Photosensitive composition, cured film using the same, optical filter, image display device, solid-state image sensor, and infrared sensor

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

[Technical Field]

[0001] This 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. [Background technology]

[0002] Video cameras, digital cameras, and portable devices with camera functions use solid-state image sensors (CCDs) and CMOSs ​​(complementary metal-oxide-semiconductors) to produce color images. Since the light-receiving section of these solid-state image sensors uses silicon photodiodes, which are sensitive to infrared light, it is necessary to correct the luminous sensitivity, and infrared cut filters are placed accordingly. Infrared cut filters are manufactured, for example, using compositions containing near-infrared absorbing dyes.

[0003] Traditionally, infrared cut filters have been used as flat films, but in recent years, there has been research into forming patterns in infrared cut filters using photolithography. However, near-infrared absorbing dyes used in infrared cut filters have low heat resistance, which leads to a decrease in near-infrared absorption during the heat treatment (post-bake) process for pattern formation. On the other hand, films with high heat resistance have problems with developability and pattern formation.

[0004] Various efforts have been made to solve the above problems. For example, Patent Document 1 discloses a thermosetting resin composition comprising two types of cyanine compounds, an epoxy resin of 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. Patent Document 2 also discloses a photosensitive resin composition for near-infrared absorbers that can obtain fine patterns, comprising a phthalocyanine compound having an absorption maximum wavelength in the near-infrared region, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2015-34252 [Patent Document 2] Japanese Patent Publication No. 2010-160380 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, none of the compositions described in Patent Documents 1 and 2 satisfy all of the requirements for developability, pattern formation, and heat resistance.

[0007] The object of the present invention is to provide a photosensitive composition that can form a cured film with excellent developability, pattern formation, and heat resistance. [Means for solving the problem]

[0008] The present invention relates to 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) comprises an alkali-soluble resin (B1) having a glass transition temperature of 10 to 150°C. The photopolymerization initiator (D) contains a photopolymerization initiator (D1) represented by the following general formula (1). This relates to photoactive compositions. General formula (1) [ka]

[0009] (In general formula (1), R1 represents 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 a heterocyclic group having 2 to 20 carbon atoms.) R2 is an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a carbon atom. This represents an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. R3 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. R4 represents any monovalent substituent. n represents an integer between 0 and 3. [Effects of the Invention]

[0010] According to the present invention described above, a photosensitive composition can be provided that can form a cured film with excellent developability, pattern formation, and heat resistance. Furthermore, the present invention can provide a cured film, an optical filter, an image display device, a solid-state image sensor, and an infrared sensor. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 shows a schematic cross-sectional view of an image display device equipped with the cured film of the present invention. [Figure 2] Figure 2 shows a schematic cross-sectional view of a solid-state image sensor equipped with the cured film of the present invention. [Figure 3] Figure 3 shows a schematic cross-sectional view of an infrared sensor equipped with the cured film of the present invention. [Modes for carrying out the invention]

[0012] The following describes in detail embodiments for carrying out the photosensitive composition of the present invention. However, the present invention is not limited to the following embodiments and can be modified and implemented within the scope of solving the problem.

[0013] In this invention, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; issued by The Society of Dyers and Colourists). A polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compounds in this invention, for low molecular weight compounds whose molecular weight can be determined, the value is calculated or measured by ESI-MS (electrospray ionization mass spectrometry). For compounds with a molecular weight distribution, the weight-average molecular weight in polystyrene terms is measured by gel permeation chromatography using tetrahydrofuran as the solvent. Monomers are compounds that form resins through polymerization. Monomers are in an unreacted state, and mono A mer unit is a state in which monomers have polymerized to form a resin.

[0014] <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), The alkali-soluble resin (B) comprises 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) [ka]

[0015] (In general formula (1), R1 represents 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 a heterocyclic group having 2 to 20 carbon atoms.) R2 is an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a carbon atom. This represents an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. R3 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. R4 represents any monovalent substituent. n represents an integer between 0 and 3.

[0016] The components included in or potentially included in one embodiment of the photosensitive composition will be described in detail below.

[0017] [Near-infrared absorbing dye (A)] The photosensitive composition of the present invention contains a near-infrared absorbing dye (A).

[0018] The near-infrared absorbing dye (A) is a compound having maximum absorption at wavelengths of 700 to 2,000 nm, and may be a pigment (also called a near-infrared absorbing pigment) or a dye (also called a near-infrared absorbing dye). A near-infrared absorbing pigment and a near-infrared absorbing dye may also be used in combination. From the viewpoint of heat resistance, a near-infrared absorbing pigment is preferred. In the present invention, the near-infrared absorbing pigment preferably has a solubility of less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less in 100 g of propylene glycol monomethyl ether acetate at 25°C.

[0019] Examples of near-infrared absorbing dyes (A) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and crokonium compounds. Among these, naphthalocyanine compounds, pyrrolopyrrole compounds, and squarylium compounds are preferred from the viewpoint of heat resistance, and naphthalocyanine compounds and squarylium compounds are more preferred.

[0020] Cyanine compounds are described in International Publication No. 2006 / 006573, International Publication No. 2010 / 073857, Japanese Patent Publication No. 2013-241598, Japanese Patent Publication No. 2016-113501, Japanese Patent Publication No. 2016-113504, etc.; Phthalocyanine compounds are described in Japanese Patent Publication No. Hei 4-23868, Japanese Patent Publication No. Hei 06-192584, Japanese Patent Publication No. 2000-63691 Japanese Patent Publication No. 2014 / 208514, etc.; Naphthalocyanine compounds: Japanese Patent Publication No. 11-152414, Japanese Patent Publication No. 2000-86919, Japanese Patent Publication No. 2009-29955, Japanese Patent Publication No. 2018 / 186490, etc.; Indigo compounds: Japanese Patent Publication No. 2013-230412, etc.; Immonium compounds: Japanese Patent Publication No. 2005-3361 Japanese Patent Publication No. 50, Japanese Patent Publication No. 2007-197492, Japanese Patent Publication No. 2008-88426, etc.; for anthraquinone compounds, Japanese Patent Publication No. 62-903, Japanese Patent Publication No. 1-172458, etc.; for pyrrolopyrrole compounds, Japanese Patent Publication No. 2009-263614, Japanese Patent Publication No. 2010-90313, Japanese Patent Publication No. 2011-068731; squarylium compounds Examples of materials include those described in Japanese Patent Publication No. 2011-132361, Japanese Patent Publication No. 2016-142891, International Publication No. 2017 / 135359, International Publication No. 2018 / 225837, Japanese Patent Publication No. 2019-001987, International Publication No. 2020 / 054718, etc.; examples of croconium compounds include those described in International Publication No. 2019 / 021767, etc.

[0021] (Squallium compound) The preferred squarylium compound is one represented by the following general formula (2). General formula (2) [ka]

[0022] (In general formula (2), R 1 ~R 4 each independently represents 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 , -SO2R 23 , -SO2OR 24 , -NHSO2R 25 , -SO2NR 26 R 27 , -B(OR 28 )2, and -NHBR 29 R 30 . R 10 ~R 30 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group which may have a substituent. In addition, when R 12 of -COOR 12 is hydrogen (that is, a carboxyl group), the hydrogen atom may dissociate (that is, a carbonate group) or may be in a salt state. Also, when R 24 of -SO2OR 24 is a hydrogen atom (that is, a sulfo group), the hydrogen atom may dissociate (that is, a sulfonate group) or may be in a salt state. Further, R 1 and R 2 , R 3 and R 4 may bond to each other to form a ring.)

[0023] "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 , -SO2R 113 , -SO2OR 114 , -NHSO2R 115 or -SO2NR 116 R 117 These are some examples. R 100 ~R 117 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. Note that -COOR 102 R 102 If it is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group), and it may be in the form of a salt. Also, -SO2OR 114 R 114 If the atom is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group), and the group may be in the form of a salt.

[0024] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. 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, and particularly preferably 6 to 10. The alkyl portion of the aralkyl group is the same as that of the alkyl group described above. The aryl portion of the aralkyl group is the same as that of the aryl group described above. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and particularly preferably 7 to 25. The heteroaryl group is preferably a monocyclic or fused ring, more preferably a monocyclic or fused ring with 2 to 8 fused atoms, and particularly preferably a monocyclic or fused ring with 2 to 4 fused atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered or 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. Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, and aralkyl groups may have substituents or may be unsubstituted. Examples of substituents include the "substituents" mentioned above.

[0025] From the viewpoint of light resistance and heat resistance, the compound represented by the following general formula (3) is more preferable than the squarylium compound. General formula (3) [ka]

[0026] (In general formula (3), R 5 ~R 8 Each of these independently consists of 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, and an -OR group. 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 , -SO2R 63 , -SO2OR 64 , -NHSO2R 65 or -SO2NR 66 R 67 , -B(OR 68 )2, and -NHBR 69 R 70 represents. R 50 ~R 70 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, when R 52 of -COOR 52 is hydrogen (that is, a carboxyl group), the hydrogen atom may dissociate (that is, a carbonate group) or may be in a salt state. Also, when R 64 of -SO2OR 64 is a hydrogen atom (that is, a sulfo group), the hydrogen atom may dissociate (that is, a sulfonate group) or may be in a salt state. Further, R 5 and R 6 , R 7 and R 8 may be bonded to each other to form a ring.)

[0027] "Substituent" has the same meaning as the "substituent" described above.

[0028] Hereinafter, specific examples of squarylium compounds are shown. However, the present invention is not limited thereto.

[0029]

Chemical formula

[0030]

Chemical formula

[0031] (Pyrrolopyrrole compound) The pyrrolopyrrole compound is preferably a compound represented by the following general formula (4).

[0032] General formula (4) [Chemical formula]

[0033] (In general formula (4), R 1x and R 1y each independently represent an alkyl group, an aryl group or a heteroaryl group, R 2 and R 3 each independently represent a hydrogen atom or a substituent, R 2 and R 3 may be bonded to 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, R 4 is R 1x , R 1y and R 3 and may be covalently bonded or coordinate-bonded to at least one selected from the group consisting of, R 4x R 4y each independently represent a substituent. General formula (4) is described in JP-A-2009-263614, JP-A-2011-68731, and WO 2015 / 16687).

