TWI772456B - Oxime ester compound and photopolymerization initiator containing the same - Google Patents

Abstract

(式中，R¹ 、R² 、R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 、R⁹ 、R¹⁰ 、R¹¹ 、R¹² 及R¹³ 中，至少三者為下述通式(II)所表示之基；較佳為R³ 、R⁶ 及R¹¹ 之至少一者為通式(II)所表示之基)

The present invention provides an oxime ester compound represented by the following general formula (I).

(wherein, at least three of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the following A group represented by the general formula (II); preferably at least one of R ³ , R ⁶ and R ¹¹ is a group represented by the general formula (II))

Description

Oxime ester compound and photopolymerization initiator containing the same

The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator used in a photosensitive composition, a photopolymerization initiator containing the compound, and a photopolymerization initiator containing the photopolymerization initiator and an ethylenically unsaturated compound Photosensitive composition.

The photosensitive composition is a photopolymerization initiator added to an ethylenically unsaturated compound, which can be polymerized and cured by irradiating energy rays (light), so it can be used for photocurable inks, photosensitive printing plates, various photoresists agent, etc.

As a photopolymerization initiator used for the said photosensitive composition, the oxime ester photopolymerization initiator which has a carbazole skeleton is proposed in patent document 1. Moreover, in patent document 2, the polymerization initiator containing the oxime ester compound which has a triarylamine skeleton is proposed. However, the oxime ester compounds described in Patent Documents 1 and 2 cannot simultaneously achieve satisfactory levels of sensitivity, heat resistance (low sublimation), and transparency (high brightness of a color filter).

Moreover, since the coloring alkali-developable photosensitive composition containing a colorant, such as a color filter, is required to have high sensitivity, it is necessary to make the photopolymerization initiator in a photoresist high density|concentration. However, a photopolymerization initiator with a high concentration of the photopolymerization initiator causes the generation of residues due to the deterioration of developability, or the contamination of the mask or heating furnace due to the sublimation, and the coloration of the hardened material, resulting in a change in brightness. Poor wait. Prior Art Documents Patent Documents

Patent Document 1: International Publication No. 2008/138732 Patent Document 2: International Publication No. 2017/033880

Therefore, the subject of the present invention is to provide an oxime ester compound useful as a photopolymerization initiator with high sensitivity and high transmittance in the visible light region, a photopolymerization initiator using the compound, and a photosensitive composition, and to provide a A color filter with higher brightness and a display device containing the color filter.

The present invention solves the above-mentioned problems by providing the following [1] to [9].

[1] An oxime ester compound represented by the following general formula (I),

(式中，R¹ 、R² 、R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 、R⁹ 、R¹⁰ 、R¹¹ 、R¹² 及R¹³ 分別獨立地表示下述通式(II)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、胺基、R²¹ 、OR²¹ 、SR²¹ 、NR²² R²³ 、COR²¹ 、SOR²¹ 、SO₂ R²¹ 或CONR²² R²³ ， R¹ 、R² 、R³ 、R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 、R⁹ 、R¹⁰ 、R¹¹ 、R¹² 及R¹³ 中，至少三者為下述通式(II)所表示之基， R²¹ 、R²² 及R²³ 分別獨立地表示碳原子數1～20之烴基或碳原子數2～20之含雜環基， 存在R²¹ 、R²² 及R²³ 所表示之基中之氫原子被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸酯基或碳原子數2～20之含雜環基之情形， 存在R²¹ 、R²² 及R²³ 所表示之基中之亞甲基被取代為-O-、-CO-、-COO-、-OCO-、-NR²⁴ -、-NR²⁴ CO-、-S-、-CS-、-SO₂ -、-SCO-、-COS-、-OCS-或CSO-之情形， R²⁴ 表示氫原子、碳原子數1～20之烴基， X¹ 不存在或表示直接鍵、-CO-、-O-或-S-)。[hua 1]

(wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent the following general formula Group represented by (II), hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, amino group, R ²¹ , OR ²¹ , SR ²¹ , NR ²² R ²³ , COR ²¹ , SOR ²¹ , SO ₂ R ²¹ or CONR ²² R ²³ , at least three of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is a group represented by the following general formula (II), R ²¹ , R ²² and R ²³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and R ²¹ , The hydrogen atoms in the groups represented by R ²² and R ²³ are substituted with halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryl groups, epoxy groups, vinyl groups, ethylene groups In the case of an ether group, a mercapto group, an isocyanate group or a heterocyclic group containing 2 to 20 carbon atoms, the methylene group in the groups represented by R ²¹ , R ²² and R ²³ is substituted with -O-, -CO- , -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO-, R ²⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, X ¹ does not exist or represents a direct bond, -CO-, -O- or -S-).

(式中，R³¹ 及R³² 分別獨立地表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之烴基或碳原子數2～20之含雜環基， 存在R³¹ 及R³² 所表示之基中之氫原子被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸酯基或碳原子數2～20之含雜環基之情形， 亦存在R³¹ 及R³² 所表示之基中之亞甲基被取代為-O-、-CO-、-COO-、-OCO-、-NR³³ -、-NR³³ CO-、-S-、-CS-、-SO₂ -、-SCO-、-COS-、-OCS-或CSO-之情形， R³³ 表示氫原子、碳原子數1～20之烴基， n表示0或1，*表示鍵結鍵)。[hua 2]

(in the formula, R ³¹ and R ³² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, and R ³¹ and The hydrogen atom in the group represented by R ³² is substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryl group, an epoxy group, a vinyl group, a vinyl ether group, In the case of a mercapto group, an isocyanate group or a heterocyclic group containing 2 to 20 carbon atoms, the methylene group in the groups represented by R ³¹ and R ³² is also substituted with -O-, -CO-, -COO-, In the case of -OCO-, -NR ³³ -, -NR ³³ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO-, R ³³ represents a hydrogen atom , a hydrocarbon group with 1 to 20 carbon atoms, n represents 0 or 1, and * represents a bond).

[2] The oxime ester compound according to [1], wherein at least one of R ³ , R ⁶ and R ¹¹ in the general formula (I) is a group represented by the general formula (II).

[3] A photopolymerization initiator containing the oxime ester compound as described in [1] or [2].

[4] A photosensitive composition containing the photopolymerization initiator (A) as described in [3] and an ethylenically unsaturated compound (B).

[5] The photosensitive composition according to [4], which further contains a colorant (C).

[6] An alkali-developable photosensitive resin composition comprising the photosensitive composition according to [4] or [5] and an alkali-developable compound (D).

[7] A cured product of the photosensitive composition according to [4] or [5] or the cured product of the alkali-developable photosensitive resin composition according to [6].

[8] A display device comprising the cured product according to [7].

[9] A method for producing a cured product, comprising: the photosensitive composition according to [4] or [5] or the alkali-developable photosensitive resin composition according to [6] by light irradiation or heating Hardening step.

Hereinafter, the oxime ester compound of the present invention and the photopolymerization initiator (A) containing the compound will be described in detail based on a preferred embodiment.

The oxime ester compound of the present invention is a novel compound represented by the aforementioned general formula (I). The oxime ester compound exists as geometric isomers based on the double bond of the oxime, but these are not distinguished. That is, in this specification, the compound represented by the above-mentioned general formula (I) and its exemplified compounds represent one or a mixture of two or more of these geometric isomers, and are not limited to the structures representing specific isomers.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ to R ²⁴ in the above general formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, or a hydrocarbon group having 2 to 20 carbon atoms. Alkenyl group, cycloalkyl group having 3 to 20 carbon atoms, cycloalkylalkyl group having 4 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, and the like.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopropyl pentyl, third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, third octyl, nonyl, isononyl, decyl, isodecyl, undecyl, Dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc., particularly preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl group, ethylidene group, 2-propenyl group, 3-butenyl group, 2-butenyl group, 4-pentenyl group, and 3-pentenyl group. , 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4 -Decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecenyl allyl, etc. Especially preferred is an alkenyl group having 1 to 10 carbon atoms.

The above-mentioned cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. As a saturated monocyclic group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, etc. are mentioned, for example. As a saturated polycyclic type, an adamantyl group, a decahydronaphthyl group, an octahydrocyclopentadiene group, a bicyclo[1.1.1]pentyl group, and the like are mentioned.

The above-mentioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted with the cycloalkyl group. For example, cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononyl Ethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl and decalinylpropyl, etc.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and a benzene group substituted at one or more points with the above-mentioned alkyl group. base, biphenyl, naphthyl, anthracenyl, etc.

The above-mentioned arylalkyl group having 7 to 30 carbon atoms means a group having 7 to 30 carbon atoms in which the hydrogen atom of the alkyl group is substituted with an aryl group. For example, a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, a naphthylpropyl group, and the like are mentioned.

Among the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms, in terms of good sensitivity as a photopolymerization initiator, alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an arylalkyl group having 7 to 15 carbon atoms.

Examples of the above-mentioned general formula (I) include a heterocyclic group containing 2 to 20 carbon atoms represented by R ²¹ to R ²³ and a carbon in which a hydrogen atom in the group represented by R ²¹ to R ²³ may be substituted. Examples of the heterocyclic group having 2 to 20 atoms include pyrrolyl, pyridyl, pyridylethyl, pyrimidinyl, pyridyl, piperyl, piperidinyl, pyranyl, and pyranylethyl , pyrazolyl, triazolyl, triazolyl methyl, pyrrolidinyl, quinolinyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, furyl (furyl), furanyl (furanyl) ), benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzothiazolyl azolyl, isothiazolyl, isoxazolyl, indolyl, 𠮻rolidyl, 𠰌olinyl, thio𠰌olinyl, 2-pyrrolidin-1-yl, 2-piperidin-1-yl , 2,4-Dioxyimidazolidin-3-yl and 2,4-Dioxyoxazolidin-3-yl, etc.

There are also methylene groups in the groups represented by R ²¹ to R ²³ in the above general formula (I) are substituted with -O-, -CO-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ In the case of CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO-, the substitution can be one or more than two groups, and in the case of continuous In the case of a substituted group, there is also a case where two or more places are continuously substituted under the condition that the oxygen atoms are not adjacent to each other.

Among the above-mentioned heterocyclic groups having 2 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms is particularly preferable in terms of good sensitivity as a photopolymerization initiator.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ³¹ to R ³³ in the above general formula (II) include those represented by R ²¹ to R ²⁴ in the above general formula (I) having 1 to 20 carbon atoms. The hydrocarbon group of 20 is the same.

Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R ³¹ and R ³² in the above-mentioned general formula (II), and carbon in which hydrogen atoms in the groups represented by R ³¹ and R ³² may be substituted The heterocyclic group having 2 to 20 atoms includes the same ones as the hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ to R ²³ in the general formula (I).

There are also methylene groups in the groups represented by R ³¹ and R ³² in the above general formula (II) are replaced by -O-, -CO-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ In the case of CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO-, the substitution can be one or more than two groups, and in the case of continuous In the case of a substituted group, there is also a case where two or more places are continuously substituted under the condition that the oxygen atoms are not adjacent to each other.

As a halogen atom in the said general formula (I) and (II), fluorine, chlorine, bromine, and iodine are mentioned.

