KR102391780B1 - Photosensitive composition - Google Patents

Abstract

A photosensitive composition having excellent sensitivity, a cured product of the photosensitive composition, an insulating film made of a cured product of the photosensitive composition, a color filter including a cured product of the photosensitive composition, a display device having the color filter, and a display device using the photosensitive composition A method for forming a cured film is provided.
An oxime ester compound containing a carbazole ring or a fluorene ring as a main skeleton, from an arylene group having an electron withdrawing group on the carbazole ring or fluorene ring, a heteroarylene group, a carbon-carbon double bond and a carbon-carbon triple bond A compound having a chain aliphatic hydrocarbon group containing at least one selected at least one bond is blended into the photosensitive composition as a photopolymerization initiator.

Description

Photosensitive composition {PHOTOSENSITIVE COMPOSITION}

The present invention relates to a photosensitive composition, a cured product of the photosensitive composition, an insulating film made of a cured product of the photosensitive composition, a color filter including a cured product of the photosensitive composition, a display device including the color filter, and curing using the photosensitive composition It relates to a method of forming a film.

BACKGROUND ART A display device such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which electrodes forming a pair are formed opposite to each other. And the color filter which consists of pixel areas of each color, such as red (R), green (G), and blue (B), is formed inside one board|substrate. In this color filter, in general, a black matrix is formed so as to partition each pixel area of red, green, blue, or the like.

In general, color filters are manufactured by a lithographic method. That is, first, a black photosensitive composition is applied on a substrate, dried, exposed and developed to form a black matrix. Then, coating, drying, exposure and development are repeated for each color photosensitive composition such as red, green, and blue to form a pixel region of each color at a specific position to manufacture a color filter.

In recent years, in the manufacture of display apparatuses, such as a liquid crystal display display, the trial which improves the light-shielding property by a black matrix to further improve the contrast (contrast) of the image displayed on a display apparatus is made|formed. For this purpose, it is necessary to contain a light-shielding agent in a large amount in the photosensitive composition for forming the black matrix. However, when the photosensitive composition contains a large amount of the light-shielding agent in this way, when the film of the photosensitive composition applied on the substrate is exposed, the light for curing the photosensitive composition becomes difficult to reach to the bottom of the film, and the sensitivity of the photosensitive composition is remarkable. The deterioration will result in curing failure.

As a photosensitive composition, the composition containing an oxime ester compound is used widely. An oxime ester compound is widely used as a photoinitiator for polymerizing a photopolymerizable compound. In addition, the oxime ester compound has a property of generating a base upon exposure, and uses this property to accelerate curing of an epoxy compound or the like, or to promote a photosensitive curing reaction such as an imidization reaction of a polyimide precursor. It is used as a (reaction accelerator) agent. It is also used as a photosensitizer of a composition for LED exposure. Accordingly, it is known that the sensitivity of the photosensitive composition is affected by the types of the photopolymerization initiator and the photosensitive curing accelerator contained therein.

Moreover, in recent years, the production amount of a color filter is also increasing with the increase in the number of production units of display devices, such as a liquid crystal display display. Therefore, from the viewpoint of productivity improvement, a highly sensitive photosensitive composition capable of forming a pattern with a low exposure dose is further demanded.

As a photoinitiator which can make the sensitivity of the photosensitive composition favorable in such a situation, the oxime ester compound which has a cycloalkyl group is proposed by patent document 1. In the Examples described in Patent Document 1, compounds represented by the following formulas (a) and (b) are specifically disclosed.

People's Republic of China Laid-Open Patent Publication No. 101508744

However, the exposure amount at the time of exposing the coating film which consists of a photosensitive composition at the time of manufacturing various display panel panels using a photosensitive composition is calculated|required from a viewpoint of the productivity improvement of a panel to be further reduced. Even the photosensitive composition containing the compound of patent document 1 may not fully meet such a request|requirement in some cases. Therefore, the composition excellent in sensitivity further than the photosensitive composition containing the compound of patent document 1 is calculated|required.

The present invention has been made in view of the above problems, and includes a photosensitive composition having excellent sensitivity, a cured product of the composition, an insulating film made of a cured product of the photosensitive composition, a color filter comprising the cured product of the photosensitive composition, and the color filter An object of the present invention is to provide a display device comprising: and a method for forming a cured film using the photosensitive composition.

The present inventors are an oxime ester compound comprising a carbazole ring or a fluorene ring as a main skeleton, and an aryl group having an electron withdrawing group on the carbazole ring or the fluorene ring, respectively, a heteroaryl group, a carbon-carbon double bond and carbon- It has been found that the above problems can be solved by blending a compound having a chain aliphatic hydrocarbon group including at least one bond selected from carbon triple bonds, or a group combining them as a photopolymerization initiator in the photosensitive composition, and completing the present invention reached

A 1st aspect of this invention is a composition containing the compound represented by following formula (1).

(In formula (1), R ¹ represents an electron withdrawing group, and R ⁶ is a chain aliphatic hydrocarbon containing at least one bond selected from an arylene group, a heteroarylene group, a carbon-carbon double bond and a carbon-carbon triple bond. a group or a combination thereof, R ⁶ may have one or more substituents selected from an electron withdrawing group, a thiol group, and a monovalent organic group, R ⁴ represents a monovalent organic group or a hydrogen atom, and R ⁵ is 1 represents a valent organic group or hydrogen atom, n represents 0 or 1, and T represents the following formula (T _C ) or formula (T _N ):

is a group represented by

In formulas ( _TC ) and (T _N ), R ² and R ³ each independently represent an optionally substituted alkyl group or hydrogen atom, * represents a bond, and in formula ( _TC ), R ² and R ³ may be combined to form a ring.)

A 2nd aspect of this invention is the hardened|cured material of the composition containing (A) a photopolymerizable compound as the photosensitive composition which concerns on 1st aspect, The photosensitive composition is a hardened|cured material which may also contain (C) a coloring agent.

A third aspect of the present invention is an insulating film made of the cured product according to the second aspect.

A 4th aspect of this invention is a color filter containing the hardened|cured material which concerns on 2nd aspect, Comprising: The photosensitive composition is a color filter which may contain the (C) coloring agent.

A fifth aspect of the present invention is a display device provided with the color filter according to the fourth aspect.

A sixth aspect of the present invention is the photosensitive composition according to the first aspect, comprising (A) coating a composition containing a photopolymerizable compound on a substrate to form a coating film, and exposing the coating film to light As a film formation method, a photosensitive composition is a formation method of the cured film which may also contain (C) a coloring agent.

According to the present invention, a photosensitive composition having excellent sensitivity, a cured product of the photosensitive composition, an insulating film made of a cured product of the photosensitive composition, a color filter including a cured product of the photosensitive composition, a display device including the color filter, and the The formation method of the cured film using a photosensitive composition can be provided.

1 is a schematic diagram showing the cross-sectional shape of a pattern formed using a photosensitive composition in the width direction, (a) is a diagram showing the cross-sectional shape of a normal pattern, (b) is a cross-sectional shape of the pattern in which the undercut 21 is made It is a drawing showing

<Photosensitive composition>

The photosensitive composition contains the compound represented by following formula (1). The compound represented by Formula (1) has a function as a photoinitiator which superposes|polymerizes the photopolymerizable compound which has an ethylenically unsaturated double bond, for example, and the function which generate|occur|produces a base by exposure. Therefore, the compound represented by Formula (1) is used as a component that imparts photosensitivity to the composition for various purposes. It is used not only as a photosensitive component of ultraviolet rays such as 365 nm and 385 nm, but also as a photosensitizer component for LED exposure including h line of 405 nm and g line of 435 nm.

As a photosensitive composition, the composition containing the compound represented by Formula (1), and the (A) photopolymerizable compound mentioned later as a photosensitive composition, for example, The curable compound which has a compound represented by Formula (1), and an oxsilane ring or an oxetane ring. A composition containing, and a composition containing a compound represented by Formula (1) and a polyimide precursor are preferred.

The photosensitive composition may contain various additives other than the compound represented by Formula (1), the (A) photopolymerizable compound mentioned later, the sclerosing|hardenable compound and polyimide precursor which have an oxylan ring and an oxetane ring as needed.

Specifically, the additives include colorants, solvents, sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, defoamers, surfactants, etc. is exemplified

About the preferable example of a coloring agent and a solvent, it mentions below in detail as a component of the composition containing the (A) photopolymerizable compound which is a preferable photosensitive composition.

<Compound represented by Formula (1)>

Below, the compound represented by following formula (1) is demonstrated.

(In formula (1), R ¹ represents an electron withdrawing group, and R ⁶ is a chain aliphatic hydrocarbon containing at least one bond selected from an arylene group, a heteroarylene group, a carbon-carbon double bond and a carbon-carbon triple bond. group, or a group combining these, wherein R ⁶ may have one or more substituents selected from an electron withdrawing group, a thiol group and a monovalent organic group, R ⁴ represents a monovalent organic group or a hydrogen atom, and R ⁵ is represents a monovalent organic group or a hydrogen atom, n represents 0 or 1, and T represents the following formula (T _C ) or formula (T _N ):

is a group represented by

In formulas ( _TC ) and (T _N ), R ² and R ³ each independently represent an optionally substituted alkyl group or hydrogen atom, * represents a bond, and in formula ( _TC ), R ² and R ³ may be combined to form a ring.)

(for R ¹ and R ⁶ )

The compound represented by Formula (1) is excellent in sensitivity by having a group containing an electron withdrawing group represented by R ¹ -R ⁶ - on a fluorene ring or a carbazole ring in combination with a group having a predetermined structure .

The substituent which R ⁶ may have or the electron withdrawing group as R ¹ is not particularly limited as long as it is a functional group generally recognized as an electron withdrawing group in the chemical field.

Preferred examples of the electron withdrawing group include a benzenesulfonyl group, a toluenesulfonyl group, an alkanesulfonyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom, and a halogenated alkyl group. Among the electron withdrawing groups, the number of nitro groups, cyano groups and carbon atoms is from the point of chemical stability, sensitivity to light of the compound represented by Formula (1), and ease of synthesis of the compound represented by Formula (1). A fluoroalkyl group of 1 to 6 is preferred.

R ⁶ is a chain aliphatic hydrocarbon group including at least one bond selected from an arylene group, a heteroarylene group, a carbon-carbon double bond and a carbon-carbon triple bond, or a group combining them. Further, R ⁶ may have one or more substituents selected from an electron withdrawing group, a thiol group, and a monovalent organic group.

When R ⁶ is an arylene group, the arylene group is not particularly limited as long as two hydrogen atoms are removed from the aromatic hydrocarbon. It is preferable that the arylene group consists of one or more benzene rings. When the arylene group contains two or more benzene rings, a plurality of benzene rings may be bonded to each other by a single bond, or may be condensed with each other to form a condensed ring such as a naphthalene ring.

The arylene group preferably contains 1 to 3 benzene rings, and more preferably 1 or 2 benzene rings.

Preferred examples of the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene group. -1,5-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7- Diyl group, biphenyl-4,4'-diyl group, biphenyl-3,3'-diyl group, biphenyl-2,2'-diyl group, biphenyl-3,4'-diyl group, phenyl-3 ,2'-diyl group and biphenyl-2,4'-diyl group.

When R ⁶ is a heteroarylene group, the heteroarylene group is not particularly limited as long as two hydrogen atoms are removed from the aromatic heterocycle. The heteroarylene group is a group consisting of a 5- or 6-membered aromatic ring, and preferably includes at least one 5- or 6-membered aromatic heterocycle.

When the heteroarylene group is a group consisting of a 5- or 6-membered aromatic ring and includes at least one 5- or 6-membered aromatic heterocycle, a plurality of 5- or 6-membered aromatic rings are bonded to each other by a single bond. may be used or may be condensed with each other to form a condensed ring.

The heteroarylene group preferably contains 1 to 3 5- or 6-membered aromatic rings, and more preferably 1 or 2 5- or 6-membered aromatic rings.

Preferred examples of the heteroarylene group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine. , benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, syn In aromatic heterocyclic compounds, such as noline and quinoxaline, the group except two hydrogen atoms couple|bonded with a carbon atom is mentioned.

For a chain aliphatic hydrocarbon group containing at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond, the number of carbon atoms or the number of carbon-carbon double bonds and carbon-carbon triple bonds is for the purpose of the present invention. It will not specifically limit if it is a range which does not impair.

In addition, the chain aliphatic hydrocarbon group containing at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond may be straight-chain or branched, and preferably straight-chain.

The number of carbon atoms in the chain aliphatic hydrocarbon group including at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond is preferably 2 to 10, more preferably 2 to 6, and 2 to 4 Especially preferred.

The chain aliphatic hydrocarbon group is preferably an alkenylene group containing one carbon-carbon double bond or an alkenylene group containing one carbon-carbon triple bond.

Preferred examples of the chain aliphatic hydrocarbon group including at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond include ethylene-1,2-diyl group, ethyne-1,2-diyl group, propa -1-ene-1,2-diyl group, propazylene group and pentyrylene group.

For example, preferred examples of the group combining a chain aliphatic hydrocarbon group including at least one bond selected from an arylene group, a carbon-carbon double bond and a carbon-carbon triple bond include the following divalent groups.

