TWI784029B - Photosensitive composition, pattern forming method, cured product, and display device - Google Patents

Abstract

The present invention provides a photosensitive composition, a pattern forming method using the photosensitive composition, a cured product of the photosensitive composition, a photosensitive adhesive containing the above photosensitive composition, and a quilt using the above photosensitive composition. The method of bonding objects, the photosensitive composition of the present invention has good light transmittance and sensitivity to exposure, can form a fully cured hardened product by exposure, and when exposed through a half-tone mask, not only In the formed pattern, there is a sufficient height difference between the full-tone exposed part and the half-tone exposed part, and it is possible to ensure that the half-tone exposed part has a sufficient height. In the present invention, as the photopolymerization initiator (A), two or more kinds having peaks in the wavelength region of 320 nm to less than 400 nm in the absorption spectrum and having different maximum wavelengths are used in combination. Oxime ester compounds, and do not use compounds showing a gram absorption coefficient of 10 or more at any wavelength in the wavelength region above 400 nm.

Description

Photosensitive composition, pattern forming method, cured product, and display device

The present invention relates to a photosensitive composition, a pattern forming method using the photosensitive composition, a cured product formed using the photosensitive composition, and a display device equipped with the cured product.

In a panel for a display device such as a liquid crystal display device, a material such as an insulating film or a spacer needs to efficiently transmit light emitted from a light source such as a backlight. Therefore, the pattern of an insulating film or a spacer is formed using the photosensitive composition which can become a transparent cured film by exposure. By selectively exposing such a photosensitive composition, a pattern of a transparent cured film can be formed.

Moreover, in the panel for a display device, the patterned light-shielding film, such as a black matrix or a black spacer, is often formed. For this purpose, various photosensitive compositions including a sunscreen agent and a photopolymerization initiator for forming a light shielding film have been proposed in the industry. Since the photosensitive composition for forming a light-shielding film contains a light-shielding agent, a higher sensitivity of the photopolymerization initiator is required.

For example, regarding a photosensitive composition containing a photopolymerization initiator with excellent sensitivity, the industry has proposed a photosensitive composition containing an oxime ester compound as a photopolymerization initiator. Skeleton (see Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-218353

[Problem to be solved by the invention]

Moreover, when manufacturing the panel for image display apparatuses etc., elements, such as TFT, may be arrange|positioned on the layer adjacent to the patterned cured film formed using the photosensitive composition. In this case, exposure is performed through a halftone mask, and patterns of different heights are often formed in consideration of device height. However, although the photosensitive composition described in Patent Document 1 is excellent in sensitivity, when exposing through a half-tone mask, it may not be easy to make the difference between the full-tone exposed part and the half-tone exposed part in the pattern formed. There is a sufficient height difference, and there is a problem of securing a sufficient height of the halftone exposed portion.

The present invention was made in view of the above problems, and an object of the present invention is to provide a photosensitive composition, a pattern forming method using the photosensitive composition, a cured product of the photosensitive composition, and a photosensitive adhesive containing the photosensitive composition , and the bonding method of the adhered object using the above photosensitive composition, the photosensitive composition of the present invention has good light transmittance and sensitivity to exposure, and can form a fully cured hardened product by exposure, and can be separated by half When the tone mask is exposed, not only can there be a sufficient height difference between the full-tone exposed portion and the half-tone exposed portion in the formed pattern, but also the half-tone exposed portion can be ensured to have a sufficient height. [Technical means to solve the problem]

The inventors of the present invention found that, in the photosensitive composition containing the photopolymerization initiator (A), the combined use has a peak in the wavelength region of 320 nm or more and less than 400 nm in the absorption spectrum, and the peak is extremely large. Two or more oxime ester compounds with different wavelengths are used as the photopolymerization initiator (A), and the photopolymerization initiator (A) is not contained at any wavelength in the wavelength range of 400 nm or more to show 10 or more Compounds with a gram light absorption coefficient can solve the above-mentioned problems, thereby completing the present invention.

The first aspect of the present invention is a photosensitive composition, which contains a photopolymerization initiator (A), and the photopolymerization initiator (A) contains two or more kinds, and the absorption spectrum is more than 320 nm and less than 400 nm. An oxime ester compound having a peak in the wavelength region of nm, and the photopolymerization initiator (A) does not contain a compound showing a gram absorption coefficient of 10 or more at any wavelength in the wavelength region of 400 nm or more, and two or more The maximum wavelengths of the peaks of the oxime ester compounds are different.

A second aspect of the present invention is a method for forming a cured product, comprising: forming a coating film using the photosensitive composition of the first aspect; and exposing the coating film.

The third aspect of the present invention is a cured product of the photosensitive composition of the first aspect.

A fourth aspect of the present invention is a photosensitive adhesive comprising the photosensitive composition of the first aspect.

The fifth aspect of the present invention is a bonding method of a bonded surface, which includes: forming an adhesive layer containing the photosensitive adhesive of the fourth aspect on one or both sides of the facing bonded surface; Harden the adhesive layer. [Effect of Invention]

According to the present invention, there are provided a photosensitive composition, a pattern forming method using the photosensitive composition, a cured product of the photosensitive composition, a photosensitive adhesive containing the above photosensitive composition, and a photosensitive composition using the above photosensitive composition. The method of bonding objects to be bonded, the photosensitive composition of the present invention has good light transmittance and sensitivity to exposure, and can form a fully cured hardened object by exposure, and in the case of exposure through a half-tone mask In this case, not only can there be a sufficient height difference between the full-tone exposed portion and the half-tone exposed portion in the formed pattern, but also the half-tone exposed portion can be ensured to have a sufficient height.

≪Photosensitive composition≫ The photosensitive composition of the present invention contains a photopolymerization initiator (A). The photopolymerization initiator (A) contains 2 or more types of oxime ester compounds which have a peak in the wavelength region of 320 nm or more and less than 400 nm in an absorption spectrum. Among them, the maximum wavelengths of the peaks related to two or more oxime ester compounds are different. Therefore, when exposing the said photosensitive composition, it becomes easy to make full use of the light of exposure, and the photosensitive composition is excellent in sensitivity.

In the case where the maximum wavelength on the longest wavelength side is λ _max-r and the maximum wavelength on the shortest wavelength side is λ _max-b among the maximum wavelengths of the above-mentioned peaks of two or more oxime ester compounds, λ _max- The difference between _r and λ _max-b is preferably 20 nm or more. The upper limit is, for example, 70 nm or less, preferably 50 nm or less. Also, λ _max-r is preferably in the range of 350 nm to 400 nm, and λ _max-b is preferably in the range of 320 nm to 360 nm. In this case, even when the wavelength region of the exposure light used for exposing the photosensitive composition is wide, it is easy to efficiently use the energy of the exposure light for curing, regardless of the light source. Achieve good sensitivity.

Moreover, the photoinitiator (A) does not contain the compound which shows the gram light absorption coefficient of 10 or more in any wavelength in the wavelength range of 400 nm or more. The photopolymerization initiator preferably does not contain a compound showing a gram absorption coefficient of 5 or more at any wavelength in the wavelength range of 400 nm or more, and more preferably does not contain a compound showing a gram absorption coefficient of 1 or more. When the photopolymerization initiator (A) contains a compound having a gram light absorption coefficient of 10 or more at any wavelength in the wavelength region of 400 nm or more, the light transmittance of the photosensitive composition tends to be low. For this reason, the sensitivity as a photosensitive composition falls, or it may become difficult to form a pattern with desired height by halftone exposure. However, since the said photosensitive composition does not contain the compound which shows the gram light absorption coefficient of 10 or more at any wavelength in the wavelength range of 400 nm or more in the photopolymerization initiator (A), it is excellent in translucency. As a result, it is easy to make full use of the exposure light, and it is easy to form a pattern with a desired height by halftone exposure.

Moreover, when using a photosensitive composition as a photosensitive adhesive agent, a photosensitive adhesive agent is apply|coated thickly in many cases. However, since the photosensitive adhesive agent containing the photosensitive composition containing a photoinitiator (A) is excellent in light transmittance as mentioned above, even if it coats thickly, a photosensitive adhesive agent can harden favorably.

Moreover, when forming a pattern by halftone exposure using the said photosensitive composition, it becomes easy to make sufficient height difference exist between the full tone exposure part and the halftone exposure part in the formed pattern.

As mentioned above, a photoinitiator (A) contains 2 or more types of photoinitiators in combination. However, as mentioned above, a photoinitiator (A) must contain 2 or more types of oxime ester compounds. The content of each photoinitiator contained in a photoinitiator (A) is not specifically limited in the range which does not impair the object of this invention. The ratio of the content of each photopolymerization initiator to the mass of the photopolymerization initiator (A) is preferably at least 1% by mass, more preferably at least 5% by mass, still more preferably at least 10% by mass, especially Preferably, it is at least 20% by mass. In addition, the ratio of the content of each photopolymerization initiator to the mass of the photopolymerization initiator (A) is preferably at most 99% by mass, more preferably at most 95% by mass, still more preferably at most 90% by mass , preferably 80% by mass or less. Also, the ratio of the content of the oxime ester compound having λ _max-r to the mass of the photopolymerization initiator (A) is preferably at least 1% by mass and at most 99% by mass, more preferably at least 5% by mass and 95 mass % or less, More preferably, it is 10 mass % or more and 90 mass % or less, Most preferably, it is 15 mass % or more and 80 mass % or less. The ratio of the content of the oxime ester compound having λ _max-b to the mass of the photopolymerization initiator (A) is preferably from 1% by mass to 99% by mass, more preferably from 5% by mass to 95% by mass % or less, more preferably 10 mass % or more and 90 mass % or less, particularly preferably 20 mass % or more and 85 mass % or less. Other oxime ester initiators having a maximum wavelength not equivalent to λ _max-r and λ _max-b in the range above 320 nm and less than 400 nm relative to the mass of the photopolymerization initiator (A) The ratio of the content is preferably from 0% by mass to 98% by mass, more preferably from 0% by mass to 90% by mass, still more preferably from 0% by mass to 80% by mass, particularly preferably at least 0% by mass And 65% by mass or less. When the photopolymerization initiator (A) includes the first oxime ester compound and the second oxime ester compound, the ratio M1/M2 of the mass M1 of the first oxime ester compound to the mass M2 of the second oxime ester compound is preferably 1/9 or more and 9/1 or less, more preferably 2/8 or more and 8/2 or less, particularly preferably 3/7 or more and 7/3 or less.

Hereinafter, each component contained in a photosensitive composition is demonstrated.

<Photopolymerization initiator (A)> As mentioned above, a photopolymerization initiator (A) contains two or more oxime ester compounds which have a peak in the wavelength region of 320 nm or more and less than 400 nm in an absorption spectrum. Moreover, the photoinitiator (A) does not contain the compound which shows the gram light absorption coefficient of 10 or more in any wavelength in the wavelength range of 400 nm or more.

The photoinitiator (A) may contain other photoinitiators other than the oxime ester compound. The amount of the oxime ester compound in the photopolymerization initiator (A) is preferably at least 50% by mass, more preferably at least 70% by mass, further preferably at least 80% by mass, still more preferably at least 90% by mass, especially More than 95% by mass is preferred, and 100% by mass is most preferred. When a photoinitiator (A) contains other photoinitiators other than an oxime ester compound, a photoinitiator (A) may contain 2 or more types of other photoinitiators in combination.

As another photopolymerization initiator other than the oxime ester compound, a compound having a gram absorption coefficient of 10 or more at any wavelength in the wavelength range of 400 nm or more that is known as a photopolymerization initiator can be used.

、2-氯9-氧硫𠮿

、2,4-二甲基-9-氧硫𠮿

、1-氯-4-丙氧基-9-氧硫𠮿

、硫𠮿

、2-氯硫𠮿

、2,4-二乙基硫𠮿

、2-甲基硫𠮿

、2-異丙基硫𠮿

、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮二異丁腈、過氧化苯甲醯、氫過氧化異丙苯、2-巰基苯并咪唑、2-巰基苯并㗁唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(對甲氧基苯基)-4,5-二苯基咪唑二聚物、2,4,5-三芳基咪唑二聚物、二苯甲酮、2-氯二苯甲酮、4,4'-雙二甲基胺基二苯甲酮(即米其勒酮)、4,4'-雙二乙基胺基二苯甲酮(即乙基米其勒酮)、4,4'-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、苯偶醯、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、安息香丁醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、對二甲胺基苯乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、9-氧硫𠮿

、2-甲基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

、二苯并環庚酮、4-二甲基胺基苯甲酸戊酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三𠯤、2,4,6-三(三氯甲基)均三𠯤、2-甲基-4,6-雙(三氯甲基)均三𠯤、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)均三𠯤、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)均三𠯤、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)均三𠯤、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)均三𠯤、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)均三𠯤、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)均三𠯤、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)均三𠯤、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基均三𠯤、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基均三𠯤、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基均三𠯤、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基均三𠯤等。 其他光聚合起始劑可根據所測得之400 nm以上之波長區域中之克吸光係數，自該等化合物群中選擇。Specific examples of well-known photopolymerization initiators other than oxime ester compounds include: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linylpropane-1- Ketone, 2-benzyl-2-dimethylamino-1-(4-alphalinylphenyl)-butan-1-one, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 4-benzoyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene Ethyl formate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, benzyl- β-Methoxyethyl acetal, benzoyl dimethyl ketal, methyl phthalyl benzoate, 2,4-diethyl-9-oxothiophene

, 2-Chloro9-oxosulfur 𠮿

, 2,4-Dimethyl-9-oxosulfur 𠮿

, 1-Chloro-4-propoxy-9-oxosulfur

, sulfur 𠮿

, 2-chlorosulfur

, 2,4-Diethylsulfur 𠮿

, 2-Methylsulfur 𠮿

, 2-Isopropylthio 𠮿

, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, isohydroperoxide Propylbenzene, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o- Chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxy Phenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triaryl imidazole dimer benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie Micheler's ketone), 4,4'-bisdiethylaminodiphenone Benzophenone (i.e. ethyl michelerone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoyl, benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p- Dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-th Tributyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, 9-oxothiophenone

, 2-methyl-9-oxosulfur

, 2-isopropyl-9-oxothio𠮿

, dibenzocycloheptanone, amyl 4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridyl)heptane, 1,5-bis-( 9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytrimethoxytrimethalone, 2,4,6-tris(trichloromethyl)serotonin, 2- Methyl-4,6-bis(trichloromethyl)s-trimethanone, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)same Trisulphonium, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)strisalphatium, 2-[2-(4-diethylamino-2- Methylphenyl)vinyl]-4,6-bis(trichloromethyl)s-trimethanone, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis (Trichloromethyl)-S-Trisyl, 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-S-Tri-G, 2-(4-Ethoxystyryl)- 4,6-bis(trichloromethyl)-tri-tri-sulfone, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-tri-tri-methanium, 2,4-bis-tri- Chloromethyl-6-(3-bromo-4-methoxy)phenyl-tris-trimethalone, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s Trisulphur, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-tris-throne, 2,4-bis-trichloromethyl-6-( 2-Bromo-4-methoxy) styrylphenyl s-trimethanone, etc. Other photopolymerization initiators can be selected from these compound groups according to the measured gram light absorption coefficient in the wavelength region of 400 nm or more.

The combination of several types of oxime ester compounds in a photoinitiator (A) will not be specifically limited as long as it satisfies the said requirement regarding a photoinitiator (A). As a preferable combination of an oxime ester compound, the combination of the oxime ester compound (A1) represented by following formula (a1) and the oxime ester compound (A2) represented by following formula (a2) is mentioned. The photopolymerization initiator (A) may contain 1 type, or 2 or more types of oxime ester compounds (A1), and 1 type, or 2 or more types of oxime ester compounds (A2). Hereinafter, the oxime ester compound (A1) and the oxime ester compound (A2) are demonstrated.

(式(a1)中，R¹ 為1價有機基，R² 為可具有取代基之烴基、或可具有取代基之雜環基，R³ 為1價有機基，R⁴ 為1價有機基，R⁵ 及R⁶ 分別獨立為可具有取代基之苯環、或可具有取代基之萘環，m1、m2及m3分別為0或1) 表示，且滿足下述(1)～(3)： (1) R¹ 包含-OR⁷ 所表示之基，R⁷ 為鹵烷基； (2) m2為1，R⁴ 包含-OR⁷ 所表示之基，R⁷ 為鹵烷基； (3) R³ 為可具有取代基之支鏈狀烷基； 中之至少一個條件之化合物。[Oxime ester compound (A1)] The oxime ester compound (A1) has the following formula (a1): [Chem. 1]

(In formula (a1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group that may have a substituent, or a heterocyclic group that may have a substituent, R ³ is a monovalent organic group, R ⁴ is a monovalent organic group , R ⁵ and R ⁶ are each independently a benzene ring that may have a substituent, or a naphthalene ring that may have a substituent, m1, m2 and m3 are respectively 0 or 1), and satisfy the following (1)-(3) : (1) R ¹ comprises a base represented by -OR ⁷ , R ⁷ is a haloalkyl group; (2) m2 is 1, R ⁴ comprises a base represented by -OR ⁷ , and R ⁷ is a haloalkyl group; (3) R ³ is a branched alkyl group which may have a substituent; and a compound of at least one condition.

In formula (a1), R ⁵ and R ⁶ are a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent. The ring including the nitrogen atom bonded to ^R3 shown in formula (a1) is condensed with the benzene ring or naphthalene ring by sharing any carbon-carbon bond in the benzene ring or naphthalene ring. Therefore, the ring containing the nitrogen atom bonded to ^R in the formula (a1) is a nitrogen atom, 2 carbon atoms derived from R ⁵ , and 2 carbon atoms derived from R ⁶ as ring-forming atoms 5 member ring. That is, the compound represented by the formula (a1) has a 3- to 5-ring condensed ring including R ⁵ , R ⁶ and the above-mentioned 5-membered ring as a central skeleton.

When R ⁵ and/or R ⁶ are naphthalene rings, the condensation form of the above-mentioned 5-membered ring including the nitrogen atom bonded to R ³ and the naphthalene ring is not particularly limited. When at least one of R ⁵ and R ⁶ is a naphthalene ring, the condensed ring containing R ⁵ , R ⁶ and the above-mentioned 5-membered ring including a nitrogen atom bonded to R ³ may be any of the following. [Chem 2]

When the benzene ring or naphthalene ring as R ⁵ and R ⁶ has substituents, the type and number of the substituents are not particularly limited as long as the purpose of the present invention is not impaired. Suitable examples of the substituent include: an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, An alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group of an alkyl group having 1 to 6 carbon atoms, a thiol-1-yl group, a piper-1-yl group, a halogen atom, a cyano group, and the like. When the benzene ring or naphthalene ring as R ⁵ and R ⁶ has substituents, the number of the substituents is not limited within the range that does not impair the object of the present invention, but is preferably 1 or more and 4 or less. When there are a plurality of substituents, the plurality of substituents may be the same or different.

When R ⁵ has a substituent, the substituent on R ⁵ may be bonded to R ¹ or R ³ to form a ring. Also, when R ⁶ has a substituent, the substituent on R ⁶ may be bonded to R ³ to form a ring.