In the general formula (I), the oxime ester compound in which X ¹ does not exist or is a direct bond is preferable in terms of excellent brightness when used as a photopolymerization initiator, and X ¹ is an oxime ester compound with a direct bond In addition to brightness, it is particularly preferable in that the sensitivity is more excellent. In the present invention, the absence of X ¹ means that no atom exists at the position of X ¹ , and the oxime ester compound represented by the general formula (I) has a triphenylamine skeleton.

When R ¹ to R ¹³ are groups other than those of the general formula (II), R ¹ to R ¹³ are hydrogen atoms or cyano groups, especially hydrogen atoms, and are preferred because they are easy to synthesize.

At least one of R ³ , R ⁶ and R ¹¹ in the general formula (I), preferably both, more preferably all of the oxime ester compounds represented by the general formula (II) is a good synthesis yield. , and is also easy to refine. When all of R ³ , R ⁶ and R ¹¹ in the general formula (I) are groups represented by the general formula (II), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ^9. The oxime ester compound in which R ¹⁰ , R ¹² and R ¹³ are hydrogen atoms is preferable because it is easy to synthesize.

In the above-mentioned general formula (II), the cured product using the oxime ester compound of n=1 as the photopolymerization initiator (A) is preferable because it is excellent in transparency and brightness.

In the above general formula (II), R ³¹ is preferably an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 7 carbon atoms, because of its high solubility in organic solvents. R ³² is preferably an alkyl group having 1 to 4 carbon atoms, especially a methyl group, an ethyl group or a phenyl group, because of its high reactivity.

Preferred specific examples of the oxime ester compound of the present invention represented by the general formula (I) include the following compounds No. 1 to No. 261. However, the present invention is not limited by the following compounds.

[hua 3]

[hua 4]

[hua 5]

[hua 6]

[hua 7]

[hua 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[hua 20]

[Chemical 21]

[Chemical 22]

[Chemical 23]

The oxime ester compound of the present invention represented by the aforementioned general formula (I) is not particularly limited, and can be synthesized, for example, by the method shown below.

When n in the general formula (II) is 0, it can be synthesized by the following reaction scheme. Specifically, the ketone compound 1 is obtained by reacting a known nitrogen-containing compound with a known and commercially available acyl chloride, and the oxime compound 1 is obtained by reacting the obtained ketone compound 1 with hydroxylamine hydrochloride. Next, the oxime compound 1 and acyl chloride are reacted in the presence of triethylamine (TEA) to obtain the oxime ester compound 1 of the present invention represented by the general formula (I). The oxime compound and the oxime ester compound can also be produced by the method described in International Publication No. 2008/078678.

[Chemical 24]

In the above reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ³¹ , R ³² and X ¹ and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² of general formula (I) and general formula (II) , R ¹³ , R ³¹ , R ³² and X ¹ are the same.

When n in the general formula (II) is 1, it can be produced by the following method according to the following reaction formula. That is, the ketone compound 2 is obtained by reacting a known nitrogen-containing compound with acyl chloride, and the oxime compound 2 is obtained by reacting the ketone compound 2 with isobutyl nitrite. Next, the oxime compound 2 of the present invention represented by the general formula (I) is obtained by reacting the oxime compound 2 with an acid anhydride or acyl chloride.

[Chemical 25]

In the above reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ³¹ , R ³² and X ¹ and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² of general formula (I) and general formula (II) , R ¹³ , R ³¹ , R ³² and X ¹ are the same.

The novel oxime ester compound of the present invention described above is useful for medicines, agricultural chemicals, alkali generators, photopolymerization initiators, etc. Among photopolymerization initiators, it is especially useful as a radical polymerization initiator (photofree radical polymerization initiators or thermal radical polymerization initiators) are useful. Moreover, the novel oxime ester compound of this invention can also be used suitably as a sensitizer.

The photosensitive composition of the present invention contains the photopolymerization initiator (A) and the ethylenically unsaturated compound (B) of the present invention, and further contains a colorant (C), an alkali developable compound (D), an inorganic compound, and a solvent in combination and other components as arbitrary components.

The photopolymerization initiator (A) of the present invention contains at least one oxime ester compound of the present invention represented by the general formula (I), and other photopolymerization initiators may be used in combination. The content of the oxime ester compound of the present invention in the photopolymerization initiator (A) is preferably 30 to 100 mass %, more preferably 50 to 100 mass %. Moreover, the photopolymerization initiator (A) of this invention is useful as a photopolymerization initiator of an ethylenically unsaturated compound (B).

系化合物、氧化膦系化合物及二茂鈦系化合物等作為較佳者。As other photopolymerization initiators not belonging to the general formula (I), as long as they generate radicals by light irradiation, they are not particularly limited, and previously known compounds can be used, for example, oxime ester-based compounds, styrene ethyl Ketone-based compounds, benzoin-based compounds, benzophenone-based compounds, 9-oxosulfur

System compounds, phosphine oxide-based compounds, titanocene-based compounds, and the like are preferred.

Examples of the oxime ester-based compound include compounds having a group represented by the general formula (II), and the like. Among the above-mentioned photopolymerization initiators, they can be preferably used in the present invention in terms of good sensitivity. Photosensitive composition.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ³¹ to R ³³ in the general formula (II) is the same as the hydrocarbon group having 1 to 20 carbon atoms described in the general formula (I).

R ³¹ and R ³² in the above-mentioned general formula (II), and a group having 2 to 20 carbon atoms containing a heterocyclic ring in which the group represented by R ³¹ or R ³² may be modified and described in the general formula (I) The groups containing 2 to 20 carbon atoms of a heterocyclic ring are the same.

Among the oxime ester-based compounds having the group represented by the general formula (II), the compound represented by the following general formula (III) is preferably used for the photosensitivity of the present invention, especially in terms of high sensitivity. sexual composition.

Among the oxime ester-based compounds having the group represented by the general formula (I), the compound represented by the following general formula (III) is preferably used for the photosensitivity of the present invention, especially in terms of high sensitivity. sexual composition.

[Chemical 26]

(in the formula, R ³¹ , R ³² and n are respectively the same as R ³¹ , R ³² and n in the general formula (II), R ⁴¹ and R ⁴² independently represent a direct bond, a hydrogen atom, a nitro group, a cyano group, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a group containing a heterocyclic ring having 2 to 20 carbon atoms, X ¹¹ represents an oxygen atom , sulfur atom, selenium atom, CR ⁴³ R ⁴⁴ , CO, NR ⁴⁵ or PR ⁴⁶ , X ¹² represents no bond, direct bond, hydrocarbon group with 1 to 20 carbon atoms, CO, and R ⁴³ to R ⁴⁶ each independently represent hydrogen Atoms, hydrocarbon groups with 1 to 20 carbon atoms or groups with 2 to 20 carbon atoms containing a heterocyclic ring, and there are also hydrogen atoms in the groups represented by R ⁴³ to R ⁴⁶ substituted with halogen atoms, nitro groups, cyano groups , hydroxyl, amine group, carboxyl group, methacryloyl group, acryl group, epoxy group, vinyl group, mercapto group, isocyanate group, and heterocyclic group, there are also groups represented by R ⁴¹ to R ⁴⁶ . Methylene group is substituted with -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ -, -SCO- or -COS- under the condition that oxygen is not adjacent, also exists When R ⁴¹ to R ⁴⁶ each independently form a ring together with any adjacent benzene ring, a represents the number of 0 to 4, and b represents the number of 0 to 3).

The hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ in the general formula (III) are the same as the hydrocarbon groups having 1 to 20 carbon atoms described in the general formula (I).

Groups containing 2 to 20 carbon atoms of a heterocyclic ring represented by R ⁴¹ to R ⁴⁶ in the above general formula (III) and groups containing 2 to 20 carbon atoms of a heterocyclic ring described in the above general formula (I) same.

As a preferable oxime ester type compound represented by the said general formula (III), the compound No.A2-1 to No.A2-28 shown below are mentioned, for example. However, the polymerization initiator (A) used in the present invention is not limited by the following compounds.

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[Chemical 28]

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In the general formula (III), when X ¹ is a sulfur atom and X ² is a bondless case, it becomes an oxime ester compound having a diphenyl sulfide skeleton represented by the above-mentioned compounds No. A2-1 to A2-7 , and use together with the oxime ester compound of the present invention as a polymerization initiator, whereby a photosensitive composition with good sensitivity can be obtained, which is preferable in this respect.

In the general formula (III), when X ¹ is NR ⁵⁵ and X ² is a direct bond, it becomes an oxime ester compound having a carbazole skeleton represented by the above-mentioned compound Nos. A2-8 to A2-28, which can be In this respect, it is especially preferable to obtain a photosensitive composition with good sensitivity.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2 -Methyl propiophenone, 2-hydroxymethyl-2-methyl propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone , p-tert-butyl dichloroacetophenone, p-tert-butyl trichloroacetophenone, p-azidobenzylidene acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-(Methylthio)phenyl]-2-𠰌olinylacetone-1, 2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butanone-1, Benzoin, Benzoin methyl ether, Benzoin ether, Benzoin isopropyl ether, Benzoin n-butyl ether, Benzoin isobutyl ether and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl -1-Propan-1-one, etc.

As said benzil compound, benzil etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4'-dichlorobenzophenone and 4-benzyl-4'-methyl diphenyl sulfide, etc.

系化合物，可列舉：9-氧硫

、2-甲基-9-氧硫

、2-乙基-9-氧硫

、2-氯-9-氧硫

、2-異丙基-9-氧硫

、2,4-二乙基-9-氧硫

等。As the above-mentioned 9-oxosulfur

series of compounds, such as: 9-oxosulfur

, 2-methyl-9-oxothio

, 2-ethyl-9-oxothio

, 2-chloro-9-oxosulfur

, 2-isopropyl-9-oxothio

, 2,4-diethyl-9-oxothio

Wait.

Examples of the phosphine oxide-based compound include phosphine oxide-based compounds such as 2,4,6-trimethylbenzyldiphenylphosphine oxide. As a titanocene-based compound, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyrrol-1-yl)]titanium etc. are mentioned.

Commercially available free radical initiators include: Adeka Optomer N-1414, N-1717, N-1919, Adeka ARKLS NCI-831, NCI-930 (the above are manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907 , IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (the above are manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (the above are manufactured by TRONLY), etc.

In the photosensitive composition of the present invention, the content of the photopolymerization initiator (A) is not particularly limited, but is preferably 1 to 70 parts by mass relative to 100 parts by mass of the ethylenically unsaturated compound (B), more preferably It is 1-50 mass parts, Preferably it is 5-30 mass parts.

