KR20170101153A - Compositions Containing Carboxylic esters - Google Patents

Abstract

A composition containing a carboxylic acid ester containing a skeleton having excellent transparency and heat resistance derived from an alicyclic tetracarboxylic dianhydride having a specific structure, a method of producing a carboxylic acid ester containing a skeleton having excellent transparency and heat resistance, a method of producing a carboxylic acid ester having transparency and heat resistance And an acid dianhydride ring-opening esterified product of a tetracarboxylic acid dianhydride containing this excellent skeleton.
(A) at least one hydroxyl group-containing compound selected from the group consisting of a phenol compound and an alcohol, and (B) a norbornane-2-spiro-a-cycloalkanone-a'-spiro- -5,5 ", 6,6 " -tetracarboxylic acid dianhydrides in the presence of a carboxylic acid ester compound.

Description

Compositions Containing Carboxylic esters < RTI ID = 0.0 >

The present invention relates to a composition containing a carboxylic acid ester containing a specific structure, a method for producing a carboxylic acid ester containing a specific structure, and an acid anhydride ring-opening esterification product of a tetracarboxylic acid dianhydride having a specific structure.

Compositions containing carboxylic acid esters are widely used in a variety of applications. As such a composition, for example, a photosensitive resin composition containing a compound having a central skeleton composed of an aromatic ring called a carboxyl resin as a carboxylic acid ester is known (see, for example, Patent Document 1)

Japanese Patent Laid-Open Publication No. 2009-204805

However, conventionally known ester compounds such as the cardo resin disclosed in Patent Document 1 have insufficient transparency of the film formed when blended with a photosensitive resin composition or the like, or there is room for improvement due to heat resistance.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a composition containing a carboxylate ester containing a skeleton derived from alicyclic tetracarboxylic dianhydride having a specific structure and having excellent transparency and heat resistance and a skeleton excellent in transparency and heat resistance And an acidic dianhydride ring-opening esterified product of a tetracarboxylic acid dianhydride containing a skeleton excellent in transparency and heat resistance.

(A) at least one hydroxyl group-providing compound selected from the group consisting of a phenol compound and an alcohol and (B) a norbornane-2-spiro- [alpha] -cycloalkanone- By using a carboxylic acid ester compound which can be prepared by reacting norbornane-5,5 ' ', 6,6 " -tetracarboxylic acid dianhydrides in the presence of a carboxylic acid ester compound. It came to the following. Specifically, the present invention provides the following.

A first aspect of the present invention is a composition containing a carboxylic acid ester having a structure represented by the following formula (A1).

However,

(A1)

(Formula (A1) of, R ^c1 and R ^c2 are each independently a hydrogen atom or a hydroxy group, X is a tetravalent organic group represented by the formula ^{(A2), Y 1 ~ Y} 3 is a carbon atom number of 1 to 20 Wherein j1 is an integer of 0 to 7, k1 is an integer of 0 to 7, j1 + 1k is an integer of 0 to 7, and Gi is an integer of 0 to 7, and Z is an organic group of j1 + A group represented by the following formula (A3) or (A4), and p ₁ to p ₃ are integers from 0 to 4.)

[Figure 2]

(In the formula (A2), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 * Represents a binding position.)

[Figure 3]

(A3)

[Figure 4]

(Formula (A3) and (A4) ^{of, R c1, R c2, X} , Y 1 ~ Y 3, Z, and p ₁ ~ p ₃ are as defined above and, G _{i +1} are the same carboxylic acid ester structure, and G _i a [However, in G _{i +1,} j _i, k _i and G _{i +1} of the G _i denotes a j _{i +1,} k _{i +1,} and G _{i +2,} j _{i +1,} k _{i +1} and the G _{i +2} is be the same as each other independently, and G _i j _i, k _i and G _{i +} each independently represents a j _i, k _i and G _{i +1} and ₁ corresponding in, and this applies in the same manner after the G _{i + 2.].)}

A second embodiment of the present invention is a composition containing a carboxylic acid ester having a structure represented by the following formula (A1-a).

[Figure 5]

... (A1-a)

(In the formula (A1-a), R ^c1 and R ^c2 are each independently a hydrogen atom or a hydroxy group, X is a tetravalent organic group represented by the following formula (A2), Y ¹ to Y ³ are each a hydrogen atom, Wherein j is an integer of 1 to 7, m1 is an integer of 1 to 7, k1 is an integer of 1 to 6, k is an integer of 1 to 6, is an integer of 0 ~ 7, j1 is at least m1, j1 + 1k is an integer of 0 ~ 7, Gi is a group represented by the formula (A3-a) or (A4), p of ₁ ~ p ₃ is 0-4 It is an integer.)

[6]

(In the formula (A2), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 * Represents a binding position)

[Figure 7]

... (A3-a)

[Figure 8]

(Formula (A3-a) and (A4) ^{of, R c1, R c2, X} , Y 1 ~ Y 3, Q, Z, and p ₁ ~ p ₃ are as defined above and, G _{i +1} are G _i and the same carboxylic acid is an ester structure [However, in G _{i +1,} j _i, m _i, k _i and G _{i +1} of the G _i is a j _{i +1,} m _{i + 1,} k _{i +1,} and is represented by G _{i +2,} j _{i +1,} m _{i + 1,} k _{i +1} and the G _{i +2} is j _i, m _i, each independently and k _i and G _{i + 1} j _i, m _i, k _i and G _{i + 1} corresponding in independently and G _i to each other (This applies equally to G _{i + 2} and so on.

In a third aspect of the present invention,

(A) at least one hydroxyl group-providing compound selected from the group consisting of a phenol compound and an alcohol,

(B) a norbornane-2-spiro-? -Cycloalkanone-? '- spiro-2 "-norbornane-5,5' ', 6,6" A carboxylic acid anhydride, and a carboxylic acid anhydride to react with each other to produce a carboxylic acid ester.

[Figure 9]

(In the formula (b1), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 Lt; / RTI >

A fourth embodiment of the present invention is a norbornane-2-spiro- [alpha] -cycloalkanone- [alpha] ' -spiro-2 " -norbornane-5,5 ", 6,6 '' - tetracarboxylic acid dianhydrides.

