Compound, latent base generator, photosensitive resin composition containing the compound and cured product

Abstract

The object of the present invention is to provide a novel compound that exhibits sufficient absorption of long-wavelength ultraviolet light (particularly 365 nm) and has satisfactory sensitivity (base generating ability), a latent base generator containing the compound, a photosensitive resin composition containing the compound as a polymerization initiator, and a cured product thereof. The present invention provides a compound represented by the following general formula (I). Furthermore, the present invention provides a latent base generator containing the compound, a polymerization initiator containing the compound, a photosensitive resin composition containing the polymerization initiator (A) and a photosensitive resin (B), and a cured product thereof and a method for producing the same. (Refer to the specification for the definitions of the symbols in the formula.)

Description

Technical Field

[0001] The present invention relates to a novel compound useful as a polymerization initiator used in a photosensitive resin composition, a latent base generator containing the compound, a photosensitive resin composition containing the compound in a photosensitive resin, and a cured product of the photosensitive resin composition. Background Art

[0002] Generally, a photosensitive resin composition is a composition obtained by adding a photopolymerization initiator to a photosensitive resin. It can be polymerized or developed by irradiation with energy rays (light) and is therefore used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, and the like.

[0003] Photopolymerization initiators are classified into photoradical generators, photoacid generators, and photobase generators according to the different active species generated by irradiation with energy rays (light). Photoradical generators have the advantages of fast curing speed and no residual active species after curing. On the other hand, they have the disadvantage that a layer that blocks oxygen must be provided during the curing of the film because of the occurrence of curing hindrance caused by oxygen. Photoacid generators have the advantage of not being hindered by oxygen. On the other hand, they have the disadvantages of corroding the metal substrate or modifying the cured resin due to the acid of the residual active species. Photobase generators have attracted attention because they are not prone to the above-mentioned problems of curing hindrance caused by oxygen and corrosion caused by residual active species. However, they generally have the problem of low sensitivity (low curability) compared to photoacid generators. Photobase generators are disclosed, for example, in Patent Documents 1 to 4.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent document 1: US6551761

[0007] Patent document 2: US8957212

[0008] Patent Document 3: WO2010 / 064632

[0009] Patent document 4: US9594302 Summary of the invention

[0010] Therefore, the object of the present invention is to provide a new compound that shows sufficient absorption of long-wavelength ultraviolet rays (especially 365 nm) and has satisfactory sensitivity (base generating ability), a latent base generator containing the compound, a photosensitive resin composition containing the compound as a polymerization initiator, and its cured product.

[0011] The present inventors have conducted intensive studies and have found that a compound having a specific structure has high sensitivity (base generating ability) as a polymerization initiator.

[0012] The present invention achieves the above-mentioned object by providing the following [1] to [9].

[0013] [1] A compound represented by the following general formula (I).

[0014] [Chemistry 1]

[0015]

[0016] (Where R 1 represents a hydrogen atom, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

[0017] R 2 , R 4 , R 5 , R 6 and R 7 Each independently represents a hydrogen atom, a cyano group, a nitro group, -OR 8 、-COOR 8 、-CO-R 8 、-SR 8 , a halogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms,

[0018] R 3 represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted or substituted group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0019] R 8 represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted or substituted group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0020] X 1 For-NR 11 R 12 , a group represented by the following (a) or the following (b),

[0021] R 11 and R 12are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

[0022] Or, R 11 and R 12 are linked to each other to form a ring having 1 to 20 carbon atoms and consisting of hydrogen atoms, nitrogen atoms and carbon atoms which is unsubstituted or has a substituent, or a ring having 1 to 20 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms which is unsubstituted or has a substituent,

[0023] n represents 0 or 1. )

[0024] [Chemistry 2]

[0025]

[0026] (Where R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

[0027] Or, R 13 With R 14 , R 15 With R 16 , R 17 With R 18 , R 19 With R 20 and R 21 With R 22 At least one of the groups is linked to each other to form a ring having 1 to 20 carbon atoms and composed of hydrogen atoms, nitrogen atoms and carbon atoms which is unsubstituted or substituted, or a ring having 1 to 20 carbon atoms and composed of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms which is unsubstituted or substituted,

[0028] * indicates a bonding end. )

[0029] [2] The compound described in [1] above, wherein R in the general formula (I) 2 , R 3 , R 4 , R 5 , R 6 and R 7At least one of the groups is a group having a nitro group, a benzoyl group or an o-methylbenzoyl group as a substituent.

[0030] [3] The compound described in [1] or [2] above, wherein R in the general formula (I) is 2 , R 3 , R 4 , R 5 , R 6 and R 7 At least one of them is a group represented by the following general formula (II).

[0031] [Chemistry 3]

[0032]

[0033] (Where R 25 , R 26 , R 27 , R 28 and R 29 Each independently represents a hydrogen atom, a cyano group, a nitro group, -OR 30 、-COOR 30 、-CO-R 30 、-SR 30 , a halogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic ring-containing, unsubstituted or substituted group having 2 to 20 carbon atoms, or a group represented by the following general formula (III),

[0034] R 30 represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted or substituted group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0035] R 25 , R 26 , R 27 , R 28 and R 29 At least one of them represents a nitro group, -CO-R 30 or a group represented by the following general formula (III),

[0036] * indicates a bonding end. )

[0037] [Chemistry 4]

[0038]

[0039] (Where R 31represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

[0040] X 2 For-NR 32 R 33 , a group represented by (a') or (b') below,

[0041] R 32 and R 33 are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

[0042] Or, R 32 and R 33 are linked to each other to form a ring having 1 to 20 carbon atoms and consisting of hydrogen atoms, nitrogen atoms and carbon atoms which is unsubstituted or has a substituent, or a ring having 1 to 20 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms which is unsubstituted or has a substituent,

[0043] m represents 0 or 1, and * represents a bonding end. )

[0044] [Chemistry 5]

[0045]

[0046] (Where R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and R 43 are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

[0047] Or, R 34 With R 35 , R 36 With R 37 , R 38 With R 39 , R 40 With R 41 and R 42 With R 43At least one of the groups is linked to each other to form a ring having 1 to 20 carbon atoms and composed of hydrogen atoms, nitrogen atoms and carbon atoms which is unsubstituted or substituted, or a ring having 1 to 20 carbon atoms and composed of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms which is unsubstituted or substituted,

[0048] * indicates a bonding end. )

[0049] [4] A latent base generator comprising the compound according to any one of [1] to [3].

[0050] [5] A polymerization initiator comprising the compound according to any one of [1] to [3].

[0051] [6] A photosensitive resin composition comprising the polymerization initiator (A) according to [5] and a photosensitive resin (B).

[0052] [7] The photosensitive resin composition according to [6], wherein the photosensitive resin (B) is an epoxy resin or a phenolic resin.

[0053] [8] A cured product obtained from the photosensitive resin composition according to [6] or [7].