The above-mentioned ethylenically unsaturated compound (B) has an ethylenically unsaturated bond. The ethylenically unsaturated compound (B) is not particularly limited, and those previously used in photosensitive compositions can be used, and examples thereof include ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, and vinylidene fluoride. Unsaturated aliphatic hydrocarbons such as ethylene and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, isobutylene acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, methyl fumaric acid, mono[2-(meth)acrylooxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate 2-(meth)acryloyloxyethyl]ester, ω-carboxypolycaprolactone mono(meth)acrylate equal to mono(meth)acrylate of polymer with carboxyl and hydroxyl groups at both ends; hydroxyethyl Hydroxypropyl (meth)acrylate/maleate, hydroxypropyl (meth)acrylate/maleate, dicyclopentadiene maleate or those with one carboxyl group and two or more (methyl) ) Unsaturated polybasic acids such as polyfunctional (meth)acrylates of acrylyl groups; (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate glycidyl Esters, the following compounds No.A1 to No.A4, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylate base) cyclohexyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate , Methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, (meth)acrylate base) dimethylaminopropyl acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, Ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylate Benzyl acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate base) acrylate, tricyclodecane dimethanol di(meth)acrylate, tris[(meth)acryloethyl]isocyanurate, polyester (meth)acrylate oligomer, etc. Saturated monobasic acid and ester of polyhydric alcohol or polyphenol; metal salt of unsaturated polybasic acid such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydro Phthalate Acid anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-di Anhydrides of unsaturated polybasic acids such as carboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylbicycloheptenedicarboxylic anhydride; (meth)propylene Acrylamide, methylene bis(meth)acrylamide, diethylenetriamine tri(meth)acrylamide, xylylene bis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth)acrylamide and other unsaturated monobasic acids and polyamine amides; unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α-chloroacrylonitrile, dicyanoidene , unsaturated nitrile such as allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinyl Unsaturated aromatic compounds such as vinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether; Unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl methyl alcohol Ether, vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether and other vinyl ethers; maleimide, N-phenylmaleimide, N-cyclohexylmaleimide Unsaturated imines such as imide; indene such as indene, 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polyphenylene Ethylene, poly(methyl)acrylate, poly(n-butyl)(meth)acrylate, polysiloxane are macromonomers with a mono(meth)acryloyl group at the end of the polymer molecular chain; vinyl chloride, Vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, Vinylcarbazole, vinylpyrrolidone, vinylpyridine, hydroxy-containing vinyl monomers and vinyl urethane compounds of polyisocyanate compounds, ethylene of hydroxy-containing vinyl monomers and polyepoxy compounds base epoxy compound.

As said ethylenically unsaturated compound (B), a commercial item can be used, for example, KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (made by Nippon Kayaku Co., Ltd.), SPC -1000, SPC-3000 (manufactured by Showa Denko), ARONIX M-140, M-215, M-350 (manufactured by Toagosei Co., Ltd.), NK ESTER A-DPHA-TMPT, A-DCP, A-HD-N, A -9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), etc.

Among these, mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups, non- Esters of saturated monobasic acid and polyhydric alcohol or polyhydric phenol are suitable for the alkali-developable photosensitive resin composition of the present invention.

The ethylenically unsaturated compounds may be used alone or in combination of two or more, and when two or more of them are used in combination, these may be copolymerized in advance and used as a copolymer.

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

A coloring agent (C) can be further contained in the photosensitive composition of this invention, and it can be set as a coloring photosensitive composition. As this coloring agent (C), a pigment, a dye, a natural coloring matter, etc. are mentioned. These colorants (C) can be used individually or in mixture of 2 or more types.

化合物；喹啉化合物；蒽醌化合物；香豆素化合物；酞菁化合物；異吲哚啉酮化合物；異吲哚啉化合物；喹吖啶酮化合物；蒽締蒽酮化合物；哌瑞酮化合物；苝化合物；二酮基吡咯并吡咯化合物；硫靛藍化合物；二㗁 𠯤化合物；三苯基甲烷化合物；喹酞酮化合物；萘四羧酸；偶氮染料、花青染料之金屬錯合物；色澱顏料；藉由爐法、槽法或熱法所獲得之碳黑、或者乙炔黑、科琴黑或燈黑等碳黑；利用環氧樹脂調整或被覆上述碳黑而成者、預先於溶劑中利用樹脂對上述碳黑進行分散處理而吸附20～200 mg/g之樹脂而成者、對上述碳黑進行酸性或鹼性表面處理而成者、平均粒徑為8 nm以上且DBP(dibutyl phthalate，鄰苯二甲酸二丁酯)吸油量為90 ml/100 g以下者、根據950℃下之揮發成分中之CO及CO₂ 算出之總氧量相對於每100 m² 碳黑之表面積為9 mg以上者；石墨、石墨化碳黑、活性碳、碳纖維、奈米碳管、螺旋碳纖維、碳奈米角、碳氣凝膠、富勒烯；苯胺黑、顏料黑7、鈦黑；氧化鉻綠、米洛麗藍、鈷綠、鈷藍、錳系、亞鐵氰化物、磷酸鹽群青、鐵藍、群青、天藍、濃綠、翡翠綠、硫酸鉛、黃丹、鋅黃、鐵丹(紅色氧化鐵(III))、鎘紅、合成鐵黑、棕土等有機或無機顏料。該等顏料可單獨或混合複數種而使用。As the above-mentioned pigments, for example, nitroso compounds; nitro compounds; azo compounds; diazo compounds can be used;

Compounds; Quinoline Compounds; Anthraquinone Compounds; Coumarin Compounds; Phthalocyanine Compounds; Isoindolinone Compounds; Isoindoline Compounds; Compounds; Diketopyrrolopyrrole compounds; Thioindigo compounds; Diptero compounds; Triphenylmethane compounds; Quinophthalone compounds; Naphthalene tetracarboxylic acid; Metal complexes of azo dyes and cyanine dyes; Lakes Pigment; carbon black obtained by furnace method, tank method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black; prepared by adjusting or coating the above carbon black with epoxy resin, used in a solvent in advance The resin is obtained by dispersing the above carbon black and adsorbing 20 to 200 mg/g of the resin, and the above carbon black is subjected to acid or basic surface treatment, and the average particle size is 8 nm or more and DBP (dibutyl phthalate, Dibutyl phthalate) oil absorption is 90 ml/100 g or less, and the total oxygen content calculated from CO and CO ₂ in the volatile components at 950 ℃ is 9 mg per 100 m ² surface area of carbon black The above; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green , Milori blue, cobalt green, cobalt blue, manganese series, ferrocyanide, phosphate ultramarine, iron blue, ultramarine, sky blue, dark green, emerald green, lead sulfate, yellow red, zinc yellow, iron red (red Organic or inorganic pigments such as iron (III) oxide), cadmium red, synthetic iron black, and umber. These pigments may be used alone or in combination.

As the above-mentioned pigment, commercially available pigments can also be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

染料、茜素染料、吖啶染料、二苯乙烯染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、㗁 𠯤染料、酞菁染料、花青染料等染料等，該等亦存在混合複數種而使用之情形。Examples of the above-mentioned dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes,

Dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamide dyes, 㗁𠯤 dyes, phthalocyanine dyes, cyanine dyes, etc., There are also cases where a plurality of these are mixed and used.

In the photosensitive composition of the present invention, the content of the colorant (C) is preferably 10 to 200 parts by mass, more preferably 10 to 100 parts by mass relative to 100 parts by mass of the ethylenically unsaturated compound (B) .

The alkali-developable compound (D) can be further contained in the photosensitive composition of this invention, and it can be set as an alkali-developable photosensitive resin composition. What contains a coloring agent (C) and an alkali-developable compound (D) at the same time is also called a coloring alkali-developable photosensitive resin composition.

As said alkali-developable compound (D), if it is soluble in an alkaline aqueous solution, it will not specifically limit, For example, the resin etc. which are described in Unexamined-Japanese-Patent No. 2004-264414 are mentioned.

Moreover, as said alkali developable compound (D), the copolymer of acrylate, phenol novolak epoxy resin, cresol novolak epoxy resin, polyphenylmethane type epoxy resin having a polyfunctional epoxy group can be used , Epoxy acrylate resins, polymers having carboxyl groups, and epoxy groups of epoxy compounds such as epoxy compounds represented by the following general formula (IV) and unsaturated monobasic acid, and then obtained by the action of polybasic acid anhydrides of resin. The above-mentioned so-called epoxy acrylate resins are obtained by reacting an epoxy compound with (meth)acrylic acid, and examples thereof include Ripoxy SPC-2000, DICLITE UE-777 manufactured by DIC Corporation, and Ripoxy SPC-777 manufactured by Japan U-Pica Corporation. U-Pica 4015 et al. Among these compounds, epoxy acrylate resins and polymers having a carboxyl group are preferred.

The above-mentioned polymer having a carboxyl group is not particularly limited as long as it contains a structural unit having a carboxyl group (hereinafter referred to as "structural unit (U1)"). In addition to the structural unit (U1), the above-mentioned polymer having a carboxyl group preferably also contains a crosslinkable group such as a methacryloyl group, an acryl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, and an isocyanate group. The structural unit (hereinafter referred to as "structural unit (U2)"), the structural unit having a silyl group (hereinafter referred to as "structural unit (U3)"). The polymer which has the said carboxyl group may have the structural unit (henceforth "structural unit (U4)") other than the said structural unit (U1)-(U3).

The above-mentioned structural unit (U1) is preferably a structural unit derived from at least one compound (hereinafter referred to as "compound (u1)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride. As said compound (u1), the acid anhydride of a monocarboxylic acid, a dicarboxylic acid, and a dicarboxylic acid etc. are mentioned, for example. Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, and 2-acryloyloxy Ethylhexahydrophthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid, etc. As said dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, etc. are mentioned, for example. As an acid anhydride of the said dicarboxylic acid, the acid anhydride of the above-mentioned dicarboxylic acid, etc. are mentioned. Among these compounds, acrylic acid, methacrylic acid, 2-acrylooxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, 2- Methacryloyloxyethylsuccinic acid or maleic anhydride. The polymer which has the said carboxyl group may have 1 type of structural unit (U1) derived from 1 type of compound (u1), and may have 2 or more types of structural units (U1) derived from 2 or more types of compounds (u1).

It is preferable that the said structural unit (U2) is a structural unit derived from the polymerizable unsaturated compound (henceforth "compound (u2)") which has an epoxy group or an oxetanyl group. The above-mentioned compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.

Examples of the polymerizable unsaturated compound having an epoxy group include ethylene oxide (cyclo)alkyl (meth)acrylate, α-alkylacrylate (cyclo)alkyl, and ethylene oxide (cyclo)alkyl (meth)acrylate. Glycidyl ether compounds having a polymerizable unsaturated bond, etc. As a polymerizable unsaturated compound which has an oxetanyl group, the (meth)acrylate etc. which have an oxetanyl group are mentioned, for example.

Specific examples of ethylene oxide (cyclo)alkyl (meth)acrylate include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and (methyl) glycidyl (meth)acrylate. ) 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxy (meth)acrylate Cyclohexyl ester, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate, etc. Specific examples of α-alkylacrylate oxiranyl (cyclo)alkyl esters include, for example, α-ethyl glycidyl acrylate, α-n-propyl acrylate, and α-n-butyl acrylate. Glycidyl ester, 6,7-epoxyheptyl α-ethacrylate, 3,4-epoxycyclohexyl α-ethacrylate, etc. As a specific example of the glycidyl ether compound which has a polymerizable unsaturated bond, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. are mentioned, for example. Specific examples of (meth)acrylates having oxetanyl groups include, for example, 3-((meth)acrylooxymethyl)oxetane, 3-((meth)propylene Ethyloxymethyl)-3-ethyloxetane, 3-((meth)propenyloxymethyl)-2-methyloxetane, 3-((meth)propene Ethyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)propenyloxyethyl)oxetane, 3-methyl-3-( Meth)acryloyloxymethyl oxetane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, and the like. Among these compounds, in terms of polymerizability, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and methacrylic acid are particularly preferred. 3,4-epoxycyclohexyl methyl ester, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl methacrylate, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate, 3 - Methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane or 3-ethyl-3-methyl Acryloyloxymethyloxetane. The polymer which has the said carboxyl group may have 1 type of structural unit (U2) derived from 1 type of compound (u2), and may have 2 or more types of structural units (U2) derived from 2 or more types of compounds (u2).