[0034] R 1x and R 1y each independently are preferably an aryl group or a heteroaryl group, more preferably an aryl group. Also, 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, -SO2R 13 Examples include R. 11 ~R 13 Each of these independently represents a hydrocarbon group or a heteroaryl group. Furthermore, examples of substituents include those described in paragraphs 0020-0022 of Japanese Patent Publication No. 2009-263614. Among these, examples of substituents include alkoxy groups, hydroxyl groups, halogen atoms, cyano groups, nitro groups, and -OCOR groups. 11 -SOR 12 , -SO2R 13 R is preferable. 1x and R 1y The group represented by this can be an alkoxy group having a branched alkyl group, or -OCOR 11 It is preferable that the aryl group has a group represented by as a substituent. The branched alkyl group has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.

[0035] R 2 and R 3 At least one of them is preferably an electron-withdrawing group, R 2 represents an electron-withdrawing group, R 3 It is more preferable that R represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. Furthermore, the heteroaryl group is preferably a monoring or a fused ring, preferably a monoring or a fused ring with 2 to 8 fused rings, and more preferably a monoring or a fused ring with 2 to 4 fused rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. It is preferable that the heteroaryl group has one or more nitrogen atoms. The two R in general formula (4) 2 The two Rs in general formula (4) may be the same or different. 3 The same or different items may be identical or different.

[0036] R 4 is a hydrogen atom, alkyl group, aryl group, heteroaryl group, or -BR 4x R 4y It is preferably a group represented by -BR, which is a hydrogen atom, an alkyl group, an aryl group, or a hydrogen atom, an alkyl group, or an alkyl group.4x R 4y It is more preferable that the group be represented by -BR 4x R 4y It is particularly preferable that the group be represented by R. 4x R 4y The substituents represented by are preferably halogen atoms, alkyl groups, alkoxy groups, aryl groups, or heteroaryl groups, more preferably alkyl groups, aryl groups, or heteroaryl groups, and particularly preferably aryl groups. These groups may have further substituents. The two R in general formula (4) 4 They may be the same or different.

[0037] The following are specific examples of pyrrolopyrrole compounds. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. Examples of pyrrolopyrrole compounds include those described in paragraphs 0016-0058 of Japanese Patent Publication No. 2009-263614, paragraphs 0037-0052 of Japanese Patent Publication No. 2011-68731, paragraphs 0014-0027 of Japanese Patent Publication No. 2014-130343, and paragraphs 0010-0033 of International Publication No. 2015 / 166873. However, the present invention is not limited to these.

[0038] [ka]

[0039] (Naphthalocyanine compounds) The naphthalocyanine compound is preferably a compound represented by the following general formula (5).

[0040] General formula (5) [ka] (In general formula (5), R 1 ~R 24Each of these independently represents a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group. . Z represents a polymer moiety containing the monomer unit shown in general formula (6), or a phosphorus compound moiety represented by general formula (7), and * represents a bond with Al. General formula (6) [ka] (In general formula (6), X is -CONH-R 25 -,-COO-R 26 -, -CONH-R 27 -O-, -COO-R 28 -O-, R 25 ~R 28 R represents an alkylene or arylene group in which carbon atoms may be linked together by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. 31 (This represents a hydrogen atom or a methyl group.)

[0041] General formula (7) [ka] (In general formula (7), R 29 and R 30 Each of these independently represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group, R 29 and R 30 They may also join together to form a ring.

[0042] The following are specific examples of naphthalocyanine compounds. However, the present invention is not limited to these. [ka]

[0043] Near-infrared absorbing dyes (A) can be used alone or in combination of two or more. When using two or more in combination, it is preferable to use at least two compounds with different maximum absorption wavelengths. This broadens the waveform of the absorption spectrum compared to using a single near-infrared absorbing dye (A), allowing for absorption of near-infrared light across a wider wavelength range.

[0044] From the viewpoint of near-infrared absorption, the content of the near-infrared absorbing dye (A) is preferably 0.5 to 70% by mass, and more preferably 1 to 50% by mass, of 100% by mass of the non-volatile content of the photosensitive composition.

[0045] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B1) as the alkali-soluble resin (B), having a glass transition temperature of 10 to 150°C. This results in a cured film with good developability, pattern formation, and heat resistance.

[0046] (Alkali-soluble resin (B1)) The alkali-soluble resin (B1) can be any resin that has a glass transition temperature of 10 to 150°C and dissolves in an alkaline developer; known resins can be used.

[0047] The glass transition temperature of the alkali-soluble resin (B1) is preferably 10 to 120°C, and more preferably 10 to 80°C, from the viewpoint of developability, pattern formation, and heat resistance.

[0048] The glass transition temperature (hereinafter also referred to as Tg) can be measured using a measured Tg obtained through actual measurement. Specifically, the measured Tg can be the value obtained by differential scanning calorimetry (DSC). However, if measurement is difficult due to resin decomposition or other reasons, the calculated Tg obtained by the following formula shall be applied. 1 / Tg=W1 / Tg1+W2 / Tg2+······+W n / Tg n Here, the resins to be calculated are W1 to W n Assuming that n monomer components up to W are copolymerized, n Tg is the weight fraction of the nth monomer. n is the glass transition temperature (absolute temperature) of the homopolymer of the nth monomer. The glass transition temperature values ​​for each monomer homopolymer (hereinafter also called homopolymer) are those shown in "Polymer Handbook, Third edition, John Wiley & Sons, 1989" edited by Brandrup, J. Immergut, EH.

[0049] From the viewpoint of pattern formation and heat resistance, the alkali-soluble resin (B1) preferably contains alicyclic hydrocarbon-containing monomer units (b1) and aromatic ring-containing monomer units (b2) whose homopolymer glass transition temperature is 80°C or higher.

[0050] [Monomer units containing alicyclic hydrocarbons with a glass transition temperature of 80°C or higher (b1)] Monomers that form alicyclic hydrocarbon-containing monomer units (b1) with a glass transition temperature of 80°C or higher include, for example, isoboronyl acrylate, isoboronyl methacrylate, adamantyl acrylate, adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl acrylate, and dicyclopentanyl methacrylate. Among these, isoboronyl methacrylate, adamantyl methacrylate, and dicyclopentanyl methacrylate are preferred.

[0051] [Aromatic ring-containing monomer units (b2) with a glass transition temperature of 80°C or higher for homopolymers] Monomers that form aromatic ring-containing monomer units (b2) with a glass transition temperature of 80°C or higher include, for example, styrene, α-methylstyrene, and vinylnaphthalene. Among these, styrene and α-methylstyrene are preferred.

[0052] The total content of alicyclic hydrocarbon-containing monomer units (b1) and aromatic ring-containing monomer units (b2) is preferably 10 to 70 mol%, and more preferably 20 to 60 mol%, of the total constituent units of the alkali-soluble resin (B1), from the viewpoint of pattern formation and heat resistance.

[0053] The ratio of alicyclic hydrocarbon-containing monomer units (b1) and aromatic ring-containing monomer units (b2) is preferably 40:60 to 90:10, and more preferably 50:50 to 80:20, from the viewpoint of pattern formation and heat resistance.

[0054] [Polymerizable unsaturated group-containing monomer unit (b3)] From the viewpoint of pattern formation and heat resistance, the alkali-soluble resin (B1) preferably contains polymerizable unsaturated group-containing monomer units (b3).

[0055] The alkali-soluble resin (B1) contains polymerizable unsaturated group-containing monomer units (b3). Examples of methods include the following (i) to (iii).

[0056] <Method (i)> One method (i) involves adding a carboxyl group from a carboxyl group-containing monomer to an epoxy group from an epoxy group-containing monomer unit contained in an alkali-soluble resin (B1).

[0057] Monomers that form epoxy group-containing monomer units include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0058] Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among these, acrylic acid and methacrylic acid are preferred.

[0059] From the viewpoint of developability, a polymerizable unsaturated group-containing monomer unit (b3) is also useful when an epoxy group containing an epoxy group is added to the epoxy group of a carboxyl group-containing monomer unit, and then reacted with an acid anhydride.

[0060] Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0061] <Method (ii)> (ii) is a method in which an epoxy group-containing monomer is added to the carboxyl group of a carboxyl group-containing monomer unit contained in an alkali-soluble resin (B1).

[0062] <Method (iii)> (iii) is a method in which the hydroxyl group of a hydroxyl group-containing monomer unit contained in an alkali-soluble resin (B1) is reacted with the isocyanate group of an isocyanate group-containing monomer.

[0063] Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates such as 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.

[0064] Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0065] From the viewpoint of pattern formation and heat resistance, the content of polymerizable unsaturated group-containing monomer units (b3) is preferably adjusted so that the double bond equivalent of the alkali-soluble resin (B1) is 200 to 1000, more preferably 200 to 800, and particularly preferably 200 to 700. 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)

[0066] [Other monomer units (b4)] Alkali-soluble resin (B1) is other monomer units (b4) other than (b1) to (b3) It can contain.

[0067] Other monomers that form monomer units (b4) include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Hydroxyl group-containing (meth)acrylates such as 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; Polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide, etc., to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc.; Epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and 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; Vinyl acetate or vinyl propionate, and other fatty acid vinyl compounds; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl) N-substituted maleimides such as reimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimide acridine; Examples include 2-(meth)acryloyloxyethyl acid phosphate, and phosphate ester group-containing (meth)acrylates such as compounds obtained by reacting the hydroxyl group of the hydroxyl group-containing (meth)acrylate mentioned above with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0068] From the viewpoint of pattern formation and heat resistance, the content of alkali-soluble resin (B1) is preferably 40% by mass or more, and 60% by mass or more, out of 100% by mass of alkali-soluble resin (B). preferable.

[0069] Alkali-soluble resin (B1) can be used alone or in combination of two or more types.

[0070] The weight-average molecular weight (Mw) of the alkali-soluble resin (B1) is preferably 5,000 to 40,000, and more preferably 5,000 to 30,000, from the viewpoint of heat resistance.

[0071] From the viewpoint of developability, the acid value of the alkali-soluble resin (B1) is preferably 30 to 200 mg KOH / g, and more preferably 60 to 150 mg KOH / g.

[0072] (Alkali-soluble resin (B2)) The photosensitive composition of the present invention may contain an alkali-soluble resin (B2) other than alkali-soluble resin (B1) as alkali-soluble resin (B), as long as it does not impair the effects of the present invention.

[0073] The content of alkali-soluble resin (B) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0074] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0075] Polymerizable compounds (C) include monomers and oligomers. Polymerizable unsaturated groups include, for example, vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups. Polymerizable compounds (C) include, for example, lactone-modified polymerizable compounds, polymerizable compounds having acid groups, polymerizable compounds having urethane bonds, and other polymerizable compounds.