[10]

(In the formula (b1), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 Lt; / RTI >

According to the present invention, it is possible to provide a positive photosensitive resin composition comprising a polyimide resin which can form a pattern well by photolithography and which gives a pattern having excellent heat resistance. Further, according to the present invention, a method of forming a polyimide resin pattern using the above-described positive photosensitive resin composition can be provided. Further, according to the present invention, it is possible to provide a patterned polyimide resin film formed by the above-described method of forming a polyimide resin pattern.

&Quot; First composition "

The first composition is a composition containing a carboxylic acid ester having a structure represented by the following formula (A1). The carboxylic acid ester having a structure represented by the following formula (A1) includes a skeleton excellent in transparency and heat resistance represented by the formula (A2). Therefore, the first composition is also excellent in transparency and heat resistance.

[Figure 11]

(A1)

(Formula (A1) of, R ^c1 and R ^c2 are each independently a hydrogen atom or a hydroxy group, X is a tetravalent organic group represented by the formula ^{(A2), Y 1 ~ Y} 3 is a carbon atom number of 1 to 20 Wherein j1 is an integer of 0 to 7, k1 is an integer of 0 to 7, j1 + 1k is an integer of 0 to 7, and Gi is an integer of 0 to 7, and Z is an organic group of j1 + A group represented by the following formula (A3) or (A4), and p ₁ to p ₃ are integers from 0 to 4.)

[Figure 12]

(In the formula (A2), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 * Represents a binding position.)

[Figure 13]

(A3)

[14]

(Formula (A3) and (A4) ^{of, R c1, R c2, X} , Y 1 ~ Y 3, Z, and p ₁ ~ p ₃ are as defined above and, G _{i +1} are the same carboxylic acid ester structure, and G _i a [However, in G _{i +1,} j _i, k _i and G _{i +1} of the G _i denotes a j _{i +1,} k _{i +1,} and G _{i +2,} j _{i +1,} k _{i +1} and the G _{i +2} is be the same as each other independently, and G _i j _i, k _i and G _{i +} each independently represents a j _i, k _i and G _{i +1} and ₁ corresponding in, and this applies in the same manner after the G _{i + 2.].)}

The carboxylic acid ester represented by the formula (A1) contained in the first composition has excellent heat resistance because it contains the skeleton of the formula (A2) which is excellent in thermal stability. Therefore, when the carboxylic acid ester is incorporated in the composition, the heat resistance of the composition or a coating film or a cured product formed by using the composition is increased.

When R ^c1 and / or R ^c2 in the formula (A1) is a hydroxy group, a carboxy group is bonded to the group X. When a carboxylic acid ester represented by the formula (A1) having a carboxyl group is incorporated into the composition, the composition is imparted with alkali solubility.

Any one of R ^c1 and / or R ^c2 in the formula (A1) is preferably a hydroxy group, and it is preferable that both R ^c1 and / or R ^c2 are hydroxyl groups.

The production method of the carboxylic acid ester having the structure represented by the formula (A1) is not particularly limited.

Typically, (A) at least one hydroxyl group-providing compound selected from the group consisting of a phenol compound and an alcohol,

(B) a norbornane-2-spiro-? -Cycloalkanone-? '- spiro-2 "-norbornane-5,5' ', 6,6" Reacting carboxylic acid dianhydrides to give the esterified product.

, A carboxylic acid ester having a structure represented by the formula (A1) is produced.

[Figure 15]

(In the formula (b1), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 Lt; / RTI >

Hereinafter, the hydroxyl group-providing compound to be used in the above reaction is also referred to as " component (A) ", and the tetracarboxylic acid dianhydride having a predetermined structure in the above reaction is also referred to as " component (B) ".

≪ (A) Hydroxyl group providing compound >

(A) the hydroxyl group-providing compound is at least one compound selected from the group consisting of a phenol compound and an alcohol.

(A) The hydroxyl group-providing compound may be a monofunctional phenol compound or alcohol having one hydroxyl group, or a polyfunctional phenol compound having two or more hydroxyl groups and an alcohol.

The multifunctional hydroxyl group-providing compound may be a compound having a combination of a phenolic hydroxyl group and an alcoholic hydroxyl group.

A compound represented by the following formula (A5) is usually used as the (A) hydroxyl group-providing compound.

[16]

(Formula (A5) of ^{the, Z, Y 1 ~ Y 3} , p 1 ~ p 3, j1, and k1 is the same as equation (A1).)

For example, the expression in (A1), if j1 and k1 are both zero, (B) a compound represented by the formula (A5) of the reaction component is Z - [- OY ¹ -] of the monofunctional represented by _p1 -OH Phenol or alcohol.

The expression in (A1), if ji + k1 is 1 or more integer, because the same normal Y ² and Y ^3, (B) component and the following general formula for the reaction the compound represented by the formula (A5) of formula (A1-1) .

^{(H - [- OY 2 -} ] p -O-) (j1 + k1) -Z - [- OY 1 -] p1 -OH

(A1-1)

(B) and a hydroxyl group-providing compound represented by the formula (A1-1) are reacted with each other in a hydroxyl group-containing compound represented by the formula (A1-1)

(K) of the groups represented by the formula (H - [- OY ² -] _p -O-) - are reacted with the component (B) or the component (B) Gi - [- OY ³ -] _p -O-) - is formed.

In the hydroxy group-providing compound represented by the formula (A1-1), j1 + k1 is preferably an integer of 0 to 3.

As described above, an ester having a structure represented by the following formula (A1a) is formed by reacting the hydroxyl group-providing compound represented by the formula (A1-1) with the component (B) having a predetermined structure.

[Figure 17]

(A1a)

The reaction of the hydroxyl group-providing compound represented by the formula (A1-1) with the component (B) having a predetermined structure is preferably carried out in the presence of a catalyst.

Then, if necessary, the carboxyl group can be converted to an aldehyde group by reducing part or all of the carboxyl groups contained in the structure represented by the formula (A1a) according to the conventional method. The carboxyl group contained in the group G _i is also reduced to an aldehyde group, if necessary.