As a preferred example of a group combining a chain aliphatic hydrocarbon group including at least one bond selected from a heteroarylene group, a carbon-carbon double bond, and a carbon-carbon triple bond, the arylene group included in the following divalent group includes various hetero The group substituted with the arylene group is mentioned.

With respect to R ⁶ , an arylene group, a heteroarylene group, or a chain aliphatic hydrocarbon group containing at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond is an electron withdrawing group, a thiol group, and a monovalent organic group You may have one or more substituents chosen.

The electron withdrawing device is the same as described above. Examples of the monovalent organic group as a substituent which R ⁶ may have include an alkyl group (eg, a methyl group, an ethyl group) and an alkoxy group (eg, a methoxy group, an ethoxy group). In the case of R ⁶ being an arylene group, it is preferably substituted at the m position.

As the group containing the electron withdrawing group represented by R ¹ -R ⁶ - described above, an aryl group substituted with a nitro group is preferable, and a phenyl group substituted with a nitro group is more preferable.

Although the number of substitutions of a nitro group in an aryl group is not specifically limited, 1-3 are preferable, 1 or 2 are more preferable, and 1 is especially preferable.

Specific examples of the aryl group substituted with a nitro group include an o ^- nitrophenyl group, m-nitrophenyl group, p-nitrophenyl group, 2,3- Dinitrophenyl group, 2,4-dinitrophenyl group, 2,5-dinitrophenyl group, 2,6-dinitrophenyl group, 3,4-dinitrophenyl group, 3,5-dinitrophenyl group, 2-nitronaphthalene-1 -yl group, 3-nitronaphthalen-1-yl group, 4-nitronaphthalen-1-yl group, 5-nitronaphthalen-1-yl group, 6-nitronaphthalen-1-yl group, 7-nitronaphthalen-1-yl group, 8- and a nitronaphthalen-1-yl group, a 3-nitronaphthalen-2-yl group, a 6-nitronaphthalen-2-yl group and a 7-nitronaphthalen-2-yl group.

Among these groups, o-nitrophenyl group, p-nitrophenyl group, 2,4-dinitrophenyl group, 2,6-dinitrophenyl group, 2-nitronaphthalen-1-yl group, 4-nitronaphthalen-1-yl group, 5 -Nitronaphthalen-1-yl group, 3-nitronaphthalen-2-yl group, 6-nitronaphthalen-2-yl group, 8-nitronaphthalen-2-yl group, 1-nitronaphthalen-2-yl group are preferable, p-nitro A phenyl group is particularly preferred.

(for R ² and R ³ included in formula (T _C ) and formula (T _N ))

T in Formula (1) is group represented by the above-mentioned formula (T _C ), or group represented by a formula (T _N ). R ² and R ³ contained in the formulas ( _TC ) and (T _N ) are each an optionally substituted alkyl group or a hydrogen atom. In the formula ( _TC ), R ² and R ³ may be bonded to each other to form a ring. Among these groups, an optionally substituted alkyl group is preferable as R ² and R ³ . When R ² and R ³ are optionally substituted alkyl groups, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group.

When R ² and R ³ are an alkyl group having no substituent, the number of carbon atoms in the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 6. Specific examples of when R ² and R ³ are an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a n-pentyl group. , isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isono A nyl group, an n-decyl group, an isodecyl group, etc. are mentioned.

When R ² and R ³ are an alkyl group having a substituent, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. The alkyl group which has a substituent may be linear or branched, and it is preferable that it is linear.

The substituent which an alkyl group may have is not specifically limited if it is a range which does not impair the objective of this invention. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, an alkoxy group and an alkoxycarbonyl group.

A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.

Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group.

3-10 are preferable and, as for carbon atom number of a cycloalkyl group, 3-6 are more preferable. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a pentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, etc. are mentioned.

The heterocyclyl group is a 5-membered or 6-membered single ring containing one or more N, S, and O, or a heterocyclyl group in which such single rings or a single ring and a benzene ring are condensed. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala and gin, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran. When R ² and R ³ are a heterocyclyl group, the heterocyclyl group may further have a substituent.

The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, iso pentyloxy group, sec-pentyloxy group, tert-pentyloxy group and n-hexyloxy group are mentioned.

The alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and it is preferable that it is linear. 1-10 are preferable and, as for the number of carbon atoms of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxy group and a carbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, and n-hexyloxycarbonyl group.

When the alkyl group has a substituent, the number of the substituents is not particularly limited. The preferred number of substituents depends on the number of carbon atoms in the chain alkyl group. The number of substituents is generally 1-20, 1-10 are preferable, and 1-6 are more preferable.

R ² and R ³ may be bonded to each other to form a ring. The group consisting of a ring formed by R ² and R ³ is preferably a cycloalkylidene group. When R ² and R ³ combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered or 6-membered ring, more preferably a 5-membered ring.

When the group formed by bonding of R ² and R ³ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with the cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, A pyrazine ring, a pyrimidine ring, etc. are mentioned.

Among R ² and R ³ described above, a group represented by the formula -A ¹ -A ² is exemplified as a preferable example of the group. In the formula, A ¹ is a straight-chain alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

1-10 are preferable and, as for carbon atom number of the linear alkylene group of A< ¹ >, 1-6 are more preferable. When ^A2 is an alkoxy group, linear or branched form may be sufficient as an alkoxy group, and it is preferable that it is linear. 1-10 are preferable, as for carbon atom number of an alkoxy group, 1-6 are more preferable, and 1-4 are especially preferable.

When ^A2 is a halogen atom, it is preferable that they are a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and it is more preferable that they are a fluorine atom, a chlorine atom, and a bromine atom.

When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. A halogenated alkyl group may be linear or branched, and it is preferable that it is linear.

When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ² and R ³ have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group which R ² and R ³ have as a substituent.

Preferred specific examples of R ² and R ³ include an alkyl group such as an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy group -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phene alkoxyalkyl groups such as a tyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano group cyanoalkyl groups such as -n-heptyl and 8-cyano-n-octyl; 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and a phenylalkyl group such as an 8-phenyl-n-octyl group; 2-cyclohexyl ethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl group -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentyl ethyl group, 3-cyclopentyl-n-propyl group, 4- cyclopentyl-n-butyl group, 5-cyclopentyl-n-pene cycloalkylalkyl groups such as a tyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group; 2- Methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl group -n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and 8 - Alkoxycarbonylalkyl groups, such as an ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5 Halogenated alkyl groups, such as a heptafluoro-n-pentyl group, are mentioned.

As R ² and R ³ , preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, 2-methoxyethyl group, 2-cyanoethyl group, and 2-phenyl group. Ethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5 , a 5-heptafluoro-n-pentyl group.

(for R ⁴ )

R ⁴ is a monovalent organic group or a hydrogen atom. The monovalent organic group will not be specifically limited as long as it is a range which does not impair the objective of this invention.

Examples of the preferable organic group for R ⁴ include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted phenyl group, and an optionally substituted phenoxy group. Period, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the phenoxyalkyl group which may have a substituent, even if it has a substituent phenylthioalkyl group, N-substituted aminoalkyl group, N,N-disubstituted aminoalkyl group, naphthyl group which may have a substituent, naphthaloxy group which may have a substituent, naphthoyl group which may have a substituent, even if it has a substituent A naphthaloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a naphthyloxyalkyl group which may have a substituent, a naphthylthioalkyl group which may have a substituent, or a substituent and a heterocyclyl group, optionally a heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

Moreover, as R< ⁴ >, a cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable.

When ^R4 is an alkyl group, 1-20 are preferable and, as for the number of carbon atoms of an alkyl group, 1-6 are more preferable. Moreover, when R< ⁴ > is an alkyl group, linear or branched form may be sufficient. Specific examples of when R ⁴ is an alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopene tyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n - A decyl group, an isodecyl group, etc. are mentioned. Moreover, when ^R4 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethyl group, a methoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When ^R4 is an alkoxy group, 1-20 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 are more preferable. Moreover, when R< ⁴ > is an alkoxy group, linear or branched form may be sufficient as it. Specific examples when R ⁴ is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. Moreover, when R< ⁴ > is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group and a methyl group Toxypropyloxy group, etc. are mentioned.

When ^R4 is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and, as for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, 3-6 are more preferable. Specific examples when R ⁴ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ⁴ is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ⁴ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples of when R ⁴ is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples of when R ⁴ is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoyloxy group Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n- Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When ^R4 is an alkoxycarbonyl group, 2-20 are preferable and, as for the number of carbon atoms of the alkoxycarbonyl group, 2-7 are more preferable. Specific examples when R ⁴ is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec- Butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxy group carbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group and isodecyloxycarbonyl group, etc. are mentioned.

When ^R4 is a phenylalkyl group, 7-20 are preferable and, as for the number of carbon atoms of a phenylalkyl group, 7-10 are more preferable. Moreover, when R< ⁴ > is a naphthylalkyl group, 11-20 are preferable and, as for carbon atom number of a naphthylalkyl group, 11-14 are more preferable.

Specific examples when R ⁴ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.

Specific examples when R ⁴ is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group.

When R ⁴ is a phenylalkyl group or a naphthylalkyl group, R ⁴ may further have a substituent in a phenyl group or a naphthyl group.

When R ⁴ is a phenoxy alkyl group, a phenylthioalkyl group, a naphthoxyalkyl group, and a naphthylthioalkyl group, the number of carbon atoms in the alkylene group contained in these groups is preferably 1 to 20, more preferably 1 to 6; Moreover, linear or branched form may be sufficient as the said alkylene group, and linear form is preferable.

Specific examples of the phenoxyalkyl group include 2-phenoxyethyl group, 3-phenoxy-n-propyl group, 4-phenoxy-n-butyl group, 5-phenoxy-n-pentyl group and 6-phenoxy-n - A hexyl group is mentioned.

Specific examples of the phenylthioalkyl group include 2-phenylthioethyl group, 3-phenylthio-n-propyl group, 4-phenylthio-n-butyl group, 5-phenylthio-n-pentyl group and 6-phenylthio-n - A hexyl group is mentioned.

Specific examples of the naphthoxyalkyl group include 2-(α-naphthoxy)ethyl group, 3-(α-naphthoxy)-n-propyl group, 4-(α-naphthoxy)-n-butyl group, 5-(α -naphthoxy)-n-pentyl group, 6-(α-naphthoxy)-n-hexyl group, 2-(β-naphthoxy)ethyl group, 3-(β-naphthoxy)-n-propyl group, 4- (β-naphthoxy)-n-butyl group, 5-(β-naphthoxy)-n-pentyl group, and 6-(β-naphthoxy)-n-hexyl group are mentioned.

Specific examples of the naphthylthioalkyl group include 2-(α-naphthylthio)ethyl group, 3-(α-naphthylthio)-n-propyl group, 4-(α-naphthylthio)-n-butyl group, 5-(α-naphthylthio)-n-pentyl group, 6-(α-naphthylthio)-n-hexyl group, 2-(β-naphthylthio)ethyl group, 3-(β-naphthylthio) -n-propyl group, 4-(β-naphthylthio)-n-butyl group, 5-(β-naphthylthio)-n-pentyl group and 6-(β-naphthylthio)-n-hexyl group can be heard

When ^R4 is a phenoxyalkyl group, a phenylthioalkyl group, a naphthoxyalkyl group, or a naphthylthioalkyl group, ^R4 may further have a substituent in a phenyl group or a naphthyl group.

When R ⁴ is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered single ring containing one or more N, S, O, or a heterocyclyl group in which such single rings or a single ring and a benzene ring are condensed. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr and talazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. When R ⁴ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ⁴ is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the same as when R ⁴ is a heterocyclyl group.

When R ⁴ is an N-substituted aminoalkyl group or an N,N-disubstituted aminoalkyl group, the substituent bonded to the nitrogen atom is preferably an organic group.

Preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a saturated aliphatic acyloxy group having 2 to 21 carbon atoms, Has a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a substituent and a naphthylalkyl group and heterocyclyl group having 11 to 20 carbon atoms which may be present.

1-20 are preferable and, as for the number of carbon atoms of an N-substituted aminoalkyl group or the alkylene group containing a N,N- disubstituted aminoalkyl group, 1-6 are more preferable. Moreover, linear or branched form may be sufficient as the said alkylene group.

Specific examples of the N-substituted aminoalkyl group include 2-(methylamino)ethyl group, 2-(ethylamino)ethyl group, 2-(n-propylamino)ethyl group, 2-(n-butylamino)ethyl group, 3-(methyl Amino) n-propyl group, 3-(ethylamino) n-propyl group, 3-(n-propylamino) n-propyl group, 3-(n-butylamino) n-propyl group, 2-(methylamino) n-propyl group, 2-(ethylamino)n-propyl group, 2-(n-propylamino)n-propyl group, 2-(n-butylamino)n-propyl group, 2-(acetylamino)ethyl group, 2-(propionylamino)ethyl group, 2-(acetoxyamino)ethyl group, 2-(propionyloxyamino)ethyl group, 3-(acetylamino)n-propyl group, 3-(propionylamino)n-propyl group , 3-(acetoxyamino)n-propyl group, 3-(propionyloxyamino)n-propyl group, 2-(acetylamino)n-propyl group, 2-(propionylamino)n-propyl group, 2 -(acetoxyamino)n-propyl group, and 2-(propionyloxyamino)n-propyl group are mentioned.