[0054] [9] A method for producing a cured product, comprising the step of irradiating the photosensitive resin composition according to [6] or [7] with energy rays. DETAILED DESCRIPTION

[0055] Hereinafter, preferred embodiments of the present invention will be described in detail.

[0056] The novel compound of the present invention is a carbamoyl oxime compound represented by the above general formula (I). The carbamoyl oxime compound has geometrical isomers based on the double bond of the oxime, but the above general formula (I) does not distinguish between them.

[0057] That is, in the present specification, the compound represented by the above general formula (I), and the compounds of preferred embodiments of the compound and exemplary compounds described below represent a mixture or any one of geometric isomers, and are not limited to the structural isomers shown.

[0058] In addition, R in the general formula (I) 1 ~R 8 , R 11 ~R 22 When a methylene group in the groups shown is substituted with a group containing a carbon atom, the number of carbon atoms including the number of carbon atoms in these groups becomes the specified number of carbon atoms.

[0059] As R in the above general formula (I) 1 ~R 8 , R 11~R 22 The unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and the like. In addition, R 1 ~R 8 , R 11 ~R 22 The methylene groups in these aliphatic hydrocarbon groups may be substituted with -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO2-, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'-, wherein these substituted divalent groups are not adjacent.

[0060] R and R' are unsubstituted aliphatic hydrocarbon groups. Examples of the unsubstituted aliphatic hydrocarbon group include the same as those mentioned above for R 1 ~R 8 , R 11 ~R 22 The groups exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same groups as those exemplified above.

[0061] As R in the above general formula (I) 1 ~R 8 , R 11 ~R 22 The unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms represented by , includes phenyl, naphthyl, phenanthrenyl, pyrenyl and biphenyl, and phenyl, naphthyl, phenanthrenyl, pyrenyl and biphenyl substituted with an aliphatic hydrocarbon group. 1 ~R 8 , R 11 ~R 22 Preferably, the alkylene moiety in these aromatic hydrocarbon groups or the methylene group at the bonding portion between the aromatic ring and the aliphatic hydrocarbon group is substituted by -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO2-, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'-. However, these substituted divalent groups are not adjacent.

[0062] Examples of the aliphatic hydrocarbon group include the following: 1 ~R 8 , R 11 ~R 22The groups exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same groups as those exemplified above.

[0063] R and R' are unsubstituted aliphatic hydrocarbon groups. Examples of the unsubstituted aliphatic hydrocarbon group include the same as those mentioned above for R 1 ~R 8 , R 11 ~R 22 The groups exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same groups as those exemplified above.

[0064] As R 1 ~R 8 , R 11 ~R 22 The aliphatic hydrocarbon group having 1 to 20 carbon atoms and R 1 ~R 8 , R 11 ~R 22 The aromatic hydrocarbon group having 6 to 20 carbon atoms and having a substituent shown may include a group in which the unsubstituted hydrogen atom described above is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO2H.

[0065] As R 11 With R 12 , R 13 With R 14 , R 15 With R 16 , R 17 With R 18 , R 19 With R 20 and R 21 With R 22 , and R 32 With R 33 , R 34 With R 35 , R 36 With R 37 , R 38 With R 39 , R 40 With R 41 and R 42 With R 43 A ring consisting of hydrogen atoms, nitrogen atoms and carbon atoms having 1 to 20 carbon atoms is formed by at least one group of which are linked to each other. As the group containing the bonded nitrogen atom, there can be mentioned pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, piperazinyl and the like. The hydrogen atoms in these rings may be substituted by fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, hydroxyl groups, thiol groups, -COOH, -SO2H or aliphatic hydrocarbon groups.

[0066] Examples of the aliphatic hydrocarbon group include the following: 1 ~R 8 , R 11 ~R 22 The groups exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same groups as those exemplified above.

[0067] As R 11 With R 12 , R 13 With R 14 , R 15 With R 16 , R 17 With R 18 , R 19 With R 20 and R 21 With R 22 , and R 32 With R 33 , R 34 With R 35 , R 36 With R 37 , R 38 With R 39 , R 40 With R 41 and R 42 With R 43 A ring composed of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms having 1 to 20 carbon atoms formed by at least one group of which are linked to each other. As the group containing the bonded nitrogen atom, there can be mentioned morpholinyl, oxazolyl, oxazolinyl, oxadiazolyl and the like. The hydrogen atoms in these rings may be substituted by fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, hydroxyl groups, thiol groups, -COOH, -SO2H or aliphatic hydrocarbon groups.

[0068] Examples of the aliphatic hydrocarbon group include the following: 1 ~R 8 , R 11 ~R 22 The groups exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same groups as those exemplified above.

[0069] As R in the above general formula (I) 2 ~R 8The unsubstituted heterocyclic group having 2 to 20 carbon atoms represented by , includes tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, morpholinylfuranyl, thienyl, methylthienyl, hexylthienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl and piperazinyl, and tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, morpholinylfuranyl, thienyl, methylthienyl, hexylthienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, pyrazolyl, pyrazolidinyl, piperidinyl and piperazinyl substituted with an aliphatic hydrocarbon group. In addition, R 2 ~R 8 The alkylene part and the methylene group of the bonding part between the heterocycle and the alkyl group in these heterocycle-containing groups may be substituted by -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO2-, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'-. However, these substituted divalent groups are not adjacent.

[0070] In the present specification, "2 to 20" in "a heterocyclic group having 2 to 20 carbon atoms" does not mean the number of carbon atoms in the "heterocyclic ring" but defines the number of carbon atoms in the "heterocyclic ring-containing group".

[0071] Examples of the aliphatic hydrocarbon group include the above-mentioned R 1 ~R 8 , R 11 ~R 22 The groups are exemplified by unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms.

[0072] R and R' are unsubstituted aliphatic hydrocarbon groups. Examples of the unsubstituted aliphatic hydrocarbon group include the same as those mentioned above for R 1 ~R 8 , R 11 ~R 22 The groups exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same groups as those exemplified above.

[0073] As R 2 ~R 8 The heterocyclic group having 2 to 20 carbon atoms with a substituent shown in the above description may include a group in which the hydrogen atom of the unsubstituted heterocyclic group described above is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO2H. It should be noted that when the substituted group contains carbon atoms and when it has a substituent, the number of carbon atoms including them becomes the specified number of carbon atoms.

[0074] When the novel compound represented by the general formula (I) is used in a photosensitive resin composition, X 1 For-NR 11 R 12 The group shown is preferably R 11 or R 12 A compound in which R is phenyl 11 and R 12 A compound in which R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms 11 and R 12 A compound in which hydrogen atoms, nitrogen atoms and carbon atoms are linked to each other to form a ring having 1 to 20 carbon atoms, or R 11 and R 12 A compound in which hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms are linked to each other to form a ring having 1 to 20 carbon atoms.