[0076] (Lactone-modified polymerizable compound) From the viewpoint of heat resistance, the photosensitive composition of the present invention preferably contains a lactone-modified polymerizable compound.

[0077] Lactone-modified polymerizable compounds are compounds that have a structure modified with lactone within their molecule. Lactone-modified polymerizable compounds are obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compounds are preferably those represented by the following general formula (8).

[0078] General formula (8) [ka]

[0079] In general formula (8), all six Rs are groups represented by the following general formula (9), or among the six Rs One to five of the groups are represented by the following general formula (9), and the remaining groups are represented by the following general formula (10).

[0080] General formula (9) [ka]

[0081] In general formula (9), R 1 represents a hydrogen atom or a methyl group, m is an integer between 1 and 2, and * is a bond that connects to the oxygen atom in general formula (8).

[0082] General formula (10) [ka]

[0083] In general formula (10), R 1 represents a hydrogen atom or a methyl group, and * represents a bond that connects to the oxygen atom in general formula (8).

[0084] Lactone-modified polymerizable compounds are commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd., such as DPCA-20 (where m=1 in the above general formulas (8) to (10), the number of groups represented in general formula (9) = 2, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-30 (in the above general formulas (8) to (10), m=1, number of groups represented in general formula (9)=3, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-60 (in the above general formulas (8) to (10), m=1, number of groups represented in general formula (9)=6, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-120 (in the above general formulas (8) to (10), m=2, number of groups represented in general formula (9)=6, R 1 Examples include compounds in which all atoms are hydrogen atoms.

[0085] 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 in general formula (9) = 2 to 6, and R 1 Compounds in which all atoms are hydrogen atoms are preferred, and in the above general formulas (8) to (10), m=1, the number of groups represented in general formula (9) = 2 or 3, R 1 Compounds in which all atoms are hydrogen atoms are more preferable.

[0086] 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 even more preferably 20 to 60% by mass, based on 100% by mass of polymerizable compound (C).

[0087] (Polymerizable compounds containing acidic groups) The photosensitive composition of the present invention preferably contains a polymerizable compound having an acidic group, from the viewpoint of developability and pattern formation. Examples of acidic groups in polymerizable compounds include sulfonic acid groups, carboxyl groups, and phosphate groups. Among these, carboxyl groups are preferred.

[0088] Examples of polymerizable compounds having acidic groups include esters of polyhydric alcohols and (meth)acrylic acid poly(meth)acrylates containing free hydroxyl groups with dicarboxylic acids; and esters of polyhydric acids with monohydroxyalkyl (meth)acrylates. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid. Examples of polycarboxylic 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, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0089] Examples of commercially available polymerizable compounds containing acid groups include Viscoat #2500P from Osaka Organic Co., Ltd., and Aronics M-5300, M-5400, M-5700, M-510, M-520, and M-521 from Toagosei Co., Ltd.

[0090] From the viewpoint of developability and pattern formation, the content of polymerizable compounds having acid groups is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on 100% by mass of polymerizable compound (C).

[0091] (Polymerizable compound containing urethane bonds) 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).

[0092] Polymerizable compounds having a urethane bond include, for example, urethane (meth)acrylates obtained by reacting a hydroxyl-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl-containing (meth)acrylate.

[0093] The above-mentioned (meth)acrylate having a hydroxyl group is, for example, 2-hydroxyethyl(meth) Acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane (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-acryloy Examples include propyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

[0094] Examples of the polyfunctional isocyanates mentioned above 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 diisocyanates such as isophorone diisocyanate, as well as their bilets, isocyanate nulates, and trimethylolpropane adducts.

[0095] Polymerizable compounds having urethane bonds are also preferably having acidic groups from the viewpoint of developability. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups. However, a carboxyl group is preferred.

[0096] One method for introducing an acid group into a polymerizable compound having a urethane bond is to first react the (meth)acrylate having the hydroxyl group with the polyfunctional isocyanate, and then add a mercapto compound having a carboxyl group to the product.

[0097] Examples of mercapto compounds having the carboxyl group mentioned above include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0098] From the viewpoint of pattern formation, the number of polymerizable unsaturated groups in a polymerizable compound having a urethane bond is preferably 3 to 15, and more preferably 5 to 12.

[0099] From the viewpoint of pattern formation, the content of the polymerizable compound having a urethane bond is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on 100% by mass of polymerizable compound (C).

[0100] (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, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Examples include 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, various acrylic acid esters and methacrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, epoxy(meth)acrylate, urethane acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

[0101] 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-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330 from Nippon Kayaku Co., Ltd., and Aronix M-303, M-305 from Toagosei Co., Ltd. M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #3 manufactured by Osaka Organic Co., Ltd. Examples include 35HP, #700, #295, #330, #360, #GPT, #400, #405, NK ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4 from Shin Nakamura Chemical Co., Ltd., EBECRYL 40, 130, 140, 145 from Daicel Ornex Co., Ltd., AH-600, AT-600 from Kyoeisha Chemical Co., Ltd., and OGSOL EA-0200, 0300 from Osaka Gas Chemical Co., Ltd.

[0102] Polymerizable compound (C) can be used alone or in combination of two or more types.

[0103] From the viewpoint of developability, pattern formation, and heat resistance, the polymerizable compound (C) preferably includes at least one selected from the group consisting of lactone-modified polymerizable compounds, polymerizable compounds having acid groups, and polymerizable compounds having urethane bonds.

[0104] The content of polymerizable compound (C) is preferably 1 to 60% by mass, and more preferably 2 to 50% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0105] [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 the photopolymerization initiator (D). This improves reactivity and provides good pattern formation and heat resistance.

[0106] General formula (1) [ka]

[0107] (In general formula (1), R1 represents 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 a heterocyclic group having 2 to 20 carbon atoms.) R2 is an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a carbon atom. This represents an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. R3 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. R4 represents any monovalent substituent. n represents an integer between 0 and 3.

[0108] In general formula (1), R1 represents 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 a heterocyclic group having 2 to 20 carbon atoms. Alkyl groups having 1 to 20 carbon atoms may be linear, branched, cyclic, or combined, for example, methyl group, ethyl group, 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, Examples include cyclohexylmethyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group. Examples of heterocyclic groups having 2 to 20 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. Among the above, from the viewpoint of reactivity, methyl groups, ethyl groups, or phenyl groups are preferred, and methyl groups or ethyl groups are more preferred.

[0109] In general formula (1), R2 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. Alkyl groups having 3 to 20 carbon atoms may be linear, branched, cyclic, or combined. Examples include 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, and cyclohexylmethyl group. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group. Examples of heterocyclic groups having 2 to 20 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. 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.

[0110] In general formula (1), R3 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. Alkyl groups having 3 to 20 carbon atoms may be linear, branched, cyclic, or combined. Examples include 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, and cyclohexylmethyl group. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group. Examples of heterocyclic groups having 2 to 20 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. 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 The 2-ethylhexyl group is particularly preferred.

[0111] In general formula (1), R4 represents any monovalent substituent. Examples of optional monovalent substituents include C1-C20 alkyl groups such as methyl and ethyl groups; C1-C20 alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as F, Cl, Br, and I; C1-C20 acyl groups; C1-C20 alkyl ester groups; C1-C20 alkoxycarbonyl groups; C1-C20 halogenated alkyl groups and C4-C20 aromatic ring groups; amino groups; C1-C20 aminoalkyl groups; hydroxyl groups; nitro groups; cyano groups; benzoyl groups which may have substituents; and tenoyl groups which may have substituents. Examples of substituents that the benzoyl or tenoyl group may have include C1-C10 alkyl groups, C1-C10 alkoxy groups, and C1-C10 alkoxycarbonyl groups, and may have 1 to 3 substituents. Among the above, from the viewpoint of reactivity and heat resistance, benzoyl groups that may have substituents are preferred, and benzoyl groups in which the substituent is an alkoxycarbonyl group are more preferred.

[0112] In general formula (1), n ​​represents an integer between 0 and 3. Furthermore, from the viewpoint of radical generation efficiency, n is preferably 0 or 1, and more preferably 1.

[0113] The method for producing the photopolymerization initiator (D1) is not particularly limited, and known methods can be used. For example, these are described in International Publication No. 2008 / 078678, International Publication No. 2014 / 050738, and Japanese Patent Publication No. 2016-519675.

[0114] The following are specific examples of photopolymerization initiators (D1) represented by general formula (1). However, the present invention is not limited to these examples.

[0115] [ka] [ka]

[0116] 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.

[0117] The photopolymerization initiator (D1) can be used alone or in combination of two or more types.

[0118] The content of the photopolymerization initiator (D1) is preferably 10 to 100% by mass, and more preferably 30 to 90% by mass, based on 100% by mass of the photopolymerization initiator (D).

[0119] ((D2) - Photopolymerization initiators other than (D1)) From the viewpoint of developability and pattern formation, the photopolymerization initiator (D) preferably includes a photopolymerization initiator (D2) other than the photopolymerization initiator (D1) represented by general formula (1) (hereinafter also referred to as other photopolymerization initiator (D2)).

[0120] Other photopolymerization initiators (D2) are not particularly limited as long as they are compounds capable of initiating the polymerization of polymerizable compound (C) by light, and known photopolymerization initiators can be used.

[0121] The photopolymerization initiator (D2) is specifically an acetophenone-based photopolymerization initiator such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; Triazine-based photopolymerization initiators such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Oxime-based photopolymerization initiators such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole3-yl]-,1-(O-acetyl oxime) (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)biidazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2 Examples include imidazole-based photopolymerization initiators such as 2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Among these, acetophenone-based photopolymerization initiators, acylphosphine oxide-based polymerization initiators, and oxime-based photopolymerization initiators (excluding photopolymerization initiator (D1)) are preferred from the viewpoint of developability and pattern formation.

[0122] Commercially available acetophenone-based photopolymerization initiators include Omnirad907, 369, and 379EG from IGM Resins. Examples of commercially available acylphosphine oxide polymerization initiators include Omnirad819 and TPO from IGM Resins. Commercially available oxime-based photopolymerization initiators (excluding photopolymerization initiator (D1)) include IRGACURE OXE-01, 02, 03, 04 from BASF Japan, ADEKA Arcules N-1919, NCI-730, 831, 930 from ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 from Changzhou Strong New Materials Co., Ltd., OMNIRAD 1312, 1314, 1316 from IGM Resins, SPI-02, 03, 04, 05, 06, 07 from Samyang Corporation, and DFI-020, 306, EOX-01 from Daito Chemix Co., Ltd.