Among the above-mentioned structural units (U2), as the structural unit having a methacryloyl group or an acryl group as a crosslinkable group, a structural unit having a (meth)acryloyloxy group can be preferably used. The structural unit which has the said (meth)acryloyloxy group is obtained by making the carboxyl group in a polymer react with the (meth)acrylate which has an epoxy group. The structural unit having a (meth)acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U).

(式中，R¹⁰⁰⁰ 及R¹⁰⁰¹ 分別獨立地表示氫原子或甲基， u表示1～6之整數， R¹⁰⁰² 表示下述式(Uα)或下述式(Uβ)所表示之二價基， *表示鍵結鍵)。[Chemical 34A]

(wherein, R ¹⁰⁰⁰ and R ¹⁰⁰¹ each independently represent a hydrogen atom or a methyl group, u represents an integer of 1 to 6, and R ¹⁰⁰² represents a divalent group represented by the following formula (Uα) or the following formula (Uβ), * indicates a bond key).

(式中，R¹⁰⁰³ 表示氫原子或甲基， *表示鍵結鍵)。[Chemical 34B]

(In the formula, R ¹⁰⁰³ represents a hydrogen atom or a methyl group, and * represents a bond).

Regarding the structural unit represented by the above formula (U), for example, when a copolymer having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methyl glycidyl methacrylate, the formula (U) Among them, R ¹⁰⁰² becomes formula (Uα). When a copolymer having a carboxyl group is reacted with a compound such as 3,4-epoxycyclohexylmethyl methacrylate, R ¹⁰⁰² in the formula (U) becomes the formula (Uβ).

The reaction between the carboxyl group in the above polymer and an unsaturated compound such as (meth)acrylate having an epoxy group is preferably in the presence of an appropriate catalyst as needed, preferably in a polymer containing a polymerization inhibitor. An unsaturated compound having an epoxy group is put into the solution, and the mixture is stirred under heating for a predetermined time. As said catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As said polymerization inhibitor, p-methoxyphenol etc. are mentioned, for example. The reaction temperature is preferably 70°C to 100°C. The reaction time is preferably 8 hours to 12 hours.

In the above-mentioned structural unit ratio of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth)acryloyloxy group as a crosslinkable group is preferably 10 mol % of all structural units of the polymer having a carboxyl group ~70 mol%, more preferably 20 mol% to 50 mol%. When the ratio of the structural unit which has a (meth)acryloyloxy group is the said range, the heat resistance and the image development defect at the time of image development are reduced, and the generation|occurence|production of image development residue can be suppressed.

The above-mentioned structural unit (U3) is preferably a structural unit derived from a polymerizable unsaturated compound having a silyl group (hereinafter referred to as "compound (u3)").

As said compound (u3), 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxy, Silane, 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyltriethoxysilane, etc. When the above-mentioned polymer having a carboxyl group has a structural unit U3, it may have one type of structural unit (U3) derived from one type of compound (u3), or may have two types of compounds (u3) derived from two or more types. The above structural unit (U3).

The above-mentioned structural unit (U4) is a structural unit other than the above-mentioned (U1) to (U3), preferably a polymerizable unsaturated compound derived from other than the above-mentioned (u1) to (u3) (hereinafter referred to as "compound (u4)" ) of the structural unit. Examples of the above-mentioned compound (u4) include alkyl (meth)acrylate, cycloalkyl (meth)acrylate, aryl (meth)acrylate, aralkyl (meth)acrylate, non- Saturated dicarboxylic acid dialkyl esters, (meth)acrylates having a 5-membered oxa ring or a 6-membered oxa ring, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds. Specific examples of the alkyl (meth)acrylate include methyl acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate base) 2-butyl acrylate and 3-butyl (meth)acrylate, etc. Specific examples of cycloalkyl (meth)acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo(meth)acrylate [5.2. 1.0 ^2,6 ] Decan-8-yl ester, 2-(tricyclo[5.2.1.0 ^2,6 ] Decan-8-yloxy)ethyl (meth)acrylate, and (meth)acrylic acid isoflurane base ester, etc. As a specific example of aryl (meth)acrylate, phenyl acrylate etc. are mentioned, for example. As a specific example of aralkyl (meth)acrylate, benzyl (meth)acrylate etc. are mentioned, for example. Specific examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate, diethyl fumarate, and the like. Specific examples of (meth)acrylates having a 5-membered oxa ring or a 6-membered oxa ring include tetrahydrofuran-2-yl (meth)acrylate, tetrahydropyridine (meth)acrylate, for example. Pyran-2-yl ester and (meth)acrylate 2-methyltetrahydropyran-2-yl ester, etc. As a specific example of a vinyl aromatic compound, styrene, (alpha)-methylstyrene etc. are mentioned, for example. As a specific example of a conjugated diene compound, 1, 3- butadiene, isoprene, etc. are mentioned, for example. As a specific example of another polymerizable unsaturated compound, 2-hydroxyethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. are mentioned, for example. Among the compounds (u4) listed above, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, methacrylic acid are preferred. Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, and the like. When the above-mentioned polymer having a carboxyl group has a structural unit (U4), it may have one kind of structural unit (U4) derived from one kind of compound (u4), or may have one kind of structural unit (U4) derived from two or more kinds of compounds (u4). Two or more structural units (U4).

The polymer having a preferable carboxyl group in the present embodiment can be synthesized by copolymerizing a mixture of the polymerizable unsaturated compounds containing the above-mentioned compounds (u1) to (u4) in the following ratios, respectively. In addition, by reacting the carboxyl group in the structural unit derived from the compound (u1) in the obtained copolymer with the (meth)acrylate having an epoxy group, a compound having a (meth)acryloyl group can be prepared. The structural unit of oxygen.

Compound (u1): preferably 0.1 mol % to 30 mol %, more preferably 1 mol % to 20 mol %, more preferably 5 mol % to 15 mol % Compound (u2): preferably It is preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, and more preferably 20 mol% to 30 mol% Compound (u3): preferably 50 mol% Below, it is more preferably 1 mol% to 40 mol%, more preferably 10 mol% to 30 mol% Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, more preferably 25 mol% to 50 mol%

A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of a polymerizable unsaturated compound containing the compound (u1) to the compound (u4) in the above range is not impaired in good coatability. In this case, since a higher resolution is achieved, even a high-definition pattern can obtain a cured film in which the balance of physical properties can be highly adjusted, so it is preferable.

The weight average molecular weight (Mw) of the polymer having a carboxyl group is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. By using a polymer having a carboxyl group having an Mw in this range, a higher resolution can be achieved without impairing good coatability, so even a high-definition pattern can provide a high degree of balance of characteristics. Earth-adjusted hard film. In the present invention, the weight average molecular weight (Mw) refers to the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC).

The polymer having a carboxyl group can be produced by polymerizing the mixture of the above-mentioned polymerizable unsaturated compound, preferably in a suitable solvent, preferably in the presence of a radical polymerization initiator.

Examples of the solvent used for the polymerization of the mixture of polymerizable unsaturated compounds include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether. Methyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol Acetate, benzyl alcohol, 3-methoxybutanol, etc. These solvents may be used alone or in combination of two or more.

It does not specifically limit as said radical polymerization initiator, For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azo Azo compounds such as bis(2-methylpropionic acid) dimethyl ester and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used individually by 1 type, or may be used in mixture of 2 or more types.

Among the polymers having a carboxyl group, the polymers described in Japanese Patent Laid-Open No. 2005-234362 are preferred, wherein the epoxy group of the epoxy compound represented by the following general formula (VI) is reacted with an unsaturated monobasic acid. And further react with polybasic acid anhydride to obtain the polymer.

In addition, as the alkali-developable compound (D), copolymers of acrylates, phenol and/or cresol novolak epoxy resins, polyphenylmethane-type epoxy resins having polyfunctional epoxy groups, and cyclic epoxy resins can be used. Oxyacrylate resin and resin obtained by reacting an epoxy group of an epoxy compound such as an epoxy compound represented by the following general formula (III) with an unsaturated monobasic acid, and further reacting with a polybasic acid anhydride. Here, the epoxy acrylate resin is a product obtained by reacting the above-mentioned epoxy compound with (meth)acrylic acid, and examples thereof include Ripoxy SPC-2000, DICLITE UE-777 manufactured by DIC Corporation, and Japan U-Pica Corporation. Manufactured U-Pica 4015 etc. Among these, the epoxy acrylate resin and the resin obtained by making the epoxy group of the epoxy compound represented by following general formula (IV) react with an unsaturated monobasic acid, and further react with a polybasic acid anhydride are preferable. Moreover, it is preferable that the said compound which may have an ethylenically unsaturated bond which has alkali developability contains 0.2-1.0 equivalent of an unsaturated group.

(式中，X²¹ 表示直接鍵、亞甲基、碳原子數1～4之亞烷基、碳原子數3～20之脂環式烴基、-O-、-S-、-SO-₂ 、-SS-、-SO-、-CO-、-OCO-或下述[化36]、[化37]或[化38]所表示之基，亦存在上述亞烷基經鹵素原子取代之情形，R⁵¹ 及R⁵² 分別獨立地表示碳原子數1～5之烷基、碳原子數1～8之烷氧基、碳原子數2～5之烯基或鹵素原子，亦存在上述烷基、烷氧基及烯基經鹵素原子取代之情形， 於分別存在複數個R⁵¹ 及R⁵² 之情形時，存在相同之情形，亦存在不同之情形， c為0～4之整數， d為0～4之整數， m為0～10之整數， 於m不為0之情形時存在之光學異構物可為任意異構物)。[Chemical 35]

(wherein, X ²¹ represents a direct bond, a methylene group, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO- ₂ , -SS-, -SO-, -CO-, -OCO- or the group represented by the following [Formula 36], [Formula 37] or [Formula 38], there is also a case where the above-mentioned alkylene group is substituted by a halogen atom, R ⁵¹ and R ⁵² each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the above-mentioned alkyl groups and alkanes also exist. In the case where the oxy and alkenyl groups are substituted by halogen atoms, when there are plural R ⁵¹ and R ⁵² respectively, there are the same cases or different cases, c is an integer from 0 to 4, and d is 0 to 4 Integer, m is an integer of 0-10, when m is not 0, the optical isomer that exists can be any isomer).

[Chemical 36]

(in the formula, Z ¹ represents a hydrogen atom, a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or an alkyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or A cycloalkyl group having 3 to 10 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms, Y ¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, 2-10 alkenyl or halogen atoms, the above-mentioned alkyl, alkoxy and alkenyl may be substituted by halogen atoms, e represents an integer from 0 to 5, * represents a bond)

[Chemical 37]

(in the formula, * represents a bond bond).