Specific examples of the N,N-disubstituted aminoalkyl group include 2-(N,N-dimethylamino)ethyl group, 2-(N,N-diethylamino)ethyl group, 2-(N,N-di-n-propyl group Amino)ethyl group, 2-(N,N-di-n-butylamino)ethyl group, 3-(N,N-dimethylamino)n-propyl group, 3-(N,N-diethylamino)n-propyl group , 3-(N,N-di-n-propylamino)n-propyl group, 3-(N,N-di-n-butylamino)n-propyl group, 2-(N,N-dimethylamino)n -Propyl group, 2-(N,N-diethylamino)n-propyl group, 2-(N,N-di-n-propylamino)n-propyl group, 2-(N,N-di-n- Butylamino) n-propyl group, 2-(N,N-diacetylamino)ethyl group, 2-(N,N-dibutylamino)ethyl group, 2-(N,N-diacetoxyamino)ethyl group, 2- (N,N-dibutyloxyamino)ethyl group, 3-(N,N-diacetylamino)n-propyl group, 3-(N,N-dibutylamino)n-propyl group, 3-(N,N -Diacetoxyamino)n-propyl group, 3-(N,N-dibutyloxyamino)n-propyl group, 2-(N,N-diacetylamino)n-propyl group, 2-(N,N -Dibutylamino)n-propyl group, 2-(N,N-diacetoxyamino)n-propyl group, 2-(N,N-dibutyloxyamino)n-propyl group, 2-(N-acetyl -N-acetoxyamino)ethyl group, 2-(N-propionyl-N-propionyloxyamino)ethyl group, 3-(N-acetyl-N-acetoxyamino)n-propyl group, 3-(N-propy onyl-N-propionyloxyamino)n-propyl group, 2-(N-acetyl-N-acetoxyamino)n-propyl group, and 2-(N-propionyl-N-propionyloxyamino)n- A profiler may be mentioned.

When the phenyl group, naphthyl group and heterocyclyl group included in R ⁴ have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and saturated having 2 to 7 carbon atoms. An aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group and cyano group having When the phenyl group, naphthyl group and heterocyclyl group included in R ⁴ further have a substituent, the number of the substituents is not limited as long as it does not impair the object of the present invention, but 1 to 4 are preferable. When the phenyl group, naphthyl group and heterocyclyl group included in R ⁴ have a plurality of substituents, the plurality of substituents may be the same or different.

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

Further, as R ⁴ , a group represented by -A ³ -CO-OA ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. ^A4 is a monovalent organic group, and it is preferable that it is a monovalent|monohydric hydrocarbon group.

When ^A3 is an alkylene group, linear or branched shape may be sufficient as an alkylene group, and it is preferable that it is linear. When ^A3 is an alkylene group, 1-10 are preferable, as for carbon atom number of an alkylene group, 1-6 are more preferable, and 1-4 are especially preferable.

Preferred examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group phenyl group , a naphthyl group, a benzyl group, a phenethyl group, an α-nathylmethyl group, and a β-nathylmethyl group.

Preferred specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, and 2-n-butyloxy group. Carbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl -n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group, etc. are mentioned.

Although R ⁴ has been described above, R ⁴ is preferably a group represented by the following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ⁷ and R ⁸ are each an organic group, p is an integer from 0 to 4, and R ⁷ and R ⁸ are present at adjacent positions on the benzene ring. In this case, R ⁷ and R ⁸ may be bonded to each other to form a ring, q is an integer from 1 to 8, r is an integer from 1 to 5, s is an integer from 0 to (r+3), R ⁹ is an organic group.)

Examples of the organic group for R ⁷ and R ⁸ in the formula (R4-1) are the same as those for R ¹ . R ⁷ is preferably an alkyl group or a phenyl group. When R ⁷ is an alkyl group, the number of carbon atoms thereof is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ⁷ is most preferably a methyl group. When R ⁷ and R ⁸ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by the formula (R4-1) wherein R ⁷ and R ⁸ form a ring include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can be heard In said formula (R4-1), p is an integer of 0-4, It is preferable that it is 0 or 1, It is more preferable that it is 0.

In the formula (R4-2), R ⁹ is an organic group. The organic group is the same as the organic group described for R ¹ . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1-10 are preferable, as for carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R< ⁹ >, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are preferable, and among these, a methyl group is more preferable.

In said formula (R4-2), r is an integer of 1-5, the integer of 1-3 is preferable, and 1 or 2 is more preferable. In said formula (R4-2), s is 0-(r+3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, 0 is especially preferable. In said formula (R4-2), q is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, 1 or 2 is especially preferable.

(About R ⁵ )

In Formula (1), R< ⁵ > is a monovalent organic group or a hydrogen atom. As a monovalent organic group, it is a C1-C11 alkyl group which may have a substituent, or an aryl group which may have a substituent, for example. When R< ⁵ > is an alkyl group, a phenyl group, a naphthyl group, etc. are preferable as for the substituent which you may have. Moreover, as for the substituent which you may have when R< ¹ > is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. can be illustrated preferably.

In formula (1), as R ⁵ , a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. are preferable, and among these, a methyl group or a phenyl group is more preferable.

When T in formula (1) is a group represented by formula (T _C ), the compound represented by formula (1) is preferably a compound represented by the following formula (1C).

(In formula (1C), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are the same as above.)

Moreover, among the compounds represented by formula (1C), compounds represented by the following formula (1C-1) or (1C-2) are preferable.

In the case where T in the formula (1) is a group represented by the formula (T _N ), the compound represented by the formula (1) is preferably a compound represented by the following formula (1N).

(In formula (1N), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and n are the same as above.)

Moreover, among the compounds represented by formula (1N), compounds represented by the following formula (1N-1) or (1N-2) are preferable.

Preferred specific examples of the compound represented by the formula (1) include the following compounds 1 to 139.

The compound represented by Formula (1) demonstrated above is highly sensitive and provides the photosensitive composition excellent in sensitivity.

<Method for producing compound represented by formula (1)>

The manufacturing method of the compound represented by Formula (1) mentioned above is not specifically limited.

The compound represented by Formula (1), when n is 0, for example,

(I) the formula (1a):

(In the formula (1a), T is the same as above.)

Introducing a group represented by -R ⁶ -R ¹ by a cross-coupling reaction into the ring skeleton represented by

(II) After introducing the acyl group represented by -CO-R ⁴ into the ring skeleton represented by the formula (1a), the group represented by -CO-R ⁴ is a group represented by -C(=N-OH)-R ⁴ conversion and further esterifying the group represented by -C(=N-OH)-R ⁴ to convert to the group represented by -C(=NO-CO-R ⁵ )-R ⁴ .

In addition, the compound represented by Formula (1), when n is 1, for example,

(I) the formula (1a):

(In the formula (1a), T is the same as above)

Introducing a group represented by -R ⁶ -R ¹ by a cross-coupling reaction into the ring skeleton represented by

(II) After introducing the acyl group represented by -CO-CH ₂ -R ⁴ into the ring skeleton represented by the formula (1a), the group represented by -CO-CH ₂ -R ⁴ is -CO-C(=N-OH) ) to the group represented by -R ⁴ , and further esterifying the group represented by -CO-C(=N-OH)-R ⁴ to the group represented by -CO-C(=NO-CO-R ⁵ )-R ⁴ . prepared by a method comprising transforming.

In the above method, either step (I) or step (II) may be performed first. In addition, although the process (II) includes operation of several steps, the process (I) may be implemented at any timing of the process (II).

In the above method, the method for converting the oxime group (=N-OH) to the oxime ester group represented by =NO-COR ⁵ in step (II) is not particularly limited. Generally, the method of making the hydroxyl group ⁱⁿ an oxime group react with the acylating agent which provides the acyl group represented by -COR5 is mentioned. Examples of the acylating agent include an acid anhydride represented by (R ⁵ CO) ₂ O and an acid halide represented by R ⁵ COHal (Hal is a halogen atom).

When n is 0, the compound represented by Formula (1) can be synthesized, for example, according to Scheme 1 below.

In addition, in Scheme 1 below, a cross-coupling reaction is performed using a halogenated compound having a ring skeleton represented by Formula (1a) and a boron compound including a group represented by -R ⁶ -R ¹ , but in Formula (1a) The cross-coupling reaction may be carried out using a boron compound having a ring skeleton shown and a halogenated compound containing a group represented by -R ⁶ -R ¹ .

Also, the cross-coupling reaction is

After introducing the acyl group represented by -CO-R ⁴ into the ring skeleton represented by the formula (1a),

After converting the group represented by -CO-R ⁴ to the group represented by -C(=N-OH)-R ⁴ ,

It may be carried out at any timing after esterification of the group represented by -C(=N-OH)-R ⁴ and conversion to the group represented by -C(=NO-CO-R ⁵ )-R ⁴ .

First, compound 1B is obtained by introducing an acyl group represented by -CO-R ⁴ into compound 1A by a Friedel-Crafts acylation reaction. The acylating agent for introducing the acyl group represented by -CO-R ⁴ may be a halocarbonyl compound represented by Hal-CO-R ⁴ or (R ⁴ CO) ₂ O acid anhydride. The acylating agent is preferably a halocarbonyl compound represented by Hal-CO-R ⁴ . Hal is a halogen atom. The position at which the acyl group is introduced can be selected by appropriately changing the Friedel-Crafts reaction conditions or by performing protection and deprotection at a position different from the acylated position.

When T in compound 1A is a group represented by the formula ( _TC ), for example, a halogenated fluorene such as bromofluorene (preferably 2-bromofluorene) is combined with a base such as potassium tert-butoxide Compound 1A can be obtained by reaction with R ² -Hal and R ³ -Hal. In R ² -Hal and R ³ -Hal, Hal is a halogen atom, preferably a bromine atom.

In addition, when T is a group represented by the formula (T _C ), when synthesizing Compound 1A, a compound in which two R ² or two R ³ is bonded at the 9 position on the fluorene ring is produced as a by-product there is. In this case, only a desired product can be separated and obtained by a known method such as column chromatography.

Subsequently, compound 1C is obtained by condensing a boron compound containing a group represented by R ¹ -R ⁶ -, such as compound 1B and R ¹ -R ⁶ -B(OH) ₂ by a so-called Suzuki-Miura coupling reaction.

In addition, the cross-coupling reaction is not limited to the Suzuki Miura coupling reaction, and can be appropriately selected from known cross-coupling reactions.

The type of the boron compound is not particularly limited as long as the group represented by R ¹ -R ⁶ - can be introduced into the compound 1B.

The catalyst used for the Suzuki Miura coupling reaction is not particularly limited as long as it has been conventionally used for the reaction. For example, suitable catalysts include [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloride-dichloromethaneadduct (Pd(dppf)Cl ₂ .CH ₂ Cl ₂ ), tetrakis (triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ ), 1,2-bis(diphenylphosphinoethane)palladium(II)dichloride (PdCl ₂ (dppe)), 1,3-bis (diphenylphosphinopropane)palladium (II) dichloride (PdCl ₂ (dppp)), [1,1'-bis (diphenylphosphino) ferrocene] nickel (II) dichloride-dichloromethane adduct (Ni ( dppf)Cl ₂ •CH ₂ Cl ₂ ), bis(triphenylphosphine)nickel(II)dichloride (NiCl ₂ (Ph ₃ ) ₂ ), and the like. In addition, palladium acetate or palladium chloride and an appropriate ligand may be mixed in the system for use.

The solvent used in this reaction is not particularly limited as long as it does not inhibit the progress of the reaction, and for example, tetrahydrofuran (THF), methanol, ethanol, propanol, n-butanol, 2-butanol, toluene, ethyl acetate, N-methylpyrrolidone, cyclopentylmethyl ether, dimethylformamide, dimethylacetamide and water can be used. From the point that it is easy to proceed satisfactorily the Suzuki Miura reaction, N,N,N', such as N,N,N',N'-tetramethylurea, N,N,N',N'-tetraethylurea, N'-tetraalkylurea is also preferably used as the solvent.

Next, the group represented by -CO-R ⁴ in Compound 1C is converted to a group represented by -C(=N-OH)-R ⁴ to obtain Compound 1D. The method for converting the group represented by -CO-R ⁴ to the group represented by -C(=N-OH)-R ⁴ is not particularly limited, but oximation with hydroxylamine is preferable. By reacting Compound 1D with an acid anhydride ((R ⁵ CO) ₂ O) or an acid halide (R ⁵ COHal, Hal is a halogen atom), a compound represented by Formula (1) in which n is 0 can be obtained.

<Scheme 1>

In addition, when n is 1, the compound represented by Formula (1) can be synthesize|combined according to the following Scheme 2, for example.

In addition, in Scheme 2 below, a cross-coupling reaction is carried out using a halogenated compound having a ring skeleton represented by Formula (1a) and a boron compound containing a group represented by -R ⁶ -R ¹ , but in Formula (1a) The cross-coupling reaction may be carried out using a boron compound having a ring skeleton as shown and a halogen compound containing a group represented by -R ⁶ -R ¹ .

Also, the cross-coupling reaction is

After introducing the acyl group represented by -CO-CH ₂ -R ⁴ into the ring skeleton represented by the formula (1a),

After converting the group represented by -CO-CH ₂ -R ⁴ to the group represented by -CO-C(=N-OH)-R ⁴ ,

It may be carried out at any timing after esterification of the group represented by -CO-C(=N-OH)-R ⁴ and conversion to the group represented by -CO-C(=NO-CO-R ⁵ )-R ⁴ .