The ring formed by the bond between the substituent of R ⁵ and R ¹ may be a hydrocarbon ring or a heterocycle. The heteroatom contained in the heterocycle is not particularly limited. N, O, S, etc. are mentioned as a preferable hetero atom. The ring formed by the substituents of R ⁵ and/or R ⁶ bonded to R ³ may contain other heteroatoms in addition to the nitrogen atom bonded to R ³ . The heteroatom contained in the heterocycle is not particularly limited. N, O, S, etc. are mentioned as a preferable hetero atom.

(式(a1-1-a)～(a1-1-h)中，R¹ 、R² 、R⁴ 、m1、m2及m3與式(a1)中相同，R⁸ 為烷基) 所表示之化合物。When the substituent of R ⁵ or the substituent of R ⁶ is bonded to R ³ to form a ring, the compound represented by the formula (a1) is preferably the following formula (a1-1-a )～(a1-1-h): [chemical 3]

(In formulas (a1-1-a) to (a1-1-h), R ¹ , R ² , R ⁴ , m1, m2 and m3 are the same as in formula (a1), and R ⁸ is an alkyl group) compound.

The alkyl group as R ⁸ may be linear or branched. The number of carbon atoms in the alkyl group of R ⁷ is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10.

(式(a1-1-i)～(a1-1-l)中，R² 、R³ 、R⁴ 、m2及m3與式(a1)中相同，R⁸ 為碳原子數1以上且20以下之烷基) 所表示之化合物。作為R⁸ 之烷基可為直鏈狀，亦可為支鏈狀。When the substituent of R ⁵ is bonded to R ¹ to form a ring, in formula (a1), m1 is preferably 0. In this case, the compound represented by the formula (a1) is preferably the following formulas (a1-1-i) to (a1-1-l): [Chem. 4]

(In formulas (a1-1-i) to (a1-1-l), R ² , R ³ , R ⁴ , m2, and m3 are the same as in formula (a1), and R ⁸ is 1 to 20 carbon atoms The compound represented by the alkyl group). The alkyl group as R ⁸ may be linear or branched.

(式(a1-I)～(a1-IV)中，R¹ 、R² 、R³ 、R⁴ 、m1、m2及m3與式(a1)中相同) 所表示之化合物，更佳為式(a1-II)或式(a1-III)所表示之化合物，尤佳為式(a1-III)所表示之化合物。Considering the preferred combination of R ⁵ and R ⁶ described above, the compound represented by formula (a1) is preferably the following formulas (a1-I) to (a1-IV):

(In formulas (a1-I) to (a1-IV), R ¹ , R ² , R ³ , R ⁴ , m1, m2 and m3 are the same as in formula (a1)), more preferably the compound represented by formula ( a1-II) or a compound represented by formula (a1-III), particularly preferably a compound represented by formula (a1-III).

As the compound represented by the above-mentioned formulas (a1-I) to (a1-IV), preferably the compound represented by the following formulas (a1-Ia) to (a1-IV-a), more preferably the compound represented by the formula (a1- II-a) or a compound represented by formula (a1-III-a), particularly preferably a compound represented by formula (a1-III-a). [chemical 6]

As the compound represented by the above formulas (a1-Ia) to (a1-IV-a), preferably the compound represented by the following formulas (a1-Ib) to (a1-IV-b), more preferably the compound represented by the formula ( a1-II-b) or a compound represented by formula (a1-III-b), particularly preferably a compound represented by formula (a1-III-b). [chemical 7]

Suitable examples ^of the monovalent organic group as R include: alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, Optionally substituted phenyl, optionally substituted phenoxy, optionally substituted benzoyl, optionally substituted phenoxycarbonyl, optionally substituted benzoyloxy, optionally substituted Substituent phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthoyl, optionally substituted naphthyloxycarbonyl, optionally substituted Naphthyloxyl group, naphthylalkyl group which may have substituent, heterocyclic group which may have substituent, heterocyclic carbonyl group which may have substituent, amino group substituted with one or two organic groups, thioline -1-yl, and piper-1-yl, etc.

When R ¹ is an alkyl group, the number of carbon atoms in the alkyl group is preferably from 1 to 20, more preferably from 1 to 6. Also, when R ¹ is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R is ^an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl Base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n- Decyl, and isodecyl, etc. Also, when R ¹ is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethyl Oxyethyl, and methoxypropyl etc.

When R ¹ is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably from 1 to 20, more preferably from 1 to 6. Also, when R ¹ is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R is ^an alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy , the third butoxyl, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. Also, when R ¹ is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy , propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ¹ is cycloalkyl or cycloalkoxy, the number of carbon atoms in the cycloalkyl or cycloalkoxy is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ¹ is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples of the case where R ¹ is a cycloalkoxy group include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When R is ^a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or a saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more And 7 or less. Specific examples of the case where R is ^a saturated aliphatic acyl group include: acetyl, propionyl, n-butyryl, 2-methylacryl, n-pentyl, 2,2-dimethyl Propyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl Carbonyl, n-pentadecanyl, and n-hexadecanyl, etc. Specific examples of the case where R is ^a saturated aliphatic aliphatic oxy group include: acetyloxy, acryloxy, n-butyryloxy, 2-methylacryloxy, n-pentyloxy , 2,2-Dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadedecyloxy, n-hexadecanyloxy, and the like.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where R is ^an alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, second pentyloxycarbonyl, third pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy octylcarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl etc.

When R ¹ is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably from 7 to 20, more preferably from 7 to 10. Also, when R ¹ is naphthylalkyl, the number of carbon atoms in the naphthylalkyl is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the case where R ¹ is phenylalkyl include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples of the case where R is naphthylalkyl include: α ^- naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl) base) ethyl. When R ¹ is phenylalkyl or naphthylalkyl, R ¹ may further have a substituent on the phenyl or naphthyl.

When R ¹ is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing more than one N, S, O, or a monocyclic ring consisting of each other, or a monocyclic ring and a benzene ring. The heterocyclic group formed by condensation. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocycle constituting the heterocyclic group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Catalyst, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinone phenoline, quinazoline, phthaloline, phenoline, and quinoline, etc. When R ¹ is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclic group contained in the heterocyclylcarbonyl group is the same as when R ¹ is a heterocyclyl group.

When R is ^an amino group substituted with one or two organic groups, suitable examples of the organic group include: an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 10 carbon atoms Cycloalkyl groups, saturated aliphatic acyl groups with 2 to 21 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, and benzoyl groups that may have substituents with 7 to 20 carbon atoms The following phenylalkyl groups, naphthyl groups which may have substituents, naphthoyl groups which may have substituents, naphthylalkyl groups which may have substituents and have 11 to 20 carbon atoms, heterocyclic groups, etc. Specific examples ^of such suitable organic groups are the same as for R1. Specific examples of amino groups substituted with one or two organic groups include: methylamino group, ethylamino group, diethylamino group, n-propylamine group, di-n-propylamino group, isopropylamine group group, n-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, benzene Nylamine, naphthylamine, acetylamino, propionylamine, n-butyrylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine , n-decylamine, benzoylamine, α-naphthylamine, and β-naphthylamine, etc.

As the substituent when the phenyl, naphthyl and heterocyclic group contained in R1 further have ^a substituent, examples include: an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Alkoxy, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, Monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, oxalin-1-yl, piperyl-1-yl , halogen, nitro, and cyano, etc. When the phenyl, naphthyl, and heterocyclic groups contained in R ¹ further have substituents, the number of the substituents is not limited within the range that does not impair the object of the present invention, but is preferably 1 or more and 4 or less. When the phenyl, naphthyl and heterocyclic groups contained in R ¹ have multiple substituents, the multiple substituents may be the same or different.

Also, R ¹ is also preferably cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, or phenylthioalkyl which may have a substituent on the aromatic ring. The optional substituents of the phenoxyalkyl group and the phenylthioalkyl group are the same as the optional substituents of the phenyl group included in R ¹ .

Among the monovalent organic groups, R ¹ is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably an alkyl group having 1 to 4 carbon atoms. Preferably methyl. Among the phenyl groups which may have a substituent, methylphenyl is preferred, and 2-methylphenyl is more preferred. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably from 5 to 10, more preferably from 5 to 8, particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, especially preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms in the alkylene group contained in the thiophenylalkyl group which may have a substituent on the aromatic ring is preferably from 1 to 8, more preferably from 1 to 4, especially preferably 2. Among the thiophenylalkyl groups which may have substituents on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

As mentioned above, the compound represented by the formula (a1) needs to satisfy the following (1)-(3): (1) R ¹ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group. (2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group. (3) R ³ is a branched alkyl group which may have a substituent. at least one of the conditions. Therefore, R ¹ is preferably substituted with a substituent represented by -OR ⁷ . R ⁷ is haloalkyl. When R ¹ is substituted by a group represented by -OR ⁷ , the number of groups represented by -OR ⁷ contained in R ¹ is not particularly limited. When R ¹ is substituted by a group represented by -OR ⁷ , the number of groups represented by -OR ⁷ contained in R ¹ is preferably 1 or 2, more preferably 1. Also, the number of groups represented by -OR ⁷ that the compound represented by formula (a1) has is also preferably 1 or 2, more preferably 1.

As a halogen atom contained in a haloalkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. The haloalkyl group may contain one kind of halogen atom, or may contain two or more kinds of halogen atoms in combination. The number of halogen atoms contained in the haloalkyl group is not particularly limited as long as the object of the present invention is not impaired. The number of halogen atoms contained in the haloalkyl group is preferably 1 or more, more preferably 2 or more, especially preferably 3 or more. In terms of good compatibility between the compound represented by formula (a1) and other components in the photosensitive composition, the upper limit of the number of halogen atoms contained in the haloalkyl group is preferably 7 or less, more preferably 6 or less , preferably below 5. Also, the number of halogen atoms contained in the compound represented by formula (a1) is preferably 1 or more, more preferably 2 or more, especially preferably 3 or more, and preferably 7 or less, more preferably 6 or less, Preferably it is 5 or less.

The number of carbon atoms in the haloalkyl group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms in the haloalkyl group is preferably 1 or more, more preferably 2 or more, especially preferably 3 or more. The upper limit of the number of carbon atoms in the haloalkyl group is preferably 10 or less, more preferably 7 or less, especially preferably 5 or less. As the haloalkyl group, a fluorinated alkyl group is particularly preferred. Specific examples of preferred haloalkyl groups include: 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2, 2,3,3,3-pentafluoropropyl, and 2,2,3,3,4,4,5,5-octafluoropentyl, etc. Among them, 2,2,3,3-tetrafluoropropyl is preferred in terms of the ease of manufacture of the compound represented by formula (a1), and the like.

(式(a1-01)中，R⁷ 如上所述，R⁹ 為作為R¹ 之苯基可具有之取代基，m4為1或2，m4＋m5為1以上且5以下之整數) 所表示之基。 作為R⁹ ，較佳為碳原子數1以上且6以下之烷基、及碳原子數1以上且6以下之烷氧基，更佳為碳原子數1以上且6以下之烷基，進而較佳為甲基及乙基，尤佳為甲基。 m5較佳為1。Regarding the group substituted with a haloalkyl group as R ¹ , it is preferably a phenyl group substituted with 1 or 2 haloalkyl groups. Specifically, the group substituted by haloalkyl as R ¹ is preferably the following formula (a1-01): [Chem. 8]

(In the formula (a1-01), R ⁷ is as above, R ⁹ is a substituent that the phenyl group of R ¹ may have, m4 is 1 or 2, and m4+m5 is an integer of 1 to 5) . R ⁹ is preferably an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably Preferred are methyl and ethyl, particularly preferred is methyl. m5 is preferably 1.

(式(a1-02)中，R¹ 、R² 、R³ 、R⁴ 、R⁵ 、R⁶ 、m1、m2及m3與式(a1)中相同，R¹⁰ 為2價有機基) 所表示之基。Also, R ¹ can also be the following formula (a1-02): [Chemical 9]

(In formula (a1-02), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m1, m2, and m3 are the same as in formula (a1), and R ¹⁰ is a divalent organic group) foundation.

The divalent organic as R ¹⁰ is not particularly limited as long as the object of the present invention is not impaired. Suitable examples of the divalent organic group as R10 include: alkanediyl groups having 1 to ¹⁰ carbon atoms (such as methylene, ethane-1,2-diyl, propane-1,3- Diyl, butane-1,4-diyl, etc.), and aryl (p-phenylene, m-phenylene, o-phenylene, 1,1'-biphenyl-4,4'-di base, etc.).

Specific examples of the compound represented by the formula (a1) when R ¹ is a group represented by the above formula (a1-02) include compounds represented by the following formula. [chemical 10]

Among R ¹ described above, a group represented by the following formula is preferable. [chemical 11]

In formula (a1), R ² is a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent. As the hydrocarbon group which may have a substituent, an alkyl group having 1 to 11 carbon atoms which may have a substituent or an aryl group which may have a substituent are preferable. As the aryl group, phenyl and naphthyl are preferred, and phenyl is preferred. As a substituent which ^R2 may have when it is an alkyl group, a phenyl group, a naphthyl group etc. can be illustrated preferably. In addition, as the substituent that R ² may have when it is an aryl group, preferable examples include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like.

When R ² is a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. When R ² is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing more than one N, S, O, or a combination of the monocyclic rings, or the monocyclic ring and the benzene ring. The heterocyclic group formed by condensation. When the heterocyclic group is a condensed ring, the number of rings is at most 3. As the heterocycle constituting the heterocyclic group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Catalyst, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinone phylloline, quinazoline, phthaloline, phenoline, quinoline, piperidine, piperidine, phenoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R ² is a heterocyclic group, examples of substituents that the heterocyclic group may have include hydroxyl, alkoxy groups having 1 to 6 carbon atoms, halogen atoms, cyano groups, nitro groups, and the like.

R ² is preferably a methyl group, a phenyl group, and a thienyl group, more preferably a methyl group.

In formula (a1), R ³ is a monovalent organic group. R ³ can be selected from various organic groups within the range that does not impair the purpose of the present invention. Suitable examples of ^R3 include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and an optionally substituted cycloalkyl group having 2 or more carbon atoms. And 20 or less saturated aliphatic acyl groups that may have substituents, alkoxycarbonyl groups that may have substituents with 2 or more and 20 or less carbon atoms, phenyl that may have substituents, benzoyl that may have substituents Group, phenoxycarbonyl group which may have a substituent, phenylalkyl group which may have a substituent with 7 to 20 carbon atoms, naphthyl group which may have a substituent, naphthylcarbonyl group which may have a substituent, naphthalyl group which may have a substituent, Naphthyloxycarbonyl which may have substituents, naphthylalkyl groups which may have 11 to 20 carbon atoms which may have substituents, heterocyclic groups which may have substituents, heterocyclic carbonyl groups which may have substituents, etc.

Among R ³ , an alkyl group having 1 to 20 carbon atoms is preferable. This alkyl group may be linear or branched. In terms of the good solubility of the compound represented by formula (a1) in the photosensitive composition, the number of carbon atoms of the alkyl group as ^R3 is preferably 2 or more, more preferably 5 or more, especially preferably 7 above. Also, in terms of the compound represented by the formula (a1) in the photosensitive composition having good compatibility with other components, the number of carbon atoms of the alkyl group as ^R3 is preferably 15 or less, more preferably 10 or less .

When ^R3 has a substituent, suitable examples of the substituent include: hydroxyl group, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon atom Represented by an aliphatic acyl group having a number of 2 to 20, an aliphatic acyloxy group having a carbon number of 2 to 20, a phenoxy group, a benzoyl group, a benzoyloxy group, and -PO(OR) ₂ (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group, a heterocyclic group, and the like. Suitable examples of the heterocyclic group as the substituent are the same as the suitable examples of the heterocyclic group as R ² .

As mentioned above, the compound represented by the formula (a1) needs to satisfy the following (1)-(3): (1) R ¹ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group. (2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group. (3) R ³ is a branched alkyl group which may have a substituent. at least one of the conditions. Therefore, R ³ is preferably a branched chain alkyl group which may have a substituent.

(式(a1-03)中，R¹ 、R² 、R⁴ 、R⁵ 、R⁶ 、m1、m2及m3與式(a1)中相同，R¹¹ 為2價有機基)Also, R ³ is the following formula (a1-03): [Chem. 12]

(In formula (a1-03), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , m1, m2, and m3 are the same as in formula (a1), and R ¹¹ is a divalent organic group)

The divalent organic as R ¹¹ is not particularly limited as long as the object of the present invention is not impaired. Suitable examples of the divalent organic group as R ¹¹ include: alkanediyl groups having 1 to 10 carbon atoms (such as methylene, ethane-1,2-diyl, propane-1,3- Diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8- Diyl, etc.), aryl (p-phenylene, m-phenylene, o-phenylene, 1,1'-biphenyl-4,4'-diyl, etc.).

In addition, the following groups are also applicable to the divalent organic group as R ¹¹ . In the following formula, R ¹² is an alkylene group having 1 to 20 carbon atoms. Regarding the alkylene group as R ¹² , methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1, 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl. [chemical 13]

Specific examples of the compound represented by the formula (a1) when R ³ is a group represented by the above formula (a1-03) include compounds represented by the following formula. [chemical 14]

Suitable specific examples of ^R3 as described above include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl , isopentyl, neopentyl, pentane-3-yl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl. As mentioned above, ^R is preferably a branched chain alkyl group. In this regard, among the above-mentioned alkyl groups, preferably isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, Neopentyl, pentan-3-yl, second pentyl, third pentyl, and 2-ethylhexyl. Moreover, n-octyl and 2-ethylhexyl are preferable, and 2-ethylhexyl is more preferable at the point which the solubility to the photosensitive composition of the compound represented by a formula (a1) is favorable.

R ⁴ in the formula (a1) is a monovalent organic group. As the monovalent organic group as R ⁴ , the same ones as the monovalent organic group as R ¹ can be mentioned.

R ⁴ is bonded to the main skeleton of the compound represented by formula (a1) in the form of a group represented by R ⁴ -(CO) _m3- . Preferable specific examples of the group represented by R ⁴ -(CO) _m3- include groups represented by the following formulae. In the following formula, m3 is 1 or 0 as in formula (a1). [chemical 15]

[chemical 16]

[chemical 17]

Among the suitable examples of the group represented by the above R ⁴ -(CO) _m3 -, 1,3,5-trimethylbenzoyl group is particularly preferable.

As mentioned above, the compound represented by the formula (a1) needs to satisfy the following (1)-(3): (1) R ¹ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group. (2) m2 is 1, R ⁴ contains a group represented by -OR ⁷ , and R ⁷ is a haloalkyl group. (3) R ³ is a branched alkyl group which may have a substituent. at least one of the conditions. Therefore, R ⁴ is preferably substituted with a substituent represented by -OR ⁷ . R ⁷ is haloalkyl. ^{R7 is} as described above.

Regarding the group substituted with a haloalkyl group as R ⁴ , it is preferably a phenyl group substituted with 1 or 2 haloalkyl groups. Specifically, it is the same as the group substituted with a haloalkyl group as R ¹ , preferably a group represented by the above formula (a1-01).