[Chemical 38]

(in the formula, Y ² and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms that can be substituted by a halogen atom, an aryl group that can be substituted by a halogen atom having 6 to 20 carbon atoms, and an aryl group that can be substituted by a halogen atom. aryloxy group with 6 to 20 carbon atoms, arylthio group with 6 to 20 carbon atoms that can be substituted with halogen atoms, arylalkenyl group with 6 to 20 carbon atoms that can be substituted with halogen atoms, and arylalkenyl groups with 6 to 20 carbon atoms that can be substituted with halogen atoms Atom-substituted arylalkyl group with 7 to 20 carbon atoms, heterocyclic group with 2 to 20 carbon atoms that can be substituted with halogen atom, or halogen atom, and the methylene group in the group represented by Y ² is substituted In the case of an unsaturated bond, -O- or -S-, Z ² can be adjacent Z ² to form a ring, f represents an integer of 0 to 4, g represents an integer of 0 to 8, and h represents an integer of 0 to 4 , i represents an integer from 0 to 4, the sum of the numbers of h and i is an integer from 2 to 4, and * represents a bond)

Examples of the above-mentioned unsaturated monobasic acid that acts on the above-mentioned epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate/maleate, and hydroxyethyl acrylic acid Ester/maleate, hydroxypropyl methacrylate/maleate, hydroxypropylacrylate/maleate, dicyclopentadiene/maleate, etc.

As the above-mentioned polybasic acid anhydride which acts after the above-mentioned unsaturated monobasic acid acts, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphenyltetracarboxylic dianhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trianhydrotrimellitate, hexamethylene glycol Hydrogen phthalic anhydride, methyltetrahydrophthalic anhydride, terrestrial anhydride, methyl terrestrial anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2 ,5-Dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecene base succinic anhydride, methyl bicycloheptenedicarboxylic anhydride, etc.

It is preferable that the reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride is as follows. That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the above-mentioned unsaturated monobasic acid are added to one epoxy group of the above-mentioned epoxy compound, the acid anhydride structure of the above-mentioned polybasic acid anhydride is preferred. The ratio is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct. The reaction of the above-mentioned epoxy compound, the above-mentioned unsaturated monobasic acid, and the above-mentioned polybasic acid anhydride can be carried out according to an ordinary method.

The alkali-developable photosensitive resin composition of the present invention, which is one of the embodiments of the photosensitive composition of the present invention, contains a photopolymerization initiator (A), an ethylenically unsaturated compound (B), and an alkali-developable compound ( D) As an essential component, components such as an inorganic compound and a solvent are contained in combination as optional components. In addition, what contains the coloring agent (C) in the alkali-developable photosensitive resin composition of this invention is also called especially the coloring alkali-developable photosensitive resin composition of this invention. The said alkali developable compound (D) may be used individually by 1 type, and may use 2 or more types together. When the above-mentioned alkali-developable compound (D) has an ethylenically unsaturated bond, the alkali-developable compound (D) may be included in the category of the ethylenically unsaturated compound (B). When the alkali-developable compound (D) is also an ethylenically unsaturated compound (B), the composition containing the alkali-developable compound (D) is a photosensitive composition and is also an alkali-developable photosensitive resin composition .

In order to adjust the acid value and improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention, in addition to the above-mentioned alkali-developable compound which may have an ethylenically unsaturated bond, a monofunctional or polyfunctional epoxy compounds. The above-mentioned compounds with alkali developability that can have ethylenically unsaturated bonds are preferably in the range of the acid value of the solid content of 5 to 120 mgKOH/g, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably to satisfy The above acid value is selected.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isopropyl glycidyl ether, and Butyl glycidyl ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethyl acetate Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether Ether, tolyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycidyl ether Glyceryl ether, 2,3-glycidyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, ethylene monoxide, 1,2-epoxy-4-ethylene Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexane oxide, propylene oxide, the aforementioned compounds No. A2, No. A3, and the like.

As the polyfunctional epoxy compound, when one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers are used, it is possible to obtain (colored) alkali-developable photosensitivity with better properties. A resin composition is therefore preferred. As said bisphenol type epoxy compound, in addition to the epoxy compound represented by the said general formula (IV), for example, a bisphenol type epoxy compound, such as a hydrogenated bisphenol type epoxy compound, can also be used. Moreover, as said glycidyl ethers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether , triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, 1,1,1-tris( Glycidoxymethyl)propane, 1,1,1-tris(glycidoxymethyl)ethane, 1,1,1-tris(glycidoxymethyl)methane, 1,1,1, 1-Tetrakis(glycidoxymethyl)methane, etc. In addition to these, it is also possible to use: phenol novolac type epoxy compound, biphenyl novolak type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, dicyclopentadiene novolac type Novolak-type epoxy compounds such as varnish-type epoxy compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4 - Alicyclic epoxy compounds such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; Glycidyl esters, diglycidyl tetrahydrophthalate, glycidyl dimer acid and other glycidyl esters; tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, N, Glycidyl amines such as N-diglycidyl aniline; 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate and other heterocyclic epoxy compounds ; Dioxide compounds such as dicyclopentadiene dioxide; Naphthalene-type epoxy compounds; Triphenylmethane-type epoxy compounds; Dicyclopentadiene-type epoxy compounds, etc.

In particular, when the photosensitive composition of the present invention is made into an alkali-developable photosensitive resin composition, the content of the above-mentioned alkali-developable compound which may have an ethylenically unsaturated bond is in the alkali-developable photosensitive resin composition of the present invention. In the resin composition, it is preferably 1 to 20% by mass, particularly preferably 3 to 12% by mass.

A solvent can be further added to the photosensitive composition of this invention. As the solvent, a solvent that can dissolve or disperse the above-mentioned components (photopolymerization initiator (A), ethylenically unsaturated compound (B), etc.) as necessary, such as methyl ethyl ketone, methyl ethyl ketone, Amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; ether, diethyl ketone, tetrahydrofuran, 1,2-diethyl ketone Ether-based solvents such as methoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, Cyclohexyl acetate, ethyl lactate, dimethyl succinate, TEXANOL and other ester solvents; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and other cellosolve solvents; methanol, ethanol, isopropanol or n-propyl alcohol Alcohol, isobutanol or n-butanol, amyl alcohol and other alcohol solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, Ether ester solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, and ethoxyethyl ether propionate; BTX (Benzene Toluene Xylene, benzene-toluene- xylene) solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swazol #310 (Cosmo Matsuyama Oil company), Solvesso #100 (Exxon Chemical company) and other alkane-based solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon-based solvents; chlorobenzene Halogenated aromatic hydrocarbon solvents; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide ( DMAc); N-methylpyrrolidone; dimethyl sulfoxide; water, etc., these solvents can be used 1 type, or can be used as a mixed solvent of 2 or more types. Among them, ketones, ether ester-based solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. in the photosensitive composition, photoresist and photopolymerization initiator (A ) has good compatibility, so it is preferable.

In addition, the following conventional additives may be added to the photosensitive composition of the present invention as needed: p-anisole, hydroquinone, catechol, tert-butyl catechol, inorganic compounds, latent additives, Organic polymers, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; defoaming agents; leveling agents; surface conditioners ; Antioxidant; Ultraviolet Absorber; Dispersion Auxiliary; Anti-agglomeration Agent; Catalyst; Effect Accelerator; Cross-linking Agent;

A dispersant for dispersing a colorant (C) and/or an inorganic compound may be added to the photosensitive composition of the present invention. The dispersing agent is not limited as long as it can disperse and stabilize the colorant (C) or the inorganic compound, and commercially available dispersing agents such as BYK series manufactured by BYK-Chemie Japan can be used. In particular, the following polymer dispersants can be suitably used, which contain a polyester, polyether, or polyurethane having a basic functional group, and having a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is: Amine and/or its quaternary salt, and the amine value is 1-100 mgKOH/g.

The above-mentioned latent additives are represented by the following general formulae (A) to (C).

(式中，環A¹ 係六員環之脂環、芳香環或雜環，R⁸¹ 、R⁸² 、R⁸³ 、R⁸⁴ 及R⁸⁵ 表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基、碳原子數2～20之含雜環基或-O-R⁶⁶ ， R⁸¹ 、R⁸² 、R⁸³ 、R⁸⁴ 及R⁸⁵ 中至少一者不為氫原子， R⁸⁶ 表示碳原子數1～20之烷基、碳原子數2～20之烯基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基、碳原子數2～20之含雜環基或三烷基矽烷基)[Chemical 39]

(In the formula, Ring A ¹ is a six-membered alicyclic, aromatic or heterocyclic ring, and R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, Carboxyl group, optionally substituted alkyl group with 1 to 40 carbon atoms, aryl group with 6 to 20 carbon atoms, arylalkyl group with 7 to 20 carbon atoms, and heterocyclic group with 2 to 20 carbon atoms or -OR ⁶⁶ , at least one of R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is not a hydrogen atom, and R ⁸⁶ represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms , aryl group with 6 to 20 carbon atoms, arylalkyl group with 7 to 20 carbon atoms, heterocyclic group or trialkylsilyl group with 2 to 20 carbon atoms)

(式中，環A¹ 及R⁹¹ 與上述通式(A)相同， X⁷ 為下述通式(1)所表示之基，R⁹² 、R⁹³ 、R⁹⁴ 及R⁹⁵ 表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基或碳原子數2～20之含雜環基，R⁹² 、R⁹³ 、R⁹⁴ 及R⁹⁵ 中至少一者不為氫原子)。[Chemical 40]

(in the formula, ring A ¹ and R ⁹¹ are the same as the above general formula (A), X ⁷ is a group represented by the following general formula (1), R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ represent a hydrogen atom, a halogen Atom, cyano group, hydroxyl group, nitro group, carboxyl group, optionally substituted alkyl group with 1 to 40 carbon atoms, aryl group with 6 to 20 carbon atoms, arylalkyl group with 7 to 20 carbon atoms, or carbon A heterocyclic group containing 2 to 20 atoms, and at least one of R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ is not a hydrogen atom).