Through such a process, a carboxylic acid ester represented by the following formula (A1) is produced.

[Figure 18]

(A1)

[Phenol compound]

The phenol compound is not particularly limited as long as it is a compound having a phenolic hydroxyl group.

Suitable examples of phenolic compounds include, for example, phenol; cresols such as o-cresol, m-cresol and p-cresol; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Sileenol; ethylphenol, m-ethylphenol, p-ethylphenol and the like, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m- Phenol and p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; Alkylpolyphenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (all of the above alkyl groups have 1 to 4 carbon atoms); naphthols such as? -naphthol,? -naphthol, 2,6-naphthalene diol and 1,4-naphthalene diol; Hydroxydiphenyl and the like.

Also, the polyhydric phenols described below which give a group suitable as a group Z in the formula (A1) are also suitably used as a phenol compound.

[Alcohol]

The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group. The alcohol may be an aliphatic alcohol or an alcohol containing an aromatic group such as benzyl alcohol, phenoxyethanol, and xylylene glycol. When the alcohol contains an aromatic group, the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

Of the hydroxyl group-providing compounds (A), suitable examples of the alcohol include alcohols having (A1-2) (meth) acryloyloxy groups. By reacting the alcohol with the component (B), the resulting carboxylic acid ester can be polymerized. Such carboxylic acid esters are suitable as a component of the photosensitive composition.

(Alcohol having (A1-2) (meth) acryloyloxy group)

The alcohol having (A1-2) (meth) acryloyloxy group is not particularly limited as long as it is a compound having an alcoholic hydroxyl group and a (meth) acryloyloxy group.

Examples of the alcohol having (A1-2) (meth) acryloyloxy group include mono (meth) acrylate of aliphatic diol.

When the mono (meth) acrylate of an aliphatic diol is reacted with a carboxyl group in a resin having a carboxyl group as an alkali-soluble group in accordance with a conventional method, for example, an unsaturated double bond is introduced into the alkali-soluble resin to impart polymerizability .

Specific examples of the mono (meth) acrylate of the aliphatic diol include ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, 1,3-propanediol mono (meth) acrylate, 1,4-butanediol mono (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono , And dipropylene glycol mono (meth) acrylate.

As the alcohol having (A1-2) (meth) acryloyloxy group, an alcohol represented by the following formula (y0) is preferable.

[19]

In the formula (y0), Z ¹ is an organic group having s + j ₁ + k ₁ and has an end composed of a group having 1 to 4 aromatic hydrocarbon rings having 6 to 10 carbon atoms and an unsaturated double bond, An aliphatic group which may contain an ester bond (-CO-O-), an ether bond or a carbonyl group (-CO-), a carbon atom which may be substituted with an aromatic group having 6 to 10 carbon atoms or may have a hetero atom To about 30 saturated aliphatic groups.

R ^a1 is a hydrogen atom or a methyl group. Y ^x and Y ^y are each independently a linear or branched alkylene group. q and r are integers of 0 to 4, and s + j ₁ + k ₁ is an integer of 1 to 6. Y ² to Y ³ , p ₂ to p ₃ , j 1, and k 1 are the same as in formula (A1).

Since it is preferable that j ₁ + k ₁ is 0 in the formula (y0), the alcohol represented by the following formula (y) is preferable as the alcohol having the (A1-2) (meth) acryloyloxy group.

[20]

In the formula (y), Z ¹ is an organic group of s, which may have a substituent, a group having 1 to 4 aromatic hydrocarbon rings having 6 to 10 carbon atoms or an unsaturated double bond and having an ester bond -CO-O-), an ether bond or a carbonyl group (-CO-), an aromatic group having 6 to 10 carbon atoms or an aromatic group having 5 to 30 carbon atoms Saturated aliphatic group.

R ^a1 is a hydrogen atom or a methyl group. Y ^x and Y ^y are each independently a linear or branched alkylene group. q and r are integers of 0 to 4, and s is an integer of 1 to 6.

Y ^x and Y ^y are linear or branched alkylene groups, preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms And most preferred are ethane-1,2-diyl group, propane-1,2-diyl group, and propane-1,3-diyl group.

The method for producing the alcohol represented by the formula (y) is not particularly limited. For example, the alcohol represented by the formula (y) can be produced by the following method using the hydroxyl group-providing compound represented by the following formula (x). Z ¹ , Y ^x , q, and s in the formula (x) are the same as in the formula (y).

The hydroxy group-providing compound represented by the formula (x) will be described later in detail.

Z ¹ - (- O - [- Y ^x - O -] _q --H) _s (x)

First, the hydroxyl group-providing compound represented by the above formula (x) is subjected to glycidyl etheration according to the conventional method to prepare an epoxy compound represented by the following formula (x1). Z ¹ , Y ^x , q, and s in the formula (x1) are the same as in the formula (y), and Gly is a residue of the glycidyl group-

Z ¹ - (- O - [- Y ^x -O-] _q -Gly) _s (x 1)

As such a conventional method, a hydroxy group-containing compound represented by the formula (x) and a glycidyl group-containing compound having a halogen element at the terminal of epichlorohydrin or the like are reacted in the presence of a catalyst such as an interphase transfer catalyst and then a base such as sodium hydroxide A ring-opening epoxidation may be performed.

Then, the epoxy compound represented by the formula (x1) is reacted with the glycol represented by HO - [- Y ^y --O -] _{r -} H to obtain an alcohol represented by the following formula (x1a).

[Figure 21]

Next, an esterification reaction is carried out by using a hydroxyl group-providing compound represented by the formula (x1a) and (meth) acrylic acid, (meth) acrylic acid halide, (meth) acrylic acid ester, or di (meth) acrylic acid anhydride, y) is obtained.

An alcohol represented by the formula (y) is produced by reacting an epoxy compound represented by the formula (x1) with a (meth) acrylic acid or a (meth) acrylic acid ester represented by the following formula (x2)

CH = C (R ^a1 ) -CO- [-OY ^y -] _r -OH (x 2)

(r) is 0 and the compound represented by the formula (x2) is (meth) acrylic acid, an epoxy compound represented by the formula (x1) and (meth) acrylic acid are reacted in the presence of a catalyst to obtain an alcohol represented by the formula .