(式(a1-04)中，R¹ 、R³ 、R⁵ 、R⁶ 、m1、m2及m3與式(a1)中相同，R¹³ 為2價有機基) 所表示之基。In addition, R ⁴ is also preferably represented by the following formula (a1-04): [Chem. 18]

(In formula (a1-04), R ¹ , R ³ , R ⁵ , R ⁶ , m1, m2, and m3 are the same as in formula (a1), and R ¹³ is a divalent organic group).

The divalent organic as ^R13 is not particularly limited as long as the object of the present invention is not impaired. Suitable examples of the divalent organic group as ^R13 include: alkanediyl groups having 1 to 10 carbon atoms (such as methylene, ethane-1,2-diyl, propane-1,3- Diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8- Diyl, etc.), aryl (p-phenylene, m-phenylene, o-phenylene, 1,1'-biphenyl-4,4'-diyl, etc.).

In addition, the following groups are also applicable to the divalent organic group as R ¹³ . In the following formula, R ¹³ is an alkylene group having 1 to 20 carbon atoms which may be substituted by a halogen atom. Regarding the alkylene group as R ¹⁴ , methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1, 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl. Also, a group in which all hydrogen atoms in the alkylene group are replaced by halogen atoms, especially fluorine atoms is also applicable to R ¹⁴ . [chemical 19]

In formula (a1), m1, m2 and m3 are all 0 or 1. As m1, 0 is preferable. As m2, 1 is preferable, and as m3, 1 is preferable.

Preferable specific examples of the compound represented by the formula (a1) described above include the following compounds. [chemical 20]

[chem 21]

[chem 22]

[chem 23]

[chem 24]

[chem 25]

[chem 26]

(式(a2)中，CR為下述式(a2a)或下述式(a2b)： [化28]

所表示之基，R^a1 為氫原子、硝基或1價有機基，R^a2 及R^a3 分別為可具有取代基之鏈狀烷基、可具有取代基之鏈狀烷氧基、可具有取代基之環狀有機基、或氫原子，R^a2 與R^a3 亦可相互鍵結而形成環，R^a4 為1價有機基，R^a5 為氫原子、可具有取代基之碳原子數1以上且20以下之脂肪族烴基、或可具有取代基之芳基，n1為0以上且4以下之整數，n2為0或1) 所表示之化合物。 就式(a2)所表示之肟酯化合物之易合成性或易獲得性、或者藉由選擇R^a2 及R^a3 而容易調整肟酯化合物之特性等方面而言，作為式(a2)中之CR，較佳為式(a2a)所表示之基。[Oxime ester compound (A2)] The oxime ester compound (A2) has the following formula (a2): [Chem. 27]

(In the formula (a2), CR is the following formula (a2a) or the following formula (a2b):

In the group represented, R ^a1 is a hydrogen atom, a nitro group or a monovalent organic group, R ^a2 and R ^a3 are respectively a chain-like alkyl group that may have a substituent, a chain-like alkoxy group that may have a substituent, and a chain-like alkoxy group that may have a substituent A cyclic organic group or a hydrogen atom, R ^a2 and R ^a3 may be bonded to each other to form a ring, R ^a4 is a monovalent organic group, R ^a5 is a hydrogen atom, and the number of carbon atoms that may have substituents is 1 or more and A compound represented by an aliphatic hydrocarbon group of 20 or less, or an aryl group which may have a substituent, n1 is an integer of 0 to 4, and n2 is 0 or 1). In terms of the ease of synthesis or availability of the oxime ester compound represented by formula (a2), or the ease of adjusting the characteristics of the oxime ester compound by selecting R ^a2 and R ^a3 , as CR in formula (a2) , preferably a group represented by formula (a2a).

所表示之結構中之＊所示之位置。於R^a1 為複數個之情形時，複數個R^a1 可相同亦可不同。In the group represented by formula (a2a) or formula (a2b) which is CR in formula (a2), R ^a1 is a hydrogen atom, a nitro group or a monovalent organic group. R ^a1 is a 6-membered aromatic ring that is bonded to the condensed ring in formula (a2a) or formula (a2b) and is different from the aromatic ring bonded to the group represented by -(CO) _n2- . The bonding position of R ^a1 in formula (a2a) or formula (a2b) is not particularly limited. When the compound represented by the formula (a2) has one or more R ^a1 , in terms of the ease of synthesis of the compound represented by the formula (a2), etc., it is preferably one of the more than one R ^a1 Bonded to the following formula (a2a-1) and formula (a2b-1): [Chemical 29]

The position indicated by * in the structure indicated. When R ^a1 is plural, the plural R ^a1 may be the same or different.

When R ^a1 is an organic group, R ^a1 is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from various organic groups. Suitable examples when R ^a1 is an organic group include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, saturated aliphatic acyloxy, alkoxycarbonyl, Optionally substituted phenyl, optionally substituted phenoxy, optionally substituted benzoyl, optionally substituted phenoxycarbonyl, optionally substituted benzoyloxy, optionally substituted Substituent phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthoyl, optionally substituted naphthyloxycarbonyl, optionally substituted Naphthyloxyl group, naphthylalkyl group which may have substituent, heterocyclic group which may have substituent, heterocyclic carbonyl group which may have substituent, amino group substituted with one or two organic groups, thioline -1-yl, and piper-1-yl, etc.

When R ^a1 is an alkyl group, the number of carbon atoms in the alkyl group is preferably from 1 to 20, more preferably from 1 to 6. Also, when R ^a1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^a1 is an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl Base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n- Decyl, and isodecyl, etc. Also, when R ^a1 is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethyl Oxyethyl, and methoxypropyl etc.

When R ^a1 is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably from 1 to 20, more preferably from 1 to 6. Also, when R ^a1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^a1 is an alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy , the third butoxyl, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. Also, when R ^a1 is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy , propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^a1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ^a1 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples of the case where R ^a1 is a cycloalkoxy group include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When R ^a1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or a saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more And 7 or less. Specific examples of the case where R ^a1 is a saturated aliphatic acyl group include acetyl, acryl, n-butyryl, 2-methylacryl, n-pentyl, and 2,2-dimethyl Propyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl Carbonyl, n-pentadecanyl, and n-hexadecanyl, etc. Specific examples of the case where R ^a1 is a saturated aliphatic oxy group include: acetyloxy, propionyloxy, n-butyryloxy, 2-methylacryloxy, n-pentyloxy , 2,2-Dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadedecyloxy, n-hexadecanyloxy, and the like.

When R ^a1 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where R ^a1 is an alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, second pentyloxycarbonyl, third pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy octylcarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl etc.

When R ^a1 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably from 7 to 20, more preferably from 7 to 10. Also, when R ^a1 is naphthylalkyl, the number of carbon atoms in the naphthylalkyl is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the case where R ^a1 is phenylalkyl include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples of the case where R ^a1 is naphthylalkyl include: α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl) base) ethyl. When R ^a1 is phenylalkyl or naphthylalkyl, R ^a1 may further have a substituent on phenyl or naphthyl.

When R ^a1 is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing more than one N, S, O, or a monocyclic ring formed by each other, or a monocyclic ring and a benzene ring. The heterocyclic group formed by condensation. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocycle constituting the heterocyclic group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Catalyst, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinone phylloline, quinazoline, phthaloline, phenoline, quinoline, piperidine, piperidine, phenoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R ^a1 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^a1 is a heterocyclylcarbonyl group, the heterocyclic group contained in the heterocyclylcarbonyl group is the same as when R ^a1 is a heterocyclic group.

When R ^a1 is an amino group substituted with one or two organic groups, suitable examples of the organic group include: an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 10 carbon atoms Cycloalkyl groups, saturated aliphatic acyl groups with 2 to 21 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, and benzoyl groups that may have substituents with 7 to 20 carbon atoms The following phenylalkyl groups, naphthyl groups which may have substituents, naphthoyl groups which may have substituents, naphthylalkyl groups which may have substituents and have 11 to 20 carbon atoms, heterocyclic groups, etc. Specific examples of such suitable organic groups are the same as for R ^a1 . Specific examples of amino groups substituted with one or two organic groups include: methylamino group, ethylamino group, diethylamino group, n-propylamine group, di-n-propylamino group, isopropylamine group group, n-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, benzene Nylamine, naphthylamine, acetylamino, propionylamine, n-butyrylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine , n-decylamine, benzoylamine, α-naphthylamine, and β-naphthylamine, etc.

Examples of substituents when the phenyl, naphthyl, and heterocyclic groups contained in R ^a1 further have substituents include alkyl groups having 1 to 6 carbon atoms, and alkyl groups having 1 to 6 carbon atoms. Alkoxy, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, Monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, oxalin-1-yl, piperyl-1-yl , halogen, nitro, and cyano, etc. When the phenyl, naphthyl and heterocyclic groups contained in R ^a1 further have substituents, the number of the substituents is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less. When the phenyl, naphthyl and heterocyclic groups contained in R ^a1 have multiple substituents, the multiple substituents may be the same or different.

Among the groups described above, when R ^a1 is a group represented by nitro or R ^a6 -CO-, the sensitivity tends to be improved, which is preferable. R ^a6 is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of the group suitable as R ^a6 include: an alkyl group having 1 to 20 carbon atoms, a phenyl group that may have a substituent, a naphthyl group that may have a substituent, and a heterocyclic group that may have a substituent . Among these groups, R ^a6 is particularly preferably 2-methylphenyl, thien-2-yl, and α-naphthyl. Moreover, when R ^a1 is a hydrogen atom, since transparency tends to be favorable, it is preferable. Furthermore, when R ^a1 is a hydrogen atom and R ^a3 is a group represented by the following formula (a2-a) or (a2-b), there exists a tendency for transparency to be more favorable.

In formula (a2a), R ^a2 and R ^a3 are respectively a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^a2 and R ^a3 may be bonded to each other to form a ring. Among these groups, R ^a2 and R ^a3 are preferably chain alkyl groups which may have substituents. When R ^a2 and R ^a3 are chain alkyl groups which may have substituents, the chain alkyl groups may be linear or branched.

When R ^a2 and R ^a3 are chained alkyl groups without substituents, the number of carbon atoms in the chained alkyl group is preferably from 1 to 20, more preferably from 1 to 10, especially preferably 1 Above and below 6. Specific examples of the case where R ^a2 and R ^a3 are chain alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third Butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, Isononyl, n-decyl, and isodecyl, etc. Moreover, when R ^a2 and R ^a3 are an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethyl Oxyethyl, and methoxypropyl etc.

When R ^a2 and R ^a3 are chained alkyl groups having substituents, the number of carbon atoms in the chained alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and especially preferably from 1 to 10. And 6 or less. In this case, the carbon number of the chain alkyl group does not include the carbon number of the substituent. The linear alkyl group having a substituent is preferably linear. The substitution which an alkyl group may have is not specifically limited in the range which does not impair the objective of this invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. As a cyclic organic group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group are mentioned. Specific examples of the cycloalkyl group are the same as suitable examples when R ^a1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthrenyl. Specific examples of the heterocyclic group are the same as suitable examples when R ^a1 is a heterocyclic group. When R ^a1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably from 1 to 10, more preferably from 1 to 6.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, more preferably 1 to 6 inclusive.

When R ^a2 and R ^a3 are chain alkoxy groups without substituents, the number of carbon atoms in the chain alkoxy group is preferably from 1 to 20, more preferably from 1 to 10, especially preferably 1 or more and 6 or less. Specific examples of the case where R ^a2 and R ^a3 are chain alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, Second butoxy, third butoxy, n-pentoxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyl oxy, 2nd octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. Also, when R ^a2 and R ^a3 are alkoxy groups, the alkoxy groups may include an ether bond (—O—) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy , propoxyethoxyethoxy, and methoxypropoxy, etc. When R ^a2 and R ^a3 are chain alkoxy groups having substituents, the substituents that alkoxy groups may have are the same as when R ^a2 and R ^a3 are chain alkyl groups.

When R ^a2 and R ^a3 are cyclic organic groups, the cyclic organic groups may be alicyclic groups or aromatic groups. Examples of the cyclic organic group include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups. When R ^a2 and R ^a3 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ^a2 and R ^a3 are chain alkyl groups.

When R ^a2 and R ^a3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings foundation. When the aromatic hydrocarbon group is a phenyl group, or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably The preferred value is 2 or less, and the preferred value is 1. Preferable specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthrenyl.

When R ^a2 and R ^a3 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably from 3 to 20, more preferably from 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, northyl, isothyl, tricyclononyl, Tricyclodecanyl, tetracyclododecyl, and adamantyl, etc.

When R ^a2 and R ^a3 are heterocyclic groups, the heterocyclic groups are 5-membered or 6-membered monocyclic rings containing more than one N, S, and O, or between the monocyclic rings, or from the monocyclic rings. A heterocyclic group condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocycle constituting the heterocyclic group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Catalyst, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinone phylloline, quinazoline, phthaloline, phenoline, quinoline, piperidine, piperidine, phenoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc.

R ^a2 and R ^a3 may be bonded to each other to form a ring. The group comprising a ring formed by R ^a2 and R ^a3 is preferably a cycloalkylene group. When R ^a2 and R ^a3 are bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-6-membered ring, more preferably a 5-membered ring.

When the group formed by the bonding of R ^a2 and R ^a3 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that can be condensed with the cycloalkylene ring include: benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyrimidine ring, pyrimidine ring, etc.

Among R ^a2 and R ^a3 described above, examples of suitable groups include groups represented by formulas -A ¹ -A ² . In the formula, examples of A ¹ include linear alkylene groups, and examples of A ² include alkoxy groups, cyano groups, halogen atoms, halogenated alkyl groups, cyclic organic groups, or alkoxycarbonyl groups.

The number of carbon atoms in the linear alkylene group of A ¹ is preferably from 1 to 10, more preferably from 1 to 6. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group is preferably from 1 to 10, more preferably from 1 to 6. When ^A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. When ^A2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, preferably linear. When ^A2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^a2 and R ^a3 have as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R ^a2 and R ^a3 have as substituents.

Suitable specific examples of R ^a2 and R ^a3 include: alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3 -Methoxy n-propyl, 4-methoxy n-butyl, 5-methoxy n-pentyl, 6-methoxy n-hexyl, 7-methoxy n-heptyl, 8-methoxy n-octyl Base, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy Alkoxyalkyl groups such as n-heptyl and 8-ethoxyn-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl , 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl and other cyanoalkyl groups; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n- Butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl and other phenylalkyl groups; 2-cyclohexylethyl, 3-cyclo Hexyl n-propyl, 4-cyclohexyl n-butyl, 5-cyclohexyl n-pentyl, 6-cyclohexyl n-hexyl, 7-cyclohexyl n-heptyl, 8-cyclohexyl n-octyl, 2-cyclopentyl ethyl Base, 3-cyclopentyl n-propyl, 4-cyclopentyl n-butyl, 5-cyclopentyl n-pentyl, 6-cyclopentyl n-hexyl, 7-cyclopentyl n-heptyl, and 8-cyclopentyl n-heptyl Cycloalkylalkyl such as pentyl n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl n-propyl, 4-methoxycarbonyl n-butyl, 5-methoxycarbonyl n-pentyl , 6-methoxycarbonyl n-hexyl, 7-methoxycarbonyl n-heptyl, 8-methoxycarbonyl n-octyl, 2-ethoxycarbonyl ethyl, 3-ethoxycarbonyl n-propyl, 4 -ethoxycarbonyl n-butyl, 5-ethoxycarbonyl n-pentyl, 6-ethoxycarbonyl n-hexyl, 7-ethoxycarbonyl n-heptyl, and 8-ethoxycarbonyl n-octyl and other alkanes Oxycarbonylalkyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n- Octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, Halogenated alkyl groups such as 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

R ^a2 and R ^a3 are preferably ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5, 5,5-Heptafluoro-n-pentyl.

Examples of suitable organic groups for R ^a4 include, in the same manner as R ^a1 , alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic Cycloacyloxy group, phenyl group which may have substituent, phenoxy group which may have substituent, benzoyl group which may have substituent, phenoxycarbonyl group which may have substituent, benzoyl group which may have substituent Oxygen, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthoyl, optionally substituted naphthyloxycarbonyl, Naphthyloxyl group which may have substituent, naphthylalkyl group which may have substituent, heterocyclic group which may have substituent, heterocyclic carbonyl group which may have substituent, substituted by one or two organic groups Amino group, 𠰌line-1-yl group, piper 𠯤-1-yl group, etc. Specific examples of these bases are the same as those described for R ^a1 . Also, R ^a4 is also preferably cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, or phenylthioalkyl which may have a substituent on the aromatic ring. The optional substituents of the phenoxyalkyl group and the phenylthioalkyl group are the same as the optional substituents of the phenyl group included in R ^a1 .

Among the organic groups, R ^a4 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably an alkyl group having 1 to 4 carbon atoms. Preferably methyl. Among the phenyl groups which may have a substituent, methylphenyl is preferred, and 2-methylphenyl is more preferred. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably from 5 to 10, more preferably from 5 to 8, particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, especially preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms in the alkylene group contained in the thiophenylalkyl group which may have a substituent on the aromatic ring is preferably from 1 to 8, more preferably from 1 to 4, especially preferably 2. Among the thiophenylalkyl groups which may have substituents on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

Also, R ^a4 is also preferably a group represented by -A ³ -CO-OA ⁴ . A ³ is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When ^A3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A3 is an alkylene group, the number of carbon atoms in the alkylene group is preferably from ¹ to 10, more preferably from 1 to 6, even more preferably from 1 to 4.

Suitable examples of A4 include: an alkyl group having ¹ to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Suitable specific examples of A4 include: methyl, ethyl, n ^- propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, n-hexyl , phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl, etc.

Specific examples of suitable groups represented by -A ³ -CO-OA ⁴ include: 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methyl Oxycarbonyl n-propyl, 3-ethoxycarbonyl n-propyl, 3-n-propoxycarbonyl n-propyl, 3-n-butoxycarbonyl n-propyl, 3-n-pentyloxycarbonyl n-propyl, 3-n-hexyloxycarbonyl n-propyl, 3-benzyloxycarbonyl n-propyl, 3-phenoxycarbonyl n-propyl and the like.

(式(a2-a)及(a2-b)中，R^a7 及R^a8 分別為有機基，n3為0以上且4以下之整數，於R^a7 及R^a8 在苯環上處於鄰接位置之情形時，R^a7 與R^a8 亦可相互鍵結而形成環，n4為1以上且8以下之整數，n5為1以上且5以下之整數，n6為0以上且(n5＋3)以下之整數，R^a9 為有機基)R ^a4 has been described above, but R ^a4 is preferably a group represented by the following formula (a2-a) or (a2-b). [chem 30]

(In formulas (a2-a) and (a2-b), R ^a7 and R ^a8 are organic groups respectively, n3 is an integer between 0 and 4, and when R ^a7 and R ^a8 are adjacent to the benzene ring In this case, R ^a7 and R ^a8 may be bonded to each other to form a ring, n4 is an integer of 1 to 8, n5 is an integer of 1 to 5, n6 is an integer of 0 to (n5+3), R ^a9 for organic base)

Examples of the organic groups of R ^a7 and R ^a8 in the formula (c2-a) are the same as those of R ^a1 . R ^a7 is preferably an alkyl group or a phenyl group. When R ^a7 is an alkyl group, the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5, especially preferably from 1 to 3, most preferably 1. That is, R ^a7 is preferably methyl. When R ^a7 and R ^a8 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (c2-a) when R ^a7 and R ^a8 form a ring include: naphthalene-1-yl or 1,2,3,4-tetrahydronaphthalen-5-yl, etc. . In the above formula (c2-a), n3 is an integer between 0 and 4, preferably 0 or 1, more preferably 0.