In Scheme 2, the aforementioned compound 1A is used as a raw material. Compound 1E can be obtained by introducing an acyl group represented by -CO-CH ₂ -R ⁴ by Friedel-Crafts reaction as in Scheme 1 with respect to Compound 1A. The acylating agent is preferably a carboxylic acid halide represented by Hal-CO-CH ₂ -R ⁴ .

Then, compound 1E and the boron compound represented by R ¹ -R ⁶ -B(OH) ₂ are condensed by a so-called Suzuki-Miura coupling reaction to obtain compound 1F. The condensation method by the Suzuki Miura coupling reaction is the same as in Scheme 1.

Compound 1G is obtained by oximeizing the methylene group present between R ⁴ and the carbonyl group in the obtained compound 1F. The method of oximeizing the methylene group is not particularly limited, but a method of reacting a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid is preferable. Subsequently, compound 1G may be reacted with an acid anhydride ((R ⁵ CO) ₂ O) or an acid halide (R ⁵ COHal, Hal is a halogen atom) to obtain a compound represented by Formula (1) wherein n is 1.

<Scheme 2>

In Scheme 1, R ⁴ contained in Compound 1B, Compound 1C, Compound 1D and the final product may be the same or different. That is, Compound 1B, Compound 1C, Compound 1D, and R ⁴ included in the final product may receive a chemical modification in the synthesis process represented by Scheme 1. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. The chemical formula that R ⁴ may accept is not limited thereto.

In Scheme 2, compound 1E, compound 1F, compound 1G, and R ⁴ contained in the final product may be the same or different. Compound 1E, Compound 1F, Compound 1G, and R ⁴ included in the final product may receive the same chemical modification as in Scheme 1 in the synthesis process represented by Scheme 2.

The compound represented by formula (1), which can be synthesized by the method described above, is suitably produced according to conventional methods such as washing with a solvent, recrystallization, column purification, etc. It is suitably used for photosensitizer applications such as photopolymerization initiators. .

In addition, the use of the compound represented by Formula (1) is not limited to a photoinitiator. The compound represented by Formula (1) can be used for the various photosensitizer uses for which an oxime ester compound is conventionally used.

<(A) Photosensitive composition containing photopolymerizable compound>

As a photosensitive composition, the composition containing (B) sulfur polymerization initiator containing (A) a photopolymerizable compound and the compound represented by Formula (1) is preferable.

Hereinafter, essential or optional components included in the photosensitive composition will be described.

<(A) photopolymerizable compound>

(A) The photopolymerizable compound contained in the photosensitive composition is not specifically limited, A conventionally well-known photopolymerizable compound can be used. Among them, a resin or a monomer having an ethylenically unsaturated group is preferable, and a combination thereof is more preferable. By combining the resin which has an ethylenically unsaturated group, and the monomer which has an ethylenically unsaturated group, sclerosis|hardenability of a photosensitive composition can be improved and pattern formation can be made easy.

(resin having an ethylenically unsaturated group)

Examples of the resin having an ethylenically unsaturated group include (meth)acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol Monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra Ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolpropanetetra(meth)acrylate, penta Erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth) ) oligomers in which acrylates, cardoepoxydiacrylates, etc. are polymerized; Polyester (meth)acrylate obtained by making (meth)acrylic acid react with the polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; Polyurethane (meth)acrylate obtained by making a polyol and the compound which has two isocyanate groups react, and then making (meth)acrylic acid react; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol and epoxy (meth)acrylate resins obtained by reacting (meth)acrylic acid with epoxy resins such as polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene type epoxy resins. Moreover, resin which made polybasic acid anhydride react with epoxy (meth)acrylate resin can be used preferably. In addition, in this specification, (meth)acryl means acryl or methacryl.

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound and an unsaturated group containing carboxylic compound react with a polybasic acid anhydride can be used preferably.

Among these, the compound represented by the following formula (a1) is preferable. The compound represented by Formula (a1) is preferable at the point itself having high photocurability.

In the formula (a1), X represents a group represented by the following formula (a2).

In the formula (a2), R ^1a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^2a each independently represents a hydrogen atom or a methyl group, W is a single bond or The group represented by structural formula (a3) is shown. In addition, in formula (a2) and structural formula (a3), * means the terminal of the bond of a divalent group.

In said formula (a1), Y represents the residue except the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorenedic anhydride, methyltetrahydrophthalic anhydride, Glutaric anhydride, etc. are mentioned.

In addition, in said formula (a1), Z represents the residue which removed two acid anhydride groups from tetracarboxylic acid anhydride. Examples of the tetracarboxylic anhydride include pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and biphenylethertetracarboxylic anhydride. In addition, in said Formula (a1), a represents the integer of 0-20.

It is preferable that it is 10-150 mgKOH/g in resin solid content, and, as for the acid value of resin which has an ethylenically unsaturated group, it is more preferable that it is 70-110 mgKOH/g. When the acid value is 10 mgKOH/g or more, sufficient solubility in the developer can be obtained, so it is preferable. Moreover, since sufficient sclerosis|hardenability can be acquired by making an acid value into 150 mgKOH/g or less, surface property can be made favorable, it is preferable.

Moreover, it is preferable that it is 1,000-40,000, and, as for the mass average molecular weight of resin which has an ethylenically unsaturated group, it is more preferable that it is 2,000-30,000. Since favorable heat resistance and film strength can be obtained by making a mass average molecular weight into 1,000 or more, it is preferable. Moreover, since favorable developability can be acquired by making a mass average molecular weight into 40,000 or less, it is preferable.

(monomer having an ethylenically unsaturated group)

The monomer having an ethylenically unsaturated group includes a monofunctional monomer and a polyfunctional monomer. Hereinafter, the monofunctional monomer and the polyfunctional monomer will be sequentially described.

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acryl Rate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) acrylates, and half (meth)acrylates of phthalic acid derivatives. These monofunctional monomers may be used independently and may be used in combination of 2 or more type.

Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate. Acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth) ) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth) ) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydie Toxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycol Cidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth)acrylate, urethane (meth)acrylate (ie, a reaction product of toluene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate) methylenebis (meth) acrylamide and polyfunctional monomers such as (meth)acrylamide methylene ether, a condensate of a polyhydric alcohol and N-methylol (meth)acrylamide, and triacryl foam. These polyfunctional monomers may be used alone or in combination of two or more.

(A) It is preferable that content of a photopolymerizable compound is 10-99.9 mass parts with respect to a total of 100 mass parts of solid content of a photosensitive composition. (A) By setting the content of the photopolymerizable compound to 10 parts by mass or more with respect to 100 parts by mass of the total solid content, it is easy to form a film excellent in heat resistance, chemical resistance and mechanical strength using the photosensitive composition.

<(B) Photoinitiator>

A preferable photosensitive composition contains the (B) photoinitiator containing the compound represented by Formula (1). The compound represented by Formula (1) is as described above. Since the photosensitive composition contains the compound represented by Formula (1) as (B) photoinitiator, it is excellent in a sensitivity.

(B) The photoinitiator may contain other photoinitiators with the compound represented by Formula (1). Other photoinitiators can be suitably selected from the various photoinitiators conventionally mix|blended with various photosensitive compositions.

Specifically as other photoinitiators, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropa-1-one, 1-[4-(2-hydroxyethoxy) Phenyl]-2-hydroxy-2-methyl-1-propa-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropa-1-one, 1- (4 -Dodecylphenyl)-2-hydroxy-2-methylpropa-1-one, bis(4-dimethylaminophenyl)ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4 '-Methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylamino methyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino butyl benzoate, 4-dimethylamino-2-ethylbenzoic acid, 4-dimethylamino-2- Isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4- Diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-di Ethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobis Isobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5 -diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5- Triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (mihirazketone), 4,4'-bisdiethylaminobenzophenone (ethylmihirazketone) ), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoisopropyl ether, benzoin-n-butyl Ether, benzoin isobutyl ether, benzoin ether, acetophenone, 2, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone , pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3 -Bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl )-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan- 2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis( Trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methyl Toxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 -n-Butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s -triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bro Mo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, IRGACURE OXE02 , IRGACURE OXE01, IRGACURE 369, IRGACURE 651, IRGACURE 907 (trade name: manufactured by BASF), and NCI-831 (trade name: manufactured by ADEKA). These other photoinitiators can be used individually or in combination of 2 or more types.

When the compound represented by the formula (1) is a compound having a nitro group bonded to the aromatic ring, the compound represented by the formula (1) and having a nitro group bonded to the aromatic ring and the compound represented by the formula (B1) described below It is preferable from the viewpoint of the sensitivity of the photosensitive composition to use the (B) photoinitiator containing an oxime ester compound in combination.

In particular, when the photosensitive composition is a transparent composition that does not contain the (C) colorant described later, the photosensitive composition contains the (B) photoinitiator, so that a cured product having excellent transparency can be easily formed.

Moreover, with respect to the compound represented by Formula (1) and which has a nitro group couple|bonded with an aromatic ring, and the oxime ester compound represented by following formula (B1), you may use combining photoinitiators other than these compounds.

As a compound represented by Formula (1) and which has a nitro group couple|bonded with an aromatic ring, the said compounds 1-17 and compounds 69-85 are preferable, for example, and compounds 1-17 are more preferable.

(B) 1-100 mass % is preferable, as for the mass ratio of the compound represented by Formula (1) with respect to the mass of a photoinitiator, 50-100 mass % is more preferable, and 70-100 mass % is especially preferable. . When it has a light-shielding agent as (C) coloring agent mentioned later, or when using it as a photosensitive composition for LED exposure, as for the mass ratio of the compound represented by Formula (1), 5-100 mass % is more preferable, and 70-100 mass % is particularly preferred.

(B) When the photoinitiator includes a compound represented by the formula (1) and having a nitro group bonded to an aromatic ring, and a compound represented by the formula (1) and having no nitro group in combination, (B) the photopolymerization initiator With respect to the mass, the mass ratio of the compound represented by the formula (1) and having a nitro group bonded to the aromatic ring can be appropriately modified depending on the use of the cured product, but is preferably 0.5 to 99 mass%, and 1 to 80 mass% is more preferable, and 2-50 mass % is especially preferable.

(B) When the photoinitiator contains a combination of a compound represented by Formula (1) and having a nitro group bonded to an aromatic ring, and an oxime ester compound represented by Formula (B1), (B) With respect to the mass of the photoinitiator , The mass ratio of the compound represented by the formula (1) and having a nitro group bonded to the aromatic ring can be appropriately modified depending on the use of the cured product, but is preferably 0.5 to 99 mass%, more preferably 1 to 80 mass% and 2-50 mass % is especially preferable. When used as a photosensitive composition requiring transparency, or when a colorant other than a light-shielding agent is used as the colorant (C) to be described later, the ratio is particularly preferably 0.5 to 20% by mass. Moreover, 1-99.5 mass % is preferable, as for the mass ratio of the oxime ester compound represented by Formula (B1) with respect to the mass of (B) photoinitiator, 50-99 mass % is more preferable, 70-98 mass % is Especially preferred.

(Oxime ester compound represented by Formula (B1))

Below, the oxime ester compound represented by Formula (B1) used suitably with the compound represented by Formula (1) is demonstrated.

(R ^b1 is a hydrogen atom or a monovalent organic group, R ^b2 and R ^b3 are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively, and R ^b2 and R ^b3 are bonded to each other to form a ring, R ^b4 is a monovalent organic group, R ^b5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and n1 is 0 It is an integer of ~4, and n2 is 0 or 1. However, the compound represented by formula (B1) does not have a nitro group.)

Therefore, as an oxime compound for manufacturing the oxime ester compound of Formula (B1), the compound represented by a following formula (B2) is preferable.

(R ^b1 , R ^b2 , R ^b3 , R ^b4 , n1 and n2 are the same as in formula (B1).)

In formulas (B1) and (B2), R ^b1 is a hydrogen atom or a monovalent organic group. R ^b1 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by -(CO) _n2 - on the fluorene ring in the formula (B1). In formula (B1), the bonding position of R ^b1 to the fluorene ring is not particularly limited. When the compound represented by the formula (B1) has one or more R ^b1 , from the ease of synthesis of the compound represented by the formula (B1), any one of the one or more R ^b1 is bonded to the 2-position in the fluorene ring It is preferable to do When R ^b1 is plural, plural R ^b1s may be the same or different.

When R ^b1 is an organic group, R ^b1 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. However, R ^b1 is not an organic group having a nitro group. Preferred examples when R ^b1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted phenyl group, and an optionally substituted phenoxy group. Group, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, which may have a substituent Naphthyloxy group, naphthoyl group which may have a substituent, naphthaloxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocycle which may have a substituent and a ryl group, an optionally substituted heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^b1 is an alkyl group, 1-20 are preferable and, as for the number of carbon atoms of an alkyl group, 1-6 are more preferable. Further, when R ^b1 is an alkyl group, it may be linear or branched. Specific examples when R ^b1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopene. tyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n - A decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^b1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group. .

When R ^b1 is an alkoxy group, 1-20 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 are more preferable. Further, when R ^b1 is an alkoxy group, it may be linear or branched. Specific examples when R ^b1 is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. In addition, when R ^b1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group and a methyl group Toxypropyloxy group, etc. are mentioned.