[0075] In addition, R is preferred from the viewpoints of excellent UV sensitivity, longer absorption wavelength, and excellent solubility in resin. 2 , R 3 , R 4 , R 5 , R 6 and R 7 At least one of them is a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a thiol group, or a group having these groups as a substituent, and more preferably R 2 , R 3 , R 4 , R 5 , R 6 and R 7 A compound in which at least one of the groups is a nitro group or a group having a nitro group as a substituent, and R 3 The compound is a group having a nitro group as a substituent. As the group having a nitro group as a substituent, nitrophenyl is preferred.

[0076] Furthermore, when used as a polymerization initiator, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 At least one of them is benzoyl, o-methylbenzoyl or trifluoromethyl, or is a compound having these groups as substituents, and R is particularly preferred. 3 The compound is a group having a benzoyl group as a substituent. As the group having a benzoyl group as a substituent, benzoylphenyl is preferred.

[0077] In the above general formula (I), R2 , R 3 , R 4 , R 5 , R 6 and R 7 The compound in which at least one of the groups is a group having a nitro group, a benzoyl group or an o-methylbenzoyl group as a substituent has a longer absorption wavelength region (365 nm) and is preferred because it has excellent sensitivity when used as a polymerization initiator.

[0078] In the present invention, the following compounds are preferred because they are excellent in UV sensitivity and curability when used in a photosensitive resin composition and excellent in sensitivity when used as a polymerization initiator.

[0079] In the above general formula (I), R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R 2 , R 4 , R 5 , R 6 and R 7 is a hydrogen atom, X 1 For-NR 11 R 12 The group shown, and R 11 and R 12 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or R 11 and R 12 are linked to each other to form a ring having 1 to 20 carbon atoms consisting of hydrogen atoms, nitrogen atoms and carbon atoms, or a ring having 1 to 20 carbon atoms consisting of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms, R 3 A compound having a nitro group or a benzoyl group as a substituent.

[0080] In the above general formula (I), R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The compound in which at least one of the groups is a group represented by the general formula (II) has a longer absorption wavelength region (365 nm) and is preferably excellent in sensitivity when used as a polymerization initiator.

[0081] In the general formula (II), R 25 ~R 43 The unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 20 carbon atoms shown in the formula (A) include the same as the above R 1 ~R 8 , R 11 ~R 22The groups exemplified as the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and the unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms are the same groups as those shown.

[0082] In the general formula (II), R 25 ~R 30 The unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms as represented by 2 ~R 8 The unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms shown are the same groups.

[0083] In the above general formula (I), R 2 , R 3 , R 4 , R 5 , R 6 and R 7 A compound in which one of the moieties is a group represented by the above general formula (II) and the others are a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 12 carbon atoms is preferred in terms of excellent sensitivity and ease of manufacture.

[0084] From the viewpoint of easy production, it is preferred that R in the above general formula (I) 1 A compound which is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0085] The compound wherein n is 0 in the general formula (I) is preferred because it has excellent sensitivity when used as a polymerization initiator.

[0086] The compound wherein n is 1 in the general formula (I) is preferred because a cured product having excellent transparency can be obtained when used as a polymerization initiator.

[0087] Specific examples of the novel compound represented by the general formula (I) above, wherein n is 0, include the following compounds No. 1 to No. 74. However, the present invention is not limited to the following compounds.

[0088] [Chemistry 6]

[0089]

[0090] [Chemistry 7]

[0091]

[0092] [Chemistry 8]

[0093]

[0094] [Chemistry 9]

[0095]

[0096] [Chemistry 10]

[0097]

[0098] [Chemistry 11]

[0099]

[0100] [Chemistry 12]

[0101]

[0102] [Chemistry 13]

[0103]

[0104] [Chemistry 14]

[0105]

[0106] Specific examples of the novel compound represented by the general formula (I) above, wherein n is 1, include the following compounds No. 75 to No. 152. However, the present invention is not limited to the following compounds.

[0107] [Chemistry 15]

[0108]

[0109] [Chemistry 16]

[0110]

[0111] [Chemistry 17]

[0112]

[0113] [Chemistry 18]

[0114]

[0115] [Chemistry 19]

[0116]

[0117] [Chemistry 20]

[0118]

[0119] [Chemistry 21]

[0120]

[0121] [Chemistry 22]

[0122]

[0123] [Chemistry 23]

[0124]

[0125] The carbamoyl oxime compound of the present invention represented by the above general formula (I) is not particularly limited, and when n=0, it can be produced according to the following reaction formula 1 by the following method.

[0126] That is, by reacting a known and commercially available indole compound 1 with a halogenated aryl or halogenated alkyl compound, an indole compound 2 is obtained. By reacting the indole compound 2 with an acid chloride to obtain a ketone compound, the ketone compound is reacted with hydroxylamine hydrochloride to obtain an oxime compound. Next, 4-nitrophenyl chloroformate and a primary or secondary amine are reacted with the oxime compound in the presence of triethylamine to obtain the carbamoyl oxime compound of the present invention represented by the above general formula (I).

[0127] It should be noted that in the following reaction formula 1, X 1 For-NR 11 R 12 However, by changing the amine used, X can also be produced. 1 A compound which is a group represented by the above (a) or (b).

[0128] Oxime compounds and carbamoyl oxime compounds can also be produced by the method described in Japanese Patent No. 4223071.

[0129] Reaction 1

[0130] [Chemistry 24]

[0131]

[0132] (Where R 1 ~R 12 Same as the above general formula (I).

[0133] The compound wherein n=1 in the general formula (I) is not particularly limited and can be produced according to the following reaction formula 2 by the following method.

[0134] That is, the indole compound 2 is reacted with an acid chloride to obtain a ketone compound 2, and the ketone compound is reacted with isobutyl nitrite to obtain an oxime compound 2. Next, 4-nitrophenyl chloroformate and a primary or secondary amine are reacted with the oxime compound 2 in the presence of triethylamine to obtain the carbamoyl oxime compound 2 of the present invention represented by the general formula (I).

[0135] It should be noted that in the following reaction formula 2, X 1 For-NR 11 R 12 However, by changing the amine used, X can also be produced. 1 A compound which is a group represented by the above (a) or (b).

[0136] Oxime compounds and carbamoyl oxime compounds can also be produced by the method described in Japanese Patent No. 4223071.

[0137] Reaction 2

[0138] [Chemistry 25]

[0139]

[0140] (Where R 1 ~R 12 Same as the above general formula (I).

[0141] The novel compound of the present invention is excellent in curability of photosensitive resins and has high sensitivity to energy rays, and can be suitably used as a polymerization initiator as a photobase generator described below, and can also be used in chemically amplified resists and the like.

[0142] Next, the polymerization initiator, latent base generator and photosensitive resin composition of the present invention are described. In addition, for the aspects not particularly described, the description in the novel compound of the present invention can be appropriately applied.

[0143] <Latent base generator>

[0144] The latent base generator of the present invention contains at least one compound represented by the general formula (I). The content of the compound represented by the general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass.