In the above formula (a2-b), R ^a9 is an organic group. Examples of the organic group include the same ones as those described for R ^a1 . Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, even more preferably from 1 to 3. Preferred examples of R ^a9 include methyl, ethyl, propyl, isopropyl, and butyl, among which methyl is more preferred.

In the above formula (a2-b), n5 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (a2-b), n6 is an integer of 0 to (n5+3) inclusive, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, especially preferably 0. In the above formula (a2-b), n4 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, particularly preferably 1 or 2.

In formula (a2), R ^a5 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group. As a substituent which R ^a5 may have when it is an aliphatic hydrocarbon group, a phenyl group, a naphthyl group, etc. are illustrated preferably. In addition, as the substituent which R ^a1 may have when it is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like are preferably exemplified.

In formula (a2), as R ^a5 , preferably, hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-cyclopentylethyl, 2-cyclobutylethyl Among them, methyl or phenyl is more preferred.

Preferable specific examples of the compound represented by the formula (a2) include the following compounds. [chem 31]

[chem 32]

[chem 33]

[chem 34]

[chem 35]

Content of the photoinitiator (A) in a photosensitive composition is not specifically limited in the range which does not impair the object of this invention. The content of the photopolymerization initiator (A) is preferably from 0.1% by mass to 50% by mass, more preferably from 0.3% by mass to 30% by mass, with respect to the mass of the solid content of the photosensitive composition, especially Preferably, it is not less than 0.5% by mass and not more than 20% by mass. By using the photopolymerization initiator (A) in the amount within this range, the effect expected by using the photopolymerization initiator (A) can be easily obtained without impairing the mechanical properties, solvent resistance, Chemical resistance etc.

<Polymerizable base material component (B)> The photosensitive composition may contain a polymerizable base material component (B) further. The polymerizable substrate component (B) (hereinafter also referred to as "component (B)") is a component that imparts photopolymerization and film-forming ability to the photosensitive composition. The polymerizable base material component (B) will not be specifically limited as long as it contains the component which can be polymerized by a photoinitiator (A), and can prepare the photosensitive composition which can form a film. The polymerizable base material component (B) may be used alone or in combination of two or more.

The polymerizable base material component (B) typically contains a photopolymerizable compound (B1), or contains a photopolymerizable compound (B1) and a resin (B2). The photopolymerizable compound (B1) may be a low-molecular compound or a high-molecular compound. The photopolymerizable compound (B1) and resin (B2) can be used individually or in combination of 2 or more types, respectively. The photopolymerizable compound (B1) and the resin (B2) can be distinguished, for example, by the following method: the resin (B2) is a polymer of one or two or more monomer compounds and has a weight average molecular weight of 1000 or more, and The compound which does not correspond to resin (B2) and has a photopolymerizable functional group is used as a photopolymerizable compound (B1).

In terms of photopolymerization, the polymerizable substrate component (B) is preferably a combination of a low-molecular-weight photopolymerizable compound (B1) that is not a polymer, and a crosslinkable group-containing resin (B2). resin. Moreover, when a polymeric base material component (B) contains resin (B2), it is preferable that resin (B2) contains alkali-soluble resin from a developable viewpoint. The alkali-soluble resin may contain a crosslinkable group. An alkali-soluble resin containing a crosslinkable group (containing a crosslinkable group as a substituent in a structural unit) is preferable from both viewpoints of photopolymerization and alkali developability.

Hereinafter, the photopolymerizable compound (B1) and resin (B2) are demonstrated sequentially.

[Photopolymerizable Compound (B1)] As the photopolymerizable compound (B1) contained in the photosensitive composition, a compound having an ethylenically unsaturated double bond can be preferably used. Suitable examples of the compound having such an ethylenically unsaturated double bond include monofunctional monomers and polyfunctional monomers.

Examples of monofunctional monomers include: (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (methyl) Acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-hydroxymethyl(meth)acrylamide (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, butyl Acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, tertiary butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate -Hydroxybutyl ester, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate ester, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylate base) 2,2,3,3-tetrafluoropropyl acrylate, half (meth)acrylate of phthalic acid derivatives, etc. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, examples of polyfunctional monomers include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate (1,6-hexanediol dimethacrylate), 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12- Dodecanediol Di(meth)acrylate, Ethoxylated Hexylene Glycol Di(meth)acrylate, Tricyclodecane Dimethanol Di(meth)acrylate, 2-Hydroxy(meth)acrylate -3-(meth)acryloxypropyl ester, dipentaerythritol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol Di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, poly(ethylene glycol Alcohol-propylene glycol) di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate (meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetra Ethylene Glycol Di(meth)acrylate, Propylene Glycol Di(meth)acrylate, Polypropylene Glycol Di(meth)acrylate, Butylene Glycol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate Acrylates, 1,6-hexanediol di(meth)acrylate (1,6-hexaneglycol dimethacrylate), trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri Acrylates, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol pentaacrylate (Meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4- (Meth)acryloxypolyethoxyphenyl) propane, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether bis(methyl) ) acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(methyl) ) acrylates, urethane (meth)acrylates (i.e. toluene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate etc. with 2-hydroxyethyl (meth)acrylate reactants), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensation product of polyol and N-methylol(meth)acrylamide, triacrylamide Formal, 2,4,6-trioxohexahydro-1,3 ,5-Tri-alcohol-1,3,5-triethanol triacrylate, and 2,4,6-trioxohexahydro-1,3,5-tri-alcohol-1,3,5-triethanol diacrylic acid Esters etc. These polyfunctional monomers can be used individually or in combination of 2 or more types.

Among these compounds having ethylenically unsaturated double bonds, polyfunctional monomers with trifunctional or higher functions are preferred in terms of obtaining a photosensitive composition capable of forming a cured product having excellent strength and adhesion to substrates. . From the viewpoint of controlling the glass transition point (Tg), monofunctional monomers or difunctional monomers can also be used in combination with trifunctional or higher polyfunctional monomers. Among these, 1,6- Hexylene glycol di(meth)acrylate.

The content of the photopolymerizable compound (B1) is preferably from 5% by mass to 97% by mass, more preferably from 10% by mass to 95% by mass, based on the solid content of the photosensitive composition. Curability becomes favorable by making content of the photopolymerizable compound (B1) in a photosensitive composition into the said range. Moreover, if it is 60 mass % or less (preferably 5 mass % or more and 40 mass % or less) with respect to the solid content of a photosensitive composition, it will be easy to realize the sensitivity, developability, and resolution of a photosensitive composition. The tendency of the balance between imagery.

[Resin (B2)] It is preferable that the photosensitive composition contains the said photopolymerizable compound (B1) and resin (B2) together as a polymeric base material component (B). It does not specifically limit as resin (B2) in the range which does not impair the object of this invention, The resin component prepared previously with various photosensitive compositions can be used. Hereinafter, preferable examples of the resin (B2) will be described.

(Crosslinkable group-containing resin) When a photosensitive composition contains a crosslinkable group-containing resin as resin (B2), it exists in the tendency which becomes easy to form a hardened|cured material using this photosensitive composition. The crosslinkable group-containing resin is a resin having a crosslinkable group, and preferably includes a unit derived from a (meth)acrylate having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a functional group capable of crosslinking the crosslinkable group-containing resin mainly by heating, and is preferably an epoxy group or an ethylenically unsaturated double bond. The crosslinking group can be introduced into the crosslinking group by including, for example, at least one selected from the group consisting of a unit derived from (meth)acrylate having an epoxy group and a unit having an ethylenically unsaturated double bond. In the resin of the linking group.

As crosslinkable group containing resin, resin containing the unit derived from the (meth)acrylate which has an epoxy group is preferable. By having this unit, the adhesiveness or mechanical strength to the base material of the cured film formed using the photosensitive composition can also be improved.

The (meth)acrylate having an epoxy group may be a (meth)acrylate having a chain aliphatic epoxy group, or a (meth)acrylate having an alicyclic epoxy group as described below .

The (meth)acrylate which has an epoxy group may also have an aromatic group. In this specification, an aromatic group is a group which has an aromatic ring. As an example of the aromatic ring which comprises an aromatic group, a benzene ring and a naphthalene ring are mentioned. Examples of (meth)acrylates having an aromatic group and an epoxy group include: 4-glycidyloxyphenyl (meth)acrylate, 3-glycidyloxyphenyl (meth)acrylate , 2-glycidyloxyphenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate, and (meth)acrylate Base) 2-glycidyloxyphenylmethyl acrylate, etc.

When transparency is required for a film formed using a photosensitive composition, the (meth)acrylic acid having an epoxy group is preferably one that does not have an aromatic group.

Examples of (meth)acrylates having a chain aliphatic epoxy group include epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. A (meth)acrylate in which a chain aliphatic epoxy group is bonded to the oxygen group (-O-) in the ester group (-O-CO-). The chain aliphatic epoxy in such (meth)acrylate may contain one or more oxy groups (-O-) in the chain. The number of carbon atoms in the chain aliphatic epoxy group is not particularly limited, but it is preferably from 3 to 20, more preferably from 3 to 15, and particularly preferably from 3 to 10.

Specific examples of (meth)acrylates having a chain aliphatic epoxy group include: glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, (meth)acrylic acid 3,4-epoxybutyl, 6,7-epoxyheptyl (meth)acrylate and other epoxyalkyl (meth)acrylates; 2-glycidyloxyethyl (meth)acrylate, (meth)acrylate Base) 3-glycidyloxy-n-propyl acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate, 6-glycidyl(meth)acrylate Epoxyalkyloxyalkyl (meth)acrylates such as glyceryloxy-n-hexyl ester.

As a specific example of the (meth)acrylate which has an alicyclic epoxy group, the compound represented by following formula (d2-1) - (d2-16) is mentioned, for example. Among these, compounds represented by the following formulas (d2-1) to (d2-6) are preferred, and more preferred are the compounds represented by the following formula (d2-1) in order to impart appropriate developability to the photosensitive composition. Compounds represented by ~(d2-4). In addition, in each of these compounds, the bonding position of the oxygen atom of the ester group on the alicyclic ring is not limited to what is shown here, and some positional isomers are also included.

[chem 36]

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent aliphatic saturated hydrocarbon group with 1 to 6 carbon atoms, R ^d6 represents a divalent hydrocarbon group with 1 to 10 carbon atoms, and n represents An integer between 0 and 10. R ^d5 is preferably a linear or branched alkylene group, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylene, pentamethylene, hexamethylene base. R ^d6 is preferably, for example, methylene, ethylidene, propylidene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH ₂ -Ph-CH ₂ - (Ph represents a phenylene group).

If the (meth)acrylate with epoxy group is the (meth)acrylate with alicyclic epoxy group as above, compared with the (meth)acrylate with chain aliphatic epoxy group, The cross-linkable group-containing resin containing the unit derived from the (meth)acrylate, and the storage stability of the photosensitive composition are excellent, and the temperature range in which pre-baking can be performed when forming a cured film (pre-baking temperature range) is extended, so it is better.

Also, the resin containing a crosslinkable group may be a resin containing a unit having an ethylenically unsaturated double bond as a crosslinkable group (in this specification, sometimes referred to as "resin having an ethylenically unsaturated double bond") ). The ethylenically unsaturated double bond preferably constitutes a part of the (meth)acryloyloxy group.

As resin which has an ethylenically unsaturated double bond, the resin which has a (meth)acryloxy group is mentioned, for example. The resin having a (meth)acryloyloxy group can be obtained, for example, by making at least a part of the carboxyl group contained in a polymer containing a unit derived from an unsaturated carboxylic acid, and the above-mentioned (methyl) group having an alicyclic epoxy group. Acrylate and/or the (meth)acrylate having chain aliphatic epoxy group are reacted and prepared.

When the crosslinkable group-containing resin is a resin having an ethylenically unsaturated double bond, it may have photopolymerization. By making the photosensitive composition contain the photopolymerizable resin which has this ethylenically unsaturated double bond as resin (B2), the curability of a photosensitive composition can be improved, and a pattern can be formed easily.

In the crosslinkable group-containing resin, the amount of units derived from a (meth)acrylate having a crosslinkable group is preferably at least 20% by mass and at most 80% by mass relative to the mass of the resin, more preferably at least 80% by mass. It is 30 mass % or more and 70 mass % or less, More preferably, it is 33 mass % or more and 65 mass % or less. In the crosslinkable group-containing resin, the amount of units derived from (meth)acrylate having an epoxy group is preferably at least 10% by mass and at most 90% by mass relative to the mass of the resin, more preferably 15 mass % or more and 80 mass % or less, More preferably, it is 20 mass % or more and 70 mass % or less. In the crosslinkable group-containing resin, the amount of units having an ethylenically unsaturated double bond is preferably at least 1% by mass and at most 40% by mass, more preferably at least 5% by mass and not more than 35% by mass, relative to the mass of the resin. Mass% or less. As the crosslinkable group-containing resin, it is preferably a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate esters. In the case of this polymer, in the polymer The content of the unit derived from the (meth)acrylate which has a crosslinkable group with respect to resin mass is also the same as above.

Resins containing crosslinkable groups may contain both units derived from (meth)acrylates with epoxy groups and units with ethylenically unsaturated double bonds, and may also contain units derived from (meth)acrylates with epoxy groups. ) acrylate units or units having an ethylenically unsaturated double bond preferably contain only units derived from (meth)acrylates having an epoxy group as a crosslinkable group.

The crosslinkable group-containing resin is preferably both a crosslinkable group-containing resin and an alkali-soluble resin. Alkali developability can be provided to a photosensitive composition by compounding this alkali-soluble resin in a photosensitive composition.

In this specification, the so-called alkali-soluble resin refers to the following: use a resin solution with a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) to form a resin film with a film thickness of 1 μm on the substrate, and use a resin solution with a concentration of 0.05% by mass % KOH aqueous solution for 1 minute, the film thickness of 0.01 μm or more will dissolve.

When the crosslinkable group-containing resin is also an alkali-soluble resin, it usually has an alkali-soluble group. The alkali-soluble group is not particularly limited as long as it is a functional group that imparts the above-mentioned solubility in alkali to the crosslinkable group-containing resin, but is preferably a carboxyl group or a group that generates a carboxyl group by deprotection, for example, by A unit derived from an unsaturated carboxylic acid described below or introduced into a crosslinkable group-containing resin by polymerizing a monomer containing a (meth)acrylate providing an alkali-soluble group. In this specification, the (meth)acrylate which provides an alkali-soluble group does not include the (meth)acrylate which has the said crosslinkable group.

As the crosslinkable group-containing resin, when it is also an alkali-soluble resin, it may not have a functional group that inhibits or suppresses the solubility of the crosslinkable group-containing resin in the above-mentioned alkali (hereinafter sometimes referred to as The resin of "alkali-soluble inhibitory group" or "dissolution inhibitory group") is preferably a resin having an alkali-soluble group and a dissolution inhibitory group. The dissolution inhibitory group may also be called a poorly alkali-soluble group because it has the function of reducing the solubility of the crosslinkable group-containing resin in alkali. The resin containing a crosslinkable group can adjust the solubility in alkali by having an alkali-soluble group and a dissolution-inhibiting group, thereby adjusting the alkali developability of the photosensitive composition. As the dissolution inhibiting group, for example, the following styrene or styrene derivatives can be cited; unsaturated imides; (meth)acrylates having an alicyclic skeleton (wherein, those having epoxy groups are excluded); (meth)acrylate having an aromatic group, such as benzyl meth)acrylate, etc. In this specification, the (meth)acrylate which provides a dissolution inhibiting group does not include the above-mentioned (meth)acrylate which has a crosslinkable group.

Among crosslinkable group-containing resins, polymerization of monomers with ethylenically unsaturated double bonds is preferred in terms of excellent film-forming properties and easy adjustment of resin properties by selecting monomers. things. Examples of monomers having ethylenically unsaturated double bonds include: (meth)acrylic acid; (meth)acrylate; (meth)acrylamide; crotonic acid; acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids; allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, Allyl compounds such as allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol; hexyl vinyl ether, octyl vinyl ether, decyl Vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl cresyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthalene ether, and vinyl anthracene ether Vinyl Ether; Vinyl Butyrate, Vinyl Isobutyrate, Vinyl Trimethyl Acetate, Vinyl Diethyl Acetate, Vinyl Pivalate, Vinyl Hexanoate, Vinyl Chloroacetate, Vinyl Dichloroacetate, Methoxyvinyl acetate, butoxyvinyl acetate, vinylphenyl acetate, acetovinyl acetate, vinyl lactate, vinyl-beta-phenyl butyrate, vinyl benzoate, vinyl salicylate , vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl esters such as vinyl naphthoate; styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, Diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethyl Oxymethylstyrene, Acetyloxymethylstyrene, Methoxystyrene, 4-methoxy-3-methylstyrene, Dimethoxystyrene, Chlorostyrene, Dichlorostyrene , trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene , and styrene or styrene derivatives such as 4-fluoro-3-trifluoromethylstyrene; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1 -butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl Base-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, Alkenes such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; maleimide, N-phenylmaleene Unsaturated imides such as diimide and N-cyclohexylmaleimide.

When the crosslinkable group-containing resin is a polymer of a monomer having an ethylenically unsaturated double bond, it generally contains a unit derived from an unsaturated carboxylic acid. Examples of unsaturated carboxylic acids include: (meth)acrylic acid; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, Aconic acid, anhydrides of these dicarboxylic acids. The amount of units derived from unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali solubility . The amount of the unsaturated carboxylic acid-derived unit in the resin used as the alkali-soluble resin is preferably at least 5 mass % and at most 25 mass %, more preferably at least 8 mass % and at most 16 mass %, based on the mass of the resin , when the crosslinkable group-containing resin has the following dissolution inhibiting group, the equivalent amount is especially preferable. When the crosslinkable group-containing resin does not have the following dissolution inhibiting group, the amount of units derived from unsaturated carboxylic acid in the resin is preferably 50% by mass or more and 80% by mass with respect to the mass of the resin or less, more preferably 60% by mass or more and 70% by mass or less.

Among the polymers of monomers having an ethylenically unsaturated double bond that are polymers of one or more monomers selected from the monomers exemplified above, those selected from (meth)acrylic acid and (meth)acrylic acid are preferred. ) A polymer of one or more monomers in acrylate. Hereinafter, a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate will be described.

The (meth)acrylate used to prepare the polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate is not particularly limited insofar as it does not impair the purpose of the present invention. (Meth)acrylic esters can be selected appropriately.

Examples of suitable (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate Linear or branched alkyl (meth)acrylate such as tertiary octyl acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, (meth)acrylate Base) 2-hydroxyethyl acrylate, trimethylolpropane mono(meth)acrylate, furfuryl (meth)acrylate; benzyl (meth)acrylate and other (meth)acrylates with aromatic groups; A (meth)acrylate having an alicyclic skeleton. The detailed description about the (meth)acrylate which has an alicyclic frame|skeleton is described below.