When R ^b1 is a cycloalkyl group or a cycloalkoxy group, the cycloalkyl group or the cycloalkoxy group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. Specific examples when R ^b1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^b1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^b1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples of when R ^b1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples when R ^b1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoyloxy group Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n- Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^b1 is an alkoxycarbonyl group, 2-20 are preferable and, as for the number of carbon atoms of the alkoxycarbonyl group, 2-7 are more preferable. Specific examples when R ^b1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec- Butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxy group carbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group and isodecyloxycarbonyl group, etc. are mentioned.

When R ^b1 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. Further, when R ^b1 is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. Specific examples when R ^b1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when R ^b1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ^b1 is a phenylalkyl group or a naphthylalkyl group, R ⁴ may further have a substituent in a phenyl group or a naphthyl group.

When R ^b1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered single ring containing one or more N, S, O, or a heterocyclyl group in which these single rings or a single ring and a benzene ring are condensed. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr and talazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. When R ^b1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^b1 is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the same as when R ^b1 is a heterocyclyl group.

When R ^b1 is an amino group substituted with an organic group of 1 or 2, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic group having 2 to 21 carbon atoms. An acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a naphthylalkyl group and heterocyclyl group having 11 to 20 carbon atoms which may have a substituent. Specific examples of such a preferable organic group are the same as R ^b1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n- Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n- Butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. can be heard

When the phenyl group, naphthyl group and heterocyclyl group included in R ^b1 have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and saturated having 2 to 7 carbon atoms. An aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group and cyano group having When the phenyl group, naphthyl group and heterocyclyl group included in R ^b1 further have a substituent, the number of the substituents is not limited as long as it does not impair the object of the present invention, but 1 to 4 are preferable. When the phenyl group, naphthyl group and heterocyclyl group included in R ^b1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^b1 is preferably a group represented by R ^b6 -CO- because the sensitivity tends to improve. R ^b6 is not particularly limited as long as it does not impair the object of the present invention, as long as it does not include a nitro group, and may be selected from various organic groups. Examples of the group preferable as R ^b6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^b6 , of these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable.

Moreover, when R ^b1 is a hydrogen atom, transparency tends to become favorable, and it is preferable. Further, when R ^b1 is a hydrogen atom and R ^b4 is a group represented by the following formula (b1b), the transparency tends to be further improved.

In formula (B1), R ^b2 and R ^b3 each represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. However, R ^b2 and R ^b3 are not groups having a nitro group. R ^b2 and R ^b3 may combine with each other to form a ring. Among these groups, as R ^b2 and R ^b3 , a chain alkyl group which may have a substituent is preferable. When R ^b2 and R ^b3 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^b2 and R ^b3 are unsubstituted chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of when R ^b2 and R ^b3 are a chain alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pene Tyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, iso A nonyl group, an n-decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^b2 and R ^b3 are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group. .

When R ^b2 and R ^b3 are a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. It is preferable that the chain|strand-chain alkyl group which has a substituent is linear.

The substituent which the alkyl group may have is not specifically limited if it is a range which does not impair the objective of this invention. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group and an alkoxycarbonyl group. A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples when R ^b1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as preferred examples in the case where R ^b1 is a heterocyclyl group. When R ^b1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and preferably linear. 1-10 are preferable and, as for carbon atom number of the alkoxy group contained in an alkoxy carbonyl group, 1-6 are more preferable.

When the chain alkyl group has a substituent, the number of the substituents is not particularly limited. The preferred number of substituents depends on the number of carbon atoms in the chain alkyl group. The number of substituents is generally 1-20, 1-10 are preferable, and 1-6 are more preferable.

When R ^b2 and R ^b3 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^b2 and R ^b3 are a cyclic organic group, the substituents that the cyclic organic group may have are the same as when R ^b2 and R ^b3 are a chain alkyl group.

When R ^b2 and R ^b3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene rings included in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 Do. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.

When R ^b2 and R ^b3 are an aliphatic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of the monocyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, A tetracyclododecyl group, an adamantyl group, etc. are mentioned.

When R ^b2 and R ^b3 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered single ring containing one or more N, S, O, or a heterocyclyl group in which these single rings or a single ring and a benzene ring are condensed. . When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala and gin, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran.

R ^b2 and R ^b3 may combine with each other to form a ring. The group consisting of a ring formed by R ^b2 and R ^b3 is preferably a cycloalkylidene group. When R ^b2 and R ^b3 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- or 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ^b2 and R ^b3 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with the cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, A pyrazine ring, a pyrimidine ring, etc. are mentioned.

Among the above-described R ^2b and R ^3b , preferred examples of the group include a group represented by the formula -A ^b1 -A ^b2 . In the formula, A ^b1 is a straight-chain alkylene group, and A ^b2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

1-10 are preferable and, as for carbon atom number of the linear alkylene group of A ^b1 , 1-6 are more preferable. When A ^b2 is an alkoxy group, the alkoxy group may be linear or branched, and it is preferable that it is linear. 1-10 are preferable and, as for carbon atom number of an alkoxy group, 1-6 are more preferable. When A ^b2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. When A ^b2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom and a bromine atom. The halogenated alkyl group may be linear or branched, but is preferably linear. When A ^b2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group which R ^b2 and R ^b3 have as a substituent. When A ^b2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group which R ^b2 and R ^b3 have as a substituent.

Preferred specific examples of R ^b2 and R ^b3 include an alkyl group such as an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy group -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phene alkoxyalkyl groups such as a tyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano group cyanoalkyl groups such as -n-heptyl and 8-cyano-n-octyl; 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and a phenylalkyl group such as an 8-phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl group -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pene cycloalkylalkyl groups such as a tyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl group -n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and 8 - Alkoxycarbonylalkyl groups, such as an ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5 Halogenated alkyl groups, such as a heptafluoro-n-pentyl group, are mentioned.

As R ^b2 and R ^b3 , preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, and 2-cyclo Hexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5-heptafluoro It is a rho-n-pentyl group.

R ^b4 is a monovalent organic group, but the organic group does not have a nitro group. Examples of a preferable organic group for R ^b4 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and a substituent, similarly to R ^b1 . A phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, The naphthyloxy group which may have a substituent, the naphthoyl group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthoyloxy group which may have a substituent, the naphthylalkyl group which may have a substituent, a substituent The heterocyclyl group which may have, the heterocyclylcarbonyl group which may have a substituent, the amino group substituted by 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, etc. are mentioned. Specific examples of such a group are the same as those described for R ^b1 . Moreover, as ^Rb4 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which may have the phenyl group contained in ^Rb1 .

Among the organic groups, R ^b4 is preferably an alkyl group, a cycloalkyl group, an optionally substituted phenyl or cycloalkylalkyl group, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable and a 2-methylphenyl group is more preferable. 5-10 are preferable, as for the number of carbon atoms of the cycloalkyl group contained in a cycloalkylalkyl group, 5-8 are more preferable, 5 or 6 are especially preferable. 1-8 are preferable, as for carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. 1-8 are preferable, as for carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent in the aromatic ring, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferable.

Also, as R ^b4 , a group represented by -A ^b3 -CO-OA ^b4 is preferable. A ^b3 is a divalent organic group, preferably a divalent hydrocarbon group, more preferably an alkylene group. A ^b4 is a monovalent organic group, preferably a monovalent hydrocarbon group

When A ^b3 is an alkylene group, the alkylene group may be linear or branched, and it is preferable that it is linear. When A ^b3 is an alkylene group, 1-10 are preferable, as for the number of carbon atoms of an alkylene group, 1-6 are more preferable, and 1-4 are especially preferable.

Preferred examples of A ^b4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred specific examples of A ^b4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group phenyl group , a naphthyl group, a benzyl group, a phenethyl group, an α-nathylmethyl group, and a β-nathylmethyl group.

Preferred specific examples of the group represented by -A ^b3 -CO-OA ^b4 include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxy group Carbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl -n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group, etc. are mentioned.

Although R ^b4 has been described above, R ^b4 is preferably a group represented by the following formula (b1a) or (b1b).

(In formulas (b1a) and (b1b), R ^b7 and R ^b8 are each an organic group, n3 is an integer from 0 to 4, and when R ^b7 and R ^b8 are present at adjacent positions on the benzene ring, R ^b7 and R ^b8 may be combined with each other to form a ring, n4 is an integer from 1 to 8, n5 is an integer from 1 to 5, n6 is an integer from 0 to (n5+3), and R ^b9 is an organic group am.)

Examples of the organic group for R ^b7 and R ^b8 in the formula (b1a) are the same as for R ^b1 . R ^b7 is preferably an alkyl group or a phenyl group. When R ^b7 is an alkyl group, the number of carbon atoms thereof is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, and most preferably from 1 . That is, R ^b7 is most preferably a methyl group. When R ^b7 and R ^b8 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by the formula (b1a) and in which R ^b7 and R ^b8 form a ring include a naphthalen-1-yl group and a 1,2,3,4-tetrahydronaphthalen-5-yl group. there is. In said formula (b1a), n3 is an integer of 0-4, It is preferable that it is 0 or 1, It is more preferable that it is 0.

In the formula (b1b), R ^b9 is an organic group. The organic group is the same as the organic group described for R ^b1 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1-10 are preferable, as for carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R ^b9 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are preferable, and among these, a methyl group is more preferable.

In said formula (b1b), n5 is an integer of 1-5, the integer of 1-3 is preferable, and 1 or 2 is more preferable. In said formula (b1b), n6 is 0-(n5+3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, 0 is especially preferable. In said formula (b1b), n4 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, 1 or 2 is especially preferable.

In formula (B1), R ^b5 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. When R ^b5 is an alkyl group, a phenyl group, a naphthyl group, etc. are preferable as a substituent which it may have. Moreover, as a substituent which you may have when R<^b5> is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are preferable.

In formula (B1), as R ^b5 , a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. are preferable, and among these, a methyl group or a phenyl group is more preferable.

The compound represented by the formula (B1) includes converting an oxime group (>C=N-OH) included in the compound represented by the formula (B2) to an oxime ester group represented by >C=NO-COR ^b5 manufactured by the method R ^b5 is the same as R ^b5 in formula (B1).

Conversion of the oxime ester group represented by >C=NO-COR ^b5 of the oxime group (>C=N-OH) is achieved by reacting the compound represented by the above formula (B2) with an acylating agent.

Examples of the acylating agent that provides the acyl group represented by -COR ^b5 include an acid anhydride represented by (R ^b5 CO) ₂ O and an acid halide represented by R ^b5 COHal (Hal is a halogen atom).

When n2 is 0, the compound represented by Formula (B1) can be synthesize|combined according to following Scheme 3, for example. Scheme 3 uses a fluorene derivative represented by the following formula (b1-1) as a raw material. When R ^b1 is a monovalent organic group, the fluorene derivative represented by formula (b1-1) is a fluorene derivative substituted with R ^b2 and R ^b3 for position 9 by introducing a substituent R ^b1 by a known method. can be obtained A fluorene derivative in which the position of 9 is substituted with R ^b2 and R ^b3 , for example, when R ^b2 and R ^b3 are an alkyl group, as described in Japanese Unexamined Patent Application Publication No. Hei 06-234668, in the presence of an alkali metal hydroxide, It can be obtained by reacting fluorene with an alkylating agent in a protic polar organic solvent. In addition, 9,9-alkyl substitution is performed by adding an alkylating agent such as an alkyl halide in an organic solvent solution of fluorene, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide to perform an alkylation reaction. fluorene can be obtained.

The fluorene derivative represented by the formula (b1-3) can be obtained by introducing an acyl group represented by -CO-R ^b4 to the fluorene derivative represented by the formula (b1-1) by Friedel-Crafts acylation reaction. . The acylating agent for introducing the acyl group represented by -CO-R ^b4 may be a halocarbonyl compound or an acid anhydride. As an acylating agent, the halocarbonyl compound represented by Formula (b1-2) is preferable. In formula (b1-2), Hal is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by appropriately changing the Friedel-Crafts reaction conditions or by performing protection and deprotection at a position different from the acylated position.

Then, in the obtained fluorene derivative represented by formula (b1-3), the group represented by -CO-R ^b4 is converted into a group represented by -C(=N-OH)-R ^b4 , and represented by the formula (b1-4) to obtain an oxime compound. The method for converting the group represented by -CO-R ^b4 to the group represented by -C(=N-OH)-R ^b4 is not particularly limited, but oximation with hydroxylamine is preferable. The oxime compound of formula (b1-4) and the acid anhydride ((R ^b5 CO) ₂ O) represented by the following formula (b1-5) or the acid halide (R ^b5 COHal, Hal) represented by the following formula (b1-6) silver halogen atom), the compound represented by a following formula (b1-7) can be obtained.

Further, in formulas (b1-1), (b1-2), (b1-3), (b1-4), (b1-5), (b1-6) and (b1-7), R ^b1 , R ^b2 , R ^b3 , R ^b4 and R ^b5 are the same as in formula (B1).

In Scheme 3, R ^b4 contained in each of formulas (b1-2), (b1-3) and (b1-4) may be the same or different. That is, R ^b4 in formulas (b1-2), (b1-3), and (b1-4) may receive a chemical modification in the synthesis process represented by Scheme 3. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. The chemical formula that R ^b4 may accept is not limited thereto.