[0145] The latent base generator is a substance that generates a base by light or heat, and can be used as a polymerization initiator, a base catalyst, or a pH adjuster. In the present invention, a latent photobase generator that generates a base by light irradiation is more preferred because of its excellent operability.

[0146] <Polymerization Initiator (A)>

[0147] In the polymerization initiator and the photosensitive resin composition of the present invention, the polymerization initiator (A) contains at least one compound represented by the general formula (I). The content of the compound represented by the general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass.

[0148] In the photosensitive resin composition of the present invention, the content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the photosensitive resin (B). By making the content of the polymerization initiator (A) 1 part by mass or more, poor curing due to insufficient sensitivity can be easily prevented, so it is preferred, and by setting it to 20 parts by mass or less, volatiles can be suppressed during light irradiation or heating, so it is preferred.

[0149] <Photosensitive resin (B)>

[0150] The photosensitive resin (B) used in the present invention means a resin that uses an anionic polymerizable functional group or a base as a catalyst to lower the curing temperature. It is a photosensitive resin that is polymerized and cured by irradiating energy rays such as ultraviolet rays or a cured resin with a low curing temperature. The above-mentioned anionic polymerizable functional group refers to a functional group that can be polymerized using a base generated from a photobase generator by active energy rays such as ultraviolet rays, and examples thereof include epoxy groups, epithio groups, cyclic monomers (δ-valerolactone, ε-caprolactam), catalysts for forming urethane bonds obtained by isocyanates and alcohols, (meth) acryloyl Michael addition catalysts, and catalysts for crosslinking reactions of silicone resins. As photosensitive resins (B), for example, epoxy resins, phenolic resins, polyamide resins, polyurethane resins, nylon resins, polyester resins, silicone resins, etc. can be cited. These resins can be used alone or in combination of two or more. Among them, from the aspects of rapid reaction and good adhesion, a combination of epoxy resins and phenolic resins is preferred.

[0151] Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyphenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tri(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, Polyglycidyl ether compounds of polynuclear polyphenol compounds such as oxybisphenol, phenol novolac, o-cresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, terpene phenol, etc.; polyglycidyl ethers of polyols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, thiodiglycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as formic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methyl tetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; epoxy compounds having a glycidylamino group such as NN-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl o-toluidine; vinylcyclohexene diepoxide, dicyclopentane diene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6 Epoxides of cyclic olefin compounds such as bis(3-(4-epoxy-6-methylcyclohexylmethyl)adipate, epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymers, epoxidized styrene-butadiene copolymers, and heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins may be epoxy resins obtained by internal crosslinking of terminal isocyanate prepolymers or epoxy resins obtained by increasing the molecular weight of polyvalent active hydrogen compounds (polyphenols, polyamines, carbonyl-containing compounds, polyphosphates, etc.).

[0152] Among the above-mentioned epoxy resins, epoxy resins having a glycidyl group are preferred, and epoxy resins having a glycidyl group having two or more functional groups are more preferred, from the viewpoint of excellent curability.

[0153] As the phenol resin, a phenol resin having two or more hydroxyl groups in one molecule is preferred, and a generally known phenol resin can be used. As phenolic resin, for example, bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac type phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, phenolic resin containing polymerizable unsaturated hydrocarbon group, and hydroxy-containing silicone resins are not particularly limited. These phenolic resins can be used alone or in combination of two or more.

[0154] Examples of the polyamide resin include resins made from ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and diamines such as (o-, m- or p-)phenylenediamine, (3,3'- or 4,4'-)diaminodiphenyl ether, diaminobenzophenone, and (3,3'- or 4,4'-)diaminodiphenylmethane.

[0155] Examples of the polyurethane resin include resins made from polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate, and polyols (polyfunctional alcohols) such as polyether polyols, polyester polyols, and polycarbonate polyols.

[0156] Examples of the nylon resin include resins made from cyclic monomers such as ε-caprolactam and lauryl lactam.

[0157] Examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone.

[0158] Examples of the silicone resin include methyl silicone resin, methyl / phenyl silicone resin, and organic resin-modified silicone resin.

[0159] <Additives>

[0160] The photosensitive resin composition of the present invention may contain additives such as an inorganic compound, a colorant, a latent epoxy curing agent, a chain transfer agent, a sensitizer, and a solvent as optional components.

[0161] As the above-mentioned inorganic compound, for example, metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon dioxide, and aluminum oxide can be cited; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder (especially glass powder), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. These inorganic compounds can be used as fillers, anti-reflective agents, conductive materials, stabilizers, flame retardants, mechanical strength enhancers, special wavelength absorbers, ink repellents, etc.

[0162] Examples of the coloring material include pigments, dyes, natural coloring materials, etc. These coloring materials may be used alone or in combination of two or more.

[0163] As the above-mentioned pigment, for example, nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolinone compounds; quinacridone compounds; anthranthredione compounds; perinone compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acids; metal complex compounds of azo dyes and cyanine dyes; lake pigments; Carbon black obtained by a furnace process, a channel process or a thermal process, or carbon black such as acetylene black, ketjen black or lamp black; a pigment obtained by adjusting or coating the above carbon black with an epoxy resin, a pigment obtained by pre-dispersing the above carbon black in a resin solution so that it adsorbs 20 to 200 mg / g of resin, a pigment obtained by subjecting the above carbon black to an acidic or alkaline surface treatment, a carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen content calculated from CO and CO2 in the volatile components at 950°C of 100 m 2 Carbon black having a surface area of ​​9 mg or more; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; organic or inorganic pigments such as chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese series, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, chrome green (viridian), emerald green, lead sulfate, chrome yellow, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, synthetic iron black, and umber. These pigments may be used alone or in combination.

[0164] As the above-mentioned pigment, commercially available pigments can also be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 15 2, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

[0165] Examples of the dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes, and a plurality of these dyes may be used in combination.

[0166] Examples of the latent epoxy curing agent include dicyandiamide, modified polyamines, hydrazides, 4,4′-diaminodiphenyl sulfone, boron trifluoride amine complex salts, imidazoles, guanamines, imidazoles, ureas, and melamine.

[0167] As the chain transfer agent or sensitizer, a sulfur atom-containing compound can be generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecane 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and the like; disulfide compounds obtained by oxidation of compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodinated alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol di (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithio Aliphatic polyfunctional thiol compounds such as glycolic acid esters, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, diethyl thioxanthone, diisopropyl thioxanthone, the following compound No. C1, tris(2-hydroxyethyl) isocyanurate of trimercaptopropionate, and Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko K.K.

[0168] [Chemistry 26]

[0169] Compound No.C1

[0170]

[0171] As the above-mentioned solvent, a solvent that can dissolve or disperse the above-mentioned components (polymerization initiator (A) and photosensitive resin (B) etc.) can be generally used, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate Ester solvents such as ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, Texanol, etc.; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol mono Ether ester solvents such as methyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; paraffin solvents such as mineral spirits, Swasol #310 (Cosmo Matsuyama Oil Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; water, etc. These solvents can be used alone or as a mixed solvent of two or more.