In addition, in the polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate, it is easy to form an insulating film with a high transmittance using a photosensitive composition , It is also preferably a resin containing a unit derived from (meth)acrylate having an alicyclic skeleton. In this specification, the (meth)acrylate which has an alicyclic skeleton does not include the (meth)acrylate which has the said crosslinkable group.

Among (meth)acrylates having an alicyclic skeleton, the group having an alicyclic skeleton is preferably a group having an alicyclic hydrocarbon group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Moreover, examples of the polycyclic alicyclic group include noryl, isoyl, tricyclononyl, tricyclodecanyl, tetracyclododecyl, and the like.

Among (meth)acrylates having an alicyclic skeleton, examples of (meth)acrylates having an alicyclic hydrocarbon group include those represented by the following formulas (d1-1) to (d1-8). compound. Among these, compounds represented by the following formulas (d1-3) to (d1-8) are preferable, and compounds represented by the following formula (d1-3) or (d1-4) are more preferable.

[chem 37]

In the above formula, R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^d3 represents a hydrogen atom or a carbon group having 1 to 5 carbon atoms. alkyl. R ^d2 is preferably a single bond, linear or branched alkylene group, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylene, pentamethylene, Hexamethylene. R ^d3 is preferably a methyl group or an ethyl group.

The crosslinkable group-containing resin is preferably a unit derived from one or more monomers selected from (meth)acrylic acid and (meth)acrylate esters and a unit derived from (methanol) having an alicyclic epoxy group. base) resins with acrylate units. The resin may further include a unit derived from a (meth)acrylate having an alicyclic skeleton. In this case, the unit derived from a (meth)acrylate having an alicyclic skeleton in the resin may be The amount of units may be 10% by mass to 35% by mass, 15% by mass to 30% by mass, or 20% by mass to 25% by mass.

In addition, in polymers containing one or more monomers selected from (meth)acrylic acid and (meth)acrylates containing units derived from (meth)acrylates having an alicyclic skeleton, relatively A resin containing a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylate having an alicyclic epoxy group is preferable. A film formed using a photosensitive composition containing such a crosslinkable group-containing resin has excellent adhesion to a substrate. Also, when such a resin is used, a self-reaction between the carboxyl group contained in the resin and the alicyclic epoxy group can be initiated. Therefore, if a photosensitive composition containing such a resin is used, the self-reaction of the carboxyl group and the alicyclic epoxy group can be induced by a method such as heating the film, and the mechanical properties such as the hardness of the formed film can be improved. .

In resins containing units derived from (meth)acrylic acid (except those with crosslinkable groups) and units derived from (meth)acrylates with alicyclic epoxy groups, the former in the resin is derived from The amount of (meth)acrylic acid units is preferably from 1% by mass to 95% by mass, more preferably from 10% by mass to 70% by mass. In the resin comprising a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylate having an alicyclic epoxy group, the resin derived from (meth)acrylate having an alicyclic epoxy group The amount of the acrylate unit is preferably from 1% by mass to 95% by mass, more preferably from 10% by mass to 50% by mass.

One or more selected from (meth)acrylic acid and (meth)acrylate containing a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylate having an alicyclic epoxy group Among the polymers of monomers, there may also be units derived from (meth)acrylic acid, units derived from (meth)acrylate having alicyclic hydrocarbon groups, and units derived from (meth)acrylates having alicyclic epoxy groups. Resins with (meth)acrylate units.

In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylate having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylate having an alicyclic epoxy group Among them, the amount of units derived from (meth)acrylic acid in the resin is preferably from 1% by mass to 95% by mass, more preferably from 10% by mass to 50% by mass. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylate having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylate having an alicyclic epoxy group Among them, the amount of units derived from (meth)acrylate having an alicyclic hydrocarbon group in the resin is preferably from 1% by mass to 95% by mass, more preferably from 10% by mass to 70% by mass. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylate having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylate having an alicyclic epoxy group Among them, the amount of units derived from (meth)acrylate having an alicyclic epoxy group in the resin is preferably from 1% by mass to 95% by mass, more preferably from 30% by mass to 80% by mass .

The mass average molecular weight (Mw: measured value obtained in terms of polystyrene based on gel permeation chromatography (GPC). The same as in this specification) of the crosslinkable group-containing resin is preferably 2,000 or more and 200,000 or less, More preferably, it is 2,000 or more and 18,000 or less. By setting it as the said range, there exists a tendency for a photosensitive composition to achieve the balance between film-forming ability and the developability after exposure easily.

(Resin having a Cardo structure) A resin having a Cardo structure described below (hereinafter also referred to as "Cardo resin") can also be preferably used as the resin (B2). As the Cardo resin, a resin having a Cardo skeleton in its structure and having specific alkali solubility can be used. The so-called Cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting the first ring structure. In addition, the 2nd cyclic structure and the 3rd cyclic structure may be the same structure, and may be different structures. As a representative example of the Cardo skeleton, a skeleton in which two aromatic rings (such as a benzene ring) are bonded to the carbon atom at the 9-position of the oxene ring is mentioned.

The resin having a Cardo structure is not particularly limited, and conventionally known resins can be used. Among them, resins represented by the following formula (b-1) are preferred. The resin represented by the following formula (b-1) functions as an alkali-soluble resin having a crosslinkable group because it has a carboxyl group and an ethylenically unsaturated double bond in its structure.

[chem 38]

In formula (b-1), X ^b represents a group represented by the following formula (b-2). t1 represents an integer of 0 to 20.

[chem 39]

In the above formula (b-2), R ^b11 independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^b12 independently represent a hydrogen atom or a methyl group, and R ^b13 independently represent a straight chain or a branched alkylene group, t2 represents 0 or 1, and W ^b represents a group represented by the following formula (b-3).

[chemical 40]

In formula (b-2), R ^b13 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 10 carbon atoms. The alkylene group of 1 to 6 is preferably ethane-1,2-diyl, propane-1,2-diyl, and propane-1,3-diyl.

Ring A ^b in formula (b-3) represents an aliphatic ring which may be condensed with an aromatic ring and which may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle. Examples of the aliphatic ring include monocycloalkane, dicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, northane, isothane, tricyclodecane, and tetracyclododecane may be mentioned. The aromatic ring that can be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

As suitable examples of the divalent group represented by the formula (b-3), the following groups are mentioned. [chem 41]

The divalent group X ^b in the formula (b-1) is introduced into the Cardo resin by reacting the tetracarboxylic dianhydride that provides the residue Z ^b with the diol compound represented by the following formula (b-2a) . [chem 42]

In formula (b-2a), R ^b11 , R ^b12 , R ^b13 and t2 are as described in formula (b-2). Ring A ^b in formula (b-2a) is as described in formula (b-3).

The diol compound represented by formula (b-2a) can be manufactured by the following method, for example. First, if necessary, replace the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (b-2b) with a group represented by -R ^b13 -OH by a conventional method, and then use epichlorohydrin and so on are glycidylated to obtain an epoxy compound represented by the following formula (b-2c). Next, the diol compound represented by the formula (b-2a) is obtained by reacting the epoxy compound represented by the formula (b-2c) with acrylic acid or methacrylic acid. In formula (b-2b) and formula (b-2c), R ^b11 , R ^b13 and t2 are as described in formula (b-2). Ring A ^b in formula (b-2b) and formula (b-2c) is as described in formula (b-3). In addition, the manufacturing method of the diol compound represented by formula (b-2a) is not limited to the said method. [chem 43]

As a suitable example of the diol compound represented by formula (b-2b), the following diol compounds are mentioned. [chem 44]

In the above formula (b-1), R ^b0 is a hydrogen atom or a group represented by -CO-Y ^b -COOH. Here, ^Yb represents the residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene Methyltetrahydrophthalic anhydride, chlorine bridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

Moreover, in said formula ( ^b -1), Zb represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include tetracarboxylic dianhydrides represented by the following formula (b-4), pyromellitic dianhydrides, benzophenone tetracarboxylic dianhydrides, and biphenyl tetracarboxylic dianhydrides. Carboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, etc. Moreover, in said formula (b-1), t1 represents the integer of 0-20.

(式(b-4)中，R^b14 、R^b15 及R^b16 分別獨立表示選自由氫原子、碳原子數1以上且10以下之烷基及氟原子所組成之群中之1種，t3表示0以上且12以下之整數)[chem 45]

(In formula (b-4), R ^b14 , R ^b15 , and R ^b16 independently represent one species selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and t3 represents An integer between 0 and 12)

The alkyl group that can be selected as R ^b14 in the formula (b-4) is an alkyl group having 1 to 10 carbon atoms. The heat resistance of the obtained carboxylate can be remarkably improved by setting the number of carbon atoms which an alkyl group has in this range. When R ^b14 is an alkyl group, the number of carbon atoms is preferably from 1 to 6, more preferably from 1 to 5, and still more preferably from the viewpoint of easily obtaining a Cardo resin excellent in heat resistance. 1 or more and 4 or less, particularly preferably 1 or more and 3 or less. When R ^b14 is an alkyl group, the alkyl group may be linear or branched.

R ^b14 in the formula (b-4) is more preferably each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint of easily obtaining a cardo resin excellent in heat resistance. R ^b14 in formula (b-4) is more preferably a hydrogen atom, methyl, ethyl, n-propyl or isopropyl, especially preferably a hydrogen atom or a methyl group. A plurality of R ^b14 in the formula (b-4) are preferably the same group from the point of view of easy preparation of high-purity tetracarboxylic dianhydride.

t3 in formula (b-4) represents the integer of 0-12. By making the value of t3 12 or less, it becomes easy to refine|purify tetracarboxylic dianhydride. The upper limit of t3 is preferably 5, more preferably 3, from the point which refine|purifies tetracarboxylic dianhydride easily. In terms of the chemical stability of tetracarboxylic dianhydride, the lower limit of t3 is preferably 1, more preferably 2. t3 in formula (b-4) is more preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^b15 and R ^b16 in the formula (b-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^b14 . R ^b15 and R ^b16 are preferably a hydrogen atom or a carbon number of 1 to 10 (preferably 1 to 6, more preferably 1 to 5) in terms of ease of purification of the tetracarboxylic dianhydride. or less, more preferably 1 or more and 4 or less, especially preferably 1 or more and 3 or less) alkyl group, especially preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (b-4) include: nor-2-spiro-α-cyclopentanone-α'-spiro-2''-nor-2-5,5 '',6,6''-tetracarboxylic dianhydride (alias "nor-spiro-2-spiro-2'-cyclopentanone-5'-spiro-2''-nor-spiro-5,5'' ,6,6''-tetracarboxylic dianhydride"), Methylnor-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnor-2''-(methylnor-)-5, 5'',6,6''-Tetracarboxylic dianhydride, nor-2-spiro-α-cyclohexanone-α'-spiro-2''-nor-2''-nor-5,5'',6 ,6''-tetracarboxylic dianhydride (alias "nor-2-spiro-2'-cyclohexanone-6'-spiro-2''-nor-spiro-5,5'',6,6 ''-tetracarboxylic dianhydride"), methylnor-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnor-2''-(methylnor-2'')-5,5'', 6,6''-Tetracarboxylic dianhydride, nor-2-spiro-α-cyclopropanone-α'-spiro-2''-nor-2-5,5'',6,6''- Tetracarboxylic dianhydride, nor-2-spiro-α-cyclobutanone-α'-spiro-2''-nor-5,5'',6,6''-tetracarboxylic dianhydride , Norale-2-spiro-α-cycloheptanone-α'-spiro-2''-norale-5,5'',6,6''-tetracarboxylic dianhydride, norale- 2-Spiro-α-Cyclooctanone-α'-Spiro-2''-Nor-Spiro-5,5'',6,6''-Tetracarboxylic Dianhydride, Nor-Spiro-2-Spiro-α -Cyclononanone-α'-spiro-2''-nor-5,5'',6,6'-tetracarboxylic dianhydride, nor-2-spiro-α-cyclodecanone- α'-Spiro-2''-Nor-Spiro-5,5'',6,6''-tetracarboxylic dianhydride, Nor-Spiro-2-Spiro-α-Cycloundecanone-α'-Spiro -2''-Norsan-5,5'',6,6''-tetracarboxylic dianhydride, norsan-2-spiro-α-cyclododecanone-α'-spiro-2'' -Northane-5,5'',6,6''-tetracarboxylic dianhydride, northane-2-spiro-α-cyclododecone-α'-spiro-2''-northane -5,5'',6,6''-Tetracarboxylic dianhydride, nor-2-spiro-α-cyclotetradecone-α'-spiro-2''-nor-5,5 '',6,6''-Tetracarboxylic dianhydride, nor-2-spiro-α-cyclopentadecone-α'-spiro-2''-nor-5,5'',6 ,6''-Tetracarboxylic dianhydride, nor-2-spiro-α-(methylcyclopentanone)-α'-spiro-2''-nor-2-5,5'',6, 6''-tetracarboxylic dianhydride, nor-spiro-2-spiro-α-(methylcyclohexanone)-α'-spiro-2''-nor-spiro-5,5'',6,6 ''-tetracarboxylic dianhydride, etc.

The weight average molecular weight of the Cardo resin is preferably from 1,000 to 40,000, more preferably from 1,500 to 30,000, still more preferably from 2,000 to 10,000. By setting it as the said range, not only favorable developability but also sufficient heat resistance and film strength can be acquired.

(Novolac resin) As resin (B2), a novolac resin can also be used. Novolak resins are equivalent to alkali-soluble resins. When making a photosensitive composition contain a novolac resin as resin (B2), when post-baking a cured film when forming a cured film using a photosensitive composition, it becomes easy to suppress excessive heat flow of a cured film. Therefore, when using a photosensitive composition to form a black spacer, if a photosensitive composition contains a novolac resin, it will become easy to form the black spacer of a desired shape.

As the novolak resin, various novolak resins conventionally prepared in the photosensitive composition can be used. The novolac resin is preferably obtained by addition condensation of aromatic compounds having phenolic hydroxyl groups (hereinafter referred to as "phenols") and aldehydes under an acid catalyst.

・Phenols Examples of phenols used in the production of novolac resins include: phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol Phenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p- Ethylphenols such as ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol and other trialkylphenols; resorcinol, catechol, hydroquinone Polyphenols such as phenol, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyphenols such as alkyl resorcinol, alkyl catechol, and alkylhydroquinone Phenols (each alkyl group has 1 to 4 carbon atoms); α-naphthol, β-naphthol; hydroxybiphenyl; and bisphenol A, etc. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferably used in combination. In this case, various characteristics, such as the heat resistance of the cured film formed using the photosensitive composition, can be adjusted by adjusting the compounding ratio of both. The blending ratio of m-cresol and p-cresol is not particularly limited, but is preferably not less than 3/7 and not more than 8/2 in terms of the molar ratio of m-cresol/p-cresol. By using m-cresol and p-cresol in the ratio of this range, the photosensitive composition which can form the cured film excellent in heat resistance can be obtained easily.

Also, a novolac resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. When this novolac resin is used, it is particularly easy to obtain a photosensitive composition capable of forming a cured film that does not easily flow excessively due to heating during post-baking. The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but it is preferably 70/30 or more based on the molar ratio of m-cresol/2,3,5-trimethylphenol And below 95/5.

・Aldehydes Examples of aldehydes used in the production of novolac resins include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

・Acid catalyst The acid catalyst used in the production of novolak resins includes, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and p-toluenesulfonate organic acids such as acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

・Molecular weight The polystyrene-equivalent weight average molecular weight (Mw; hereinafter also abbreviated as "weight average molecular weight") of novolac resin is from the viewpoint of resistance to flow caused by heating of a cured film formed using a photosensitive composition , the lower limit is preferably 2000, more preferably 5000, more preferably 10000, further preferably 15000, most preferably 20000, the upper limit is preferably 50000, more preferably 45000, and most preferably 40000 The best is 35000.

As the novolac resin, at least two types having different weight average molecular weights in terms of polystyrene can be used in combination. By combining and using those with different weight average molecular weights, a balance can be achieved between the developability of the photosensitive composition and the heat resistance of the cured film formed using the photosensitive composition.

(Modified Epoxy Resin) In terms of easily imparting higher flow resistance during baking and higher water resistance to the cured film formed using the photosensitive composition, the photosensitive composition may also contain epoxy as an epoxy resin. Modified epoxy resin of polybasic acid anhydride (b-3c) adduct product of reactant of oxygen compound (b-3a) and unsaturated group-containing carboxylic acid (b-3b) is used as resin (B2). The modified epoxy resin functions as an alkali-soluble resin having a crosslinkable group because it has a carboxyl group and an ethylenically unsaturated double bond in its structure. Furthermore, in the description and scope of the patent application of this case, the compound that meets the above definition and does not correspond to the above-mentioned resin with the Cardo structure is regarded as a modified epoxy resin.

Hereinafter, epoxy compound (b-3a), unsaturated group-containing carboxylic acid (b-3b), and polybasic acid anhydride (b-3c) are demonstrated.

・Epoxy compound (b-3a) The epoxy compound (b-3a) is not particularly limited as long as it has an epoxy group, and may be an aromatic epoxy compound containing an aromatic group, or may not contain The aliphatic epoxy compound having an aromatic group is preferably an aromatic epoxy compound containing an aromatic group. The epoxy compound (b-3a) may be a monofunctional epoxy compound, or a polyfunctional epoxy compound with more than two functions, preferably a polyfunctional epoxy compound.

Specific examples of the epoxy compound (b-3a) include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type Difunctional epoxy resins such as epoxy resins and biphenyl-type epoxy resins; glycidyl ester-type epoxy resins such as dimer acid glycidyl esters and triglycidyl esters; tetraglycidylaminodiphenylmethane, Glycidyl amine epoxy resins such as triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine, and tetraglycidyl bisaminomethylcyclohexane; triglycidyl isocyanurate, etc. Heterocyclic epoxy resin; phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2, 3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1 ,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy) Phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and other trifunctional epoxy resins; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl di Tetrafunctional epoxy resins such as benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidyloxybiphenyl.

Moreover, as an epoxy compound (b-3a), the epoxy compound which has a biphenyl skeleton is preferable. The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (b-3a-1) in the main chain. The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups. By using the epoxy compound which has a biphenyl skeleton, it becomes easy to obtain the photosensitive composition which is excellent in the balance of sensitivity and developability, and can form the cured film excellent in the adhesiveness to a board|substrate.

(式(b-3a-1)中，R^b17 分別獨立為氫原子、碳原子數1以上且12以下之烷基、鹵素原子、或可具有取代基之苯基，j為1以上且4以下之整數)[chem 46]

(In formula (b-3a-1), R ^b17 is each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, j is 1 to 4 integer)

When R ^b17 is an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl , second butyl, third butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, second Trioctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl.

When R ^b17 is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When R ^b17 is a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 to 5, preferably 0 or 1. Examples of substituents include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aliphatic acyl groups having 2 to 4 carbon atoms, and halogen atoms. , cyano, and nitro.