The epoxy compound represented by formula (x1) may be reacted with a lactone compound. Examples of the lactone compound include? -Propiolactone,? -Methyl-? -Valerolactone,? -Valerolactone,? -Caprolactone, 2-methyl-epsilon -caprolactone, 3- -Methyl- epsilon -caprolactone, 5-tertiary butyl-epsilon -caprolactone, 7-methyl-4,4,6-trimethyl- epsilon -caprolactone, and 4,6,6-trimethyl- epsilon -caprolactone And the like.

Furthermore, as the glycidyl group-containing compound having a halogen element at the end of the starting material, a compound having - [-Y ^y -O-] _r - group may be reacted with the compound of formula (x).

As the alcohol represented by the formula (y), an alcohol represented by the following formula (y1) is preferable. In formula (y1), Z ¹ , R ^a1 , q, r, and s are the same as in formula (y).

[22]

In formula (y1), q and r are preferably 0. In this case, the alcohol represented by the formula (y1) is represented by the following formula (y2). In formula (y2), Z ¹ , R ^a1 , and s are the same as in formula (y).

[23]

(Meth) an alcohol having an acryloyloxy group of acrylic, formula (y0) alcohol represented by the glycidyl group with, the formula (x) and a halogen atom at the terminal to poll the (j ₁ + k ₁ is when the 1-5) Containing compound may be appropriately adjusted.

(A particularly preferred example of the hydroxy-providing compound)

Particularly preferred examples of the hydroxyl group-providing compound as the component (A) are summarized below. In addition, particularly preferred examples described below may overlap with the above-mentioned hydroxy-providing compound.

Specifically, a hydroxyl group-providing compound represented by the following formula (A1-1) is particularly preferably used.

^{(H - [- OY 2 -} ] p -O-) (j1 + k1) -Z - [- OY 1 -] p1 -OH

(A1-1)

The carboxylic acid ester, which is the reaction product of the hydroxyl group-providing compound represented by the formula (A1-1) and the component (B), is suitably used as an ester compound, resin or the like compounded in the photosensitive composition as an alkali soluble component.

A preferable example of the reaction product of the hydroxyl group-providing compound represented by the formula (A1-1) and the polyhydric anhydride of the polyvalent carboxylic acid is an alkali-soluble component known as a cardo resin or an intermediate thereof.

In the formula (A1-1), Y ¹ and Y ² are each a divalent organic group having 1 to 20 carbon atoms, Z is an organic group having 3 to 40 carbon atoms of j1 + k1 + 1, j1 + k1 is an integer of 0 to 7 , and p1 is an integer of 0 to 4.

Y ¹ and Y ² are each a divalent organic group having 1 to 20 carbon atoms, and may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group.

The aliphatic group contained in Y ¹ and Y ² may be a saturated aliphatic group or an unsaturated aliphatic group, and a saturated aliphatic group is preferred.

The aromatic group contained in Y ¹ and Y ² may be an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group.

Suitable examples of Y ¹ and Y ² include methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, n-butane- N-hexane-1,6-diyl group, p-phenylene group, m-phenylene group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, and Naphthalene-1,4-diyl group and the like. Of these, ethane-1,2-diyl group, propane-1,2-diyl group and propane-1,3-diyl group are preferable.

Z is an organic group having 3 to 40 carbon atoms of j1 + k1 + 1. Z may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group.

The aliphatic group contained in Z may be a saturated aliphatic group or an unsaturated aliphatic group, and a saturated aliphatic group is preferable.

The aromatic group contained in Z may be an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group.

When Z is a divalent organic group, Z is preferably a residue obtained by removing two hydroxyl groups from a bisphenol compound represented by the following formula (Z1).

[24]

In the formula (Z1), R ^Z1 is a single bond or a divalent group represented by -C (R ^z2 ) (R ^z3 ) -. R ^z2 and R ^z3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a naphthyl group.

R ^z2 and R ^z3 may combine with each other to form a hydrocarbon ring having 4 to 20 carbon atoms.

R ^z4 and R ^z5 each independently represent an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, a naphthyl group or a halogen atom. When R ^z4 or R ^z5 is plural, plural R ^z4 or R ^z5 may be the same or different.

nz1 and nz2 are each independently an integer of 0 to 4;

As R ^z2 and R ^z3 , the alkyl group having 1 to 6 carbon atoms is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a tert-butyl group, and more preferably a methyl group and an ethyl group.

When R ^z2 and R ^z3 are a halogenated alkyl group, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable. The halogenated alkyl group is preferably a trifluoromethyl group.

As to R ^z2 and R ^z3 , the cycloalkyl group having 4 to 10 carbon atoms is preferably a cyclopentyl group or a cyclohexyl group.

When R ^z2 and R ^z3 are bonded to each other to form a hydrocarbon ring having 4 to 20 carbon atoms, a suitable example of the hydrocarbon ring is a cycloalkane ring or a fluorene ring having 4 to 10 carbon atoms, A bullet, a cyclohexane ring, and a fluorene ring are more preferable. When the ring formed by R ^z2 and R ^z3 is a fluorene ring, R ^z2 and R ^{z3 form} a 9H-fluorene-9,9-diyl group.

Suitable examples of the alkyl group having 1 to 6 carbon atoms, the halogenated alkyl group having 1 to 6 carbon atoms, and the cycloalkyl group having 4 to 10 carbon atoms with respect to R ^z4 and R ^z5 are the same as R ^z2 and R ^z3 .

Suitable examples of the bisphenol compound represented by the formula (Z1) include the following compounds.

[25]

When Z is a divalent organic group, residues other than the two hydroxyl groups from the following aliphatic diols are also preferable as the group Z.

[26]

When Z is a trivalent organic group, a residue other than the three hydroxyl groups from the trisphenol compound represented by the following formula (Z2) is preferable as the group Z.

[Figure 27]

In the formula (Z1), R ^z6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group.