(上述通式(1)中，X⁸ 表示-CR⁹⁷ R⁹⁸ -、-NR⁹⁹ -、二價之碳原子數1～35之脂肪族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之雜環基、或下述[化42]～[化44]所表示之任一取代基， 存在該脂肪族烴基中之亞甲基被取代為-O-、-S-、-CO-、-COO-、-OCO-或-NH-、或於氧原子不鄰接之情況下將該等組合而成之結合基之情形， R⁹⁷ 及R⁹⁸ 表示氫原子、碳原子數1～8之烷基、碳原子數6～20之芳基或碳原子數7～20之芳基烷基，Z⁵ 及Z⁶ 分別獨立地表示直接鍵、-O-、-S-、 ＞CO、-CO-O-、-O-CO-、-SO₂ -、-SS-、-SO-或＞NR¹⁰⁰ ，R⁹⁹ 及R¹⁰⁰ 表示氫原子、可具有取代基之碳原子數1～35之脂肪族烴基、可具有取代基之碳原子數6～35之芳香族烴基或可具有取代基之碳原子數2～35之雜環基，*表示鍵結鍵)[Chemical 41]

(In the above general formula (1), X ⁸ represents -CR ⁹⁷ R ⁹⁸ -, -NR ⁹⁹ -, a divalent aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or a carbon A heterocyclic group having 2 to 35 atoms, or any of the substituents represented by the following [Chemical 42] to [Chemical 44], and the methylene group present in the aliphatic hydrocarbon group is substituted with -O-, -S- , -CO-, -COO-, -OCO- or -NH-, or in the case of a binding group formed by combining these when the oxygen atoms are not adjacent, R ⁹⁷ and R ⁹⁸ represent a hydrogen atom, the number of carbon atoms An alkyl group of 1 to 8, an aryl group of 6 to 20 carbon atoms, or an arylalkyl group of 7 to 20 carbon atoms, Z ⁵ and Z ⁶ each independently represent a direct bond, -O-, -S-, > CO, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO- or >NR ¹⁰⁰ , R ⁹⁹ and R ¹⁰⁰ represent a hydrogen atom, and the number of carbon atoms which may have a substituent is 1- 35 aliphatic hydrocarbon group, optionally substituted aromatic hydrocarbon group with 6 to 35 carbon atoms, or optionally substituted heterocyclic group with 2 to 35 carbon atoms, * denotes a bond)

(上述式中，R¹⁰¹ 表示氫原子、可具有取代基之苯基、或碳原子數3～10之環烷基，R¹⁰² 表示碳原子數1～10之烷基、碳原子數1～10之烷氧基、碳原子數2～10之烯基或鹵素原子，上述烷基、烷氧基及烯基可具有取代基，f為0～5之整數，*表示鍵結鍵，*表示鍵結鍵)。[Chemical 42]

(In the above formula, R ¹⁰¹ represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group with 3 to 10 carbon atoms, and R ¹⁰² represents an alkyl group with 1 to 10 carbon atoms, 1 to 10 carbon atoms alkoxy group, alkenyl group with 2-10 carbon atoms or halogen atom, the above-mentioned alkyl group, alkoxy group and alkenyl group may have a substituent, f is an integer of 0-5, * represents a bond, * represents a bond key).

(式中，*表示鍵結鍵)。[Chemical 43]

(in the formula, * represents a bond bond).

(上述式中，R¹⁰³ 及R¹⁰⁴ 分別獨立地表示可具有取代基之碳原子數1～10之烷基、可具有取代基之碳原子數6～20之芳基、可具有取代基之碳原子數6～20之芳氧基、可具有取代基之碳原子數6～20之芳硫基、可具有取代基之碳原子數6～20之芳基烯基、可具有取代基之碳原子數7～20之芳基烷基、可具有取代基之碳原子數2～20之雜環基或鹵素原子，該烷基及芳基烷基中之亞甲基可被不飽和鍵、-O-或-S-所中斷，R¹⁰³ 可為鄰接之R¹⁰³ 彼此形成環，b表示0～4之數，c表示0～8之數，g表示0～4之數，h表示0～4之數，g與h之數之合計為2～4)。[Chemical 44]

(In the above formula, R ¹⁰³ and R ¹⁰⁴ each independently represent an optionally substituted alkyl group with 1 to 10 carbon atoms, an optionally substituted aryl group with 6 to 20 carbon atoms, and an optionally substituted carbon group Aryloxy group with 6 to 20 atoms, arylthio group with 6 to 20 carbon atoms which may have substituents, arylalkenyl groups with 6 to 20 carbon atoms which may have substituents, and carbon atoms which may have substituents 7-20 arylalkyl groups, optionally substituted heterocyclic groups with 2-20 carbon atoms or halogen atoms, the methylene groups in the alkyl and arylalkyl groups may be replaced by unsaturated bonds, -O - or -S- interrupted, R ¹⁰³ can be adjacent R ¹⁰³ to form a ring with each other, b represents the number of 0 to 4, c represents the number of 0 to 8, g represents the number of 0 to 4, and h represents the number of 0 to 4 number, the sum of the numbers of g and h is 2 to 4).

(式中，k＝2～6，X⁹ 於k＝2時為上述通式(2)所表示之基，於k＝3時為下述通式(3)所表示之基，於k＝4時為下述通式(4)所表示之基，於k＝5時為下述通式(5)，於k＝6時為下述通式(6)，R¹¹¹ 、R¹¹² 、R¹¹³ 及R¹¹⁴ 表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基或碳原子數2～20之含雜環基，R¹¹¹ 、R¹¹² 、R¹¹³ 及R¹¹⁴ 中至少一者不為氫原子，環A¹ 及R⁸⁶ 與上述通式(A)相同)。[Chemical 45]

(In the formula, k=2～6, X ⁹ is the base represented by the above general formula (2) when k=2, and is the base represented by the following general formula (3) when k=3, and when k= When 4, it is a group represented by the following general formula (4), when k=5, it is the following general formula (5), when k=6, it is the following general formula (6), R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 7 Arylalkyl of ~20 or heterocyclic group containing 2 to 20 carbon atoms, at least one of R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ is not a hydrogen atom, Ring A ¹ and R ⁸⁶ are the same as the above general formula (A) same).

(上述通式(2)中，Y¹¹ 表示三價之碳原子數3～35之脂肪族烴基、碳原子數3～35之脂環族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之雜環基，Z¹¹ 、Z¹² 及Z¹³ 分別獨立地表示直接鍵、-O-、-S-、＞CO、-CO-O-、-O-CO-、-SO₂ -、-SS-、-SO-、-NR¹²¹ -、-PR¹²¹ -或可具有取代基之碳原子數1～35之脂肪族烴基、可具有取代基之碳原子數6～35之芳香族烴基或可具有取代基之碳原子數2～35之雜環基， R¹²¹ 表示氫原子、可具有取代基之碳原子數1～35之脂肪族烴基、可具有取代基之碳原子數6～35之芳香族烴基或可具有取代基之碳原子數2～35之雜環基，亦存在該脂肪族烴基中之亞甲基被取代為碳-碳雙鍵、-O-、-CO-、-O-CO-、-CO-O-或-SO₂ -之情形)。[Chemical 46]

(In the above general formula (2), Y ¹¹ represents a trivalent aliphatic hydrocarbon group with 3 to 35 carbon atoms, an alicyclic hydrocarbon group with 3 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or a carbon A heterocyclic group having 2 to 35 atoms, Z ¹¹ , Z ¹² and Z ¹³ each independently represent a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO-, -NR ¹²¹ -, -PR ¹²¹ - or aliphatic hydrocarbon groups with 1 to 35 carbon atoms which may have substituents, aromatic groups with 6 to 35 carbon atoms which may have substituents an aliphatic hydrocarbon group or a heterocyclic group with 2 to 35 carbon atoms which may have a substituent, R ¹²¹ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 35 carbon atoms which may have a substituent, or a group with 6 carbon atoms which may have a substituent An aromatic hydrocarbon group of ~35 or a heterocyclic group with a carbon number of 2 to 35 that may have a substituent, and the methylene group in the aliphatic hydrocarbon group is also substituted with a carbon-carbon double bond, -O-, -CO- , -O-CO-, -CO-O- or -SO ₂ -).

(上述通式(3)中，Y¹² 表示碳原子、或四價之碳原子數1～35之脂肪族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之雜環基，亦存在該脂肪族烴基中之亞甲基被取代為-COO-、-O-、-OCO-、-NHCO-、-NH-或-CONH-之情形，Z¹¹ ～Z¹⁴ 分別獨立為與上述通式(2)中之Z¹¹ ～Z¹³ 所表示之基相同範圍之基)。[Chemical 47]

(In the above general formula (3), Y ¹² represents a carbon atom, or a tetravalent aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic ring with 2 to 35 carbon atoms group, there are also cases where the methylene group in the aliphatic hydrocarbon group is substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, Z ¹¹ to Z ¹⁴ are independently A group in the same range as the group represented by Z ¹¹ to Z ¹³ in the general formula (2) above).

(上述通式(4)中，Y¹³ 表示五價之碳原子數2～35之脂肪族烴基、碳原子數6～30之芳香族烴基或碳原子數2～30之雜環基，該脂肪族烴基可被-COO-、-O-、-OCO-、-NHCO-、-NH-或-CONH-所中斷，Z¹¹ ～Z¹⁵ 分別獨立為與上述通式(2)中之Z¹¹ ～Z¹³ 所表示之基相同範圍之基)。[Chemical 48]

(In the above general formula (4), Y ¹³ represents a pentavalent aliphatic hydrocarbon group with 2 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms, or a heterocyclic group with 2 to 30 carbon atoms, the aliphatic The family of hydrocarbon groups can be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z ¹¹ to Z ¹⁵ are independently the same as Z ¹¹ to Z 11 in the above general formula (2). The basis represented by Z ¹³ is the basis of the same range).

(上述通式(5)中，Y¹⁴ 表示六價之碳原子數2～35之脂肪族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之雜環基，該脂肪族烴基可被-COO-、-O-、-OCO-、-NHCO-、-NH-或-CONH-所中斷，Z¹¹ ～Z¹⁶ 分別獨立為與上述通式(2)中之Z¹¹ ～Z¹³ 所表示之基相同範圍之基)。[Chemical 49]

(In the above general formula (5), Y ¹⁴ represents a hexavalent aliphatic hydrocarbon group with 2 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, the aliphatic The family of hydrocarbon groups can be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z ¹¹ to Z ¹⁶ are independently the same as Z ¹¹ to Z 11 in the above general formula (2). The basis represented by Z ¹³ is the basis of the same range).

The properties of the cured product can also be improved by using the above-mentioned organic polymers (excluding the ethylenically unsaturated compound (B)). Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS (acrylonitrile-butadiene-styrene, acrylonitrile-butadiene-benzene Vinyl) resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, Polyamide imide resin, polyamide resin, epoxy resin, etc. Among these, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable. When using an organic polymer, the usage-amount is preferably 10-500 mass parts with respect to 100 mass parts of the polymerizable compounds which have the said ethylenically unsaturated bond.

、二異丙基-9-氧硫

、下述化合物No.C1、三巰基丙酸三(2-羥基乙基)異氰脲酸酯等脂肪族多官能硫醇化合物，昭和電工公司製造之Karenz MT BD1、PE1、NR1等。As the above-mentioned chain transfer agent or the above-mentioned sensitizer, a sulfur atom-containing compound is usually used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminocarbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-( 3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-hydroxypyridine, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) and other mercapto compounds, oxidize the Disulfide compounds obtained from mercapto compounds, iodized alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, trimethylolpropane tri(3 -Mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionic acid Esters, Butylene Glycol Dithioglycolate, Ethylene Glycol Dithioglycolate, Trimethylolpropane Trithioglycolate, Butylene Glycol Dithioglycolate, Trimethylolpropane Tris Thiopropionate, Trimethylolpropane Trithioglycolate, Pentaerythritol Tetrathiopropionate, Pentaerythritol Tetrathioglycolate, Trihydroxyethyl Trithioglycolate, Diethyl-9 -oxysulfur

, diisopropyl-9-oxothio

, The following compound No.C1, aliphatic polyfunctional thiol compounds such as tris(2-hydroxyethyl) isocyanurate of trimercaptopropionate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko Corporation.

[Chemical 50]

As the above-mentioned surfactants, fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkylcarboxylates; anionic interface surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates can be used Active agents; cationic surfactants such as higher amine hydrohalide salts, quaternary ammonium salts; polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, etc. Surfactants such as ionic surfactants; amphoteric surfactants; polysiloxane-based surfactants can also be used in combination.

As the above-mentioned silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Acryloyl or epoxy silane coupling agent.