[0172] Among them, ketone or ether ester solvents are preferably used from the viewpoint of alkali developability, patterning property, film forming property, and solubility, and propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone is particularly preferably used.

[0173] In the photosensitive resin composition of the present invention, the content of the solvent is not particularly limited as long as the various components are uniformly dispersed or dissolved and the photosensitive resin composition of the present invention is in a liquid or paste state suitable for various uses. It is usually preferred that the solvent is contained in the photosensitive resin composition of the present invention in an amount of 10 to 90% by mass of the solid content (all components other than the solvent).

[0174] In addition, the photosensitive resin composition of the present invention can also improve the properties of the cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, etc.

[0175] When the above-mentioned organic polymer is used, the amount thereof used is preferably 10 to 500 parts by mass based on 100 parts by mass of the photosensitive resin (B).

[0176] The photosensitive resin composition of the present invention may further contain a surfactant, a silane coupling agent, a melamine compound, or the like.

[0177] As the above-mentioned surfactant, there can be mentioned fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halides and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; surfactants such as silicone-based surfactants, which can be used in combination.

[0178] As the silane coupling agent, for example, silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, silane coupling agents having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403, are preferably used.

[0179] Examples of the above-mentioned melamine compounds include compounds in which all or part (at least 2) of the active methylol groups (CH2OH groups) in nitrogen compounds such as (poly)hydroxymethylmelamine, (poly)hydroxymethylglycoluril, (poly)hydroxymethylbenzoguanamine, and (poly)hydroxymethylurea are alkyl-etherified.

[0180] Here, the alkyl group constituting the alkyl ether includes a methyl group, an ethyl group or a butyl group, which may be the same or different from each other. In addition, the methylol group that is not alkyl-etherified may undergo self-condensation within one molecule or between two molecules to form an oligomer component.

[0181] Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. can be used.

[0182] Among them, alkyl-etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred from the viewpoint of solubility in a solvent and difficulty in crystallization from the photosensitive resin composition.

[0183] In the photosensitive resin composition of the present invention, the amount of optional components (excluding inorganic compounds, colorants and solvents) other than (A) the polymerization initiator and the photosensitive resin (B) is appropriately selected according to the intended use and is not particularly limited, but is preferably 50 parts by mass or less in total relative to 100 parts by mass of the photosensitive resin (B).

[0184] The photosensitive resin composition of the present invention can be irradiated with energy rays to form a cured product. The cured product is formed into a suitable shape corresponding to the purpose. For example, in the case of forming a film-like cured product, the photosensitive resin composition of the present invention can be applied to a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. by a spin coater, a roll coater, a rod coater, a die coater, a curtain coater, various printing, dipping, and other known means. In addition, it can also be temporarily applied to a supporting substrate such as a film and then transferred to another supporting substrate, and there is no limitation on its application method.

[0185] As a light source of energy rays used when curing the photosensitive resin composition of the present invention, electromagnetic wave energy having a wavelength of 2000 to 7000 angstroms obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., electron beams, X-rays, high energy rays such as radiation can be used. It is preferred to use ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light with a wavelength of 300 to 450 nm.

[0186] Furthermore, the laser direct drawing method that uses laser as exposure light source without using mask and directly forms an image according to digital information such as computer can not only improve productivity, but also can realize the improvement of resolution, position accuracy, etc., so it is useful. As this laser, it is preferred to use light with a wavelength of 340 to 430nm, but it is also possible to use lasers that emit light from the visible to infrared region such as excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers and YAG laser. When using these lasers, it is preferred to add a sensitizing dye that absorbs this region from the visible to the infrared.

[0187] In curing of the photosensitive resin composition of the present invention, it is usually necessary to heat after irradiation with the energy rays, and heating at about 40 to 150° C. is preferred from the viewpoint of the curing rate.

[0188] The photosensitive resin composition of the present invention can be used for photocurable coatings or varnishes; photocurable adhesives; coating agents for metals; printed circuit boards; color filters in liquid crystal display elements for color displays such as color televisions, PC monitors, portable information terminals, and digital cameras; color filters for CCD image sensors; electrode materials for plasma display panels; powder coatings; printing inks; printing plates; adhesives; dental compositions; gel coatings; photoresists for electronics; plating resists; etching resists; dry films; solder resists; color filters for various display applications or resists for forming structures of plasma display panels, electroluminescent display devices, and LCDs in the manufacturing process; and resists for Compositions for encapsulating electrical and electronic components; solder resists; magnetic recording materials; micromechanical components; waveguides; optical switches; masks for plating; etching masks; color test systems; glass fiber cable coatings; screen printing templates; materials for producing three-dimensional objects by stereolithography; materials for holographic recording; image recording materials; microelectronic circuits; decolorizing materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules; photoresist materials for printed circuit boards; photoresist materials for UV and visible laser direct imaging systems; photoresist materials or protective films used in the formation of dielectric layers in the sequential lamination of printed circuit boards, and the like, and the uses are not particularly limited.

[0189] The photosensitive resin composition of the present invention can be used for forming spacers for liquid crystal display panels and protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for vertical alignment type liquid crystal display elements.

[0190] The above-mentioned spacer for liquid crystal display panels is preferably formed by (1) forming a coating film of the photosensitive resin composition of the present invention on a substrate, (2) irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape, (3) baking after exposure, (4) developing the exposed coating film, and (5) heating the developed coating film.

[0191] The photosensitive resin composition of the present invention to which colorant is added is suitable for being used as a resist constituting each pixel such as RGB in a color filter, and a black matrix resist forming the partition wall of each pixel. Furthermore, in the case of a black matrix resist adding a sparse ink agent, it is preferably used for an inkjet color filter partition wall having a profile angle of more than 50 °. As the sparse ink agent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant are preferably used.

[0192] In the case of the partition wall for the inkjet color filter, the optical element is manufactured by the following method: the partition wall formed by the photosensitive resin composition of the present invention is used to divide the transfer body, and the image area is formed by applying droplets to the concave parts on the divided transfer body by the inkjet method. At this time, it is preferred that the droplets contain a colorant, and the image area is colored. In this case, the optical element manufactured by the above-mentioned manufacturing method has at least a pixel group consisting of a plurality of colored areas and a partition wall isolating each colored area of ​​the pixel group on the substrate.

[0193] The photosensitive resin composition of the present invention can also be used as a protective film or insulating film composition, and may contain an ultraviolet absorber, alkyl-modified melamine and / or acrylic-modified melamine, a mono- or di-functional (meth)acrylate monomer containing an alcoholic hydroxyl group in the molecule, and / or silica sol.