R ^z7 , R ^z8 and R ^z9 each independently represent an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, a naphthyl group, to be.

R ^z10 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.

nz3, nz4, and nz5 are each independently an integer of 0 to 4;

nz6 is 0 or 1;

Suitable examples of the alkyl group having 1 to 6 carbon atoms, the halogenated alkyl group having 1 to 6 carbon atoms, and the cycloalkyl group having 4 to 10 carbon atoms with respect to R ^z6 , R ^z7 , and R ^z8 include R ^z2 , R ^z3 .

When R ^z9 is an alkanediyl group having 1 to 4 carbon atoms, a methylene group, an ethane-1,2-diyl group, and a propane-2,2-diyl group are preferable.

Suitable specific examples of the trisphenol compound represented by the formula (Z2) include the following compounds.

[28]

When Z is a trivalent organic group, residues other than the three hydroxy groups from the following trisphenol compounds are also preferable as the group Z.

[29]

When Z is a polyvalent organic group having a valence of 4 or more, residues other than all the hydroxyl groups from the following polyphenol compounds are preferable as the group Z.

[T]

As the hydroxyl group-providing compound represented by the formula (A1-1), a compound represented by the following formula (x) is preferable, and a compound represented by the following formula (A1-1-1) is more preferable.

Z ¹ - (- O - [- Y ^x - O -] _q --H) _s (x)

In the formula (x), Z ¹ is an organic group of s, which has a terminal having an unsaturated double bond or a group having 1 to 4 aromatic hydrocarbon rings having 6 to 10 carbon atoms, which may have a substituent, and has an ester bond -CO-O-), an ether bond or a carbonyl group (-CO-), an aromatic group having 6 to 10 carbon atoms or an aromatic group having 5 to 30 carbon atoms Saturated aliphatic group.

Y ^x each independently represents a linear or branched alkylene group.

q is an integer of 0 to 4, and s is an integer of 1 to 6.

Z ¹ - (- [CH ₂ CH ₂ -O-] _q -H) _s (A1-1-1)

In formula (A1-1-1), Z ¹ , q and s are the same as in formula (x).

An example of a group suitable as Z ¹ in the formula (A1-1-1) is an organic group having a cardo structure. The organic group having a cardo structure is preferably a divalent group represented by the following formula (A1-1-1 a).

In formula (A1-1-1 a), R ^z11 is, independently of each other, a hydrogen atom or a methyl group.

However,

Suitable specific examples of the hydroxyl group-providing compound represented by the formula (A1-1) include phenol; cresols such as o-cresol, m-cresol and p-cresol; methoxyphenols such as o-methoxyphenol, m-methoxyphenol and p-methoxyphenol; Pyrogallol-1,3-dimethyl ether; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Sileenol; ethylphenol, m-ethylphenol, p-ethylphenol and the like, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m- Phenol and p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, pyrogallol monomethyl ether, and fluoroglycinol; Alkylpolyphenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (all of the above alkyl groups have 1 to 4 carbon atoms); naphthols such as? -naphthol,? -naphthol, 2,6-naphthalene diol and 1,4-naphthalene diol; Hydroxydiphenyl; Bisphenol A, and the like.

The trisphenol compound itself represented by the above-mentioned formula (Z2) may also be a suitable specific example of the hydroxyl group-providing compound represented by the formula (A1-1).

In addition, suitable examples of the hydroxyl group-providing compound represented by the formula (A1-1) include the following phenol compounds. Specific examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydro 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2' Phenone, 2,3 ', 4,4', 6-pentahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,5-penta Such as hydroxybenzophenone, 2,3 ', 4,4', 5 ', 6-hexahydroxybenzophenone, 2,3,3', and 4,4 ', 5'-hexahydroxybenzophenone, Hydroxybenzophenones; Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- 2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2' 3 ', 4'-trihydroxyphenyl) propane, 4,4' - {1- [4- [2- (4-hydroxyphenyl) -2- propyl] phenyl] ethylidene} Bis [(poly) hydroxyphenyl] alkanes such as? -Dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol; Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) Dimethylphenyl) -3,4-dihydroxyphenylmethane, and bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane. Tris (hydroxyphenyl) methanes or methyl substituents thereof; Bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) Hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl- (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl- -Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl- Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane such as bis (cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane and bis Or a methyl substituent thereof.

Suitable examples of the hydroxyl group-providing compound represented by the formula (A1-1) include the following alcohols. Specific examples of the alcohol include ethylene glycol mono (meth) acrylate, 1,3-propanediol mono (meth) acrylate, methylolvinylketone, 2-hydroxyethylvinylketone, 2-hydroxy- Unsaturated bond-containing alcohols such as 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate and 2-hydroxy-3-butoxypropyl (meth) acrylate; 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, Aliphatic having 5 to 30 carbon atoms or an aliphatic or aromatic hydrocarbon group having 6 to 30 carbon atoms such as nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether and benzyl alcohol; 30 aromatic alcohols.

The compound in which at least one hydroxy group in the compound described as a suitable specific example of the hydroxyl group-providing compound represented by the formula (A1-1), preferably a hydrogen atom in all the hydroxy groups, is substituted with a group represented by the following formula (y1a) Is preferable as the hydroxyl group-providing compound represented by the formula (A1-1). In formula (y1a), R ^a1 is a hydrogen atom or a methyl group, and q and r are integers of 0 to 4.

[0035]

The group represented by the formula (y1a) is preferably a group represented by the following formula (y2a).

[0035]

<(B) Tetracarboxylic acid dianhydride>

(B) Tetracarboxylic acid dianhydrides include norbornane-2-spiro-a-cycloalkanone-a'-spiro-2 "-norbornane-5,5" 6 &quot; -tetracarboxylic acid dianhydrides are used.

[0035]

(In the formula (b1), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 Lt; / RTI &gt;

The alkyl group which may be selected as R ^b1 in the formula (b1) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms in the alkyl group exceeds 10, the resulting carboxylic acid ester may not have good heat resistance. When R ^b1 is an alkyl group, the number of carbon atoms thereof is preferably from 1 to 6, more preferably from 1 to 5, still more preferably from 1 to 4, and still more preferably from 1 to 3, since the number of carbon atoms thereof is easy to obtain a carboxylic acid ester having excellent heat resistance. Particularly preferred.