<Scheme 3>

When n2 is 1, the compound represented by Formula (B1) can be synthesize|combined according to following Scheme 4, for example. Scheme 4 uses a fluorene derivative represented by the following formula (b2-1) as a raw material. The fluorene derivative represented by the formula (b2-1) may have an acyl group represented by -CO-CH ₂ -R ^b4 in the compound represented by the formula (b1-1) by the Friedel-Crafts reaction in the same manner as in Scheme 3 can be obtained by introducing The acylating agent is preferably a carboxylic acid halide represented by the formula (b1-8): Hal-CO-CH ₂ -R ^b4 . Next, in the compound represented by the formula (b2-1), the methylene group present between R ^b4 and the carbonyl group is oximelated to obtain a ketoxime compound represented by the following formula (b2-3). Although the method of oximeating a methylene group is not specifically limited, The method of making the nitrite ester (RONO, R is a C1-C6 alkyl group) represented by the following formula (b2-2) react in the presence of hydrochloric acid is preferable. Subsequently, the ketoxime compound represented by the following formula (b2-3) and the acid anhydride ((R ^b5 CO) ₂ O) represented by the following formula (b2-4) or an acid halide represented by the following formula (b2-5) By reacting (R ^b5 COHal, Hal is a halogen atom), a compound represented by the following formula (b2-6) can be obtained. In addition, in the following formulas (b2-1), (b2-3), (b2-4), (b2-5) and (b2-6), R ^b1 , R ^b2 , R ^b3 , R ^b4 and R ^b5 are Same as formula (B1).

When n2 is 1, there is a tendency to further reduce the occurrence of foreign matter in a pattern formed by using the composition containing the compound represented by formula (B1).

In Scheme 4, R ^b4 contained in each of the formulas (b1-8), (b2-1) and (b2-3) may be the same or different. That is, R ^b4 in the formulas (b1-8), (b2-1) and (b2-3) may receive a chemical modification in the synthesis process represented by Scheme 4. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. The chemical formula that R ^b4 may accept is not limited thereto.

<Scheme 4>

Preferred specific examples of the compound represented by the formula (B1) include the following PI-1 to PI-37.

The content of the (B) photoinitiator of the photosensitive composition is preferably 0.001 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, particularly preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the photosensitive composition (excluding the solvent). .

Further, (B) the content of the photoinitiator is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, with respect to the total of the mass of the (A) photopolymerizable compound and (B) the mass of the photoinitiator. It is preferable, and it is especially preferable that it is 1-20 mass %.

<(C) Colorant>

The photosensitive composition may further contain (C) a coloring agent. The photosensitive composition is preferably used for the use of color filter formation of display apparatuses, such as a liquid crystal display display, by including (C) a coloring agent, for example. Moreover, the photosensitive composition is used suitably for the black matrix formation use of the color filter of a display apparatus by including a light-shielding agent as (C) coloring agent, for example.

Although the colorant (C) contained in the present photosensitive composition is not particularly limited, for example, a compound classified as a pigment in the color index (C.I.; published by The Society of Dyers and Colorists), specifically the following color It is preferable to use the compound to which the index (C.I.) number is given.

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

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

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

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter, 'C.I. Pigment Red' is the same and only numbered) 2,3,4,5,6,7,8,9,10; 11,12,14,15,16,17,18,19,21,22,23,30,31,32,37,38,40,41,42,48:1,48:2,48:3, 48:4,49:1,49:2,50:1,52:1,53:1,57,57:1,57:2,58:2,58:4,10:1,63:1, 63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,18,179,180,185,187,188,190,192,193,227,228,245, 265, 217,220, 245, 265, 217, 218, 245, 216, 226, 226, 226

Examples of blue pigments that can be suitably used include: C. I. Pigment Blue 1 (hereinafter, 'C.I. Pigment Blue' is the same and only numbered) 2,15,15:3,15:4,15:6,16; 22, 60, 64 and 66.

Examples of pigments of other colors that can be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Black pigments, such as Pigment Black 7, are mentioned.

In addition, when (C) a colorant is used as a light-shielding agent, it is preferable to use a black pigment as a light-shielding agent. Examples of the black pigment include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, complex oxides, metal sulfides, metal sulfates, or metals. Various pigments are mentioned regardless of organic substances, such as a carbonate, and an inorganic substance. Among these, it is preferable to use carbon black which has high light-shielding property.

As carbon black, well-known carbon blacks, such as channel black, furnace black, thermal black, and lamp black, can be used, and it is preferable to use channel black excellent in light-shielding property. Moreover, you may use resin-coated carbon black.

Resin-coated carbon black has lower conductivity than carbon black without resin coating. Therefore, when the black matrix is formed using the photosensitive composition containing the resin-coated carbon black, it is possible to manufacture a stable, low-power display with little leakage of current from a display device such as a liquid crystal display.

Moreover, in order to adjust the hue of carbon black, you may add the said organic pigment suitably as an auxiliary pigment.

In order to disperse|distribute said (C) coloring agent uniformly in the photosensitive composition, a dispersing agent can be used. As such a dispersing agent, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the (C) colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

In addition, an inorganic pigment and an organic pigment may use individually or 2 or more types, respectively, respectively. When using together, it is preferable to use the organic pigment in the range of 10-80 mass parts with respect to 100 mass parts of total amounts of an inorganic pigment and an organic pigment, and it is more preferable to use it in the range of 20-40 mass parts.

The usage-amount of the (C) coloring agent in the photosensitive composition can be suitably determined according to the use of the photosensitive composition. For example, 5-70 mass parts is preferable with respect to 100 mass parts in total of solid content of the photosensitive composition, and 25-60 mass parts is more preferable. By setting it as the said range, since a black matrix and each colored layer can be formed in the desired pattern, it is preferable.

In particular, when the black matrix is formed using the photosensitive composition, it is preferable to adjust the amount of the light blocking agent of the photosensitive composition so that the OD value per 1 μm of the film of the black matrix is 4 or more. If the OD value per 1 µm of the black matrix film is 4 or more, sufficient display contrast can be obtained when a black matrix of a display device such as a liquid crystal display is used.

(C) It is preferable to add a colorant to the photosensitive composition after making a dispersion liquid disperse|distributed to the appropriate density|concentration using a dispersing agent.

<(D) Alkali-soluble resin>

The photosensitive composition may contain (D) alkali-soluble resin as resin other than resin used as a photopolymerizable compound. Alkali developability can be provided to the photosensitive composition by mix|blending (D) alkali-soluble resin with the photosensitive composition.

In the present specification, (D) alkali-soluble resin is formed by forming a resin film having a thickness of 1 μm on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and in a KOH aqueous solution having a concentration of 0.05% by mass. When immersed for 1 minute, it means that the film thickness is 0.01 µm or more dissolved.

(D) In alkali-soluble resin, the polymer of the monomer which has an ethylenically unsaturated double bond is preferable from the point which is excellent in film forming property, and the point which it is easy to adjust the characteristic of resin by selection of a monomer. Examples of the monomer having an ethylenically unsaturated double bond include (meth)acrylate; (meth)acrylic acid ester; (meth)acrylamide; crotonic acid; anhydrides of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and dicarboxylic acid; allyl compounds such as aryl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetacetate, allyl lactate and allyloxyethanol; Hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinylphenyl ether, vinyl ethers such as vinyltolyl ether, vinylchlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinylnaphthyl ether and vinylanthranyl ether; Vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetate vinyl esters such as acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate; Styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Methylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibro styrene or styrene derivatives such as parent styrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4- Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

The alkali-soluble resin (D), which is a polymer of a monomer having an ethylenically unsaturated double bond, generally contains units derived from an unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include (meth)acrylate; (meth)acrylamide; crotonic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the anhydrides of these dicarboxylic acids are mentioned. (D) The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali solubility. (D) The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5 to 25 mass%, more preferably 8 to 16 mass%, based on the weight of the resin.

In the copolymer of a monomer having an ethylenically unsaturated double bond, which is a polymer of one or more monomers selected from the monomers exemplified above, the polymer of one or more monomers selected from (meth)acrylate and (meth)acrylic acid ester is desirable. Hereinafter, the polymer of 1 or more types of monomers chosen from (meth)acrylate and (meth)acrylic acid ester is demonstrated.

The (meth)acrylic acid ester used for the production of a copolymer of one or more monomers selected from (meth)acrylate and (meth)acrylic acid ester is not particularly limited as long as it does not impair the object of the present invention, and known ( It may be appropriately selected from meth)acrylic acid esters.

Preferred examples of the (meth)acrylic acid ester include linear or methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and branched chain alkyl (meth)acrylate; Chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; (meth)acrylic acid ester having a group having an epoxy group; (meth)acrylic acid ester which has group which has alicyclic skeleton is mentioned. The details of (meth)acrylic acid ester having a group having an epoxy group and (meth)acrylic acid ester having a group having an alicyclic skeleton will be described later.

Among the copolymers of one or more monomers selected from (meth)acrylate and (meth)acrylic acid ester, the transparent insulating film formed using the photosensitive composition has an epoxy group in that it has excellent adhesion and mechanical strength to the substrate ( Resin containing a unit derived from meth)acrylic acid ester is preferable.

The (meth)acrylic acid ester having a group having an epoxy group may be a (meth)acrylic acid ester having a group having a chain aliphatic epoxy group or (meth)acrylic acid ester having a group having an alicyclic epoxy group as described later.

The (meth)acrylic acid ester which has group which has an epoxy group may contain the aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of the (meth)acrylic acid ester having an aromatic group and a group having an epoxy group include 4-glycidyloxyphenyl (meth)acrylate, 3-glycidyloxyphenyl (meth)acrylate, 2-glycidyl Oxyphenyl (meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate and 2-glycidyloxyphenylmethyl (meth) acrylate, etc. can be heard

When transparency is requested|required for the film|membrane formed using the photosensitive composition, it is preferable that the (meth)acrylate which has a group which has an epoxy group does not contain an aromatic group.

Examples of (meth)acrylic acid esters having a group having a chain aliphatic epoxy group include an oxy group (-O) in an ester group (-O-CO-) such as epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. (meth)acrylic acid ester in which a chain aliphatic epoxy group is bonded to -) is mentioned. The chain|strand-shaped aliphatic epoxy group which such (meth)acrylic acid ester has may contain one or more oxy groups (-O-) in a chain|strand. Although the number of carbon atoms of a chain|strand-shaped aliphatic epoxy group is not specifically limited, 3-20 are preferable, 3-15 are more preferable, 3-10 are especially preferable.

Specific examples of (meth)acrylic acid esters having a group having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6 Epoxyalkyl (meth)acrylates, such as 7-epoxyheptyl (meth)acrylate; 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyl Epoxyalkyloxyalkyl (meth)acrylates, such as oxy-n-hexyl (meth)acrylate and 6-glycidyloxy-n-hexyl (meth)acrylate, are mentioned.

Derived from (meth)acrylic acid ester having a group having an epoxy group of a polymer of one or more monomers selected from (meth)acrylate and (meth)acrylic acid ester containing a unit derived from (meth)acrylic acid ester having a group having an epoxy group The content of the unit is preferably 1-95 mass%, more preferably 40-80 mass%, based on the weight of the resin.

In addition, in the copolymer of one or more monomers selected from (meth)acrylate and (meth)acrylic acid ester, it is easy to form a transparent insulating film excellent in transparency using the photosensitive composition, Resin containing a unit derived from meth)acrylic acid ester is also preferable.

In the (meth)acrylic acid ester which has a group which has an alicyclic skeleton, the group which has an alicyclic skeleton may be a group which has an alicyclic hydrocarbon group, or the group which has an alicyclic epoxy group may be sufficient as it. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclo nonyl group, a tricyclodecyl group, tetracyclododecyl group, etc. are mentioned.

Among the (meth)acrylic acid esters having a group having an alicyclic skeleton, examples of the (meth)acrylic acid ester having a group having an alicyclic hydrocarbon group include compounds represented by the following formulas (d1-1) to (d1-8). can Among these, compounds represented by the following formulas (d1-3) to (d1-8) are preferable, and compounds represented by the following formulas (d1-3) or (d1-4) are more preferable.

In the above formula, R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^d3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms . As R ^d2 , a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. R ^d3 is preferably a methyl group or an ethyl group.

In the (meth)acrylic acid ester having a group having an alicyclic skeleton, specific examples of the (meth)acrylic acid ester having a group having an alicyclic epoxy group are, for example, represented by the following formulas (d2-1) to (d2-16) compounds can be mentioned. Among these, compounds represented by the following formulas (d2-1) to (d2-6) are preferable, and compounds represented by the following formulas (d2-1) to (d2-4) in order to develop the photosensitive composition at an appropriate level. This is more preferable.

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^d6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is 0 Represents an integer of ~10. R ^d5 is preferably a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^d6 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, -CH ₂ -Ph-CH ₂ -( Ph is preferably a phenylene group).

When the polymer of one or more monomers selected from (meth)acrylate and (meth)acrylic acid ester is a resin containing a unit derived from (meth)acrylic acid ester having a group having an alicyclic skeleton, in the resin, alicyclic 5-95 mass % is preferable, as for the quantity of the unit derived from (meth)acrylic acid ester which has group which has a formula frame|skeleton, 10-90 mass % is more preferable, 30-70 mass % is especially preferable.