[0123] Other photopolymerization initiators (D2) can be used alone or in combination of two or more types.

[0124] The content of the photopolymerization initiator (D) is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of the near-infrared absorbing dye (A), from the viewpoint of photocurability and developability.

[0125] [Sensitizer (E)] The photosensitive composition of the present invention may contain a sensitizer (E) from the viewpoint of pattern formation.

[0126] The sensitizer (E) is, for example, polymethine dyes such as chalcone compounds, unsaturated ketones represented by dibenzalacetone, 1,2-diketone compounds represented by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples include compounds such as squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyradinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxaliloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyririum compounds, thiopyrillium compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospilopyran compounds, metal arene complexes, organoruthenium complexes, or 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.

[0127] (Thioxanthone compound (E1)) Thioxanthone compounds (E1) include, for example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, and 2-isopropylthioxanthone. Examples include thon, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Among these, 2,4-diethylthioxanthone is preferred.

[0128] (Benzophenone compounds (E2)) Examples of benzophenone compounds (E2) include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0129] The sensitizer (E) can be used alone or in combination of two or more types.

[0130] From the viewpoint of pattern formation, the content of the sensitizer (E) is preferably 150 to 400 parts by mass, and more preferably 150 to 300 parts by mass, per 100 parts by mass of the photopolymerization initiator (D).

[0131] [Coloring agent (F)] The photosensitive composition of the present invention may contain a colorant (F). This allows for control of the transmittance in each wavelength region of the color filter, thereby improving color separation.

[0132] The coloring agent (F) may be either a pigment or a dye, and can be used in combination.

[0133] (Pigment) The pigment is preferably a compound classified as a pigment in the color index. Red pigments include, for example, CI 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, Examples include pigments 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 Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are even more preferred.

[0134] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0135] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12 ,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,126,127,128,129,13 Examples include pigments described in 8, 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 Japanese Patent Publication No. 2012-226110. Among these, CI Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigment described in Japanese Patent Publication No. 2012-226110 are preferred.

[0136] Examples of green pigments include CI 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, and 63. Among these, CI Pigment Green 36, 58, 59, 62, and 63 are preferred.

[0137] Examples of blue pigments include CI 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, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0138] Examples of purple pigments include CI 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, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0139] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31. Alternatively, at least two pigments selected from red, yellow, blue, green, and purple pigments may be used as the black coloring agent.

[0140] Inorganic pigments include, for example, titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium green oxide, Examples include cobalt green, amber, and synthetic iron black.

[0141] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Derivatives of these dyes, as well as lake pigments (dyes obtained by lake formation), are also examples.

[0142] Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Salt compounds are also preferred, which are salts of acid dyes with nitrogen-containing compounds such as quaternary ammonium salts, tertiary amines, secondary amines, or primary amines. Salt compounds are also preferred, which are salts of resin components having these functional groups with acid dyes. Furthermore, by sulfonamidating the salt compounds to sulfonamide compounds, it is easy to obtain photosensitive compositions with excellent resistance (lightfastness, solvent resistance). Furthermore, salt-forming compounds of acid dyes and compounds containing onium bases also exhibit resistance (lightfastness, solvent resistance). It is preferable because it has excellent resistance. Furthermore, the compound containing the onium base is preferably a resin having a cationic group.

[0143] Basic dyes can be used as is, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in salt-forming compounds of basic dyes, preferred anionic components that act as counterions are salt-forming compounds obtained by salting with organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid having a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt-forming compound is further improved if it contains polymerizable unsaturated groups in its molecule.

[0144] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), and azite dyes. Examples of dye structures derived from dyes selected from chloromethic acid dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0145] Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes is more preferred.

[0146] The coloring agent (F) can be used alone or in combination of two or more types.

[0147] The content of the coloring agent (F) is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0148] (Pigment refinement) It is preferable to use the pigment after it has been finely milled. The milling method is not particularly limited, and for example, wet milling, dry milling, or dissolution milling can all be used. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the finely milled pigment, as determined by TEM (transmission electron microscopy), is preferably 5 to 90 nm. However, from the viewpoint of dispersibility and contrast ratio, an average primary particle size of 10 to 70 nm is more preferable.

[0149] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, etc., and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions during the manufacturing process, it is possible to obtain pigments with extremely fine primary particle sizes, a narrow distribution width, and a sharp particle size distribution.

[0150] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from a cost standpoint. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of pigment, considering both processing efficiency and production efficiency.

[0151] The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is prone to evaporation, a high-boiling-point solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. 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 water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0152] A resin may be added to the salt milling process as needed. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in the organic solvent. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

[0153] [Dispersion resin (G)] The photosensitive composition of the present invention may contain a dispersion resin (G).

[0154] The dispersion resin (G) is preferably a resin having an adsorption group with a high affinity for the near-infrared absorbing dye (A). The adsorption group preferably has at least one of a basic group and an acidic group.

[0155] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring.

[0156] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0157] Examples of the resin type of the dispersion resin (G) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidines, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group and salts thereof, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adducts, phosphate ester-based, and the like.

[0158] Examples of the structure of the dispersion resin (G) include a random structure, a block structure, a graft structure, a comb type structure, and a star structure. Among these, from the viewpoint of dispersion stability, a block structure or a comb type structure is preferable.

[0159] Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P from BYK-Chemie Japan. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 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, manufactured by Lubrizol Japan, including models such as 104, P104S, 220S, Lactimon, Lactimon-WS, or Bykumen. ,76500 etc., BASF Japan's EFKA-46,47,48,452,4008,4009,4010,4015,4020,4047,4050,4055,4060,4080,4400,4401,4402,4403,4406,4408,4300,4310,4320,4330,4340,450,451,453,4540,4550,4560,4800,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503 etc., Ajisu Examples of resins include PA111, PB711, PB821, PB822, PB824, etc., as described in Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, International Publication No. 2008 / 007776, Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, Japanese Patent Publication No. 2009-251481, Japanese Patent Publication No. 2007-23195, Japanese Patent Publication No. 1996-143651, etc.

[0160] The dispersion resin (G) can be used alone or in combination of two or more kinds.

[0161] From the viewpoint of dispersion stability, the content of the dispersion resin (G) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye (A).

[0162] [Dye derivative (H)] The photosensitive composition of the present invention can contain a dye derivative (H).

[0163] The dye derivative (H) is not particularly limited, and examples thereof include dye derivatives having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. The dye derivative (H) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, etc., and amine salts thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and a compound having a neutral substituent such as a phenyl group or a phthalimidalkyl group. Examples of the organic dye include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, polyazo, etc.

[0164] Specifically, as the diketopyrrolopyrrole-based dye derivative, JP-A 2001-22052 Publication No. 0, International Publication No. 2009 / 081930, International Publication No. 2011 / 052617, International Publication No. 2012 / 102399, Japanese Patent Publication No. 2017-156397, as phthalocyanine-based dye derivatives, Japanese Patent Publication No. 2007-226161, International Publication No. 2016 / 163351, Japanese Patent Publication No. 2017-165820, Japanese Patent No. 5753266, as anthraquinone-based dye derivatives, Japanese Patent Publication No. Sho 63-264674, Japanese Patent Publication No. Hei 09-272812, Japanese Patent Publication Hei 10- Japanese Patent Publication No. 245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, International Publication No. 2009 / 025325, as a quinacridone-based dye derivative, Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, as a dioxazine-based dye derivative, Japanese Patent Publication No. 2011-162662, as a thiaidine-indigo-based dye derivative, Japanese Patent Publication No. 2007-314785, as a triazine-based dye derivative, Japanese Patent Publication No. 61-2 Japanese Patent Publication No. 46261, Japanese Patent Publication No. Hei 11-199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, Japanese Patent Publication No. 2007-314681, as a benzoisoindole-based dye derivative, Japanese Patent Publication No. 2009-57478, as a quinophthalone-based dye derivative, Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, Japanese Patent Publication No. 2012-226110, naphth Examples of known pigment derivatives include those described in Japanese Patent Publication No. 2012-208329 and 2014-5439, as well as those described in Japanese Patent Publication No. 2001-172520 and 2012-172092, as well as those described in Japanese Patent Publication No. 2004-307854, as well as those described in Japanese Patent Publication No. 2002-201377, 2003-171594, 2005-181383 and 2005-213404, as well as those described in Japanese Patent Publication No. 2005-213404, as well as those described in Japanese Patent Publication No. 2002-201377, 2003-171594, 2005-181383 and 2005-213404, as well as those described in Japanese Patent Publication No.

[0165] The dye derivative (H) can be used alone or in combination of two or more types.

[0166] The content of the dye derivative (H) is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the near-infrared absorbing dye (A).

[0167] [Thermosetting compound (I)] The photosensitive composition of the present invention may contain a thermosetting compound (I). This allows the thermosetting compound (I) to react during the heating process, increasing the crosslinking density and thus improving heat resistance.

[0168] Thermosetting compound (I) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of 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 phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0169] (Epoxy compound (I1)) Epoxy compounds (I1) include polycondensates of 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, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and phenols and various diene compounds (dicyclopene). Polymers of phenols (such as tadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnolbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), and phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α',α'-benzenedimethanol, bif Examples include polycondensates of phenols (such as phenyldimethanol and α,α,α',α'-biphenyldimethanol), polycondensates of phenols and aromatic dichloromethyl compounds (such as α,α'-dichloroxylene and bischloromethylbiphenyl), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins obtained by glycidylating alcohols.

[0170] Commercially available products include, for example, Epicote 807, 815, 825, 827, 828, 190P, and 191P from Shell Epoxy Oil & Epoxy Corporation, and TECHMORE from Mitsui Chemicals. Examples include VG3101L, EPPN-201, 501H, 502H from Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020 from Japan Epoxy Resin Co., Ltd., Epicote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 from Daicel Chemical Industries, Ltd., Celoxide 2021, EHPE-3150 from Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 from Nagase ChemteX Corporation, and TEPIC-L, H, S from Nissan Chemical Industries, Ltd.

[0171] From the viewpoint of the heat resistance of the cured film, the content of epoxy compound (I1) is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, of 100% by mass of the nonvolatile content of the photosensitive composition.

[0172] (Oxetane compound (I2)) Oxetane compounds (I2) are known compounds having an oxetane group. Examples of oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or multifunctional oxetane compounds.