When R ^b1 is an alkyl group, the alkyl group may be linear or branched.

As R ^b1 in the formula (b1), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable, independently from each other, since an ester compound having excellent heat resistance is easily obtained. R ^b1 in the formula (b1) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.

It is preferable that a plurality of R ^b1 in the formula (b1) is the same group in that the preparation of the high purity tetracarboxylic acid dianhydride is easy.

M in the formula (b1) represents an integer of 0 to 12; When the value of m exceeds 12, it is difficult to purify the tetracarboxylic dianhydride.

From the viewpoint of easy purification of the tetracarboxylic acid dianhydride, the upper limit of m is preferably 5, more preferably 3.

From the viewpoint of the chemical stability of the tetracarboxylic dianhydride, the lower limit of m is preferably 1, more preferably 2.

In the formula (b1), m is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms which may be selected as R ^b2 and R ^b3 in the formula (b1) is the same as the alkyl group having 1 to 10 carbon atoms which can be selected as R ^b1 .

R ^b2 and R ^b3 are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, still more preferably 1 To 4, particularly preferably 1 to 3) alkyl groups, and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic acid dianhydride represented by the formula (b1) include norbornane-2-spiro-a-cyclopentanone-a'-spiro-2 " 6 "-tetracarboxylic dianhydride (also called" norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5 ' -Tetracarboxylic acid dianhydride &quot;), methylnorbornane-2-spiro- [alpha] -cyclopentanone-a'-spiro-2 '' - (methylnorbornane) -5,5 ' -Tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclohexanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride Spiro-2 &quot; -norbornane-5,5 &quot;, 6,6 &quot; -tetracarboxylic dianhydride &quot;), methyl Spiro- [alpha] -cyclohexanone- [alpha] -spiro-2 &quot;-( methylnorbornane) -5,5 &quot;, 6,6 &quot; -tetracarboxylic dianhydride, norbornane -2-spiro- [alpha] -cyclopropanone-a'-spiro -2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclobutanone-a'-spiro- Borane-5,5 &quot;, 6,6 &quot; -tetracarboxylic dianhydride, norbornane-2-spiro- alpha -cycloheptanone- '', 6,6 '' -tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclooctanone-a'-spiro-2''-norbornane-5,5 '', 6,6 -'-tetracarboxylic acid dianhydride, norbornane-2-spiro-a-cyclononanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic acid 2 Spiro-α-cyclodecanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, norbornane- Spiro-a-cyclodecanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane- Cyclododecanone-a'-spiro-2 &quot; -norbornane-5,5 &quot;, 6,6 &quot; -tetracarboxylic acid 2 Norbornane-2-spiro- alpha -cyclotridecanone-alpha'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane Spiro-a-cyclotetradecanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane- -cyclopentadecanol-a'-spiro-2''-norbornane-5,5 '', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro- Pentane) -α'-spiro-2''-norbornane-5,5 '', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, and the like.

The tetracarboxylic acid dianhydride represented by the formula (b1) is preferably a tetracarboxylic acid dianhydride represented by the following formula (b1-1):

[35]

(Formula (b1-1) ^{of, R b1, R b2, R} b3, m is ^{R b1, R b2, R b3} , m and copper in the formula (b1).)

(B1-1) and the following formula (b1-2):

[36]

(Formula (b1-2) ^{of, R b1, R b2, R} b3, m is ^{R b1, R b2, R b3} , m and copper in the formula (b1).)

, And the total amount of the compound (B1-1) and the compound (B1-2) is preferably at least 30 mol%.

The compound (B1-1) represented by the formula (b1-1) is a compound represented by the formula (b1) in which two norbornane groups are trans-arranged and the carbonyl group of the cycloalkanone is in each of the two norbornane groups ) Of the tetracarboxylic acid dianhydride.

The compound (B1-2) represented by the formula (b1-2) is a compound represented by the formula (b1) in which two norbornane groups are arranged in a cis configuration and the carbonyl group of the cycloalkanone in each of the two norbornane groups is arranged in an end configuration ) Of the tetracarboxylic acid dianhydride.

The method for producing the tetracarboxylic acid dianhydride containing the above-mentioned isomers in the above proportions is also not particularly limited and a known method can be suitably employed. For example, the method described in International Publication No. 2014/034760 May be suitably employed.

&Lt; Reaction of component (A) and component (B)

The ratio of the component (A) to the component (B) when they are reacted is not particularly limited. (A) :( B) is from 90:10 to 51:49, and preferably from 70:30 to 53:47 when the molar ratio of the component (A) is higher than that of the component (B). The temperature at which the component (A) is reacted with the component (B) is not particularly limited as long as the reaction proceeds satisfactorily.

(NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylacetamide (DMAc) and the like can be used as the solvent which can be used for the reaction of the component (A) N, N-dimethylacetamide, DMF, N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imide Nitrogen-containing polar solvents such as diphenylmethane diisocyanate (DMI), pyridine, and N, N, N ', N'-tetramethylurea (TMU); lactone-based polar solvents such as? -propiolactone,? -butyrolactone,? -valerolactone,? -valerolactone,? -caprolactone, and? -caprolactone; Dimethyl sulfoxide; Hexamethylphosphoric triamide; Acetonitrile; Fatty acid esters such as ethyl lactate, and butyl lactate; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate, and ethers such as ethyl cellosolve acetate and glyme; (Poly) alkylene ethers 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; And aromatic solvents such as benzene, toluene and xylene.

The reaction time is not particularly limited. And the reaction is appropriately continued until the reaction proceeds to a desired extent. As a criterion for the completion of the reaction, there can be mentioned disappearance of an acid anhydride group in the reaction mixture. The disappearance of the acid anhydride group can be confirmed, for example, by measuring the IR spectrum.