[0194] The insulating film is used for the insulating resin layer in a laminated body having an insulating resin layer provided on a peelable supporting substrate. The laminated body can be developed with an alkaline aqueous solution. The insulating resin layer preferably has a film thickness of 10 to 100 μm.

[0195] The photosensitive resin composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound. The photosensitive paste composition can be used to form a fired product pattern such as a barrier rib pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

[0196] Example

[0197] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

[0198] [Production Example 1] Synthesis of Oxime 1

[0199] <Step 1>

[0200] In a 200 mL four-necked flask, 1.0 eq. of indole, 1.2 eq. of 4-fluoronitrobenzene, 3.0 eq. of potassium carbonate and N,N-dimethylformamide (500 wt% of theoretical yield) were added, and heated and stirred at 130°C for 3 hours under a nitrogen flow of 20 mL / min. After cooling to room temperature, 50 g of ion exchange water was added and stirred for 1 hour. After filtering the precipitate, it was dried under reduced pressure at 50°C to a constant weight to obtain N-nitrophenylindole with a yield of 85%.

[0201] <Step 2>

[0202] In a 200 mL four-necked flask, 1.0 eq. of N-nitrophenylindole obtained in step 1, 2.5 eq. of aluminum chloride and dichloroethane (500 wt% of the theoretical yield) were added and stirred at 5°C on an ice bath. 1.3 eq. of myristic acid chloride was added dropwise thereto. After warming to room temperature, the mixture was stirred for 3 hours, 50 g of ion exchange water was added, and the organic layer was separated. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and ethanol was added for crystallization. The crystals obtained by filtration were dried under reduced pressure at 50°C to a constant weight, and ketone compound 1 was obtained with a yield of 65%.

[0203] <Step 3>

[0204] In a 100 mL four-necked flask, 1.0 eq. of the ketone compound obtained in step 2, 2.0 eq. of hydroxylamine hydrochloride and pyridine (200 wt% of the theoretical yield) were added, and heated and stirred at 95°C for 2.5 hours under a nitrogen flow of 20 mL / min. After cooling to room temperature, 50 g of ion exchange water was added and the organic layer was separated. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the mixture was dried under reduced pressure at 50°C to a constant weight to obtain oxime 1 with a yield of 88%.

[0205] [Production Example 2] Synthesis of Oxime 2

[0206] The same operation was carried out in Preparation Example 1 except that 4-fluoronitrobenzene in <Step 1> was replaced by 4-fluorobenzophenone and myristoyl chloride in <Step 2> was replaced by n-octanoyl chloride to obtain oxime 2 in a total yield of 11%.

[0207] [Example 1] Synthesis of Compound No. 1

[0208] Flow nitrogen into a 100 ml four-necked flask, add 1.0 eq. of oxime 1, dichloromethane (500 wt% of the theoretical yield), and 2.0 eq. of triethylamine, and stir at 5°C on an ice bath. Add dropwise a solution obtained by dissolving 1.1 eq. of 4-nitrophenyl chloroformate in dichloromethane. After the addition is completed, stir at room temperature for 30 minutes. Cool to 5°C on an ice bath again, and then add dropwise 1.1 eq. of piperidine. Stir at room temperature for 3 hours, and distill off the solvent under reduced pressure. Add ethyl acetate and a 5% by mass aqueous NaOH solution, and separate the organic layer. Wash the organic layer three times with ion-exchanged water, and then concentrate. Add methanol to the residue for crystallization, and obtain compound No. 1 as a yellow powder compound with a yield of 70%. Analyze the TG-DTA (melting point / °C) of the obtained solid, 1 The results are shown in Tables 1 and 2.

[0209] [Example 2] Synthesis of Compound No. 2

[0210] The same operation as in Example 1 was carried out except that Oxime 1 described in Example 1 was replaced by Oxime 2 to obtain Compound No. 2 at a yield of 54%. The TG-DTA (melting point / °C) of the obtained solid was analyzed. 1 The results are shown in Tables 1 and 2.

[0211] [Production Example 3] Synthesis of Oxime 3

[0212] Ketone compound 2 was obtained by performing the same operation as in Preparation Example 1 except that 4-fluoronitrobenzene in <Step 1> was replaced by 4-fluorobenzophenone and myristoyl chloride in <Step 2> was replaced by n-octanoyl chloride.

[0213] <Step 3>

[0214] In a 100 mL four-necked flask, 1.0 eq. of the above ketone compound 2, DMF (300 wt% of the theoretical yield), and 1.2 eq. of hydrochloric acid were added in this order, and stirred at 5°C on an ice bath. 1.2 eq. of isobutyl nitrite was added dropwise thereto. After warming to room temperature, the mixture was stirred for 6 hours. Then, 50 g of ion exchange water and ethyl acetate were added to separate the organic layer. The organic layer was washed with water three times, and concentrated under reduced pressure using an evaporator to obtain oxime 3. The obtained oxime 3 was used in the next reaction without purification.

[0215] [Example 3] Synthesis of Compound No.75

[0216] Flow nitrogen into a 100 ml four-necked flask, add 1.0 eq. of oxime 3, dichloromethane (500 wt% of the theoretical yield), and 2.0 eq. of triethylamine, and stir at 5°C on an ice bath. Add dropwise a solution obtained by dissolving 1.1 eq. of 4-nitrophenyl chloroformate in dichloromethane. After the addition is complete, stir at room temperature for 30 minutes. Cool to 5°C on an ice bath again, and then add dropwise 1.1 eq. of piperidine. Stir at room temperature for 5 hours, and distill off the solvent under reduced pressure. Add ethyl acetate and a 5% by mass aqueous NaOH solution, and separate the organic layer. Wash the organic layer three times with ion-exchanged water, and then concentrate. Add methanol to the residue for crystallization, and obtain compound No. 75 as a yellow powder compound with a yield of 30%. Analyze the TG-DTA (melting point / °C) of the obtained solid, 1 The results are shown in Tables 1 and 2.

[0217] [Example 4] Synthesis of Compound No.76

[0218] The same operation as in Example 3 was carried out except that the piperidine described in Example 3 was replaced by morpholine to obtain Compound No. 76 with a yield of 51%. The obtained solid was analyzed for TG-DTA (melting point / °C),1 The results are shown in Tables 1 and 2.

[0219] [Example 5] Synthesis of Compound No.77

[0220] The same operation as in Example 3 was carried out except that 1.1 eq. of piperidine described in Example 3 was changed to 0.50 eq. of piperazine to obtain Compound No. 77 at a yield of 43%. The obtained solid was analyzed by TG-DTA (melting point / °C), 1 The results are shown in Tables 1 and 2.

[0221] [Example 6] Synthesis of Compound No.152

[0222] The same operation as in Example 3 was carried out except that the piperidine described in Example 3 was replaced with dibutylamine to obtain Compound No. 152 with a yield of 38%. The TG-DTA (melting point / °C) of the obtained solid was analyzed. 1 The results are shown in Tables 1 and 2.