[0173] Monofunctional oxetane compounds include, for example, (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, and 3-ethyl-3- Examples include hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0174] Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

[0175] Examples of bifunctional oxetane compounds include 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, and di[1-ethyl(3-oxetanyl)]methyl ether. 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, eth Lenglycos-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) Examples include 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, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

[0176] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0177] Oxetane compounds having three or more functional groups 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, resins containing an oxetane group (for example, oxetane-modified phenol novolak resins described in Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0178] The content of the oxetane compound (I2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the nonvolatile content of the photosensitive composition.

[0179] The melamine compound is a compound having a melamine ring structure. Melamine compounds are preferably methylol-type or ether-type compounds, and more preferably melamine compounds having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Appropriate numbers of methylol groups and ether groups make it easy to obtain heat resistance without excess or deficiency.

[0180] Examples of commercially available products include Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 from Nippon Cytec Industries Co., Ltd.

[0181] Among these, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 from Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are highly crosslinked. It is preferable in that it allows for a higher degree of intensity.

[0182] Thermosetting compound (I) can be used alone or in combination of two or more types.

[0183] [Hardening agent (hardening accelerator)] The photosensitive composition of the present invention may be used in combination with a curing agent (curing accelerator) to assist in the curing of the thermosetting compound (I). Examples of curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Examples of curing agents include amine compounds (e.g., 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, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine), 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.).

[0184] The hardening agent can be used alone or in combination of two or more types.

[0185] The curing agent content is preferably 0.01 to 15 parts by mass per 100 parts by mass of thermosetting compound (I).

[0186] [Thiol-based chain transfer agent (J)] The photosensitive composition of the present invention may contain a thiol-based chain transfer agent (J). When used in combination with a photopolymerization initiator (D), the thiol-based chain transfer agent (J) generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive composition.

[0187] The thiol-based chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), and more preferably a polyfunctional thiol having four or more thiol groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0188] Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol Examples include lithritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0189] Thiol-based chain transfer agents (J) can be used alone or in combination of two or more types.

[0190] The content of the thiol-based chain transfer agent (J) is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass, per 100 parts by mass of the nonvolatile content of the photosensitive composition. Including an appropriate amount improves photosensitivity and makes it less likely for wrinkles to form on the surface of the cured film.

[0191] [Polymerization inhibitor (K)] The photosensitive composition of the present invention may contain a polymerization inhibitor (K).

[0192] Polymerization inhibitor (K) is, for example, alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 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, 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n Examples include alkylresorcinol compounds such as -butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and trybenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0193] The polymerization inhibitor (K) content is preferably 0.01 to 0.4 by mass per 100% by mass of the nonvolatile content of the photosensitive composition.

[0194] [UV absorber (L)] The photosensitive composition of the present invention may contain an ultraviolet absorber (L).

[0195] The ultraviolet absorber (L) is an organic compound that has ultraviolet absorption function, and examples include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylate organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds.

[0196] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and 2-(3-t-butyl-5-methyl-2-hydroxyphenyl) (Nyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% A mixture of benzenepropanoic acid, 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3 -(3-(2H-benzotriazol2-yl)-5-t-butyl-4-hydroxyphenyl Reaction product of (nyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl-4-methylphenol, 2-(3,5- Examples include di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0197] Commercially available products include, for example, the TINUVIN P, PS, 234, 326 manufactured by BASF Japan. Examples include 329, 384-2, 900, 928, 99-2, 1130, ADEKA LA-29, LA-31RG, LA-32, LA-36 from ADEKA Corporation, KEMISORB71, 73, 74, 79, 279 from Chemipro Chemical Co., Ltd., and RUVA-93 from Otsuka Chemical Co., Ltd.

[0198] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the resulting compounds include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0199] Commercially available products include, for example, KEMISORB 102 from Chemipro Chemical Co., Ltd. and BASF Japan. TINUVIN 400, 405, 460, 477, 479, 1577ED, AD (manufactured by the company) Examples include EKA's Adeka Stab LA-46 and LA-F70, and Sun Chemical's CYASORB UV-1164.

[0200] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid 3-hydrobenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0201] Commercially available products include, for example, KEMISORB 10, 11, 11S, and 12 from Chemipro Chemical Co., Ltd. ,111, SEESORB 101,107 manufactured by Cipro Chemical Co., Ltd., and ADEKA manufactured by ADEKA Corporation. Examples include Stub 1413 and UV-12 manufactured by Sun Chemical Co., Ltd.

[0202] Examples of salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0203] The amount of ultraviolet absorber (L) is preferably 5 to 70% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (L) in 100% by mass.

[0204] [Antioxidant (M)] The photosensitive composition of the present invention may contain an antioxidant (M). The antioxidant (M) prevents yellowing caused by oxidation of the photopolymerization initiator (D) and thermosetting compound (I) in the photosensitive colored composition due to the heat process during thermal curing or ITO aneeling. 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) decreases relatively, so if the amount of photopolymerization initiator (D) is increased or a thermosetting compound is added, the cured film is prone to yellowing. 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 halogen atoms.

[0205] Antioxidants (M) include, for example, hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred.

[0206] Hindered phenol antioxidants, 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), 3-(3,5-di-t-butyl-4-hydroxyphenyl)pro Stearyl pionate, 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-trimethyl Tylbenzene, 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-hydroxyhydrocinna Muamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-Hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenicol Examples include 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-amylhydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethylphenol), 2,2'-methylene-bis-(6-(1-methylcyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methylcyclohexyl)-phenol.

[0207] Commercially available products include, for example, ADEKA's ADEKA stubs AO-20, AO-30, and AO-4. Examples include 0, AO-50, AO-60, AO-80, AO-330, KEMINOX 101, 179, 76, 9425 from Chemipro, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 from BASF Japan, and Cyanox CY-1790, CY-2777 from Sun Chemical.

[0208] Hindered amine antioxidants include, for example, 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-tetramethylpiperidine-4-yl)carbonate, and 1,2,2,6,6-pentamethyl-4-piperidyl. Tamethyl-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- Ester of piperidineethanol and 3,5,5-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-triazine-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester of decandioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bi (1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatemethyl 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,Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide.

[0209] Examples of commercially available products include ADEKA's ADEKA Stab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP; KAMISTAB29, 62, 77, 94 from Chemipro Chemical; Tinuvin111FDL, 123, 144, 249, 292, 5100 from BASF Japan; and SiaSove UV-3346, UV-3529, UV-3853 from Sun Chemical.

[0210] Phosphorus-based antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12~C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, and tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphite. Phosphosphite, tris(tridecyl)phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl)phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylidenediphenolalkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl)phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Examples include phytes, 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-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)benzene, and ethylbis(2,4-di-t-butyl-6-methylphenyl) phosphate.

[0211] Examples of commercially available products include ADEKA's ADEKA Stub PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP; BASF Japan's IRGAFOS168; and Clariant Chemicals' Hostanox P-EPQ.

[0212] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0213] Examples of commercially available products include ADEKA's ADEKA stub AO-412S and AO-503, and KEMINOXPLS from Chemipro Chemical Co., Ltd.

[0214] Antioxidants (M) can be used alone or in combination of two or more types.

[0215] The antioxidant (M) content is preferably 0.5 to 5.0% by mass of 100% by mass of the non-volatile content of the photosensitive composition. An appropriate amount improves transmittance, spectral characteristics, and sensitivity.

[0216] [Leveling agent (N)] The photosensitive composition of the present invention may contain a leveling agent (N). This further improves the wettability and drying properties to the substrate during coating. Examples of leveling agents (N) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0217] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0218] 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, 378, 3455, UV3510, 3570 from Bic Chemie, FZ-7002, 2110, 2122, 2123, 2191, 5609 from Toray Dow Corning, and X-22-4952, X-22-4272, X-22- from Shin-Etsu Chemical Co., Ltd. Examples include the 6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341.

[0219] Examples of fluorinated surfactants include surfactants or leveling agents having fluorocarbon chains.

[0220] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, as well as R-40-LM, R-41, RS-72-K, and DS-21 from DIC; FC-4430 and 4432 from Sumitomo 3M; EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals; and Futergent 602A from Neos.

[0221] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0222] Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, and 2020G-H. A, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, Examples include 704, 913R, and (meth)acrylic acid-based (co)polymers Polyflow-No. 75, No. 90, and No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0223] Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0224] Examples of commercially available products include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate, all manufactured by Kao Corporation.

[0225] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0226] Examples of commercially available products include Neos's Futergent 100 and 150, and ADEKA's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, and EC-8600.

[0227] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0228] Examples of commercially available products include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N, manufactured by Kao Corporation.

[0229] Leveling agent (N) can be used alone or in combination of two or more types.

[0230] The leveling agent (N) content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition. Including an appropriate amount further improves the balance between the coating properties and adhesion of the photosensitive composition.

[0231] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O). This stabilizes the viscosity of the photosensitive composition over time. Examples of storage stabilizers (O) include benzyltrimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphates.

[0232] The storage stabilizer (O) content is preferably 0.1 to 10 parts by mass per 100 parts by mass of near-infrared absorbing dye (A).

[0233] [Adhesion enhancer (P)] The photosensitive composition of the present invention may contain an adhesion enhancer (P). This improves the adhesion between the cured film and the substrate. Furthermore, it facilitates the formation of narrow patterns using photolithography. ru.

[0234] Adhesion enhancer (P) is, for example, a silane coupling agent. Examples of silane coupling agents include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and N-2-(aminoethyl) Silane coupling agents include aminosilanes such as -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane.

[0235] Adhesion enhancers (P) can be used alone or in combination of two or more types.

[0236] The content of the adhesion enhancer (P) is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the near-infrared absorbing dye (A).

[0237] [Organic solvent (Q)] The photosensitive composition of the present invention may contain an organic solvent (Q).

[0238] 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, 3-ethyl ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-methoxybutanol, 3-methoxybutylacetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-k Silene, o-chlorotolene, o-diethylbenzene, o-dichlorobenzene, p-chlorotolene, 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 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 Examples include 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, and dibasic acid esters. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0239] Organic solvent (Q) can be used alone or in combination of two or more types.

[0240] [Method for producing a photosensitive composition] The photosensitive composition of the present invention can be produced by manufacturing a dispersion by adding, for example, a near-infrared absorbing dye (A), a dispersion resin (G), and an organic solvent (Q) and performing a dispersion treatment. Subsequently, an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D) can be added to the dispersion and mixed. The timing of adding each material is arbitrary. Furthermore, the dispersion process can be performed multiple times.