(式(b-3a-2)中，R^b17 及j與式(b-3a-1)中相同，k表示括弧內之結構單元之平均重複數，為0以上且10以下)The epoxy compound (b-3a) having a biphenyl skeleton represented by the above formula (b-3a-1) is not particularly limited, and examples thereof include epoxy compounds represented by the following formula (b-3a-2). compound. [chem 47]

(In formula (b-3a-2), R ^b17 and j are the same as in formula (b-3a-1), and k represents the average repeating number of structural units in parentheses, which is 0 or more and 10 or less)

(式(b-3a-3)中，k與式(b-3a-2)中相同)Among the epoxy compounds represented by the formula (b-3a-2), the following formula (b-3a) is preferable in terms of being particularly easy to obtain a photosensitive composition having an excellent balance between sensitivity and developability -3) The compound represented. [chem 48]

(In formula (b-3a-3), k is the same as in formula (b-3a-2))

(Carboxylic acid (b-3b) containing unsaturated group) When preparing modified epoxy compound (b-3), make epoxy compound (b-3a) and carboxylic acid (b-3b) containing unsaturated group react. The unsaturated group-containing carboxylic acid (b-3b) is preferably a monocarboxylic acid having a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocincinnamic acid, and cinnamic acid. Moreover, unsaturated group containing carboxylic acid (b-3b) can be used individually or in combination of 2 or more types.

The epoxy compound (b-3a) and the unsaturated group-containing carboxylic acid (b-3b) can be reacted by a known method. As a preferred reaction method, for example, the following method can be cited: triethylamine, benzylethylamine and other tertiary amines, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethyl chloride Ammonium chloride, benzyltriethylammonium chloride and other quaternary ammonium salts, pyridine, or triphenylphosphine, etc., are used as catalysts to make epoxy compound (b-3a) and unsaturated carboxylic acid (b-3b) ) is reacted in an organic solvent at a reaction temperature of not less than 50°C and not more than 150°C for several hours to tens of hours.

Regarding the ratio of the amount of the two used in the reaction between the epoxy compound (b-3a) and the unsaturated group-containing carboxylic acid (b-3b), the epoxy equivalent of the epoxy compound (b-3a) and the amount containing the unsaturated group The ratio of the carboxylic acid equivalents of the carboxylic acid (b-3b) of the saturated group is usually preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, especially preferably 1:0.9 to 1: 1.1. When the ratio of the amount of epoxy compound (b-3a) used to the amount of unsaturated group-containing carboxylic acid (b-3b) used is 1:0.5 to 1:2 in terms of the above equivalent ratio, the crosslinking efficiency is improved The tendency is better.

(Polybasic acid anhydride (b-3c)) The polybasic acid anhydride (b-3c) is an acid anhydride of carboxylic acid which has 2 or more carboxyl groups. It does not specifically limit as polybasic acid anhydride (b-3c), For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Formic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydro Phthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, the following A compound represented by the formula (b-3c-1), and a compound represented by the following formula (b-3c-2). Moreover, polybasic acid anhydride (b-3c) can be used individually or in combination of 2 or more types.

(式(b-3c-2)中，R^b18 表示碳原子數1以上且10以下之可具有取代基之伸烷基)[chem 49]

(In formula (b-3c-2), R ^b18 represents an optionally substituted alkylene group having 1 to 10 carbon atoms)

As polybasic acid anhydride (b-3c), it is preferable that it is a compound which has 2 or more benzene rings at the point which is easy to obtain the photosensitive composition excellent in the balance of sensitivity and developability. Moreover, it is more preferable that polybasic acid anhydride (b-3c) contains at least one of the compound represented by said formula (b-3c-1) and the compound represented by said formula (b-3c-2).

As a method of reacting the epoxy compound (b-3a) with the unsaturated group-containing carboxylic acid (b-3b), and then reacting with the polybasic acid anhydride (b-3c), it can be appropriately selected from known methods. Also, regarding the usage ratio, the molar number of the OH group in the component after the reaction of the epoxy compound (b-3a) and the unsaturated group-containing carboxylic acid (b-3b), and the polybasic acid anhydride (b-3c) The equivalent ratio of the acid anhydride groups is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it as the said range, it becomes easy to obtain the photosensitive composition with favorable developability.

In addition, the acid value of the modified epoxy resin (b-3) is calculated based on the resin solid content, preferably not less than 10 mgKOH/g and not more than 150 mgKOH/g, more preferably not less than 70 mgKOH/g and not more than 110 mgKOH/g the following. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility in the developer can be obtained, and by setting the acid value to 150 mgKOH/g or less, sufficient curability can be obtained, and Surface properties can be improved.

In addition, the weight average molecular weight of the modified epoxy resin (b-3) is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. When the weight average molecular weight is 1000 or more, it becomes easy to form the black spacer excellent in heat resistance and strength. Moreover, by being 40000 or less, it becomes easy to obtain the photosensitive composition which shows sufficient solubility in a developing solution.

(Polymer Containing a Structural Unit Having a Ring Structure in the Main Chain) The polymer including a structural unit having a ring structure in the main chain is not particularly limited as long as it is a resin having a specific ring structure and specific alkali solubility. A suitable example of a polymer containing a structural unit having a ring structure in the main chain includes a polymer containing a maleimide-derived structural unit (hereinafter also referred to as "structural unit (A2a)") (hereinafter also referred to as "polymer (A2)"), and a polymer (hereinafter also referred to as "Polymer (A1)").

The maleimide-derived structural unit (A2a) of the polymer (A2) is not particularly limited as long as it is obtained by polymerizing a monomer having a maleimide skeleton. . Examples of monomers having a maleimide skeleton include: N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide Amide, etc.

In particular, a photosensitive composition containing a polymer (A1) containing a structural unit (A1a) having a ring structure in the main chain has good solubility in a developing solution.

[chemical 50]

In formula (A-1), ring A is a saturated aliphatic ring group having 4 or more and 6 or less carbon atoms having one oxygen atom as a ring constituting atom. Ring A is preferably a saturated aliphatic ring group with 4 or 5 carbon atoms having one oxygen atom as a ring-forming atom, more preferably a tetrahydrofuran ring or a tetrahydropyran ring, and more preferably the following formula (A -3) The tetrahydropyran ring in the structural unit represented by (hereinafter also referred to as "structural unit (A1a1)") or the structural unit represented by the following formula (A-4) (hereinafter also referred to as "structural unit (A1a1)") (A1a2)") in the tetrahydrofuran ring. [Chemical 51]

The polymer (polymer (A1)) containing the structural unit represented by the above-mentioned formula (A-1) on the main chain usually contains a plurality of structural units represented by the above-mentioned formula (A-1) on the main chain (structural unit ( A1a)). Among the plurality of structural units (A1a), the ring A contained in each structural unit (A1a) may be the same as or different from each other on one main chain constituting the polymer (A1). Specifically, one main chain constituting the polymer (A1) may have, for example, only the structural unit represented by the above-mentioned formula (A-3) as the structural unit represented by the above-mentioned formula (A-1) contained in the main chain, It is also possible to have only the structural unit represented by the above-mentioned formula (A-4) as the structural unit represented by the above-mentioned formula (A-1) contained in the main chain, or it can also have the structural unit represented by the above-mentioned formula (A-3) The structural unit and the structural unit represented by the above formula (A-4) serve as the structural unit represented by the above formula (A-1) contained in the main chain.

In the above formula (A-1), formula (A-3) and formula (A-4), R ^b1 and R ^b2 are independently hydrogen atoms or -COOR ^b3 , and R ^b3 are independently hydrogen atoms or -COOR b3, respectively. A hydrocarbon group having 1 to 25 carbon atoms having a substituent. R ^b1 and R ^b2 are preferably -COOR ^b3 . When one main chain of the polymer (polymer (A1)) comprising the structural unit represented by the above formula (A-1) contains a plurality of rings A, -COOR ^b3 bonded to each ring A is respectively Independently, the same or different groups as -COOR ^b3 may be bonded to each ring A.

The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^b1 and R ^b2 is not particularly limited. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2- Linear or branched alkyl groups such as ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isothiol, adamantyl , 2-methyl-2-adamantyl and other alicyclic groups; 1-methoxyethyl, 1-ethoxyethyl and other alkyl substituted by alkoxy; benzyl and other aryl substituted Alkyl etc.

When R ^b1 and R ^b2 are hydrocarbon groups, the number of carbon atoms in the hydrocarbon group is preferably 8 or less. As a hydrocarbon group with 8 or less carbon atoms, it is preferable that the hydrocarbon group has a free terminal bond bonded to a primary carbon atom or a secondary carbon atom in terms of being less likely to be detached by acid or heat. Hydrocarbyl. Such a hydrocarbon group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms. alkyl. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, and the like, preferably a methyl group.

When one main chain of a polymer (polymer (A1)) comprising a structural unit (structural unit (A1a)) represented by the above formula (A-1) contains a plurality of structural units (A1a), each R ^b1 and R ^b2 bonded in the structural unit (A1a) may be the same or different among the structural units (A1a). When the respective structural units (A1a) contain the same or different ring A, R ^b1 and R ^b2 are independent of each other, regardless of the type of each ring A to be bonded.

Specifically, when one main chain constituting the polymer (A1) contains a plurality of structural units (structural units (A1a1)) represented by the above formula (A-3), in each structural unit (A1a1) R ^b1 and R ^b2 may be the same or different among the respective structural units (A1a1).

When one main chain constituting the polymer (A1) contains a plurality of structural units represented by the above formula (A-4) (structural unit (A1a2)), R ^b1 and R in each structural unit (A1a2) ^b2 may be the same or different among the respective structural units (A1a2). Furthermore, the structural unit represented by the above formula (A-3) (structural unit (A1a1)) and the structural unit represented by the above formula (A-4) (structural unit In the case of (A1a2)), R ^b1 and R ^b2 in each structural unit (A1a1) and R ^b1 and R ^b2 in each structural unit (A1a2) may be the same or different.

(式(A-5)及式(A-6)中，R^b1 及R^b2 分別獨立，且與上述相同)The structural unit represented by the above formula (A-3) (structural unit (A1a1)) may be part of a repeating unit represented by the following formula (A-5) (hereinafter also referred to as "repeating unit (ar1)"). The structural unit (structural unit (A1a2)) represented by the above formula (A-4) may be part of a repeating unit represented by the following formula (A-6) (hereinafter also referred to as "repeating unit (ar2)"). [Chemical 52]

(In the formula (A-5) and the formula (A-6), R ^b1 and R ^b2 are independently independent and the same as above)

(上述式中，R^b3 分別獨立，且與上述相同)As a monomer which provides each repeating unit represented by said formula (A-5) and (A-6), the 1, 6- diene represented by the following formula is mentioned, for example. [Chemical 53]

(In the above formula, R ^b3 are independently independent and the same as above)

In the monomer composition providing the polymer (polymer (A1)) containing the structural unit (structural unit (A1a)) represented by the above-mentioned formula (A-1) on the main chain, the monomer composition containing the structural unit (A1a) is provided. The content ratio of the monomer (A1ma) of the repeating unit (which may contain the above-mentioned structural unit (A1a1) and structural unit (A1a2)) is preferably 1% by mass or more and 60% to the total amount of monomers in the monomer composition. % by mass or less, more preferably not less than 5 mass % and not more than 50 mass %, especially preferably not less than 10 mass % and not more than 40 mass %.

The polymer (A1) preferably contains a repeating unit (A1b) having an acid group in a side chain. If the polymer (A1) contains a repeating unit (A1b) having an acid group in the side chain, a photosensitive composition excellent in alkali developability can be obtained. Examples of the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain include (meth)acrylic acid, 2-(meth)acryloxyethylsuccinic acid, itaconic acid, omega -Carboxyl group-monomers with carboxyl groups such as polycaprolactone monoacrylate; monomers with carboxylic acid anhydride groups such as maleic anhydride and itaconic anhydride, etc. Among them, (meth)acrylic acid is preferred.

In the monomer composition providing the polymer (A1), the content ratio of the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain (A1mb) relative to the total amount of monomers in the monomer composition is higher than Preferably, it is 1 mass % or more and 50 mass % or less, More preferably, it is 5 mass % or more and 40 mass % or less, More preferably, it is 10 mass % or more and 35 mass % or less.

The polymer (A1) preferably contains a repeating unit (A1c) having a carbon double bond in the side chain. The repeating unit (A1c) having a carbon double bond in the side chain can be added with a carbon double bond by using part or all (preferably a part) of the acid group of the repeating unit (A1b) having an acid group in the side chain as the reaction point. obtained from the compound.

When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxyl group, as a compound having a carbon double bond, a compound having an epoxy group and a double bond, a compound having an isocyanate group and a double bond can be used. compounds etc. Examples of compounds having an epoxy group and a double bond include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m- Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and the like. As a compound which has an isocyanato group and a double bond, 2-isocyanatoethyl (meth)acrylate etc. are mentioned. When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxylic acid anhydride group, a compound having a hydroxyl group and a double bond can be used as the compound having a carbon double bond. As a compound which has a hydroxyl group and a double bond, 2-hydroxyethyl (meth)acrylate etc. are mentioned, for example.

The polymer (A1) may further contain other repeating units (A1e) derived from other monomers (A1me) copolymerizable with the above-mentioned monomers (A1ma), monomers (A1mb) and/or monomers (A1mc).

As another monomer (A1me), for example, it may further include a repeating unit having an oxyalkylene group having two or more side chains. As a repeating unit which has 2 or more oxyalkylene groups in a side chain, the repeating unit represented by the following formula is mentioned, for example. [Chemical 54]

In the above formula, R ^b7 , R ^b8 and R ^b9 are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom. R ^b10 is a linear or branched alkyl group with 1 to 20 carbon atoms, a linear or branched alkenyl group with 2 to 20 carbon atoms, or a linear or branched alkenyl group with 2 to 20 carbon atoms, or An aromatic hydrocarbon group of 6 to 20, preferably a hydrogen atom, a straight-chain alkyl group with 1 to 20 carbon atoms, a straight-chain alkenyl group with 2 to 20 carbon atoms, or a carbon An aromatic hydrocarbon group with 6 to 20 atoms, more preferably a linear alkyl group with 1 to 10 carbon atoms, or an aromatic hydrocarbon group with 6 to 12 carbon atoms, even more preferably It is a straight-chain alkyl group, phenyl group or biphenyl group having 1 to 5 carbon atoms, particularly preferably methyl group, phenyl group or biphenyl group. In addition, an alkyl group, an alkenyl group, and an aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The number of carbon atoms in the oxyalkylene group represented by AO is 2 to 20, preferably 2 to 10, more preferably 2 to 5, and still more preferably 2. The repeating unit having two or more oxyalkylene groups in the side chain may contain one or more kinds of oxyalkylene groups. x represents an integer of 0 to 2. y means 0 or 1. z represents the average addition mole number of oxyalkylene groups, and is 2 or more, preferably 2 or more and 100 or less, more preferably 2 or more and 50 or less, and still more preferably 2 or more and 15 or less.

(上述式中，R^b7 、R^b8 、R^b9 、R^b10 、AO、x、y及z如上述說明)The repeating unit having two or more oxyalkylene groups in the side chain is composed of a monomer having two or more oxyalkylene groups in the side chain. As this monomer, the monomer represented by the following formula is mentioned, for example. [Chemical 55]

(In the above formula, R ^b7 , R ^b8 , R ^b9 , R ^b10 , AO, x, y and z are as described above)

As the above-mentioned monomer having two or more oxyalkylene groups in the side chain, for example, ethoxylated o-phenylphenol (meth)acrylate (EO2 mole), phenoxydiethylene glycol (meth) base) acrylate, phenoxypolyethylene glycol (meth)acrylate (EO4 mol), methoxypolyethylene glycol (meth)acrylate (EO9 mol), methoxypolyethylene glycol (Meth)acrylate (EO13 mole), methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxydiethylene glycol (methyl) ) acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, nonylphenoxy poly Ethylene glycol (meth)acrylate (EO4～17 mol), nonylphenoxy polypropylene glycol (meth)acrylate (PO5 mol), EO modified cresol (meth)acrylate (EO2 mol ear) etc. These monomers can be used individually or in combination of 2 or more types. Among them, preferred are ethoxylated o-phenylphenol (meth)acrylate (EO2 mole), methoxypolyethylene glycol (meth)acrylate (EO9 mole), methoxypolyethylene glycol Alcohol (meth)acrylate (EO 13 mol). Further preferred are ethoxylated o-phenylphenol acrylate (EO2 mol), methoxypolyethylene glycol acrylate (EO9 mol), and methoxypolyethylene glycol acrylate (EO13 mol). In addition, in this specification, descriptions, such as "EO2 mole" and "PO5 mole" represent the average addition mole number of an oxyalkylene group.

As another monomer (A1me), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate, base) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) ) lauryl acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, biphenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxy (meth)acrylate Ethyl ester, Butoxyethylene glycol (meth)acrylate, 2-Ethylhexyl glycol (meth)acrylate, Methoxypropylene glycol (meth)acrylate, Phenoxy (meth)acrylate Ethyl ester, biphenoxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, (meth)acrylate Base) tricyclodecanyloxyethyl acrylate, nonylphenoxyethylene glycol (meth)acrylate, nonylphenoxypropylene glycol, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate (meth)acrylates such as esters, ethoxylated o-phenylphenol (meth)acrylates, etc.; Acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-isobutyl(methyl) Acrylamide, N-tert-butyl (meth)acrylamide, N-tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, N-hydroxymethyl (methyl) ) acrylamide, N-hydroxyethyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(methyl) Acrylamide, N-triphenylmethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide and other (meth)acrylamides; styrene, vinyl toluene, Aromatic vinyl compounds such as α-methylstyrene; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted vinyl compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl acetate Vinyl esters such as esters, etc. These monomers can be used individually or in combination of 2 or more types.

In the monomer composition providing the polymer (A1), the content ratio of the monomer (A1me) providing another repeating unit (A1e) is preferably 0% by mass relative to the total amount of monomers in the monomer composition It is more than or equal to 55 mass %, More preferably, it is 5 mass % or more and 50 mass % or less, More preferably, it is 10 mass % or more and 45 mass % or less.

The polymer (A1) may be a random copolymer or a block copolymer. As a polymer (A1), it can be used individually or in combination of 2 or more types.

The weight average molecular weight of the polymer (A1) is preferably 3,000 to 200,000, more preferably 3,500 as measured by gel permeation chromatography (GPC) using a tetrahydrofuran (THF) solvent. More than 100,000, more preferably 4,000 to 50,000. If it is such a range, heat resistance can be ensured, and the photosensitive composition which has the viscosity suitable for forming a coating film can be obtained.

The polymer (A1) can be obtained by polymerizing the monomer composition providing the polymer (A1) by any appropriate method. As a polymerization method, a solution polymerization method is mentioned, for example.

The monomer composition providing the polymer (A1) may contain any suitable solvent. Examples of solvents include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate , butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and other esters; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl Keiya and others. These solvents can be used individually or in combination of 2 or more types. The polymerization concentration when polymerizing the monomer composition is preferably from 5% by mass to 90% by mass, more preferably from 5% by mass to 50% by mass, still more preferably from 10% by mass to 50% by mass .