[0223] [Comparative Example 1] The following comparative compound No. 1 was used.

[0224] Table 1

[0225] Compound Melting point(℃) Example 1 Compound No.1 127 Example 2 Compound No.2 145 Example 3 Compound No.75 112 Example 4 Compound No.76 115 Example 5 Compound No.77 183 (decomposition) Example 6 Compound No.152 169 (decomposition)

[0226] Table 2

[0227]

[0228] [Evaluation Examples 1 to 5 and Comparative Evaluation Example 1] Evaluation of Photodegradation Ability

[0229] Compounds No. 1, No. 75, No. 76, No. 77, No. 152 and the following comparative compound No. 1 were prepared into acetonitrile solutions of 1.0 × 10 -4 mol and placed in a quartz box with a lid. At 100mJ / cm 2 、500mJ / cm 2 、1000mJ / cm 2 The sample was irradiated with ultraviolet light using an ultrahigh pressure mercury lamp as a light source under the conditions of 100 nm (cumulative light intensity at 365 nm) to investigate the decomposability. In the evaluation of the decomposability, the amount of decomposition was expressed as % by HPLC, with the peak without irradiation being 0. The results are shown in Table 3.

[0230] HPLC: Made by Hitachi High Technology, UV detector, Chrom master 5430

[0231] Developing solvent: acetonitrile / water / ammonium acetate

[0232] =90 / 10 / 0.2 (volume ratio)

[0233] Flow rate: 1ml / min

[0234] Column: Inertsil ODS-2

[0235] Column temperature: 40°C

[0236] Detection: 254nm

[0237] [Chemistry 27]

[0238]

[0239] Table 3

[0240]

[0241] According to the results in Table 3, the novel compound of the present invention has high decomposition properties to UV light, and therefore generates a large amount of base by decomposition, and exhibits high-sensitivity curing properties in the photosensitive resin composition.

[0242] [Examples 7 to 12 and Comparative Example 1] Preparation of Photosensitive Composition

[0243] Photosensitive compositions No. 1 to No. 6 and comparative photosensitive composition No. 1 were obtained by mixing as shown in Table 4. The numerical values ​​of the mixing in the table represent parts by mass.

[0244] In addition, the symbols of each component in the table represent the following components.

[0245] A-1 Compound No.1

[0246] A-2 Compound No.2

[0247] A-3 Compound No.75

[0248] A-4 Compound No.76

[0249] A-5 Compound No.77

[0250] A-6 Compound No.152

[0251] A'-1 Comparative Compound No.1

[0252] B-1 EPPN-201

[0253] (phenol novolac type epoxy resin, epoxy equivalent 193 g / eq., manufactured by Nippon Kayaku Co., Ltd.)

[0254] B-2 TRR-5010G

[0255] (Cresol novolac type phenolic resin, hydroxyl equivalent 120 g / eq., Mw=8000, manufactured by Asahi Organic Materials Industries, Ltd.)

[0256] C-1 FZ-2122

[0257] (Polyether-modified polysiloxane, manufactured by Dow Corning Toray Co., Ltd.)

[0258] D-1 Cyclopentanone (solvent)

[0259] Table 4

[0260]

[0261] [Evaluation Examples 6 to 17 and Comparative Evaluation Examples 2 and 3] Evaluation of Photosensitive Compositions and Cured Products

[0262] The line width sensitivity and the residual film ratio of the cured products of the photosensitive compositions No. 1 to No. 6 and the comparative photosensitive composition No. 1 and their cured products were evaluated in the following procedures.

[0263] [Evaluation sample preparation method and evaluation method]

[0264] Photosensitive compositions No. 1 to No. 6 and comparative photosensitive composition No. 1 (coating amount: about 2.0 cc) were coated on glass substrates using a spin coater (500 rpm×2 seconds→1800 rpm×15 seconds→slope×5 seconds) and pre-baked on a hot plate (90° C.×120 seconds).

[0265] Then, a Topcon exposure machine was used to perform split exposure with UV light (60, 120 mJ / cm 2 , gap: 20μm, illumination: 20.0mW / cm 2 ).

[0266] After exposure, post-baking was performed on a hot plate (120°C × 5 minutes), developed with PGMEA (temperature; 23°C, 200 rpm × 10 seconds), and cleaned with IPA (isopropyl alcohol) (200 rpm × 10 seconds → drying: 500 rpm × 5 seconds).

[0267] For the obtained samples, the line width / residual film ratio of the pattern with a mask opening of 20 μm at each exposure amount was measured.

[0268] Table 5

[0269]

[0270] The results in Table 5 show that the photosensitive composition of the present invention has a larger line width (higher sensitivity) and a higher residual film rate (higher curability) than the comparative photosensitive composition, and thus it is known that the compound of the present invention is excellent as a polymerization initiator.

[0271] [Examples 13 to 15, and Comparative Examples 2 and 3] Preparation of Photosensitive Compositions

[0272] The formulations described in Table 6 were carried out to obtain photosensitive compositions No. 7 to No. 9 and comparative photosensitive compositions No. 2 and No. 3. The numerical values ​​of the formulations in the table represent mass (g).

[0273] In addition, the symbols of each component in the table represent the following components.

[0274] A'-2 Comparative Compound No.2

[0275] B-3 KR-300

[0276] (Methyl / phenyl silicone resin, 50% xylene solution, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0277] B-4 Tetraethoxysilane

[0278] [Chemistry 28]

[0279]

[0280] Table 6

[0281]

[0282] [Evaluation Examples 18 to 20 and Comparative Evaluation Examples 4 and 5] Evaluation of Photosensitive Compositions and Cured Products

[0283] The photosensitive compositions No. 7 to No. 9, comparative photosensitive compositions No. 2 and No. 3, and their cured products were evaluated for viscosity and transparency in the following procedure. The results are collectively shown in Table 7.

[0284] [Evaluation sample preparation method and evaluation method]

[0285] Photosensitive compositions No. 7 to No. 9 and comparative photosensitive compositions No. 2 and No. 3 (coating amount of about 4.0 cc) were coated on glass substrates using a spin coater (500 rpm×2 seconds→1800 rpm×15 seconds→slope×5 seconds) and pre-baked on a hot plate (90° C.×120 seconds).

[0286] Then, the film was exposed to ultraviolet light (1000 mJ / cm2 、gap:20μm、illuminance:20.0mW / cm 2 ).

[0287] After the exposure, post-baking was performed on a hot plate (120° C.×5 minutes).

[0288] The obtained sample was rubbed on the surface with a cotton swab to confirm whether there was any residual stickiness. No residual stickiness was 0, and residual stickiness was x. Compounds evaluated as 0 were preferred as polymerization initiators because of their high curability.

[0289] In addition, the obtained samples were measured for ultraviolet and visible absorption spectra using a spectrophotometer, and the transmittance at 400 nm was compared. Compounds with a transmittance of 80% or more are preferred as polymerization initiators due to their high transparency, while compounds with a transmittance of less than 80% are not preferred as polymerization initiators for applications requiring transparency due to their low transparency.