The reaction between the component (A) and the component (B) is preferably carried out in the presence of a catalyst promoting the reaction. Examples of such a catalyst include halides of quaternary ammonium such as tetramethylammonium chloride and tetraethylammonium bromide, organic bases such as 2-ethyl-4-methylimidazole, and phosphines such as triphenylphosphine.

(Examples of preferred carboxylic acid esters)

Examples of preferred carboxylic acid esters include compounds represented by the following formula (AB1) or (AB2). Formula (AB1) and (AB2) ^{of, Z, Y 1, Y 2} , R c1, R c2, p1, p2, j1, and X are as previously described.

[37]

The compound represented by the formula (AB1) is a carboxylate ester obtained by reacting a compound in which k1 is 0 with a tetracarboxylic acid dianhydride represented by the formula (b1) as the hydroxyl group-providing compound represented by the above formula (A5).

The compound represented by formula (AB2) is a carboxylic acid ester compound in which a carboxyl group bonded to X in a compound represented by formula (AB1) is optionally converted to an aldehyde group.

Also preferred is a carboxylic acid ester compound represented by the following formula (AB3) or (AB4). The carboxylic acid ester compound represented by the formula (AB3) or (AB4) is a carboxylic acid ester obtained by reacting the compound represented by the above formula (y) with a hydroxy group-providing compound wherein s is 2 and a tetracarboxylic acid dianhydride represented by the formula (b1) .

The compound represented by formula (AB4) is a carboxylic acid ester compound in which a carboxyl group bonded to X in a compound represented by formula (AB3) is optionally converted to an aldehyde group.

In formula (AB3) and (AB4), Z ¹ , Y ^x , Y ^y , q, r, R ^a1 , R ^c1 , R ^c2 and R ^a1 are as described above.

[38]

... (AB3)

[39]

... (AB4)

The ester compound represented by formula (AB2) or formula (AB4) can be suitably used as an additive component for imparting alkali solubility and heat resistance to various compositions such as a photosensitive resin composition.

&Lt; Component of composition &gt;

The kind and amount of the other components in the first composition other than the carboxylic acid ester having the structure represented by the formula (A1) are not particularly limited. The kind and amount of the other components are not particularly limited.

The other component is preferably at least one selected from the group consisting of a photopolymerization initiator, an acid generator, and a base generator. The acid generator and the base generator may be photosensitive or thermosensitive, for example.

When the composition contains such a component, the composition is imparted with photosensitivity and thermosensitivity.

As other components other than the above, for example, various photopolymerizable monomers such as (meth) acrylate monomers, alkali soluble resins, alkali soluble resins protected with protecting groups, binder resins, acid crosslinking substances, organic solvents, A crosslinking agent, a sensitizer, a silicon-containing compound, an inorganic filler, a hydroxyl group-containing compound, a carboxyl group-containing compound, and various other various additives such as a coloring agent, a surfactant, a crystallization inhibitor, an adhesion improver, a thermal polymerization inhibitor, a defoaming agent, a curing agent, May be added. Any additive may be any conventionally known one.

Preferable examples of the composition include a composition comprising a carboxylic acid ester having a structure represented by the formula (A1), a photopolymerization initiator, optionally a photopolymerizable monomer, optionally a crosslinking agent, optionally a colorant, and optionally an alkali-soluble resin and / .

Examples of the preferable composition include a carboxylate ester having a structure represented by the formula (A1), an acid generator, and optionally an acid-crosslinkable material, optionally an alkali-soluble resin, an alkali-soluble resin protected with a protecting group, and a binder resin And a composition containing at least one of them.

Hereinafter, one preferred embodiment of the composition will be described in detail.

The composition described as a preferred embodiment is a composition comprising (I) a carboxylic acid ester, (II) a photopolymerizable monomer, (III) a photopolymerization initiator, and (IV) a colorant. Such a composition can be cured by exposure, and a colored cured film can be formed by exposing a coating film formed using the composition. When the exposure is performed in a position-selective manner using a photomask or the like, a patterned colored cured film can be formed by developing with an alkali developing solution after exposure.

((I) carboxylic acid ester)

The carboxylic acid ester (I) is a carboxylic acid ester having the structure represented by the formula (A1).

((II) photopolymerizable monomer)

As the (II) photopolymerizable monomer, a monomer having an ethylenic unsaturated group can be preferably used. Monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (Meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl Phenoxy-2-hydroxypropyl (meth) acrylate, (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and phthalic acid derivatives. . These monofunctional monomers may be used alone or in combination of two or more.

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 Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, diethylene glycol di (meth) acrylate, (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 (Meth) acrylates such as hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene di (Condensation product of polyhydric alcohol and N-methylol (meth) acrylamide), methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, And the like, or monomers, acrylic tree formal. These polyfunctional monomers may be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, a multifunctional monomer having three or more functional groups is preferable, and a multifunctional monomer having six or more functional groups is preferable because the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition tend to be enhanced. More preferable.

(II) The content of the photopolymerizable monomer in the composition is preferably from 1 to 50 mass%, more preferably from 5 to 40 mass%, based on the mass of the solid content of the composition. When the content is in the above range, there is a tendency to balance the sensitivity, developability and resolution.

((III) photopolymerization initiator)

(III) The photopolymerization initiator is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2- hydroxyethoxy) Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone, 1 (9-ethyl-6-nitro-9H-carbazol-3-yl) 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1- [4- (2-methoxy- 1 -methylethoxy) -2- methylphenyl] methanone O- Octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethyl Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl- beta -methoxyethyl acetal, benzyl Dimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- , 4-dimethylthioxanthone, 1-chloro-4-propoxycitoxone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2- Benzoyl peroxide, cumene hydroperoxide, cumene hydroperoxide, isobutyl peroxide, isobutyl peroxide, isopropyl thioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl 2 Benzophenone, 2-chlorobenzophenone, p, p'-bisdimethyl Aminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, Ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, Propylphenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, .alpha., .Alpha.-butyrolactophenone, dichloroacetophenone, trichloroacetophenone, -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytri , 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- [2- (3, 4-diethylamino-2-methylphenyl) (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) ) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl- 2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3- , 4-bis-trichloromethyl-6- (2- Mo-4-methoxy) styryl phenyl -s- triazine, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use an oxime-type photopolymerization initiator in terms of sensitivity. Among the oxime-based photopolymerization initiators, particularly preferred are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol- (O-acetyloxime), and 2- (O-benzoyloxime) -1- [4- (4-fluorophenyl) (Phenylthio) phenyl] -1,2-octanedione.