The monomer composition providing the polymer (A1) may contain any suitable polymerization initiator. Examples of the polymerization initiator include: cumene hydroperoxide, dicumyl hydroperoxide, di-tert-butyl peroxide, lauryl peroxide, benzoyl peroxide, cumyl peroxide Organic peroxides such as tert-butyl carbonate, tert-pentyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, etc.; 2,2'-azobis(isobutyl nitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methyl Azo compounds such as dimethyl propionate, etc. The content ratio of the polymerization initiator is preferably from 0.1 to 15 parts by mass, more preferably from 0.5 to 10 parts by mass, based on 100 parts by mass of all monomers in the monomer composition.

The polymerization temperature when the polymer (A1) is formed by solution polymerization is preferably from 40°C to 150°C, more preferably from 60°C to 130°C.

When obtaining the polymer (A1) containing the repeating unit (A1c) which has a carbon double bond in a side chain, after the said polymerization, the compound which has the said carbon double bond is added to the obtained polymer. Any appropriate method can be adopted as the addition method of the compound having a carbon double bond. For example, in the presence of a polymerization inhibitor and a catalyst, the compound having a carbon double bond reacts with part or all (preferably a part) of the acid groups of the repeating unit (A1b) having an acid group in the side chain to perform addition, Thereby, a repeating unit (A1c) having a carbon double bond in the side chain can be formed.

The addition amount of the above-mentioned compound having a carbon double bond is preferably 5 parts by mass or more, more preferably 10 parts by mass relative to 100 parts by mass of the polymer after the above-mentioned polymerization (that is, the polymer before adding the compound having a carbon double bond). It is at least 15 parts by mass, more preferably at least 15 parts by mass, particularly preferably at least 20 parts by mass. If it is such a range, the photosensitive composition excellent in exposure sensitivity can be obtained. When such a photosensitive composition is used, a dense cured coating film tends to be easily formed, and a pattern excellent in substrate adhesiveness also tends to be obtained. Also, if the addition amount of the compound having a carbon double bond is within the above range, a hydroxyl group is sufficiently generated by adding a compound having a carbon double bond, and a photosensitive composition having excellent solubility in an alkaline developer can be obtained. . The upper limit of the addition amount of the above-mentioned compound having a carbon double bond is preferably 170 parts by mass or less with respect to 100 parts by mass of the above-mentioned polymer after polymerization (that is, the polymer before adding the compound having a carbon double bond) It is 150 mass parts or less, More preferably, it is 140 mass parts or less. When the addition amount of the compound which has a carbon double bond exists in the said range, the storage stability and solubility of a photosensitive composition can be maintained.

Examples of polymerization inhibitors include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.

The content of the resin (B2) described above is preferably at least 1% by mass and at most 95% by mass, more preferably at least 3% by mass and at most 85% by mass, particularly preferably 5% by mass, based on the solid content of the photosensitive composition. Mass % or more and 70 mass % or less. When the photosensitive composition contains the resin (B2) in the quantity within this range, the film-forming property of the photosensitive composition becomes favorable, and it becomes easy to form a cured film with favorable mechanical properties or shape. Moreover, when resin (B2) is alkali-soluble, it becomes easy to realize favorable alkali developability.

<Colorant (C)> Depending on the use of the cured film formed using the photosensitive composition, the photosensitive composition may contain a colorant (C). The coloring agent (C) is preferably a pigment in terms of good light resistance and weather resistance and less likely to cause bleeding problems.

The pigment is not particularly limited. For example, compounds classified as pigments in the Color Index (C.I.; issued by The Society of Dyers and Colourists, Inc.) can be used. material index (C.I.) number.

Examples of yellow pigments that can be preferably used include: C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same and only the numbers are described), 3, 11, 12, 13, 14, 15, 16, 17, 20 , 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110 ,113,114,116,117,119,120,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,166,167 , 168, 175, 180, and 185.

Examples of orange pigments that can be preferably used include: C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38 , 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of purple pigments that can be preferably used include: C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39 , 40, and 50.

Examples of red pigments that can be preferably used include: C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same and only the numbers are described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments that can be preferably used include: C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same and only the numbers are described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66.

Examples of pigments of other hues that can be preferably used include green pigments such as C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. C.I. Pigment Brown 28 and other brown pigments, C.I. Pigment Black 1, C.I. Pigment Black 7 and other black pigments.

Moreover, when providing light-shielding property to a photosensitive composition, it is preferable that a photosensitive composition contains a black pigment as a coloring agent (C). The photosensitive composition containing a black pigment is suitable for forming a black matrix or a black spacer in a liquid crystal display panel, or a barrier for dividing a light-emitting layer in an organic EL element.

Examples of black pigments include: carbon black, perylene-based pigments, lactam-based pigments, metal oxides such as titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and composite oxides. Various pigments, whether organic or inorganic, such as metal sulfides, metal sulfates or metal carbonates. Among these black pigments, carbon black is preferable in terms of easy availability or the ease of forming a cured film having excellent light-shielding properties and high electrical resistance. Furthermore, the hue of the black pigment is not limited to black which is achromatic in terms of color theory, and may be black with purple, or black with blue, or black with red.

As the carbon black, known carbon blacks such as chimney black, furnace black, thermal black, and lamp black can be used. Moreover, resin-coated carbon black can also be used.

Carbon black that has been treated to introduce acidic groups is also preferred. The acidic group introduced to carbon black is an acidic functional group based on the definition of Bronsted. As a specific example of an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned. The acidic groups introduced into carbon black can also form salts. The cation which forms a salt with an acidic group is not specifically limited in the range which does not impair the object of this invention. Examples of cations include various metal ions, cations of nitrogen-containing compounds, ammonium ions, etc., preferably alkali metal ions such as sodium ions, potassium ions, and lithium ions, or ammonium ions.

Among the carbon blacks described above that have been treated to introduce acidic groups, it is preferable to have carbon blacks selected from carboxylic acid groups, carboxyl Carbon black with one or more functional groups in the group consisting of acid salt group, sulfonic acid group, and sulfonate group.

The method for introducing acidic groups to carbon black is not particularly limited. As a method of introducing an acidic group, the following methods are mentioned, for example. 1) A method of introducing sulfonic acid groups to carbon black by a direct substitution method using concentrated sulfuric acid, oleum, chlorosulfonic acid, etc., or an indirect substitution method using sulfite, bisulfite, etc. 2) A method of diazo-coupling an organic compound having an amine group and an acidic group with carbon black. 3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method. 4) A method of reacting an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group. 5) A method of deprotecting carbon black after a Friedel-Crafts reaction using an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group.

Among these methods, method 2) is preferable in terms of ease of handling and safety for introducing acidic groups. The organic compound having an amine group and an acidic group used in method 2) is preferably a compound having an amine group and an acidic group bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The molar number of acidic groups introduced into carbon black is not particularly limited within the range that does not impair the object of the present invention. The number of moles of acidic groups introduced into carbon black is preferably from 1 mmol to 200 mmol, more preferably from 5 mmol to 100 mmol, relative to 100 g of carbon black.

Resin coating treatment can also be performed on carbon black with acidic groups introduced therein. In the case of using a photosensitive composition containing resin-coated carbon black, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and having low surface reflectance. Moreover, the dielectric constant of the light-shielding cured film formed using the photosensitive composition is not particularly adversely affected by the resin coating treatment. Examples of resins that can be used to coat carbon black include: phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glycalin resins, epoxy resins, alkylbenzene resins, etc. Resin, or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, polyparaphenylene terephthalamide, Polyamideimide, polyimide, polyaminobismaleimide, polyether, polyphenylene, polyarylate, polyether ether ketone and other thermoplastic resins. The coating amount of the resin on the carbon black is preferably not less than 1% by mass and not more than 30% by mass based on the sum of the mass of the carbon black and the mass of the resin.

Moreover, a perylene-type pigment can also be used preferably as a black pigment. Specific examples of perylene-based pigments include perylene-based pigments represented by the following formula (d-1), perylene-based pigments represented by the following formula (d-2), and perylene-based pigments represented by the following formula (d-3) Represented perylene-based pigments. Among commercially available products, product names K0084 and K0086 manufactured by BASF Corporation, or Pigment Black 21, 30, 31, 32, 33, and 34 are preferably used as perylene-based pigments.

式(c-1)中，R^c1 及R^c2 分別獨立表示碳原子數1以上且3以下之伸烷基，R^c3 及R^c4 分別獨立表示氫原子、羥基、甲氧基、或乙醯基。[Chemical 56]

In the formula (c-1), R ^c1 and R ^c2 independently represent an alkylene group having 1 to 3 carbon atoms, and R ^c3 and R ^c4 independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group. .

式(c-2)中，R^c5 及R^c6 分別獨立表示碳原子數1以上且7以下之伸烷基。[Chemical 57]

In formula (c-2), R ^c5 and R ^c6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式(c-3)中，R^c7 及R^c8 分別獨立為氫原子、碳原子數1以上且22以下之烷基，亦可包含N、O、S或P之雜原子。於R^c7 及R^c8 為烷基之情形時，該烷基可為直鏈狀，亦可為支鏈狀。[Chemical 58]

In formula (c-3), R ^c7 and R ^c8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain N, O, S or P heteroatoms. When R ^c7 and R ^c8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the above-mentioned formula (c-1), the compound represented by the formula (c-2), and the compound represented by the formula (c-3) can be used, for example, in Japanese Patent Laid-Open No. 62-1753, Japanese Patent Synthesized by the method described in the Japanese Patent Publication No. 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and the heating reaction is carried out in water or an organic solvent. Furthermore, the obtained crude product can be obtained by reprecipitating in sulfuric acid, or recrystallizing in water, an organic solvent, or the mixed solvent of these.

In order to disperse the perylene-based pigment well in the photosensitive composition, the average particle diameter of the perylene-based pigment is preferably not less than 10 nm and not more than 1000 nm.

In addition, a lactam-based pigment may be included as a light-shielding agent. As a lactam type pigment, the compound represented by following formula (c-4) is mentioned, for example.

[Chemical 59]

In the formula (c-4), X ^c represents a double bond, the geometric isomers are independently E or Z, and R ^C9 independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, and a chlorine atom. , a fluorine atom, a carboxyl group, or a sulfo group, R ^c10 each independently represent a hydrogen atom, a methyl group, or a phenyl group, and R ^c11 each independently represent a hydrogen atom, a methyl group, or a chlorine atom. The compound represented by formula (c-4) can be used individually or in combination of 2 or more types. In terms of the ease of manufacture of the compound represented by formula (c-4), R ^c9 is preferably bonded to the 6-position of the indolinone ring, and R ^c11 is preferably bonded to the indolinone ring of 4 digits. From the same viewpoint, R ^c9 , R ^c10 and R ^c11 are preferably hydrogen atoms. The compound represented by the formula (c-4) exists as a geometric isomer in EE form, ZZ form, and EZ form, and may be a single compound of any of them or a mixture of these geometric isomers. The compound represented by formula (c-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the lactam-based pigment well in the photosensitive composition, the average particle diameter of the lactam-based pigment is preferably not less than 10 nm and not more than 1000 nm.

Furthermore, microparticles mainly composed of a silver-tin (AgSn) alloy (hereinafter referred to as "AgSn alloy microparticles") can also be preferably used as a black pigment. The AgSn alloy fine particles may contain other metal components such as Ni, Pd, and Au as long as AgSn alloy is the main component. The average particle size of the AgSn alloy fine particles is preferably not less than 1 nm and not more than 300 nm.

In the case where the AgSn alloy is represented by the chemical formula AgxSn, the range of x that can obtain a chemically stable AgSn alloy is 1≦x≦10, and the range of x that can obtain both chemical stability and blackness is 3≦x≦4 . Here, if the mass ratio of Ag in the AgSn alloy is obtained within the above-mentioned range of x, in the case of x=1, Ag/AgSn=0.4762, and in the case of x=3, 3·Ag/Ag3Sn=0.7317 When x=4, 4·Ag/Ag4Sn=0.7843 When x=10, 10·Ag/Ag10Sn=0.9008. Therefore, when the AgSn alloy contains 47.6% by mass to 90% by mass of Ag, its chemical properties are stable, and when it contains 73.17% by mass to 78.43% by mass of Ag, it can be effectively obtained with respect to the amount of Ag. Chemical stability and blackness.

The AgSn alloy microparticles can be produced by a common microparticle synthesis method. Examples of the microparticle synthesis method include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

AgSn alloy fine particles have high insulating properties, but considering the application of the photosensitive composition, the insulating film can be used to cover the surface to further improve the insulating properties. As a material for such an insulating film, metal oxides or organic polymer compounds are preferable. As the metal oxide, an insulating metal oxide such as silicon oxide (silica), aluminum oxide (alumina), zirconia (zirconia), yttria (yttria), titanium oxide (titania) and the like is preferably used. Also, as the organic polymer compound, insulating resins such as polyimide, polyether, polyacrylate, and polyamine compounds are preferably used.

In order to sufficiently improve the insulating properties of the surface of the AgSn alloy fine particles, the thickness of the insulating film is preferably not less than 1 nm and not more than 100 nm, more preferably not less than 5 nm and not more than 50 nm. The insulating film can be easily formed by surface modification technology or surface coating technology. In particular, if an alkoxide such as tetraethoxysilane or aluminum triethoxide is used, an insulating film with a uniform film thickness can be formed at a relatively low temperature, so it is preferable.

As the black pigment, the above-mentioned perylene-based pigments, lactam-based pigments, and AgSn alloy fine particles may be used alone or in combination. In addition, for the purpose of adjusting the color tone, the black pigment may also contain pigments of hues such as red, blue, green, and yellow. Pigments of other hues in the black pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as pigments of other hues among black pigments. The amount of pigments of other hues in the black pigment is preferably at most 15% by mass, more preferably at most 10% by mass, relative to the total mass of the black pigment.

In order to disperse the pigment demonstrated above uniformly in a photosensitive composition, you may further use a dispersing agent. As such a dispersant, it is preferable to use a polymer dispersant of polyethyleneimine type, urethane resin type, or acrylic resin type. Especially when carbon black is used as the pigment, it is preferable to use an acrylic resin-based dispersant as the dispersant. Furthermore, there are also cases where corrosive gases are generated in the cured film due to the dispersant. Therefore, it is also an example of a preferable aspect to disperse|distribute a pigment without using a dispersing agent.

In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more. In the case of combined use, it is preferably at least 10 parts by mass and 80 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. The organic pigment is used in the following range, and it is more preferable to use it in the range of 20 mass parts or more and 40 mass parts or less.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 又，關於該等染料，可藉由色澱化(成鹽化)使之分散於有機溶劑等中，將其作為著色劑(C)使用。 除該等染料以外，亦可較佳地使用例如日本專利特開2013-225132號公報、日本專利特開2014-178477號公報、日本專利特開2013-137543號公報、日本專利特開2011-38085號公報、日本專利特開2014-197206號公報等中記載之染料等。Furthermore, a pigment and a dye can also be used in combination in a photosensitive composition. The dye may be appropriately selected from known materials. As dyes that can be applied to photosensitive compositions, for example, azo dyes, metal zirconium salt azo dyes, anthraquinone dyes, triphenylmethane dyes, 𠮿

Dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, phthalocyanine dyes, etc. Moreover, these dyes can be dispersed in an organic solvent or the like by laking (salting), and can be used as a colorant (C). In addition to these dyes, Japanese Patent Laid-Open No. 2013-225132, Japanese Patent Laid-Open No. 2014-178477, Japanese Patent Laid-Open No. 2013-137543, and Japanese Patent Laid-Open No. 2011-38085 can also be preferably used. The dyes described in Japanese Patent Publication No. 2014-197206, etc.

The amount of the coloring agent (C) in the photosensitive composition can be appropriately selected within the range that does not impair the purpose of the present invention. Typically, it is preferably 2 mass with respect to the mass of the entire solid content of the photosensitive composition % to 75% by mass, more preferably 3% to 70% by mass.

When using a pigment as a colorant (C), it is preferable to add to a photosensitive composition after disperse|distributing a pigment at an appropriate concentration in presence or absence of a dispersing agent to prepare a dispersion liquid. In addition, in this specification, the usage-amount of the said pigment can be defined as the value including the dispersing agent which exists.

<Other components> The photosensitive composition may contain various additives as needed. Specifically, solvents, surface modifiers, sensitizers, hardening accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti Coagulants, thermal polymerization inhibitors, defoamers, surfactants, chain transfer agents, etc. For each additive, a conventionally known one can be used. As a surfactant, an anionic compound, a cationic compound, a nonionic compound, etc. are mentioned. As an adhesive improvement agent, the conventionally well-known silane coupling agent is mentioned. As a thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned. Examples of the antifoaming agent include silicone-based compounds, fluorine-based compounds, and the like. Examples of the chain transfer agent include thiol-based compounds, halogen-based compounds, quinone-based compounds, α-methylstyrene dimer, and the like. By containing the chain transfer agent, the shape of the pattern (especially the CD change of the hole pattern and the exposure range) can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) not only has the above effects, but also reduces sublimation, coloring, and odor. better.

When a solvent is used in the photosensitive composition, examples of usable solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethyl ether Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Monoethyl ether and other (poly) alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol Methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionate methyl ester, 2- Alkyl lactate such as ethyl hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxy acetate Butyl butyl ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoacetic acid Amyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetyl Other esters such as methyl acetate, ethyl acetylacetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformyl Amides such as amines, N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (GPMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ether (MEDG), cyclohexanone, and 3-methoxybutyl acetate (MBA) exhibit excellent solubility in the above-mentioned (A1) component, (A2) component, and optionally used (B) component, so they are more Preferably, especially propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are used. The content of the solvent may be appropriately determined depending on the use of the photosensitive composition, and as an example, it is about 50 parts by mass or more and 900 parts by mass or less with respect to a total of 100 parts by mass of solid content of the photosensitive composition.

≪Preparation method of photosensitive composition≫ The photosensitive composition of the present invention can be prepared by uniformly stirring and mixing the above-mentioned components to dissolve and disperse them uniformly, and then, if necessary, filtering with a filter such as a 0.2 μm membrane filter. .

≪Method for forming cured product, and cured product≫ The method for forming a cured product is the same as the conventional method for forming a cured product using a photosensitive composition, except that the above-mentioned photosensitive composition is used.

The method of forming a cured product using the above-mentioned photosensitive composition is not particularly limited, and may be appropriately selected from previously used methods. The cured product is formed as a molded body of a desired shape by controlling the shape of the coating film when the photosensitive composition is applied, or by combining position-selective exposure and development. As a suitable method for forming a cured product, a method including a coating film forming step of forming a coating film using the above-mentioned photosensitive composition and an exposure step of exposing the above-mentioned coating film is exemplified. In the case of site-selective exposure, the exposed coating film is developed with a developer to obtain a patterned cured product.

First, in the coating film forming step, for example, use a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a spinner (rotary coating device), a curtain type A non-contact coating device such as a surface coater coats the photosensitive composition of the present invention on a substrate to be formed into a cured product, and if necessary, removes the solvent by drying (pre-baking) to form a coating film. Furthermore, for the sake of convenience, the liquid droplets spread on the substrate, or the photosensitive composition embedded in the concave portion of the substrate with unevenness, or the photosensitive composition filled into the concave portion of the mold, etc. are also referred to as “ Coating".