In addition, in the polymer of one or more monomers selected from (meth)acrylate and (meth)acrylic acid ester containing a unit derived from (meth)acrylic acid ester having a group having an alicyclic skeleton, a unit derived from (meth)acrylic acid And resin containing the unit derived from the (meth)acrylic acid ester which has a group which has an alicyclic epoxy group is preferable. The film formed using the composition containing such (D) alkali-soluble resin is excellent in adhesiveness to a base material. In addition, when such a resin is used, it is possible to cause a self-reaction between the carboxyl group and the alicyclic epoxy group contained in the resin. Therefore, when a composition including such a resin is used, mechanical properties such as hardness of the formed film can be improved by causing a self-reaction between the carboxyl group and the alicyclic epoxy group by using a method for heating the film or the like.

In a resin comprising a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, the amount of (meth)acrylic acid-derived unit in the resin is 1 to 95% by mass. It is preferable, and 10-50 mass % is more preferable. In a resin comprising a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group in the resin 1-95 mass % is preferable, and, as for the quantity, 30-70 mass % is more preferable.

In the copolymer of one or more monomers selected from (meth)acrylic acid esters comprising a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, (meth)acrylic acid A resin containing a unit derived from a unit derived from , a unit derived from a (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylic acid ester having a group having an alicyclic epoxy group is preferable.

In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, in the resin , 1-95 mass % is preferable, and, as for the quantity of the unit derived from (meth)acrylic acid, 10-50 mass % is more preferable. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, in the resin , 1-95 mass % is preferable and, as for the quantity of the unit derived from (meth)acrylic acid ester which has an alicyclic hydrocarbon group, 10-70 mass % is more preferable. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, among the resins, 1-95 mass % is preferable and, as for the quantity of the unit derived from (meth)acrylic acid ester which has a group which has an alicyclic epoxy group, 30-80 mass % is more preferable.

(D) The mass average molecular weight of the alkali-soluble resin (Mw: measured in terms of polystyrene by Gel Permeation Chromatography (GPC). The same in this specification) is preferably 2,000 to 200,000, more preferably 2,000 to 18,000 . By setting it as the said range, it becomes easy to adjust the balance of the film formation performance of a photosensitive composition, and developability after exposure.

When the photosensitive composition contains (D) alkali-soluble resin, the content of the alkali-soluble resin in the photosensitive composition is preferably 15 to 95 mass %, more preferably 35 to 85 mass %, more preferably 50 to 70, based on the solid content of the photosensitive composition. % by mass is particularly preferred.

<Other ingredients>

The photosensitive composition may contain various additives as needed. Specifically, solvents, sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like are exemplified.

Examples of the solvent used in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl (poly)alkylene glycol monoalkyl ethers such as ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethoxy ethyl acetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide. These solvents may be used independently and may be used in combination of 2 or more type.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate is preferable because it can improve the dispersibility of the component (C) while exhibiting excellent solubility in the component (A) and component (B), propylene glycol monomethyl ether acetate, 3-methyl ether acetate Particular preference is given to using toxybutylacetate. A solvent can be suitably determined according to the use of the photosensitive composition, For example, about 50-900 mass parts can be used with respect to a total of 100 mass parts of solid content of the photosensitive composition.

Examples of the thermal polymerization inhibitor used in the photosensitive composition according to the present invention include hydroquinone and hydroquinone monoethyl ether. In addition, as an antifoaming agent, compounds, such as a silicone type and a fluorine type, are mentioned, As surfactant, compounds, such as anionic, cationic, and nonionic, can be illustrated, respectively.

<Method for producing photosensitive composition>

The photosensitive composition is prepared by mixing all of the above components with a stirrer. In addition, when the manufactured photosensitive composition does not contain insoluble components, such as a pigment, you may filter using a filter so that the photosensitive composition may become uniform.

<Cured material>

The photosensitive composition containing the (B) photoinitiator and optionally (C) a coloring agent containing the (A) photopolymerizable compound demonstrated above and the compound represented by Formula (1) is hardened|cured by exposure. The cured product of such a photosensitive composition is used for various purposes.

For example, an insulating film is mentioned as a use of hardened|cured material. When the photosensitive composition does not contain the (C) colorant, a transparent insulating film is formed. When the photosensitive composition contains (C) a colorant, a colored insulating film is formed. In particular, when (C) the colorant is a black light-shielding agent, a light-shielding black insulating film is formed.

Preferred examples of the light-shielding black insulating film include black barrier ribs in a black matrix and black column spacers included in various image display device panels.

In addition, when the photosensitive composition contains a chromatic (C) colorant such as RGB, a colored cured film can be formed in a region partitioned by a black matrix to manufacture a color filter.

For example, the color filter containing the said black matrix or a chromatic cured film as hardened|cured material is used suitably in various display apparatuses.

<Method of forming a cured film>

The method of forming the cured film used as an insulating film or a color filter using the photosensitive composition demonstrated above is demonstrated below. The film formed using the photosensitive composition may be patterned as needed.

In order to form a cured film using the photosensitive composition of the present invention, first, a contact transfer coating device such as a roll coater, reverse coater, or bar coater, or a non-contact coating device such as a spinner (rotary coating device) or a curtain flow coater is used to form a cured film on a substrate. A photosensitive composition is applied to the

Then, the coated composition is dried to form a coating film. The drying method is not particularly limited, for example, (1) a method of drying for 60 to 120 seconds at a temperature of 80 to 120 ° C., preferably 90 to 100 ° C. on a hot plate, (2) several hours at room temperature A method of leaving it to stand for several days, (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours, etc. are mentioned.

Next, the coating film is exposed by irradiating active energy rays such as ultraviolet rays or excimer lasers. The exposure may be performed position-selectively by, for example, a method of exposing through a negative-type mask or the like. Although the amount of energy to be irradiated varies with the composition of the photosensitive composition, for example, about 40 to 200 mJ/cm ² is preferable. As described above, since the photosensitive composition according to the present invention has excellent sensitivity, productivity of a display device such as a liquid crystal display panel can be improved by using the photosensitive composition of the present invention.

When the coating film is exposed regioselectively, the film after exposure is patterned into a desired shape by developing with a developer. The developing method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. The developer is appropriately selected according to the composition of the photosensitive composition. When the photosensitive composition contains an alkali-soluble component such as an alkali-soluble resin, the developer includes an organic developer such as monoethanolamine, diethanolamine, and triethanolamine and an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt, etc. can be used

Next, it is preferable to post-baking at about 200-250 degreeC with respect to the pattern after image development.

The pattern thus formed can be suitably used for, for example, an insulating film used in a display device such as a liquid crystal display, or a pixel constituting a color filter, and a black matrix. Such an insulating film, a color filter, and a display device using the color filter are also included in the present invention.

<Example>

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

Hereinafter, in Reference Examples 1-5, a schematic synthesis method of the compound represented by Formula (1) is shown.

<Reference Example 1>

(Synthesis of compound 2)

Compound 2 was synthesized according to the following synthesis method. In addition, the meaning of the abbreviation in the following synthesis scheme is as follows.

^t Bu: tert-butyl group

Pr: n-propyl group

Ac: acetyl group

After placing 500 parts by mass of tetrahydrofuran (THF) and 68.7 parts by mass of potassium tert-butoxide into the reaction vessel, 50.0 parts by mass of 2-bromofluorene was added.

Then, 56.1 mass parts of 1-bromopropane was dripped at the reaction container, and it stirred at 40 degreeC for 3 hours. After the reaction solution was cooled to room temperature, ethyl acetate and water were added, and the mixture was separated and washed with water. The oil layer was concentrated to obtain 67.2 parts by mass of 2-bromo-9,9-dipropylfluorene (yield 100%, HPLC purity 92%).

50.0 parts by mass of the obtained 2-bromo-9,9-dipropylfluorene, 500 parts by mass of methylene chloride, and 30.4 parts by mass of anhydrous aluminum chloride were placed in a reaction vessel and cooled to 0°C.

After adding 16.9 parts by mass of propionyl chloride dropwise, the mixture was stirred at 10°C for 3 hours. The reaction solution was poured into ice water for separation, and the oil layer was washed with 5% sodium bicarbonate water and water. The oil layer was concentrated and purified by silica gel column chromatography to obtain 46.8 parts by mass of compound 2a (yield 80%, HPLC purity 95%).

150 parts by mass of THF was added to 30.0 parts by mass of compound 2a, followed by addition of 15.6 parts by mass of 4-nitrophenylboronic acid and 21.5 parts by mass of potassium carbonate. Then, 0.6 parts by mass of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloridedichloromethane adduct and 3 parts by mass of water were added, followed by stirring at reflux temperature for 5 hours.

After cooling the reaction solution to room temperature, the insoluble content was filtered, and the filtrate was concentrated and dried, and then separated and produced by silica gel chromatography to obtain 24.7 parts by mass of compound 2b (yield 75%, HPLC purity 95%).

75.0 parts by mass of methanol, 7.4 parts by mass of hydroxylamine hydrochloride and 6.9 parts by mass of sodium acetate were added to 15.0 parts by mass of Compound 2b, followed by stirring at 60° C. for 5 hours. The reaction solution was cooled to room temperature, 25 parts by mass of water was added, filtered, and washed with methanol, followed by washing with water. This was dried by blow drying to obtain 15.5 parts by mass of compound 2c (yield 100%, HPLC purity 90%).

50.0 parts by mass of ethyl acetate and 9.3 parts by mass of acetic anhydride were added to 10.0 parts by mass of Compound 2c, followed by stirring at 40° C. for 5 hours. After the reaction solution was cooled to room temperature, 10.0 parts by mass of methanol was added, stirred for 30 minutes, and then the precipitated solid was filtered. The obtained solid was separated and purified by silica gel column chromatography to obtain 5.5 parts by mass of compound 2 (yield 50%, HPLC purity 98%). The structure of the obtained compound 2 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ¹ H-NMR spectrum is as follows.

δ (ppm): 8.30-8.35 (m: 2H), 7.71-7.85 (m: 6H), 7.58-7.65 (m: 2H), 2.93 (q: 2H), 2.30 (s: 3H), 1.98-2.10 ( m: 4H), 1.24 (t: 3H), 0.64-0.76 (m: 10H)

<Reference Example 2>

(Synthesis of compound 37)

The following compound 37 was obtained in the same manner as in Reference Example 1, except that propionyl chloride was changed to butyryl chloride, and 4-nitrophenylboronic acid was changed to 4-cyanophenylboronic acid.

Compound 37 was synthesized according to the following synthesis method. In addition, the meaning of the abbreviation of the following synthesis scheme is the same as that of Reference Example 1.

Compound 37a was obtained in the same manner as in Reference Example 1, except that propionyl chloride was changed to butyryl chloride.

80 parts by mass of THF, 80 parts by mass of methanol, 6.2 parts by mass of sodium acetate, and 5.2 parts by mass of hydroxylamine hydrochloride were added to 20 parts by mass of compound 37a, followed by stirring at 60° C. for 5 hours. The reaction solution was cooled to room temperature, filtered by adding 60 parts by mass of water, and then washed with methanol. It dried by blow drying to obtain 19.8 parts by mass of compound 37b (yield 95%, HPLC purity 90%).

75 parts by mass of THF was added to 15.0 parts by mass of compound 37b, followed by 6.4 parts by mass of 4-cyanophenylboronic acid and 7.6 parts by mass of potassium carbonate. Then, 0.3 parts by mass of (1,1'-bis(diphenylphosphino)ferrocene)palladium(II)dichloridedichloromethane adduct and 3 parts by mass of water were added, followed by stirring at reflux temperature for 5 hours.

After cooling the reaction solution to room temperature, the insoluble content was filtered, the filtrate was concentrated and dried, and then separated and produced by silica gel chromatography to obtain 8.1 parts by mass of compound 37c (yield 52%, HPLC purity 95%).

25.0 parts by mass of ethyl acetate and 2.4 parts by mass of acetic anhydride were added to 5.0 parts by mass of compound 37c, followed by stirring at 40°C for 5 hours. After cooling the reaction solution to room temperature, 10.0 parts by mass of methanol was added, followed by stirring for 30 minutes, and then the precipitated solid was filtered. The obtained solid was separated and purified by silica gel column chromatography to obtain 2.7 parts by mass of compound 37 (yield 50%, HPLC purity 98%).

The structure of the obtained compound 37 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ¹ H-NMR spectrum is as follows.

δ (ppm): 7.67-7.82 (m: 8H), 7.55-7.60 (m: 2H), 2.90 (t: 2H), 2.30 (s: 3H) 1.93-2.07 (m: 4H), 1.65 (sep) : 2H), 1.12 (t: 3H), 0.65-0.70 (m: 10H)

<Reference example 3>

(Synthesis of compound 20)

The following compound 20 was obtained in the same manner as in Reference Example 1, except that propionyl chloride was changed to butyryl chloride, and 4-nitrophenylboronic acid was changed to 3-nitrophenylboronic acid.

The structure of the obtained compound 20 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ¹ H-NMR spectrum is as follows.