[0241] Distributed processing machines include, for example, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0242] The average dispersed particle size (secondary particle size) of the near-infrared absorbing dye (A) in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

[0243] The method for measuring the average dispersed particle diameter (secondary particle diameter) is, for example, to use Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power-spectrum method), with particle permeability set to absorption mode, particle shape to non-spherical, and D50 particle diameter as the average diameter. The diluent solvent for measurement is the same organic solvent used for dispersion, and it is preferable to measure immediately after sample preparation of ultrasonically treated samples to obtain results with less variation.

[0244] The photosensitive composition is preferably subjected to centrifugation, sintering filter filtration or membrane filter filtration to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, more preferably 0.5 μm or larger, and any mixed dust. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0245] <Cured film> The cured film of the present invention is obtained by curing a film formed using the photosensitive composition of the present invention through a process such as exposure.

[0246] [Method for manufacturing hardened film] The method for manufacturing a cured film is not particularly limited, and for example, it can be manufactured by a step of applying a photosensitive composition to a substrate to form a layer of the composition (1), exposing the layer in a patterned manner through a mask (2), alkaline developing the unexposed areas to form a patterned cured film (3), and heat-treating the pattern (post-bake) (4).

[0247] The method for manufacturing the cured film will be described in detail below. (Process (1)) Step (1) of forming a layer of composition involves applying the photosensitive composition onto a substrate by methods such as rotary coating, roll coating, slit coating, casting coating, or inkjet coating, and then drying (pre-baking) it at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, hot plate, etc., if necessary. Examples of the substrate include glass substrates and silicon substrates. For example, an image sensor such as a CCD or CMOS may be formed on the surface of the silicon substrate. In addition, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface. The layer thickness is preferably 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5 μm.

[0248] (Process (2)) In the exposure process, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. This results in a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

[0249] (Step (3)) The cured film obtained in step (2) is subjected to alkaline development, which causes the unexposed portion of the composition to dissolve in the alkaline aqueous solution, leaving only the cured portion and resulting in a patterned cured film. Examples of developing solutions include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrol, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The developer concentration is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11-13, and more preferably 11.5-12.5. Using a moderate pH suppresses pattern roughness and peeling, and improves the residual film rate after development.

[0250] Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0251] (Step (4)) The heat treatment (post-bake) is used to fully harden the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 100 to 300°C, and more preferably 150 to 250°C. The heating time is preferably 2 minutes to 1 hour, and more preferably 3 minutes to 30 minutes.

[0252] <Optical filters> The cured film of the present invention can be used in optical filters. In particular, it can be preferably used as an infrared cut filter. It can also be used as an infrared transmittance filter. The optical filter of the present invention can be manufactured in the same manner as the cured film described above.

[0253] <Image display device> The cured film of the present invention can be used in an image display device. The form in which it is used in an image display device is not particularly limited, but it can be used as a color filter or a black matrix. Examples of black matrices include black borders provided around the periphery of image display devices such as solid-state image sensors and liquid crystal displays, grid-like and / or striped black areas between red, blue, and green pixels, and dot-like and / or linear black patterns for light shielding of TFTs.

[0254] An example of the image display device of the present invention will be described. The image display device comprises the cured film of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs, but in the present invention, it is preferable to use a white LED because it expands the red color reproduction range. Figure 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 Figure 1 comprises a pair of transparent substrates 11 and 21 arranged spaced apart and facing each other, with liquid crystal LC sealed between them.

[0255] 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 on top of it. An orientation layer 14 is provided on top of the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0256] 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).

[0257] A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0258] Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

[0259] Liquid crystal displays (LC) include TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated). The first transparent substrate 1 is oriented according to the driving mode, such as birefringence. A TFT (thin-film transistor) array 12 is formed on the inner surface of 1, and a transparent electrode layer 13 made of, for example, ITO is formed on top of it. An orientation layer 14 is provided on top of the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0260] 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).

[0261] A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0262] Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

[0263] White LED light sources include those with a fluorescent filter formed on the surface of a blue LED, and those with a phosphor contained in the resin package of a blue LED. They have a wavelength (λ3) in which the emission intensity is maximum in the range of 430nm to 485nm, a wavelength (λ4) in which the emission intensity is maximum in the range of 530nm to 580nm, and a wavelength (λ5) in which the emission intensity is maximum in the range of 600nm to 650nm, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 (I4 / I3) is between 0.2 and 0.4. Preferably, a white LED light source (LED1) has spectral characteristics in which the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3) is 0.1 or more and 1.3 or less, or a white LED light source (LED2) has spectral characteristics in which the wavelength (λ1) at which the emission intensity is maximum is in the range of 430 nm to 485 nm, the peak wavelength (λ2) of the second emission intensity is in the range of 530 nm to 580 nm, and the ratio of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 (I2 / I1) is 0.2 or more and 0.7 or less.

[0264] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0265] Examples of LED2 include the NSSW440 (manufactured by Nichia Corporation) and the NSSW304D (manufactured by Nichia Corporation).

[0266] <Solid-state image sensor> The cured film of the present invention can be used in solid-state image sensors. The form in which it is used in solid-state image sensors is not particularly limited, but for example, a substrate has a plurality of photodiodes that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, or organic CMOS image sensor, etc.), and a light-receiving element made of polysilicon or the like, and the cured film of the present invention is provided on the side of the light-receiving element formation surface or the opposite side of the formation surface. Figure 2 is a schematic cross-sectional view showing an example of the configuration of a solid-state image sensor equipped with the cured film of the present invention.

[0267] As shown in Figure 2, the solid-state imaging device 200 comprises a rectangular solid-state image sensor 201 and a transparent cover glass 203 held above the solid-state image sensor 201 and sealing the solid-state image sensor 201. Furthermore, a lens layer 211 is superimposed on the cover glass 203 via a spacer 104. The lens layer 211 is composed of a support 213 and a lens material 212. When stray light is incident on the peripheral region of the lens layer 211, the light diffusion weakens the light-gathering effect of the lens material 212, reducing the amount of light reaching the imaging unit 202. In addition, noise due to stray light occurs. For this reason, the peripheral region of the lens layer 211 is provided with the hardened film 214 of the present invention to shield it from light.

[0268] The solid-state image sensor 201 converts the optical image formed on its light-receiving surface, the imaging unit 202, into an image signal. This solid-state image sensor 201 includes a laminated substrate 205 made of two stacked substrates. The laminated substrate 205 consists of a rectangular chip substrate 206 and a circuit board 207 of the same size, with the circuit board 207 stacked on the back surface of the chip substrate 206.

[0269] An imaging unit 202 is provided in the center of the surface of the chip substrate 206. Furthermore, when stray light is incident on the peripheral region of the imaging unit 202, dark current (noise) is generated from the circuit in this peripheral region. Therefore, this peripheral region is shielded from light by being provided with the cured film (light-shielding) 215 of the present invention.

[0270] Multiple electrode pads 208 are provided on the surface edge of the chip substrate 206. The electrode pads 208 are electrically connected to the imaging unit 202 via signal lines (not shown) provided on the surface of the chip substrate 206.

[0271] On the back surface of the circuit board 207, external connection terminals 209 are provided approximately below each electrode pad 208. Each external connection terminal 209 is connected to the electrode pad 208 via a through-electrode 210 that penetrates the laminated substrate 205 vertically. Furthermore, each external connection terminal 209 is connected via wiring (not shown) to a control circuit that controls the driving of the solid-state image sensor 201, and to an image processing circuit that performs image processing on the imaging signal output from the solid-state image sensor 201.

[0272] <Infrared sensor> The cured film of the present invention can be used in infrared sensors. Figure 3 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with the cured film of the present invention. The infrared sensor shown in Figure 3 comprises a 300 and a solid-state image sensor 310.

[0273] The imaging area on the solid-state image sensor 310 is formed by combining an infrared cut filter 311 and a color filter 312. The infrared cut filter 311 transmits light in the visible light region (for example, light with a wavelength of 400-700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800-1300 nm). The color filter 312 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used.

[0274] Between the infrared transmission filter 313 and the solid-state image sensor 310, a resin film 314 is placed that can transmit light of wavelengths that have 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 near-infrared absorbing dye (A) described above can be used. The infrared transmission filter 113 preferably shields light with wavelengths of 400 to 830 nm and transmits light with wavelengths of 900 to 1300 nm.

[0275] A microlens 315 is positioned on the incident light side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed to cover the microlens 315.

[0276] In the configuration shown in Figure 3, a resin film 314 is arranged, but an infrared transmission filter 313 may be formed instead of the resin film 314.

[0277] The cured film of the present invention can be used as a light-shielding film on the edges and / or sides of the surface of the infrared cut filter 311, and when used on the inner wall of an infrared sensor, it can prevent internal reflection and / or the incidence of unintended light on the light-receiving part, thereby improving sensitivity.

[0278] This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can also be used as a biometric authentication sensor.

[0279] 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 light incident on the TFT may cause the TFT to malfunction as a switching element, and a colored spacer is used to prevent this. A colored spacer can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.

[0280] Furthermore, the cured film of the present invention can also be used in applications such as micro-LEDs (Light Emitting Diodes) and micro-OLEDs (Organic Light Emitting Diodes). While not particularly limited, it is suitably used for optical filters and optical films used in micro-LEDs and micro-OLEDs, as well as for components that provide light-shielding and anti-reflective properties. Examples of micro-LEDs and micro-OLEDs are described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

[0281] Furthermore, the cured film of the present invention can also be used in applications such as quantum dot displays. While not particularly limited, it is suitably used for optical filters and optical films used in quantum dot displays, as well as for components that provide light-shielding and anti-reflective properties. [Examples]

[0282] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" refers to "parts by mass" and "%" refers to "percentage by mass". Furthermore, in this invention, non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 280°C for 30 minutes.

[0283] Prior to the examples, each measurement method will be described.

[0284] 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 are measured as follows.

[0285] (Average molecular weight of alkali-soluble resin and dispersion resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of alkali-soluble resins and dispersed resins were measured by gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. Molecular weights are expressed on a polystyrene basis.

[0286] (Acid value of alkali-soluble resins and dispersion resins) 0.5 to 1 g of alkali-soluble resin and dispersion resin solution were mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g). The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

[0287] (Amine value of dispersed resin) The amine value of the dispersion resin is calculated by converting the total amine value (mgKOH / g), which was measured according to the ASTM D 2074 method, into a non-volatile content value.