Examples of the melamine compound include active methylol among nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. All or a part (at least two) of the groups (CH ₂ OH groups) are etherified with an alkyl group, and the like. Here, a methyl group, an ethyl group, or a butyl group is mentioned as an alkyl group which comprises an alkyl ether, and may be the same or different from each other. Moreover, the methylol group which has not been alkyl-etherified can self-condensate in one molecule, and can also condense between two molecules, and as a result, an oligomer component is formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among these, alkyl-etherified melamine such as hexamethoxymethyl melamine and hexabutoxymethyl melamine is preferable.

As the above-mentioned leveling agent, as long as it has a leveling effect, an existing leveling agent can be used, and among them, a polysiloxane-based leveling agent and a fluorine-based leveling agent can be particularly preferably used.

As the above-mentioned polysiloxane-based leveling agent, commercially available polysiloxane-based leveling agents can be used, for example: BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313 , BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-347, BYK-348, BYK -349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720 (the above are BYK-Chemie Japan manufactured); ACFS 180, AC FS 360, AC S20 (the above are manufactured by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 ( The above are manufactured by Kyoeisha Chemical Co., Ltd.); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (the above are manufactured by Shin-Etsu Chemical Industry Co., Ltd.); LP-7001, LP-7002, 8032ADDITIVE , 57 ADDITIVE, L-7604, FZ-2110, FZ-2105, 67ADDITIVE, 8618 ADDITIVE, 3ADDITIVE, 56 ADDITIVE (the above are manufactured by Dow Corning) and other commercial products.

As the above-mentioned fluorine-based leveling agent, commercially available fluorine-based leveling agents can be used, for example, OPTOOL DSX, OPTOOL DAC-HP (the above are manufactured by Daikin Industries); SURFLON S-242, SURFLON S-243, SURFLON S -420, SURFLON S-611, SURFLON S-651, SURFLON S-386 (made by AGC Seimi Chemical above); BYK-340 (made by BYK-Chemie Japan); AC110a, AC 100a (made by AlginChemie above); MEGAFAC F-114, MEGAFAC F-410, MEGAFAC F-444, MEGAFAC EXPTP-2066, MEGAFAC F-430, MEGAFAC F-472SF, MEGAFAC F-477, MEGAFAC F-552, MEGAFAC F-553, MEGAFAC F-554, MEGAFAC F-555, MEGAFAC R-94, MEGAFAC RS-72-K, MEGAFAC RS-75, MEGAFAC F-556, MEGAFAC EXPTF-1367, MEGAFAC EXP TF-1437, MEGAFAC F-558, MEGAFAC EXPTF-1537 (the above are DIC FTERGENT 100, FTERGENT 100C, FTERGENT 110, FTERGENT 150, FTERGENT 150CH, FTERGENT A-K, FTERGENT 501, FTERGENT 250, FTERGENT 251, FTERGENT 200C, FTERGENT 222F , FTERGENT 300, FTERGENT 310, FTERGENT 400SW (made by NEOS above); PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF- 652, PF-3320 (the above are manufactured by Kitamura Chemical Industry) and other commercial products.

In the photosensitive composition of the present invention, in addition to the polymerization initiator (A), ethylenically unsaturated compound (B), colorant (C), alkali developable compound (D), solvent, inorganic compound, organic polymer The usage-amount of other optional components can be appropriately selected according to the purpose of use, and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the ethylenically unsaturated compound (B).

The photosensitive composition, alkali-developable photosensitive resin composition or cured product of the present invention can be used for: photocurable paint or varnish; photocurable adhesive; printed substrate; display device (color TV, PC (Personal Computer, Personal Computer) Color filters in liquid crystal display elements of color display devices of computer) monitors, portable information terminals, digital cameras, etc.; color filters in CCD (Charge Coupled Device, charge-coupled device) image sensors; Electrode material for paste display panel; powder coating; printing ink; printing plate; adhesive; dental composition; gel coating; photoresist for electronic engineering; electroplating resist; etching resist; dry film Solder resists; resists used to form the structures of various display devices; compositions for encapsulating electrical and electronic parts; solder resists; magnetic recording materials; micromechanical parts; waveguides; optical switches; masks for plating ; Etching masks; Color test systems; Coating of fiberglass cables; Stencils for screen printing; Materials for the manufacture of three-dimensional objects by stereolithography; Materials for holographic recordings; Image recording materials; Microelectronic circuits; Decolorization Materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; UV (Ultra Violet, ultraviolet) and visible light laser direct imaging systems Photoresist material; various uses such as photoresist material or protective film used to form the dielectric layer in the sequential build-up of printed circuit boards, and the use is not particularly limited.

The photosensitive composition or alkali-developable photosensitive resin composition of the present invention can also be used for the purpose of forming a spacer for liquid crystal display panels and also for the purpose of forming protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive composition for simultaneously forming projections and spacers for vertical alignment type liquid crystal display elements.

Hereinafter, the hardening method of the photosensitive composition or alkali-developable photosensitive resin composition of this invention is demonstrated in detail.

The photosensitive composition or alkali-developable photosensitive resin composition of the present invention can be applied by a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, Known methods such as dipping are applied to support substrates such as soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics. In addition, after being temporarily applied to a support substrate such as a film, it may be transferred onto another support substrate, and the application method thereof is not limited.

Further, as a light source of energy rays used when curing the photosensitive composition or the alkali-developable photosensitive resin composition of the present invention, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, and mercury vapor arc lamps can be used. lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT (Cathode Ray Tube, cathode ray tube) light sources, etc. Electromagnetic wave energy or high-energy rays such as electron beams, X-rays, and radiation with wavelengths of 2000 angstroms to 7000 angstroms, preferably ultra-high pressure mercury lamps, mercury vapor arc lamps, and carbon arc lamps that emit light with wavelengths of 300 to 450 nm , Xenon arc lamp, etc.

Furthermore, by using laser light as the exposure light source, the laser direct drawing method in which an image is directly formed from digital information such as a computer without using a mask can not only improve productivity, but also achieve imaging performance and positional accuracy. As the laser light, light with a wavelength of 340 to 430 nm can be suitably used, and excimer lasers, nitrogen lasers, argon ion lasers, helium-cadmium lasers, helium - Neon lasers, krypton ion lasers, various semiconductor lasers and YAG (yttrium aluminum garnet, yttrium aluminum garnet) lasers that emit light from visible to infrared regions. In the case of using these lasers, sensitizing dyes that absorb from the visible to infrared region can be added.

The above-mentioned spacer for a liquid crystal display panel can be preferably formed by the following steps: (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate; (2) a pair of masks having a specific pattern shape are interposed therebetween The step of irradiating the coating film with radiation; (3) the step of baking after exposure; (4) the step of developing the film after exposure; (5) the step of heating the film after development.

The photosensitive composition of the present invention to which an ink repellent agent is added is useful as a resin composition for forming a partition wall by an inkjet method, and the composition can be used for color filters, especially preferably used for a distribution angle of 50° or more. Partitions for ink jet color filters. As the ink repellent agent, a fluorine-based surfactant and a composition containing the fluorine-based surfactant can be suitably used.

An optical element is produced by a method of dividing a transfer target body by a partition wall formed of the photosensitive composition of the present invention, and applying droplets to the concave portions on the divided transfer target body by an inkjet method to form an image area. In this case, it is preferable that the droplet contains a colorant to color the image region, and it is preferable to use a partition wall on the substrate at least to have a pixel group including a plurality of color regions and each color region separating the pixel group. And the optical element manufactured by the manufacturing method of the above-mentioned optical element. Example

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

[Examples 1-1 to 1-3] Production of Compound No. 1

[Example 1-1] Production of intermediate 1A (ketone compound) A four-necked flask was charged with triphenylamine (3.3 g) and dichloroethane (15 g), and then chlorinated chloride was added under ice-cooling. Aluminum (5.8 g), acetyl chloride (3.3 g). After stirring at room temperature for 3 hours, the reaction solution was poured into 5% dilute hydrochloric acid cooled in an ice bath, and stirred for oil-water separation. The organic layer was washed twice with a 5% HCl aqueous solution, and further washed four times with water. After the product layer was desolvated, it was purified by a silica gel column (hexane/ethyl acetate=65/35) to obtain Intermediate 1A (2.6 g: 52% yield).

[Chemical 51]

[Example 1-2] Production of Intermediate 1B (oxime compound) A four-necked flask was charged with Intermediate 1A (2.6 g), ethanol (24 g), water (12 g), and hydroxylamine hydrochloride (1.6 g), Heat to reflux for 10 hours. After cooling to room temperature, the precipitate was collected by filtration and sufficiently dried to obtain Intermediate 1B (2.8 g: 96% yield).

[Chemical 52]

[Example 1-3] Production of Compound No. 1 (oxime ester compound of the present invention) Intermediate 1B (2.1 g) and dimethylformamide (15 g) were placed in a four-necked flask, and then placed in ice Triethylamine (1.7 g) and acetyl chloride (1.3 g) were charged under bath cooling. After stirring at room temperature for 2 hours, ion-exchanged water (15 g) and ethyl acetate (30 g) were added to carry out oil-water separation. The organic layer was washed three times with water, and after solvent removal, it was purified with a silica gel column (hexane/ethyl acetate=50/50) to obtain Compound No. 1 (1.4 g: 50% yield). The NMR (nuclear magnetic resonance, nuclear magnetic resonance) data of the obtained compound No. 1 are shown in [Table 1].

[Chemical 53]

[Examples 2-1 to 2-3] Production of Compound No. 2

[Example 2-1] Production of intermediate 2A (ketone compound) A four-necked flask was charged with triphenylamine (5.9 g) and dichloroethane (40 g), and then chlorinated chloride was added under ice cooling. Aluminum (10.5 g), propionyl chloride (7.1 g). After stirring at room temperature for 5 hours, the reaction solution was poured into 5% dilute hydrochloric acid cooled in an ice bath, and stirred for oil-water separation. The organic layer was washed twice with a 5% HCl aqueous solution, and further washed four times with water. After the product layer was desolvated, it was purified by a silica gel column (hexane/ethyl acetate=80/20) to obtain Intermediate 2A (3.9 g: 39% yield).

[Chemical 54]

[Example 2-2] Production of Intermediate 2B (oxime compound) Intermediate 2A (3.9 g) and dimethylformamide (24 g) were weighed into a four-necked flask, and 35 was added dropwise under ice cooling. % hydrochloric acid (3.9 g), isobutyl nitrite (3.9 g), and stirred at room temperature for 20 hours. Ion-exchanged water (24 g) and ethyl acetate (48 g) were added to carry out oil-water separation, and the organic layer was washed three times with water. After the organic layer was desolvated, the intermediate NCIx175-b (4.5 g: 96% yield) was obtained.

[Chemical 55]

[Example 2-3] Preparation of Compound No. 2 (oxime ester compound of the present invention) A four-necked round bottom flask was charged with Intermediate 2B (4.5 g) and tetrahydrofuran (23 g), followed by cooling in an ice bath. Triethylamine (3.0 g) and acetyl chloride (2.2 g) were sequentially added dropwise, and the mixture was stirred at room temperature for 2 hours. After adding ion-exchanged water (17 g) and ethyl acetate (46 g), oil-water separation was performed, and the organic layer was washed with water 5 times. After the organic layer was desolvated, it was purified with a silica gel column (hexane/ethyl acetate=50:50) to obtain Compound No. 2 (2.7 g: 48% yield). The NMR data of the obtained compound No. 2 are shown in [Table 1].