Next, the formed coating film is subjected to an exposure step. _In the exposure step, ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, The coating film is exposed to radiation such as g-rays, i-rays, and h-rays or electromagnetic waves. Exposure to the coating film can be performed position-selectively through a negative-tone mask. The amount of exposure varies depending on the composition of the photosensitive composition, but is preferably, for example, about 10 mJ/cm ² or more and 600 mJ/cm ² or less.

The exposed coating film is developed if necessary. The above photosensitive composition is less likely to dissolve excessively in an alkaline developer after exposure. Therefore, by using the said photosensitive composition, it becomes easy to form the patterned hardened|cured material which has a good shape which makes an exposure part into a convex part, and makes an unexposed part into a concave part.

In the developing step, the exposed coating film is developed with a developing solution, thereby forming a cured product having a desired shape and pattern. The image development method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of developing solutions include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Furthermore, if necessary, post-baking may be performed on the cured product after exposure or the patterned cured product after development to further advance heat curing. The post-baking temperature is preferably not less than 150°C and not more than 270°C.

The hardened|cured material is formed using the said photosensitive composition. The cured product is preferably an insulating film or a protective film laminated on a photoresist film. When the photosensitive composition does not contain a colorant (C) and is transparent, when the above-mentioned cured product is made into a sample with a thickness of 3.5 μm (optical path length of 3.5 μm), the range of the wavelength from 400 nm to 650 nm The average value of the transmittance of the light inside is usually 90% or more, preferably 93% or more, more preferably 95% or more. In this way, the above-mentioned cured product has excellent transmittance, so it is suitable as an insulator for display devices that require an insulating film with excellent transparency, such as in-cell touch panel liquid crystal display devices and UHA (Ultra High Aperture, ultra-high aperture ratio) panels. film use.

In addition, when using the above-mentioned photosensitive composition to expose through a half-tone mask to form a patterned cured film, not only the full-tone exposed part and the half-tone area in the formed patterned cured product can be formed. There is a sufficient height difference between the exposed parts, and a sufficient height of the halftone exposed parts can be ensured. Therefore, the cured film formed using the said photosensitive composition is suitable as a spacer used in display panels, such as a liquid crystal display panel, especially a black spacer.

≪Photosensitive Adhesive, and Adhesive Method≫ The above photosensitive composition can be preferably used as a photosensitive adhesive. When using a photosensitive composition as a photosensitive adhesive agent, the photosensitive composition may contain a coloring agent (C) for the purpose of providing visibility or providing light-shielding property. As mentioned above, the photosensitive composition used as a photosensitive adhesive agent is excellent in light transmittance. Therefore, when using the said photosensitive composition as a photosensitive adhesive agent, the light which performs exposure will reach the whole adhesive agent easily, and the adhesive agent will harden rapidly by exposure. In particular, when forming an adhesive layer with a film thickness of 1 μm or more and 500 μm or less for bonding, the above-mentioned photosensitive adhesive is preferably used.

Especially if the welding, screwing, nailing and other joining operations in the manufacture of automobiles, locomotives, bicycles, rail vehicles, aircraft, ships, various building components, etc., or when industrial robots are used to manufacture various products, are replaced by the above-mentioned photosensitive Adhesives are used to help reduce the weight of the final product to be joined, or to avoid the breakage of screws or screws caused by metal fatigue when joining by screwing or nailing, or to avoid joining dissimilar metals In this case, there are various advantages such as corrosion caused by battery hardening.

The bonding method using the photosensitive adhesive is not particularly limited. The above-mentioned photosensitive adhesive can be used in the bonding method of the surface to be bonded in various articles. As a typical bonding method, a method including the steps of: forming an adhesive layer containing a photosensitive adhesive on one or both sides of the facing surfaces to be bonded; and curing the adhesive layer by exposure.

The formation method of the adhesive layer containing a photosensitive adhesive is not specifically limited. Typically, an adhesive layer is formed by applying a photosensitive adhesive to one or both of the opposing adhered surfaces. In addition, the photosensitive adhesive may be injected into the gap in the state where a gap of a desired width is formed between the surfaces to be bonded.

Next, the number of objects to be targeted may be one, or a plurality of two or more. When the material of the object to be bonded has flexibility and softness, the number of objects to be bonded to may be one. When the number of objects to be bonded is one, for example, a case where one rectangular plastic sheet is rolled into a cylindrical shape, and the joint portion of the plastic sheet is bonded is exemplified.

Exposure is performed in the same manner as in the above case of forming a cured film. When the object to be bonded is transparent, the method of irradiating the exposure light to the adhesive layer is not particularly limited. In this case, the exposure light may be irradiated to the adhesive layer through the object to be bonded, or the exposure light may be irradiated so that the exposure light enters from the end surface of the adhesive layer. When the object to be bonded includes an opaque material such as metal, exposure is performed in such a manner that the light of exposure enters from the end face of the adhesive layer.

≪Other Uses≫ The above-mentioned photosensitive composition can be used in various applications where a photosensitive composition has been previously used, such as forming an etching mask in semiconductor processing, glass processing, and the like. Moreover, the said photosensitive composition can also be applied to the formation of the photosensitive composition layer in the three-dimensional modeling method by so-called 3D printing which includes the process of forming a photosensitive composition layer. The lamination of the layer hardened by exposure in 3D printing is the so-called self-adhesion of the layer of the hardened product formed using the photosensitive composition. Therefore, the three-dimensional modeling method by 3D printing using the photosensitive adhesive agent containing the said photosensitive composition is also included in the said bonding method using the photosensitive adhesive agent as an aspect. Since the said photosensitive composition is excellent in light transmittance, even if it increases the film thickness of a photosensitive composition layer, it can harden|cure a photosensitive composition layer favorably in a short time by exposure. Therefore, if the above-mentioned photosensitive composition is applied to three-dimensional modeling using 3D printing, by increasing the film thickness of the photosensitive composition layer, the number of layers and exposure times of the photosensitive composition layer can be reduced, and the Make three-dimensional objects of the desired shape. [Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples.

[Example 1 and Comparative Examples 1 to 4] 3 parts by mass of the photopolymerization initiator (A), 38 parts by mass of the photopolymerizable compound (B1), and 62 parts by mass of the resin (B2) at a solid content concentration of 24% by mass was dissolved in an organic solvent to prepare a photosensitive composition.

As a photoinitiator (A), following PI-1, PI-2, and PI-3 were used. The light absorption properties of these photopolymerization initiators are shown in Table 1 below. The values of the gram absorption coefficient of PI-3 in Table 1 are the values at 400 nm. [Chemical 60]

[Table 1]

The types and amounts of photopolymerization initiators used in Example 1 and Comparative Examples 1-4 are described in Table 2 below.

As the photopolymerizable compound (B1), dipentaerythritol hexaacrylate was used.

As the resin (B2), an acrylic resin (Mw: 10000) containing the following structural units was used. The value in the lower right corner of the parentheses in the following formula is the content (mass %) of each structural unit in the resin. [Chemical 61]

As an organic solvent, a mixed solvent of diethylene glycol methyl ether (MEDG), propylene glycol monomethyl ether acetate (PGMEA), and 3-methoxybutyl acetate (MBA) was used (mixing ratio (mass ratio): MEDG:PGMEA:MBA=85:10:5).

Using the obtained photosensitive composition of Example 1 and Comparative Examples 1-4, halftone characteristics and the transmittance of the cured film were evaluated according to the following method. Table 2 shows the evaluation results of halftone characteristics.

<Evaluation of halftone characteristics> After coating the photosensitive composition obtained in each example and comparative example on a glass substrate using a spinner, the coating film was dried at 80° C. for 10 minutes. In the case of full-tone exposure, A coating film with a film thickness to form a cured film with a film thickness of about 3.5 μm was obtained. Next, using an exposure apparatus (manufactured by Canon, MPA600FA), the coating film was subjected to open frame exposure through a halftone mask at an exposure dose of 40 mJ/cm ² . After the exposure, an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.5% by mass was used as a developing solution, and immersion development was performed at 23° C. for 60 seconds. After the exposure, the developed coating film was post-baked at 100° C. for 100 minutes, further at 220° C. for 40 minutes, to obtain a patterned cured film.

When performing post-baking, the film thickness T1 of the coating film before post-baking and the film thickness T2 of the cured film after post-baking were measured using a stylus type surface shape measuring device (manufactured by ULVAC, Dektak 3st). From the measured T1 and T2, according to the following formula: Residual film rate (%)=T2/T1×100 Calculate the residual film rate (%). Using the calculated residual film rate (%), evaluate whether the residual film of the halftone exposed part is good or not during post-baking according to the following criteria. ○: The remaining film rate is above 65% ×: The remaining film rate is less than 65%

Moreover, the patterned cured film was obtained by the same method as the above-mentioned method except having used the full color mask. With respect to the patterned cured film after baking obtained by exposure using a panchromatic mask, the film thickness T3 was measured using a stylus surface shape measuring device (manufactured by ULVAC, Dektak 3st). From the value of T2 and T3, calculate the difference between the height of the pattern during full-tone exposure and the height of the pattern during half-tone exposure, which is ΔH (=T3-T2).

According to the obtained value of ΔH(Å), according to the following criteria, evaluate the thickness difference of the cured film under full-tone exposure and half-tone exposure. ○: ΔH value is 7500 Å or more △: ΔH value is 7000 Å or more but less than 7500 Å ×: ΔH value is less than 7000 Å

Based on the above remaining film ratio and the value of ΔH, halftone characteristics were evaluated according to the following criteria. ○: Residual film rate of 65% or more, and ΔH value of 7500 Å or more △: Residual film rate of 65% or more, but ΔH value of 7000 Å or more and less than 7500 Å ×: Residual film rate of less than 65%, or The remaining film rate is above 65% but the value of ΔH is less than 7000 Å

For the cured film with a thickness of 3.5 μm formed by full-tone exposure using the photosensitive composition of Example 1, the average value of the light transmittance in the wavelength region in the range of 400 nm to 650 nm was measured, and the result was The value is 95%. That is, the light transmittance of the cured film formed using the photosensitive composition of Example 1 was favorable.

[Table 2]

According to Table 2, it can be seen that only two kinds of oxime ester compounds having peaks in the wavelength region above 320 nm and less than 400 nm in the absorption spectrum are used as the photopolymerization initiator (A), and the photopolymerization initiator (A) The performance of the photosensitive composition of Example 1 in which the maximum wavelengths of the peaks of the two oxime ester compounds are different does not contain a compound showing a gram light absorption coefficient of 10 or more at any wavelength in the wavelength range of 400 nm or more. Good halftone characteristics.

[Example 2 and Comparative Example 5] 5 parts by mass of photopolymerization initiator (A), 10 parts by mass of photopolymerizable compound (B1), 32 parts by mass of resin (B2), 8 parts by mass of carbon black, perylene pigment 34 mass parts and 6 mass parts of dispersing agents were dissolved in the organic solvent so that the solid content concentration might be 25 mass %, and it was made to disperse|distribute, and the photosensitive composition was prepared.

As the photopolymerization initiator (A), the above-mentioned PI-1 and PI-2 were used. The type and amount of the photopolymerization initiator are as described in Table 3. As the photopolymerizable compound (B1), 3 parts by mass of tetraethylene glycol dimethacrylate and 7 parts by mass of dipentaerythritol hexaacrylate were used.

As the resin (B2), Cardo resin synthesized by the following method was used. First, in a 500 mL four-neck flask, 235 g of bisphenol-based epoxy resin (epoxy equivalent weight 235), 110 mg of tetramethylammonium chloride, 2,6-di-tert-butyl-4-methyl 100 mg of phenol and 72.0 g of acrylic acid were dissolved by heating at 90-100°C while blowing air at a rate of 25 mL/min. Then, keep the solution in a cloudy state and slowly heat up to 120°C to dissolve it completely. At this time, the solution gradually became transparent and viscous, and stirring was continued in this state. During this period, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0 mgKOH/g. It takes 12 hours for the acid value to reach the target value. Furthermore, it cooled to room temperature, and obtained the bisphenol fluorine-type epoxy acrylate represented by the following formula as a colorless transparent solid.

[chem 62]

Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the above-mentioned bisphenol fluorine-type epoxy acrylate obtained in this way and dissolving it, 80.5 g of benzophenone tetracarboxylic dianhydride and tetraethyl Add 1 g of ammonium bromide, raise the temperature slowly, and react at 110-115°C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain a Cardo resin. The disappearance of the acid anhydride group was confirmed by IR spectrum.

As an organic solvent, a mixed solvent (mixing ratio (mass ratio): MBA:PGMEA=5:95) of 3-methoxybutyl acetate (MBA) and propylene glycol monomethyl ether acetate (PGMEA) was used.

Using the obtained photosensitive composition of Example 2 and Comparative Example 5, halftone characteristics and post-development residue were evaluated according to the following method. Table 3 shows the evaluation results of halftone characteristics.

<Evaluation of Halftone Characteristics> After coating the photosensitive composition obtained in Examples and Comparative Examples on a glass substrate using a spinner, the coating film was dried at 100° C. for 120 seconds. In the case of full-tone exposure, A coating film with a film thickness to form a cured film with a film thickness of about 3.5 μm was obtained. Next, using an exposure device (manufactured by TOPCON, TME150RTO), the coating film was subjected to open-frame exposure through a halftone mask at an exposure dose of 50 mJ/cm ² . After the exposure, spray development was carried out at 25° C. for 60 seconds using an aqueous solution of potassium hydroxide with a concentration of 0.05% by mass as a developing solution. After exposure, the developed coating film was post-baked at 230° C. for 20 minutes to obtain a patterned cured film.

When performing post-baking, the film thickness T1 of the coating film before post-baking and the film thickness T2 of the cured film after post-baking were measured using a stylus type surface shape measuring device (manufactured by ULVAC, Dektak 3st). From the measured T1 and T2, according to the following formula: Residual film rate (%)=T2/T1×100 Calculate the residual film rate (%). Using the calculated residual film rate (%), evaluate whether the residual film of the halftone exposed part is good or not during post-baking according to the following criteria. ○: The remaining film rate is above 80% ×: The remaining film rate is less than 80%

Moreover, the patterned cured film was obtained by the same method as the above-mentioned method except having used the full color mask. With respect to the patterned cured film after baking obtained by exposure using a pantone mask, the film thickness T3 was measured using a stylus surface shape measuring device (manufactured by ULVAC, Dektak 3st). From the value of T2 and T3, calculate the difference between the height of the pattern during full-tone exposure and the height of the pattern during half-tone exposure, which is ΔH (=T3-T2).

According to the obtained value of ΔH(Å), according to the following criteria, evaluate the thickness difference of the cured film under full-tone exposure and half-tone exposure. ○: The value of ΔH is more than 1000 Å ×: The value of ΔH is less than 1000 Å

From the value of the above remaining film ratio and ΔH, halftone characteristics were evaluated according to the following criteria. ○: The remaining film rate is above 80%, and the ΔH value is above 1000 Å ×: The remaining film rate is less than 80%, or the remaining film rate is above 80%, but the ΔH value is less than 1000 Å

Regarding the cured film with a thickness of 3.5 μm formed by full-tone exposure using the photosensitive composition of Example 2, the presence or absence of residue in the pattern was confirmed by microscope observation, but no residue was confirmed.

[table 3]

According to Table 3, it can be seen that for the photosensitive composition containing the colorant (C), only two oxime ester compounds having peaks in the wavelength region above 320 nm and below 400 nm in the absorption spectrum are used as photopolymerization initiators agent (A), and the photopolymerization initiator (A) does not contain a compound showing a gram light absorption coefficient of 10 or more at any wavelength in the wavelength range of 400 nm or more, the peaks of the two oxime ester compounds are extremely large The photosensitive composition of Example 2 with different wavelengths exhibited good halftone properties.

Claims (9)

A photosensitive composition comprising a photopolymerization initiator (A) and two or more oxime ester compounds having a peak in the wavelength region of 320 nm or more and less than 400 nm in the light absorption spectrum, the photopolymerization initiator The initiator (A) does not contain a compound showing a gram light absorption coefficient of 10 or more at any wavelength in the wavelength region of 400 nm or more. The maximum wavelengths of the above-mentioned peaks of two or more kinds of the above-mentioned oxime ester compounds are different, and the above-mentioned light The polymerization initiator (A) comprises the following formula (a1):

(In formula (a1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group that may have a substituent, or a heterocyclic group that may have a substituent, R ³ is a monovalent organic group, R ⁴ is a monovalent organic group , R ⁵ and R ⁶ are independently a benzene ring that may have a substituent, or a naphthalene ring that may have a substituent, and m1, m2 and m3 are 0 or 1 respectively) and satisfy the following (1)~(3): (1) R ¹ contains the group represented by -OR ⁷ , R ⁷ is haloalkyl (2) m2 is 1, R ⁴ contains the group represented by -OR ⁷ , R ⁷ is haloalkyl (3) R ³ is The oxime ester compound (A1) of at least one condition among the branched alkyl groups that may have substituents, and the following formula (a2):

(In the formula (a2), CR is the following formula (a2a) or the following formula (a2b):

In the group represented, R ^a1 is a hydrogen atom, a nitro group or a monovalent organic group, R ^a2 and R ^a3 are respectively a chain-like alkyl group that may have a substituent, a chain-like alkoxy group that may have a substituent, and a chain-like alkoxy group that may have a substituent A cyclic organic group or a hydrogen atom, R ^a2 and R ^a3 may be bonded to each other to form a ring, R ^a4 is a monovalent organic group, R ^a5 is a hydrogen atom, and the number of carbon atoms that may have substituents is 1 or more and An oxime ester compound (A2) represented by an aliphatic hydrocarbon group of 20 or less, or an aryl group which may have a substituent, n1 is an integer of 0 to 4, and n2 is 0 or 1). The photosensitive composition according to claim 1, wherein the maximum wavelength on the longest wavelength side among the maximum wavelengths of the above-mentioned peaks of the above-mentioned two or more oxime ester compounds is set to λ _max-r , and the maximum wavelength on the shortest wavelength side is set to In the case of λ _max -b, the difference between the above λ _max-r and the above λ _max-b is 20 nm or more. The photosensitive composition according to claim 1, wherein in the above-mentioned formula (a2), the above-mentioned CR is a group represented by the above-mentioned formula (a2a). The photosensitive composition according to claim 1 or 2, which comprises a polymerizable substrate component (B), polymerizable The base material component (B) contains a photopolymerizable compound (B1), or contains a photopolymerizable compound (B1) and a resin (B2). A method for forming a cured product, comprising: forming a coating film using the photosensitive composition according to any one of claims 1 to 4; and exposing the coating film. The method for forming a cured product according to claim 5, wherein position-selectively exposing the above-mentioned coating film includes developing the exposed coating film. A cured product, which is a cured product of the photosensitive composition according to any one of claims 1 to 4. A photosensitive adhesive comprising a cured product of the photosensitive composition according to any one of claims 1 to 4. A method for bonding a surface to be bonded, comprising: forming an adhesive layer comprising the photosensitive adhesive according to claim 8 on one or both sides of the facing surface to be bonded; and hardening the adhesive layer by exposure.