[0288] (Glass transition temperature) The glass transition temperature of alkali-soluble resins was measured using a differential scanning thermal analyzer. 5 mg of the sample was weighed into a sample pan and heated from -20 to 200°C at a heating rate of 10°C / min under a nitrogen atmosphere.

[0289] <Manufacturing of near-infrared absorbing dye (A)> (Near-infrared absorbing dye (A-1)) 400 parts toluene, 40.0 parts 1,8-diaminonaphthalene, 32.2 parts 3,5-dimethylcyclohexanone, and 0.087 parts p-toluenesulfonic acid monohydrate were mixed and heated and stirred under a nitrogen atmosphere for 3 hours under reflux. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was complete, the toluene was distilled to obtain a dark brown solid, which was extracted with acetone and purified by recrystallization in a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts toluene and 160 parts n-butanol, and 13.8 parts 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was refluxed under a nitrogen atmosphere. The mixture was heated and stirred in an atmosphere and carried out under reflux for 8 hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was complete, the solvent was distilled, and 200 parts of hexane were added to the resulting reaction mixture while stirring. The resulting dark brown precipitate was filtered off, and then washed sequentially with hexane, ethanol, and acetone. The mixture was dried under reduced pressure to obtain the near-infrared absorbing dye (A-1) represented by the following chemical formula (17). 50 parts of the obtained near-infrared absorbing dye (A-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried overnight at 80°C and then pulverized to obtain finely ground near-infrared absorbing dye (A-1).

[0290] Chemical formula (17) [ka]

[0291] (Near-infrared absorbing dye (A-2)) 400 parts toluene, 40.0 parts 1,8-diaminonaphthalene, 50.1 parts 2-hydroxy-9-fluorenone, and 0.087 parts p-toluenesulfonic acid monohydrate were mixed and heated and stirred under a nitrogen atmosphere under reflux for 3 hours. Water produced during the reaction was removed from the system by azeotropic distillation. After the reaction was complete, the toluene was distilled to obtain a dark brown solid, which was extracted with acetone and purified by recrystallization in a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts toluene and 160 parts n-butanol, and 13.8 parts 3,4-dihydroxy-3-cyclobutene-1,2-dione was added under a nitrogen atmosphere. The mixture was heated and stirred, and the reflux reaction was carried out for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After the reaction was complete, the solvent was distilled, and 200 parts of hexane were added to the resulting reaction mixture while stirring. After filtering off the resulting dark brown precipitate, hexane, ethanol and The material was washed with acetone and dried under reduced pressure to obtain a near-infrared absorbing dye (A-2) represented by the following chemical formula (18). Near-infrared absorbing dye (A-1) was modified in the same manner to obtain a miniaturized near-infrared absorbing dye (A-2).

[0292] Chemical formula (18) [ka]

[0293] (Near-infrared absorbing dye (A-3)) In a reaction vessel, 890 parts n-amyl alcohol, 137 parts DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), 178 parts 2,3-dicyanonaphthalene, and 40 parts anhydrous aluminum chloride were mixed and stirred, and after heating, the mixture was refluxed at 136°C for 5 hours. The reaction solution, which was cooled to 30°C while stirring, was poured into a mixed solvent consisting of 5000 parts methanol and 10000 parts water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts methanol and 4000 parts water, and dried to obtain the compound of the following chemical formula (19). 5 parts diphenyl phosphate was added to 200 parts N-methylpyrrolidone and thoroughly mixed, then heated to 50°C. 10 parts of the compound of chemical formula (19) below were gradually added to this solution, and the mixture was stirred at 90°C for 120 minutes. Then, 2000 parts of this reaction solution were added to water, and the resulting precipitate was filtered, washed with water, and dried to obtain the near-infrared absorbing dye (A-3) represented by chemical formula (20) below. Near-infrared absorbing dye (A-1) was modified in the same manner to obtain a miniaturized near-infrared absorbing dye (A-3).

[0294] [ka]

[0295] (Near-infrared absorbing dye (A-4)) In accordance with International Publication No. 2019 / 058882, a near-infrared absorbing dye (A-4) represented by the following chemical formula (21) was obtained. Near-infrared absorbing dye (A-1) was modified in the same manner to obtain a miniaturized near-infrared absorbing dye (A-4).

[0296] [ka] Chemical formula (21) JPEG0007852369000023.jpg6084

[0297] <Manufacturing of alkali-soluble resin (B)> (Alkali-soluble resin (B1-1) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet tube, and stirrer into a separable four-neck flask. 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) were placed in the vessel, and the vessel was heated to 120°C while nitrogen gas was injected into it. At the same temperature, a mixture of 5.2 parts of styrene (hereinafter, St), 35.5 parts of glycidyl methacrylate (hereinafter, GMA), 41.0 parts of dicyclopentanyl methacrylate (hereinafter, DCPMA), and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2.5 hours to carry out the polymerization reaction. Next, the flask was purged with air, and 17.0 parts of acrylic acid (hereinafter referred to as AA), 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added and the mixture was reacted at 120°C for 5 hours. This reacted the epoxy group of GMA with the carboxyl group of AA, introducing a polymerizable unsaturated group-containing monomer unit (b3) (hereinafter referred to as GMA+AA). Furthermore, 30.4 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) and 0.5 parts of triethylamine were added and the mixture was reacted at 120°C for 4 hours. This caused an esterification reaction between the hydroxyl group of GMA+AA and TPHA, introducing a polymerizable unsaturated group-containing monomer unit (b3) (hereinafter referred to as GMA+AA+TPHA) modified from fatty acid anhydride. Subsequently, PGMAc was added to achieve a non-volatile content of 20% to prepare an alkali-soluble resin (B1-1) solution.

[0298] (Alkali-soluble resins (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) were synthesized by changing the composition and amount to achieve the composition and mol% ratios shown in Table 1, and PGMAc was added to bring the non-volatile content to 20%.

[0299] [Table 1]

[0300] The MAA+GMA listed in Table 1 represents a polymerizable unsaturated group-containing monomer unit (b3) obtained by adding the epoxy group of glucidyl methacrylate to the carboxyl group of methacrylic acid (MAA), a monomer unit contained in alkali-soluble resins.

[0301] The Tg ranges for the alkali-soluble resins listed in Table 1 are as follows: A: 10℃ or more and 80℃ or less B: Above 80℃ and below 120℃ C: Above 120℃ and below 150℃ D: Below 10℃ or above 150℃

[0302] The range of double bond equivalents for the alkali-soluble resins listed in Table 1 is as follows: A: 200 or more and 700 or less B: Over 700 and under 800 C: Over 800 and under 1000 D: Less than 200 or more than 1000

[0303] <Production of polymerizable compound (C)> (Polymerizable compound (C-1) containing urethane bonds) In a five-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 parts of N,N-dimethylbenzylamine were charged. The temperature was raised to 70°C, and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After addition, the mixture was reacted at a temperature of 50-70°C for 8 hours, and the reaction was measured by infrared radiation at 2180 cm- 1 The disappearance of the absorption of the isocyanate was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50-60°C for 6 hours. The non-volatile content was adjusted to 50% by mass to obtain a polymerizable compound (C-1) solution having urethane bonds with an average of 9 polymerizable unsaturated groups.

[0304] <Manufacturing of coloring agent (F)> (Finely milled green pigment (F-1)) 100 parts of CI Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This mixture was added to 3,000 parts of warm water and stirred in a high-speed mixer for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight and then pulverized to obtain finely ground green pigment (F-1).

[0305] (Finely milled red pigment (F-2)) 100 parts of CI Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture was added to warm water and stirred in a high-speed mixer for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight and then pulverized to obtain finely ground red pigment (F-2).

[0306] (Finely milled blue pigment (F-3)) 100 parts of CIPigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. This mixture was added to 3,000 parts of warm water and stirred in a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing with water to remove salt and solvent, the mixture was dried at 80°C for 24 hours and then pulverized to obtain finely ground blue pigment (F-3).

[0307] (Finely milled yellow pigment (F-4)) 100 parts of CI Pigment Yellow 138, 800 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. 3000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to approximately 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight and then pulverized to obtain finely ground yellow pigment (F-4).

[0308] (Finely milled purple pigment (F-5)) 100 parts of CI Pigment Violet 23, 800 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. 3000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to approximately 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight and then pulverized to obtain finely milled purple pigment (F-5).

[0309] <Manufacturing of Dispersed Resin (G)> (Dispersion resin (G-1) solution) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 40 parts methyl methacrylate, 10 parts n-butyl methacrylate, and 13.2 parts tetramethylethylenediamine as catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate as initiator, 5.6 parts cuprous chloride as catalyst, and 100 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen atmosphere to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or higher based on the non-volatile content. Next, 50 parts PGMAc, 40 parts dimethylaminoethyl methacrylate and 10 parts methacryloyloxyethyl benzyldimethylammonium chloride as monomers for the second block (block A) were added to this reactor, and the reaction was continued by stirring while maintaining 110°C and a nitrogen atmosphere. Two hours after the start of the reaction, the polymerization solution was sampled and its non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution was cooled to room temperature to stop the polymerization. GPC measurement results showed that the polymer had a mass-average molecular weight of 20,000, a molecular weight distribution Mw / Mn of 1.4, and a reaction conversion rate of 98.5%. In this way, a dispersion resin (G-1) with an amine value of 169.8 mgKOH / g per non-volatile content was obtained. After cooling to room temperature, approximately 2 g was sampled and heated and dried at 180°C for 20 minutes, and the non-volatile content was measured. PGMAc was added to prepare a dispersion resin (G-1) solution so that the non-volatile content was 30% by mass.

[0310] (Dispersion resin (G-2) solution) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 30 parts methyl methacrylate, 30 parts n-butyl methacrylate, 20 parts hydroxyethyl methacrylate, and 13.2 parts tetramethylethylenediamine were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate, 5.6 parts cuprous chloride, and 133 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or higher. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-711MM) as the monomer for the second block (block A) were added to the reactor, and the reaction was continued while stirring at 110°C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution The solution was cooled to room temperature to stop polymerization. PGMAc was added to dilute the solution to a non-volatile content of 30%, obtaining a dispersed resin (G-2) solution with an amine value of 57 mgKOH / g per non-volatile content and a number-average molecular weight of 4,500 (Mn).

