line pattern with a width of 5 to 25 μm was observed with an optical microscope, and the minimum line width of the remaining fine line pattern was confirmed. The evaluation criteria are as follows, and 3 or more is 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 created in Pattern Formation 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. . The evaluation criteria are as follows, and 3 or more is 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

[Heat resistance evaluation]
The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm x width of 100 mm and a thickness of 0.7 mm using a spin coater so that the dry film thickness was 1.0 μm. It was 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 to obtain a substrate for heat resistance evaluation.
The absorbance of the obtained substrate for heat resistance evaluation was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies) at an incident angle of 0° C. at the maximum absorption wavelength, and this was taken as the initial value.
Thereafter, the heat resistance evaluation substrate was heated at 210° C. for 20 minutes, and after cooling, the absorbance was measured again, and this was taken as the value after the heat resistance test. Heat resistance was calculated using the following formula. The evaluation criteria are as follows, and 3 or more is practical.
Survival rate = (absorbance after heat resistance test) ÷ (initial absorbance) x 100
5: Residual rate is 97% or more 4: Residual rate is 95% or more and less than 97% 3: Residual rate is 93% or more and less than 95% 2: Residual rate is 90% or more and less than 93% 1: Residual rate is less than 90%

10 Image display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Aligning layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal 200 Solid-state imaging device 201 Solid-state imaging device 202 Imaging section 203 Cover glass 204 Spacer 205 Laminated substrate 206 Chip substrate 207 Circuit board 208 Electrode pad 209 External connection terminal 210 Penetrating electrode 211 Lens layer 212 Lens material 213 Support 214 Cured film 215 Cured film 300 Infrared sensor 310 Solid-state image sensor 311 Infrared cut filter 312 Color filter 313 Infrared transmission filter 314 Resin film 315 Micro lens 316 Flat film

Claims (15)

A photosensitive composition comprising a near-infrared absorbing dye (A) having maximum absorption at a wavelength of 700 to 2,000 nm, an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). ,
The alkali-soluble resin (B) includes an alkali-soluble resin (B1) having a glass transition temperature of 10 to 150°C,
A photosensitive composition in which the photopolymerization initiator (D) includes a photopolymerization initiator (D1) represented by the following general formula (1).
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 any monovalent substituent. n represents an integer from 0 to 3. ) A claim in which the alkali-soluble resin (B1) contains an alicyclic hydrocarbon-containing monomer unit (b1) and an aromatic ring-containing monomer unit (b2) whose homopolymer glass transition temperature is 80° C. or higher. 1. The photosensitive composition according to 1. The total content of the alicyclic hydrocarbon-containing monomer unit (b1) and the aromatic ring-containing monomer unit (b2) is 10 to 70 mol in all the constituent units of the alkali-soluble resin (B1). % of the photosensitive composition according to claim 2. The photosensitive material according to claim 2 or 3, wherein the molar ratio of the alicyclic hydrocarbon-containing monomer unit (b1) and the aromatic ring-containing monomer unit (b2) is 40:60 to 90:10. sexual composition. The photosensitive composition according to any one of claims 1 to 4, wherein the alkali-soluble resin (B1) contains a polymerizable unsaturated group-containing monomer unit (b3). According to any one of claims 1 to 5, the photopolymerization initiator (D) further contains a photopolymerization initiator (D2) other than the photopolymerization initiator (D1) represented by the general formula (1). The photosensitive composition described. The photopolymerization initiator (D2) is an acetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and an oxime photopolymerization initiator (provided that the photopolymerization initiator represented by general formula (1) (D1 7. The photosensitive composition according to claim 6, comprising one or more selected from the group consisting of (excluding )). The photosensitive composition according to any one of claims 1 to 7, further comprising a sensitizer (E). The photosensitive composition according to claim 8, wherein the content of the sensitizer (E) is 150 to 400 parts by mass based on 100 parts by mass of the photopolymerization initiator (D). The photosensitive composition according to any one of claims 1 to 9, further comprising a colorant (F). A cured film obtained by curing the photosensitive composition according to any one of claims 1 to 10. An optical filter comprising the cured film according to claim 11. An image display device comprising the cured film according to claim 11. A solid-state imaging device comprising the cured film according to claim 11. An infrared sensor comprising the cured film according to claim 11.