[0290] Spectrophotometer: Spectrophotometer U-3900 manufactured by Hitachi High Technologies

[0291] Table 7

[0292]

[0293] From the results in Table 7, it is understood that the compound of the present invention is a polymerization initiator having excellent curability and transparency in a composition using a silicone resin.

[0294] [Examples 16 and 17, and Comparative Example 4] Preparation of photosensitive composition

[0295] Photosensitive compositions No. 10 and No. 11 and comparative photosensitive composition No. 4 were obtained by mixing as shown in Table 8. The numerical values ​​of the mixing in the table represent the mass (g).

[0296] In addition, the symbols of each component in the table represent the following components.

[0297] A'-3 Comparative Compound No.3

[0298] B-5 PEMP

[0299] (Tetrafunctional thiol monomer, manufactured by SC Organic Chemicals Co., Ltd.)

[0300] [Chemistry 29]

[0301]

[0302] Table 8

[0303]

[0304] [Evaluation Examples 21 and 22, and Comparative Evaluation Example 6] Evaluation of Photosensitive Compositions and Cured Products

[0305] The sensitivity of the photosensitive compositions No. 10 and No. 11, the comparative photosensitive composition No. 4, and the cured products thereof were evaluated in accordance with the following procedure.

[0306] [Evaluation sample preparation method and evaluation method]

[0307] Photosensitive compositions No. 10 and No. 11 and comparative photosensitive composition No. 4 (coating amount of about 4.0 cc) were coated on a glass substrate using a spin coater (500 rpm×2 seconds→1800 rpm×15 seconds→slope×5 seconds) and pre-baked on a hot plate (90° C.×120 seconds).

[0308] Then, a step exposure meter was placed on the coating film, and UV light (365 nm, 385 nm, 395 nm) was used for exposure (3000 mJ / cm 2 , Illuminance: 20.0mW / cm 2 ).

[0309] After exposure, post-baking was performed on a hot plate (100° C.×20 minutes), development was performed with PGMEA (30 seconds), and cleaning was performed with IPA (isopropyl alcohol) (10 seconds).

[0310] The number of segments of the film remaining during development was recorded for the obtained sample. A photosensitive resin composition having 5 or more segments is preferred because of its excellent sensitivity, and a sample having 10 or more segments is particularly preferred.

[0311] Table 9

[0312]

[0313] From the results in Table 9, it is understood that the compound of the present invention is a polymerization initiator having excellent curability in a composition using an epoxy resin and a thiol as a curing agent.

[0314] [Examples 18 and 19, and Comparative Example 5] Preparation of Photosensitive Composition

[0315] Photosensitive compositions No. 12 and No. 13 and comparative photosensitive composition No. 5 were obtained by mixing as shown in Table 10. The numerical values ​​of the mixing in the table represent the mass (g).

[0316] In addition, the symbols of each component in the table represent the following components.

[0317] B-6 Polyamic acid

[0318] (A product obtained by reacting 3,3',4,4'-biphenyltetracarboxylic dianhydride with bis(4-aminophenyl) ether in N,N-dimethylacetamide. The weight average molecular weight is about 10,000.)

[0319] D-2 NMP (Solvent)

[0320] Table 10

[0321]

[0322] [Evaluation Examples 23 to 26, and Comparative Evaluation Examples 7 and 8] Evaluation of Photosensitive Compositions and Cured Products

[0323] The line width sensitivity and the residual film ratio of the cured products of the photosensitive compositions No. 12 and No. 13, the comparative photosensitive composition No. 5, and their cured products were evaluated in accordance with the following procedures.

[0324] [Evaluation sample preparation method and evaluation method]

[0325] Photosensitive compositions No. 12 and No. 13 and comparative photosensitive composition No. 5 (coating amount of about 4.0 cc) were coated on a glass substrate using a spin coater (500 rpm×2 seconds→1800 rpm×15 seconds→slope×5 seconds) and pre-baked on a hot plate (100° C.×10 minutes).

[0326] Then, a Topcon exposure machine was used to perform split exposure with UV light (1000, 3000 mJ / cm 2 , gap: 20μm, illumination: 20.0mW / cm 2 ).

[0327] After exposure, post-baking was performed on a hot plate (100° C. for 30 minutes), development was performed with IPA (temperature: 23° C., 200 rpm×10 seconds→drying: 500 rpm×5 seconds), and then further heated at 300° C. for 1 hour.

[0328] For the obtained samples, the line width and residual film ratio of the pattern with a mask opening of 20 μm at each exposure amount were measured.

[0329] Table 11

[0330]

[0331] The results in Table 12 indicate that the compound of the present invention is a polymerization initiator having excellent curability in a resin composition using a polyamic acid.

[0332] Furthermore, the compound of the present invention can also be used as a thermal base generator.

[0333] [Reference Example 1]

[0334] A coating film was prepared by the same method as above using the photosensitive composition No. 11. The coating film was heated in an oven at 150° C. for 60 minutes. The obtained film was developed with IPA, and it was confirmed that the residual film ratio was 40.5%, indicating that curing had occurred.

[0335] [Reference Example 2]

[0336] Heating and development were performed in the same manner as in Reference Example 1 except that a composition not containing A-1 (Compound No. 1) was used. As a result, no film remained.

[0337] These results show that the compound of the present invention can also be used as a thermal base generator.

[0338] Industrial Applicability

[0339] When used as a polymerization initiator, the novel compound of the present invention can generate a base more efficiently than conventional photobase generators, and thus can cure a photosensitive resin even at a low exposure dose.

Claims

1. A compound represented by the general formula (I), In the formula, R 1 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R 2 , R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, X 1 For-NR 11 R 12 , R 11 and R 12 are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or, R 11 and R 12 are linked to each other to form a ring having 1 to 20 carbon atoms composed of hydrogen atoms, nitrogen atoms and carbon atoms, or a ring having 1 to 20 carbon atoms composed of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms, n represents 0 or 1, R 3 is a group represented by the following general formula (II), In the formula, R 25 , R 26 , R 27 , R 28 and R 29 Each independently represents a hydrogen atom, a nitro group, or -CO-R 30 , R 30 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 25 , R 26 , R 27 , R 28 and R 29 At least one of them represents a nitro group or a -CO-R 30 , * indicates a bonding end.

2. A latent base generator comprising the compound according to claim 1. A polymerization initiator comprising the compound according to claim 1. 4 . A photosensitive resin composition comprising the polymerization initiator (A) according to claim 3 and a photosensitive resin (B).

5. The photosensitive resin composition according to claim 4, wherein The photosensitive resin (B) is epoxy resin or phenolic resin. 6 . A cured product, which is a cured product of the photosensitive resin composition according to claim 4 or 5 . 7 . A method for producing a cured product, comprising the step of irradiating the photosensitive resin composition according to claim 4 or 5 with energy rays.

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