[0311] (Dispersion resin (G-3) solution) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc were charged and purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts 2,2'-azobisisobutyronitrile added to 90 parts PGMAc. Non-volatile content measurement confirmed that 95% had reacted. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value, the reaction was terminated. The solution was then diluted by adding PGMAc to achieve a non-volatile content of 30%, yielding a dispersion resin (G-3) solution with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0312] <Dispersion manufacturing> (Dispersion 1) After stirring and mixing the following raw materials until uniform, the mixture was dispersed for 3 hours using an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") with a 0.5 mm diameter zirconia bead, and then filtered through a 1.0 μm pore size filter to prepare dispersion 1. The organic solvent (Q-1) is PGMAc. Near-infrared absorbing dye (A-1): 15.0 parts Dispersion resin (G-1): 20.0 parts Organic solvent (Q-1): 65.0 parts

[0313] (Dispersion 2~9) Dispersions 2-9 were prepared in the same manner as dispersion 1, except that the raw materials and quantities listed in Table 2 were changed.

[0314] [Table 2]

[0315] <Manufacturing of photosensitive compositions> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and filtered through a 1.0 μm pore size filter to obtain photosensitive composition 1. Ta. 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 part Organic solvent (Q): 25.75 parts

[0316] [Examples 2-35, Comparative Examples 1-5] (Photosensitive composition 2-40) Photosensitive compositions 2 to 40 were prepared in the same manner as in Example 1, except that the raw materials and quantities of photosensitive composition 1 in Example 1 were changed to those listed in Tables 3-1 to 3-3. However, Examples 24, 26, and 27 are for reference only.

[0317] [Table 3-1]

[0318] [Table 3-2]

[0319] [Table 3-3]

[0320] [Table 3-4]

[0321] The raw materials listed in Tables 3-1 to 3-4 are as follows:

[0322] [Polymerizable compound (C)] C-1: Polymerizable compound having the urethane bond described above. C-2: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd., a lactone-modified polymerizable compound) C-3: Aronics M-521 (manufactured by Toagosei Co., Ltd., a polymerizable compound containing an acidic group) C-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) Equal amounts of (C-1) to (C-4) were mixed to obtain polymerizable compound (C).

[0323] [Photopolymerization initiator (D)] (Oxime-based 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: Photopolymerization initiator of the above chemical formula (14) D1-5: Photopolymerization initiator of the above chemical formula (15) D1-6: Photopolymerization initiator of the above chemical formula (16)

[0324] (Other photopolymerization initiators (D2)) D2-1: Omnirad 369 (manufactured by IGM Resins, acetophenone-based photopolymerization initiator) D2-2: Omnirad 907 (manufactured by IGM Resins, acetophenone-based photopolymerization initiator) D2-3: Omnirad TPO (manufactured by IGM Resins, an acylphosphine oxide-based photopolymerization initiator) D2-4: IRGACURE OXE-04 (BASF Japan, oxime-based photopolymerization initiator)

[0325] [Sensitizer (E)] (Thioxanthone compound (E1)) E1-1: 2,4-Diethylthioxanthone (Benzophenone compounds (E2)) E2-1: 4,4'-Bis(diethylamino)benzophenone

[0326] [Leveling agent (N)] N-1: BYK-330 (manufactured by Big Chemie Co., Ltd.) N-2: Megafuck F-551 (manufactured by DIC Corporation) The above preparation involved mixing (N-1) and (N-2) in 1 part each and dissolving them in 98 parts of PGMAc. The mixed solution was designated as the leveling agent (N).

[0327] [Organic solvent (Q)] Q-1: Propylene glycol monomethyl ether acetate 30 parts Q-2: Cyclohexanone 30 parts Q-3: 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-mentioned parts by mass to obtain organic solvent (Q).

[0328] <Evaluation of photosensitive compositions> The resulting photosensitive compositions 1 to 41 (Examples 1 to 36, Comparative Examples 1 to 5) were evaluated for their developability, Pattern formation and heat resistance were evaluated using the following methods. The evaluation results are shown in Table 4.

[0329] [Evaluation of developability] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Then, an illuminance of 30 mW / cm² was used with an ultra-high pressure mercury lamp.2 40 mJ / cm² 2 The substrate was then exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. After cooling the substrate to room temperature, it was spray-developed using 23°C organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for two development times (40 seconds and 70 seconds), washed with deionized water, and air-dried. The resulting substrate was post-baked in a clean oven at 230°C for 30 minutes to form a stripe pattern on the substrate. The pattern was observed with an optical microscope to evaluate the presence or absence of development residue and defects in unexposed areas. The evaluation criteria are as follows, with a score of 2 or higher indicating usability. 3. At a development time of 70 seconds, there was no development residue in the unexposed areas and no pattern defects. 2: At a development time of 70 seconds, development residue or pattern defects occurred in the unexposed areas. 1: At a development time of 40 seconds, development residue or pattern defects occurred in the unexposed areas.

[0330] [Pattern formation evaluation (1): Adhesion] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. After cooling the substrate to room temperature, it was illuminated at 30 mW / cm² using a high-pressure mercury lamp through a photomask with a 5 μm wide stripe pattern. 2 40 mJ / cm² 2 The substrate was exposed to light. Subsequently, this substrate was spray-developed using the organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with deionized water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain a substrate for adhesion evaluation. Spray development was performed for the shortest possible time that allowed for pattern formation without any remaining development on the film of each photosensitive composition, and this was defined as the appropriate development time. Fine line patterns with a width of 5 to 25 μm on the substrate used for adhesion evaluation were observed with an optical microscope to confirm the minimum line width of the remaining fine line patterns. The evaluation criteria are as follows, with a score of 3 or higher indicating practical usability. 5: Fine lines smaller than 10 μm remain. 4: Fine lines smaller than 15 μm remain. 3: Fine lines smaller than 20 μm remain. 2: Fine lines smaller than 25 μm remain. 1: No thin lines remain.

[0331] [Pattern formation evaluation (2): Linearity] The substrates created in Pattern Formation Evaluation (1) were evaluated using a Nikon ECLIPSE LV100POL Model optical microscope by measuring the maximum and minimum line widths of 10 stripe patterns and calculating the average. The evaluation criteria are as follows, with a score of 3 or higher indicating practical usability. 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 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.

[0332] [Heat resistance evaluation] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 1.0 μm, and dried on a hot plate at 70°C for 1 minute. After the substrate cooled to room temperature, it was illuminated using a high-pressure mercury lamp at an illuminance of 30 mW / cm². 2 40 mJ / cm² 2 The substrate was exposed to light to obtain a substrate for heat resistance evaluation. The absorbance of the obtained heat-resistant evaluation substrate was measured at an incident angle of 0°C at the maximum absorption wavelength using a spectrophotometer (Hitachi High-Technologies Corporation U-4100), and this was used as the initial value. Subsequently, the heat resistance evaluation substrate was heated to 210°C for 20 minutes, cooled, and its absorbance was measured again. This value was taken as the value after the heat resistance test. Heat resistance was calculated using the following formula. The evaluation criteria are as follows, with a value of 3 or higher indicating practical usability. Survival rate = (Absorbance after heat resistance test) ÷ (Initial absorbance) × 100 5: Survival rate of 97% or higher 4: Survival rate is 95% or more but less than 97% 3: Survival rate is 93% or more but less than 95% 2: Survival rate is 90% or more but less than 93% 1: Survival rate less than 90%

[0333] [Table 4] [Explanation of Symbols]

[0334] 10 Image display device 11 Transparent substrate 12 TFT arrays 13 Transparent electrode layer 14. Orientation layer 15 Polarizing plates 21 Transparent substrate 22 Color Filters 23 Transparent electrode layer 24 orientation layer 25 Polarizing plates 30 backlight units 31 White LED light source LC LCD 200 Solid State Imaging Devices 201 Solid-state image sensor 202 Imaging Department 203 Cover glass 204 Spacer 205 Multilayer substrate 206 Chip board 207 Circuit board 208 Electrode Pads 209 External connection terminals 210 Through electrode 211 Lens layer 212 Lens material 213 Support 214 Cured film 215 Cured film 300 Infrared Sensors 310 Solid-state image sensor 311 Infrared Cut Filter 312 Color Filters 313 Infrared transmission filter 314 Resin film 315 Microlens 316 Flat membrane

Claims

1. 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) comprises an alkali-soluble resin (B1) having a glass transition temperature of 10 to 150°C. The alkali-soluble resin (B1) is a (meth)acrylic resin and contains alicyclic hydrocarbon-containing monomer units (b1) whose homopolymer glass transition temperature is 80°C or higher and aromatic ring-containing monomer units (b2) whose homopolymer glass transition temperature is 80°C or higher. The photosensitive composition comprises a photopolymerization initiator (D1) represented by the following general formula (1), wherein the photopolymerization initiator (D) is (D1). General formula (1) 【Chemistry 1】 (In general formula (1), R １ This represents a methyl group or an ethyl group. R ２ This represents an alkyl group with 3 to 8 carbon atoms. R ３ This represents a branched alkyl group or hexyl group having 5 to 12 carbon atoms. R ４ This represents a nitro group or a benzoyl group which may have a substituent. n represents 1.

2. The photosensitive composition according to claim 1, wherein the total content of the alicyclic hydrocarbon-containing monomer unit (b1) and the aromatic ring-containing monomer unit (b2) is 10 to 70 mol% of the total constituent units of the alkali-soluble resin (B1).

3. The photosensitive composition according to claim 1 or 2, 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.

4. The photosensitive composition according to claim 1 or 2, wherein the alkali-soluble resin (B1) contains polymerizable unsaturated group-containing monomer units (b3).

5. The photosensitive composition according to claim 1 or 2, wherein the photopolymerization initiator (D) further comprises a photopolymerization initiator (D2) other than the photopolymerization initiator (D1) represented by general formula (1).

6. The photosensitive composition according to claim 5, wherein the photopolymerization initiator (D2) comprises one or more selected from the group consisting of acetophenone-based photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime-based photopolymerization initiators (excluding the photopolymerization initiator (D1) represented by general formula (1)).

7. Furthermore, the photosensitive composition according to claim 1 or 2, further comprising a sensitizer (E).

8. The photosensitive composition according to claim 7, wherein the content of the sensitizer (E) is 150 to 400 parts by mass per 100 parts by mass of the photopolymerization initiator (D).

9. Furthermore, the photosensitive composition according to claim 1 or 2, further comprising a coloring agent (F).

10. A cured film obtained by curing the photosensitive composition according to claim 1 or 2.

11. An optical filter having the cured film described in claim 10.

12. An image display device having a cured film according to claim 10.

13. A solid-state image sensor having the cured film described in claim 10.

14. An infrared sensor having a cured film as described in claim 10.

Images