δ (ppm): 8.52 (t: 1H), 8.19-8.25 (m: 1H), 7.96-8.02 (m: 1H), 7.58-7.86 (m: 7H), 2.91 (q: 2H), 2.29 (s: 3H), 1.96-2.12 (m: 4H), 1.58-1.70 (m: 2H), 1.02 (t: 3H), 0.58-0.75 (m: 10H)

<Reference Example 4>

(Synthesis of compound 28)

Compound 28 was synthesized according to the following synthesis method. In addition, the meaning of the abbreviation of the following synthesis scheme is the same as that of Reference Example 1.

Compound 28b was obtained in the same manner as in Reference Example 1, except that propionyl chloride was changed to butyryl chloride and 4-nitrophenylboronic acid was changed to 3-nitrophenylboronic acid.

150 parts by mass of THF and 12.0 parts by mass of 35% hydrochloric acid were added to 20 parts by mass of compound 28b. 8.1 parts by mass of isopentyl nitrite was slowly added at room temperature, and stirring was continued for 7 hours. The resulting reaction solution was concentrated to dryness, and separated and purified by silica gel column chromatography to obtain 11.9 parts by mass of compound 28c (yield 55%, HPLC purity 95%).

100 parts by mass of ethyl acetate and 2.6 parts by mass of acetic anhydride were added to 10.0 parts by mass of the obtained compound 28c, followed by stirring at 40°C for 5 hours. The reaction solution was cooled to room temperature, concentrated to dryness, and separated and purified by silica gel column chromatography to obtain 8.2 parts by mass of compound 28 (yield 75%, HPLC purity 97%).

The structure of the obtained compound 28 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ¹ H-NMR spectrum is as follows.

δ (ppm): 8.53 (t: 1H), 8.20-8.26 (m: 1H), 8.07-8.16 (m: 2H), 7.96-8.02 (m: 1H), 7.83 (q: 2H), 7.58-7.68 ( m: 3H), 2.85 (q: 2H), 2.30 (s: 3H), 1.96-2.15 (m: 4H), 1.22 (t: 3H), 0.58-0.80 (m: 10H)

<Reference example 5>

(Synthesis of compound 137)

Change 2-bromo-9,9-dipropylfluorene to N-ethyl-3-bromocarbazole, 4-nitrophenylboronic acid to 3-nitrophenylboronic acid, and propionyl chloride to 4-( The following compound 137 was obtained in the same manner as in Reference Example 1 except for changing to (1-methoxypropan-2-yl)oxy)-2-methylbenzoic acid chloride.

The structure of the obtained compound 137 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ¹ H-NMR spectrum is as follows.

δ (ppm): 8.54 (brs: 1H), 8.30 (brs: 2H), 8.00-8.20 (m: 2H), 7.86 (dd: 1H), 7.75 (dd: 1H), 7.63 (t: 1H), 7.42 (d: 1H), 7.40 (d: 1H), 7.08 (d: 1H), 6.85-6.95 (m: 2H), 4.60-4.70 (m: 1H), 4.42 (q: 2H), 3.50-3.70 (m : 2H), 3.46 (s: 3H), 2.18 (s: 3H), 2.12 (s: 3H), 1.50 (t: 3H), 1.60 (d: 3H)

<Examples 1 to 12 and Comparative Examples 1 and 2>

In Examples and Comparative Examples, Resin A and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) were used as photopolymerizable compounds. Resin A synthesized according to the following formulation was used.

First, in a 500 ml 4-neck flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid was put in, and heated to 90-100° C. while blowing air at a rate of 25 ml/min, and dissolved. Then, the solution was gradually heated in a cloudy state and heated to 120° C. to completely dissolve it. At this time, the solution was gradually clear and viscous, but stirring was continued as it was. In the meantime, the acid value was measured and heating and stirring were continued at 1.0 mgKOH/g or less. It took 12 hours for the acid value to reach the target value. Then, it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate which is colorless and transparent and is represented by the following structural formula (a4) solid.

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved, followed by mixing 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide. The temperature was gradually raised and the reaction was carried out at 110 to 115°C for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain Resin A. The disappearance of the acid anhydride group was confirmed by the IR spectrum. Resin A corresponds to the compound represented by the above formula (a1).

In Examples, the following compounds 1, 4 to 10, and 13 to 17 were used as photopolymerization initiators. The following compounds 1, 4 to 10, and 13 to 17 were synthesized in the same manner as in Reference Examples 1 to 5.

In Comparative Example, the following Comparative Compound 1 and Comparative Compound 2 were used as photopolymerization initiators.

Resin A25 parts by mass, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 10 parts by mass, 5 parts by mass of a photoinitiator of the kind shown in Table 1, and 60 parts by mass of a carbon dispersion (CF black, made by Okuni Color Co., Ltd.), 3-methyl After diluting so that the concentration of the solid content is 15% by mass in a mixed solvent consisting of toxybutyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate, the components are uniformly mixed in Examples 1 to 12, Comparative Examples 1 and Comparative Examples The composition of Example 2 was obtained. The weight ratio of each solvent of the mixed solvent was 60/20/20 for 3-methoxybutyl acetate/cyclohexanone/propylene glycol monomethyl ether acetate.

(sensitivity evaluation)

Evaluation of sensitivity was performed as follows. First, the compositions of Examples and Comparative Examples were applied using a spin coater on a glass substrate (10 cm x 10 cm), pre-baked at 90 ° C. for 120 seconds, and a coating film having a thickness of 1.0 μm was formed on the surface of the glass substrate. Thereafter, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 µm, and the coating film was irradiated with ultraviolet rays through a negative mask having a pattern of 10 µm in width. Exposure was made into 3 steps of 30, 60, and 1200 mJ/cm< ² >. Each exposure pattern was obtained by developing the exposed coating film at 26 DEG C with a 0.04 mass % KOH aqueous solution for 30 seconds and then post-baking at 230 DEG C for 30 minutes. The line width of the pattern at each exposure dose was measured with an optical microscope, and the exposure dose capable of obtaining a line width of 10 μm was calculated by calculating an approximate value using the least squares method from the line width of each exposure and exposure. Table 1 shows the data of the calculated sensitivity (mJ/cm ² ) at the development time of 30 seconds. The sensitivity data shown in Table 1 indicates the amount of exposure required to form a pattern (10 μm) with a predetermined line width, and the smaller this numerical value, the higher the sensitivity of the photosensitive composition.

(Evaluation of OD values)

After coating the compositions of Examples and Comparative Examples on a 6-inch glass substrate (a Dow Corning product, 1737 glass), the composition was dried at 90° C. for 60 seconds to form a coating film. Then, the coating film was irradiated with ghi rays at an exposure amount of 60 mJ/cm ² . Thereafter, post-baking was performed on a hot plate at 230° C. for 20 minutes to form a light-shielding film. The thickness of the formed light-shielding film was 0.8 μm, 1.0 μm, and 1.2 μm. For this light-shielding film, the OD value of each film thickness was measured using D200-II (manufactured by Macbeth), and the OD value per 1 μm was calculated from the trend curve. The calculated OD values of the light-shielding films formed using the compositions of Examples and Comparative Examples were all 4.8/μm.

(line pattern evaluation)

The photosensitive compositions of Examples and Comparative Examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater, and pre-baked at 70° C. for 120 seconds to form a coating film. Next, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 µm, and the coating film was irradiated with ultraviolet rays through a negative mask having a line pattern of 10 µm in width. The exposure was carried out in 4 steps of 20, 40, 60, and 120 mJ/cm ² . The exposed coating film was developed for 50 seconds at 26°C with a 0.04 mass% KOH aqueous solution, and then post-baked at 230°C for 30 minutes to form a line pattern having a thickness of 3.5 µm.

(Pattern Peel Evaluation)

The formed line pattern was observed with an optical microscope to confirm the presence or absence of pattern peeling. Table 1 shows the confirmation result of the presence or absence of pattern peeling.

(taper angle)

The taper angle was evaluated for a line pattern formed at an exposure amount of 40 mJ/cm ² . According to the measured taper angle, the cross-sectional shape of the line pattern was judged according to the following criteria.

(double-circle): A taper angle is 70 degrees or more and 85 degrees or less.

o: The taper angle is greater than 85° and less than or equal to 90°.

(triangle|delta): A taper angle is more than 90 degrees and 100 degrees or less.

x: A taper angle is 100 degrees or more.

As for the taper angle, it was measured as the bonding angle between the pattern and the substrate with a scanning electron microscope. This taper angle corresponds to the angle θ in Figs. 1 (a) and (b). The measured taper angle is shown in Table 1. The closer the taper angle is to 90°, the closer the cross-sectional shape of the pattern is to the desired rectangular shape. When the taper angle is an angle significantly smaller than 90° as an acute angle, no undercut occurs in the pattern, but the cross-sectional shape of the pattern is not a desired rectangular shape. When the taper angle is an obtuse angle, an undercut is occurring in the pattern.

light curing
initiator
Kinds Sensitivity
(mJ/cm2) pattern peeling taper
each
(°) cross-sectional shape
Judgment Exposure dose (mJ/cm2) 20 40 60 120 Example 1 compound 1 39 radish radish radish radish 90 ○ Example 2 compound 4 30 radish radish radish radish 85 ○ Example 3 compound 5 30 radish radish radish radish 85 ○ Example 4 compound 6 38 radish radish radish radish 89 ○ Example 5 compound 7 36 radish radish radish radish 87 ○ Example 6 compound 8 36 radish radish radish radish 87 ○ Example 7 compound 9 39 radish radish radish radish 90 ○ Example 8 compound 10 28 radish radish radish radish 80 ◎ Example 9 compound 13 21 radish radish radish radish 75 ◎ Example 10 compound 14 22 radish radish radish radish 77 ◎ Example 11 compound 15 29 radish radish radish radish 79 ◎ Example 12 compound 16 26 radish radish radish radish 79 ◎ Example 13 compound 17 25 radish radish radish radish 76 ◎ Comparative Example 1 comparison
compound 1 83 you you you radish 112 × Comparative Example 2 comparison
compound 2 61 you you radish radish 98 △

From Table 1, it can be seen that the composition of Examples including a photopolymerizable compound and a compound having a structure represented by Formula (1) as a photoinitiator has excellent sensitivity.

From Examples 8-13, it turns out that it is easy to obtain especially the composition excellent in sensitivity when the compound of which n is 1 in Formula (1) is used.

Moreover, Table 1 shows that it is hard to peel off from a board|substrate by using the photosensitive composition of an Example, and can form the line pattern whose cross-sectional shape is a desired rectangular shape.

On the other hand, it can be seen that the composition of Comparative Example including the photopolymerization initiator having a structure not included in Formula (1) has poor sensitivity. In addition, when a line pattern is formed using the composition of the comparative example, pattern peeling may occur depending on the exposure amount, and the taper angle may be an obtuse angle, and undercut may occur in the line pattern.

1 Cross section in the width direction in a pattern without undercut
2 Cross section in the width direction in a pattern with an undercut

Claims (13)

The photosensitive composition containing the compound represented by following formula (1).

(In Formula (1), R ¹ represents an electron withdrawing group, and R ⁶ represents an arylene group, a heteroarylene group, or a chain aliphatic containing at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond. a hydrocarbon group, wherein R ⁶ may have one or more substituents selected from an electron withdrawing group and a monovalent organic group, R ⁴ represents a monovalent organic group or a hydrogen atom, R ⁵ represents a monovalent organic group or a hydrogen atom , n represents 0 or 1, and T is of the formula (T _C ) or (T _N ):

represents a group represented by
In the formulas ( _TC ) and (T _N ), R ² and R ³ are each independently and represent an optionally substituted alkyl group or hydrogen atom, * represents a bond, but T is represented by the formula (T _N ) In the case where the electron withdrawing group R ¹ is a nitro group, a cyano group or a fluoroalkyl group having 1 to 6 carbon atoms, in the formula ( _TC ), R ² and R ³ may be combined to form a ring. ) The method according to claim 1,
The photosensitive composition wherein the compound represented by the formula (1) is a compound represented by the following formula (1C).

(In Formula (1C), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are the same as above.) The method according to claim 1,
The photosensitive composition wherein the compound represented by the formula (1) is a compound represented by the following formula (1N).

(In Formula (1N), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and n are the same as above.) 4. The method according to any one of claims 1 to 3,
The photosensitive composition wherein the group represented by R ¹ -R ⁶ - is an aryl group substituted with the electron withdrawing group. 5. The method according to claim 4,
The photosensitive composition wherein the aryl group substituted with the electron withdrawing group is an aryl group substituted with the electron withdrawing group at the p-position or the o-position. 4. The method according to any one of claims 1 to 3,
(A) A photosensitive composition comprising a photopolymerizable compound. 4. The method according to any one of claims 1 to 3,
(C) A photosensitive composition comprising a colorant. A cured product of the photosensitive composition according to claim 6, wherein the photosensitive composition may contain (C) a coloring agent. An insulating film made of the cured product according to claim 8 . The color filter containing the hardened|cured material of Claim 8, The said photosensitive composition may contain the (C) coloring agent. A display device comprising the color filter according to claim 10 . Forming a coating film by applying the photosensitive composition according to claim 6 on a substrate,
As a method of forming a cured film comprising exposing the coating film,
The said photosensitive composition (C) The formation method of the cured film which may contain the coloring agent. 13. The method of claim 12,
The method of forming a cured film, wherein the exposure is performed regioselectively, and further comprising developing the exposed coating film.

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