[Chemical 56]

[Examples 3-1 to 3-4] Production of compound No. 133

[Example 3-1] Production of intermediate 133A A four-necked flask was charged with fluorobenzene (27.7 g) and dichloroethane (192 g), and then aluminum chloride (40.4 g) was sequentially added under ice-cooling ), n-octyl chloride (46.8 g). After reacting at room temperature for 1 hour, the reaction solution was poured into 5% dilute hydrochloric acid cooled in an ice bath, and stirred for oil-water separation. The organic layer was washed twice with 5% dilute hydrochloric acid and three times with ion-exchanged water, followed by desolvation to obtain Intermediate 133A (50.0 g: 78% yield)

[Chemical 57]

[Example 3-2] Production of intermediate 133B (nitrogen-containing compound) A four-necked flask was charged with carbazole (20.0 g), intermediate 133A (29.3 g), potassium carbonate (24.8 g), dimethylmethylene Dust (133 g) was reacted at 160°C for 6 hours. Ion-exchanged water (173 g) was added, followed by extraction with dichloroethane (163 g). The organic layer was washed with water three times, and then desolvated to obtain an intermediate 133B (41.2 g: 93% yield).

[Chemical 58]

[Example 3-3] Production of intermediate 133C (ketone compound) A four-necked flask was charged with intermediate 133B (41.2 g) and dichloroethane (209 g), and then chlorine was added sequentially under ice-cooling Aluminum (49.1 g), n-octyl chloride (39.9 g). After reacting at the same temperature for 4 hours, the reaction solution was poured into 5% dilute hydrochloric acid cooled in an ice bath, and stirred for oil-water separation. The organic layer was washed twice with 5% dilute hydrochloric acid and three times with ion-exchanged water, followed by desolvation to obtain intermediate 133C (50.5 g: 73%)

[Chemical 59]

[Example 3-4] Preparation of Compound No. 133 (oxime ester compound) In a four-necked flask, intermediate 133C (10.0 g), dimethylformamide (50 g), hydroxylamine hydrochloride (3.7 g), Pyridine (4.2 g) was stirred at 80°C for 10 hours. After cooling by ice bath cooling, triethylamine (5.4 g) and acetyl chloride (4.2 g) were added dropwise in this order, and the mixture was stirred at room temperature for 5 hours. Ion-exchanged water (50 g) was added, followed by extraction with ethyl acetate (100 g). After the organic layer was washed with water three times, the solvent was removed, and it was purified with a silica gel column (ethyl acetate/hexane=1/4) to obtain Compound No. 133 (2.3 g: 18% yield). The NMR data of the obtained compound No. 133 are shown in [Table 1].

[Chemical 60]

[Examples 4-1 to 4-2] Production of compound No. 134

[Example 4-1] Production of Intermediate 134A (oxime compound) Intermediate 133C (10.0 g) and DMF (dimethylformamide) (10.0 g) were weighed in a four-necked flask and placed in an ice bath Under cooling, 35% hydrochloric acid (6.70 g) and isobutyl nitrite (6.63 g) were added dropwise, and the mixture was stirred at room temperature for 20 hours. Ion-exchanged water (22.8 g) and ethyl acetate (34.2 g) were added, oil-water separation was performed, and the organic layer was washed with water three times. After the organic layer was desolvated, it was purified with a silica gel column (ethyl acetate/hexane=1/4) to obtain Intermediate 134A (2.8 g: 25% yield).

[Chemical 61]

[Example 4-2] Production of Compound No. 134 (oxime ester compound) Intermediate 134A (2.7 g) and ethyl acetate (10 g) were charged into a four-necked round-bottomed flask. Triethylamine (1.3 g) and acetyl chloride (1.0 g) were sequentially added dropwise under ice-cooling, and the mixture was heated to room temperature, followed by stirring for 3 hours. After adding ion-exchanged water (12 g), oil-water separation was performed, and the organic layer was washed with water 5 times. After the organic layer was desolvated, it was purified with a silica gel column (hexane/ethyl acetate=85:15) to obtain Compound No. 134 (0.89 g: 27% yield). The NMR data of the obtained compound No. 134 are shown in [Table 1].

[Chemical 62]

[Table 1]

[Production Example 1] Production of Blue Pigment Dispersion No. 1 Using a bead mill, DISPERBYK-161 (12.5 parts by mass; manufactured by BYK-Chemie Japan) as a dispersant and Pigment Blue 15:6 ( 15 parts by mass) was dispersed in PGMEA (72.5 parts by mass) to produce a blue pigment dispersion liquid.

[Examples 5 to 7 and Comparative Examples 1 to 2] Preparation of Photosensitive Compositions According to the compositions of [Table 2] and [Table 3], each component was prepared to obtain photosensitive compositions No. 1 to 3 and comparative photosensitivity Composition No.1-2. In addition, the numbers in the table represent parts by mass. As the photopolymerization initiator, compounds No. 2, No. 133, No. 134, No. A2-3, and No. A2-11 were used alone. In addition, the symbols in the table represent the following components. A-1 Compound No.2 A-2 Compound No.133 A-3 Compound No.134 A'-4 Compound No.A2-3 A'-5 Compound No.A2-11 B-1 SPC-3000 ^* (with Acid group ethylenically unsaturated compound, solid content 42 wt% PGMEA solution; Showa Denko manufacture) B-2 KAYARAD DPHA (ethylenically unsaturated compound; Nippon Kayaku manufacture) C-1 Blue pigment dispersion liquid No.1 (Colorant PGMEA dispersion) D-1 KBE-403 (Silane coupling agent; manufactured by Shin-Etsu Chemical) D-2 F-554 (Fluorine group-containing/lipophilic group-containing oligomer; manufactured by DIC) E-1 PGMEA ( Solvent) ^* SPC-3000 is an ethylenically unsaturated compound (B), and is also an alkali developable compound (D).

[Table 2]

[table 3]

[Evaluation of Cured Products Obtained from Photosensitive Compositions] In the cured products obtained from the above-mentioned photosensitive compositions No. 1 to 3 and comparative photosensitive compositions No. 1 to 2, the evaluation of brightness was performed in the following procedure. . The results are collectively described in [Table 4].

(Brightness) The above-mentioned photosensitive compositions No. 1 to 3 and comparative photosensitive compositions No. 1 to 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, using a hot plate, After prebaking at 90°C for 90 seconds, it was cooled at 23°C for 40 seconds. Then, 100 mJ/cm< ² > was irradiated using a high pressure mercury lamp, and the evaluation sample was produced. From the transmittance of the obtained sample at 380 to 780 nm, the Y value was determined in accordance with JIS Z8701. Those with a Y value of 9.5 or more were designated as A, and those with a Y value of less than 9.5 were designated as B. A higher BY value means higher brightness, which is more useful. Those with a brightness evaluation of A can be preferably used as color filters, and those with an evaluation of B are not suitable as color filters.

[Table 4]

[Evaluation of Photosensitive Composition] The sensitivity evaluations of the photosensitive compositions No. 1 and 3 and the comparative photosensitive composition No. 1 in the evaluation of the above-mentioned brightness were performed in the following procedure. The results are collectively described in [Table 5].

(Sensitivity) The above-mentioned photosensitive compositions No. 1 to 3 and comparative photosensitive compositions No. 1 to 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, and a hot plate was used , after pre-baking at 90°C for 90 seconds, cooling at 23°C for 40 seconds. After that, exposure was performed through a mask using a high-pressure mercury lamp. After developing using a 2.5 mass %<sodium carbonate aqueous solution as a developing solution, it was sufficiently washed with water and baked at 230° C. for 30 minutes using an oven to fix the pattern. The 30 μm line width of the mask opening was measured by observing the pattern with an electron microscope with respect to the exposure amount of 40 mJ/cm ² . A line width of 35 μm or more was designated as A, a line width of 25 μm or more was designated as B, and a line width of less than 25 μm was designated as C. The larger the line width, the better the sensitivity. The photosensitive compositions whose sensitivity evaluations are A and B can be used for color filter applications, and the photosensitive compositions whose sensitivity evaluations are A are particularly preferred. The photosensitive composition whose evaluation of sensitivity is C is not suitable for use as a color filter.

[table 5]

As can be seen from the above [Table 3] to [Table 5], the oxime ester compound of the present invention has high sensitivity and the cured product of the present invention has high brightness.

Therefore, the oxime ester compound of the present invention has excellent photolithography properties, and the obtained cured product has excellent brightness, so it is useful as a photopolymerization initiator. industrial availability

The oxime ester compound of the present invention is a novel compound useful as a photopolymerization initiator having high sensitivity and excellent heat resistance (low sublimation property), and is particularly useful as a photopolymerization initiator. In particular, the photosensitive composition containing the photopolymerization initiator can provide a color filter with high brightness and a display device containing the color filter, so the oxime ester compound of the present invention is useful.

Claims (8)

An oxime ester compound, which is represented by the following general formula (I),

(wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group , carboxyl group, amine group, R ²¹ , OR ²¹ , SR ²¹ , NR ²² R ²³ , COR ²¹ , SOR ²¹ , SO ₂ R ²¹ or CONR ²² R ²³ , R ³ , R ⁶ and R ¹¹ are all of the following general formula In the group represented by (II), R ²¹ , R ²² and R ²³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group containing 2 to 20 carbon atoms, and R ²¹ , R ²² and R ²³ are present. The hydrogen atom in the represented group is substituted with halogen atom, nitro group, cyano group, hydroxyl group, amine group, carboxyl group, methacryloyl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, In the case of an isocyanate group or a heterocyclic group containing 2 to 20 carbon atoms, the methylene group in the groups represented by R ²¹ , R ²² and R ²³ is substituted with -O-, -CO-, -COO-, In the case of -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO-, R ²⁴ represents a hydrogen atom , a hydrocarbon group with 1 to 20 carbon atoms, X ¹ does not exist or represents a direct bond, -CO-, -O- or -S-) [Chemical 2]

(in the formula, R ³¹ and R ³² independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms, and R ³¹ and The hydrogen atom in the group represented by R ³² is substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryl group, an epoxy group, a vinyl group, a vinyl ether group, In the case of a mercapto group, an isocyanate group or a heterocyclic group containing 2 to 20 carbon atoms, the methylene group in the groups represented by R ³¹ and R ³² is also substituted with -O-, -CO-, -COO-, In the case of -OCO-, -NR ³³ -, -NR ³³ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO-, R ³³ represents a hydrogen atom , a hydrocarbon group with 1 to 20 carbon atoms, n represents 1, * represents a bond). A photopolymerization initiator containing the oxime ester compound as claimed in claim 1. A photosensitive composition containing the photopolymerization initiator (A) as claimed in claim 2 and an ethylenically unsaturated compound (B). The photosensitive composition of Claim 3 which further contains a coloring agent (C). An alkali-developable photosensitive resin composition comprising the photosensitive composition of claim 3 and an alkali-developable compound (D). A hardened product, which is the hardened product of the photosensitive composition of claim 3 or the hardened product of the alkali-developable photosensitive resin composition of claim 5. A display device containing the hardened product as claimed in claim 6. A method for producing a cured product, comprising the step of curing the photosensitive composition as claimed in claim 3 or the alkali-developable photosensitive resin composition as claimed in claim 5 by light irradiation or heating.