As the photopolymerization initiator, it is also preferable to use a oxime-based compound represented by the following formula (d1).

[40]

( ^Wherein R ^d1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, n 1 is an integer of 0 to 4, n 2 is 0 or 1, and R ^d2 is a substituent A phenyl group which may be substituted or a carbazolyl group which may have a substituent and R ^d3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula (d1), R ^d1 is not particularly limited within a range that does not impair the object of the present invention, and is suitably selected from various organic groups. Suitable examples of R ^d1 as the 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, a phenyl group which may have a substituent, A phenoxycarbonyl 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, a naphthoxy group , A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, An amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, And the like. When n1 is an integer of 2 ~ 4, R ^d1 is may be the same or different. The number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further having a substituent.

When R ^d1 is an alkyl group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ^d1 is an alkyl group, it may be straight chain or branched chain. Specific examples of the case where R ^d1 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- n-hexyl group, n-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- And an isodecyl group. When R ^d1 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 methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d1 is an alkoxy group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ^d1 is an alkoxy group, it may be straight chain or branched chain. Specific examples of when R ^d1 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- N-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, isohexyloxy group, isopentyloxy group, sec- tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^d1 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 propoxyoxyethoxyethoxy group, and a methoxy Propyloxy group and the like.

When R ^d1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably from 3 to 10, and more preferably from 3 to 6 carbon atoms. Concrete examples of the case where R ^d1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of the case where R ^d1 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 ^d1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably from 2 to 20, and more preferably from 2 to 7 carbon atoms. Specific examples of when R ^d1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, Decanoyl group, n-hexadecanoyl group, and the like. Specific examples of the case where R ^d1 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoyloxy group , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^d1 is an alkoxycarbonyl group, the number of carbon atoms is preferably from 2 to 20, and more preferably from 2 to 7 carbon atoms. Specific examples of when R ^d1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec- Sec-butyloxycarbonyl, n-pentyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, iso-octyloxycarbonyl, sec-pentyloxycarbonyl, Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^d1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10 carbon atoms. When R ^d1 is a naphthylalkyl group, the number of carbon atoms is preferably from 11 to 20, and the number of carbon atoms is more preferably from 11 to 14. Specific examples of the case where R ^d1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^d1 is a naphthylalkyl group include? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? -Naphthyl) ethyl group. When R ^d1 is a phenylalkyl group or a naphthylalkyl group, R ^d1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^d1 is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing 1 or more N, S, or O, or a heterocyclyl group in which the monocyclic ring is condensed with a benzene ring. And in the case where the heterocyclyl group is a condensed ring, the number of rings is 3. Examples of the heterocycle constituting the heterocyclyl 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, Ginsenosin, and quinoxaline. When R ^d1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^d1 is an amino group substituted with 1 or 2 organic groups, suitable 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 group having 2 to 20 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, A naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these suitable organic ^groups are the same as R ^d1 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, Naphthoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, .

As the substituent in the case where the phenyl group, naphthyl group and heterocyclyl group contained in R ^d1 further have a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 2 to 7 carbon atoms A saturated 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 A morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d1 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d1 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^d1 is chemically stable but less steric hindrance and easy synthesis of the oxime ester compound. The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 1 to 7 carbon atoms, more preferably an alkyl having 1 to 6 carbon atoms, and particularly preferably a methyl group.

R ^d1 is a position R ^d1 is the bonding position of the phenyl group and the oxime ester compound week combination the position of the hand in the first position, and a methyl group of a skeleton of for the phenyl group bonded to the phenyl group in the case of a two-position, the 4-position , Or 5 position is preferable, and 5 position is more preferable. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^d2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. When R ^d2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^d2 , the substituent group of the phenyl group or the carbazolyl group is not particularly limited within the scope of not impairing the object of the present invention. Examples of suitable substituents which the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a carbon atom A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent , A phenoxy group which may have a substituent, a phenylthio 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 having 7 to 20 atoms, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, A naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 2, an amino group substituted with an organic group, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When R ^d2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthocycarbonyl group which may have a substituent, a naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, A heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or carbazolyl group may have 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 naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted by 1 or 2 organic groups are the same as R ^d1 .

Examples of the substituent when the phenyl group, naphthyl group and heterocyclyl group contained in the substituent group of the phenyl group or the carbazolyl group in R ^d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent group of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited to the extent that the object of the present invention is not impaired, 4 is preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

A group represented by the following formula (d2) or (d3) is preferable, a group represented by the following formula (d2) is more preferable, and a group represented by the following formula (d2) is more preferable in view of easiness of obtaining a photopolymerization initiator excellent in sensitivity among R ^d2 As the group, a group in which A is S is particularly preferable.

[41]

( ^Wherein R ^d4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0 to 4.)

[42]

(R ^d5 and R ^d6 are each a monovalent organic group)

When R ^d4 in the formula (d2) is an organic group, it can be selected from various organic groups within the range not hindering the object of the present invention. In the formula (d2), when R ^d4 is an organic group, suitable examples include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group.

Among R ^d4 , a benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, a benzoyl group; A naphthoyl group; A 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; And a 4- (phenyl) phenylcarbonyl group is more preferable.

In the formula (d2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. if n3 is 1, with respect to coupling positions of R ^d4 is a phenyl group which is bonded to R ^d4 coupling hand in combination with an oxygen atom or a sulfur atom, preferably in the para position.

R ^d5 in the formula (d3) can be selected from various organic groups within the range not impairing the object of the present invention. Suitable examples of R ^d5 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 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, A phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl 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 nitro group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent .

R ^d5 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

The R ^d6 in the formula (d3) is not particularly limited within a range that does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of the group represented by R ^d6 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 ^d6 , a phenyl group which may have a substituent is more preferable among these groups, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group having 1 to 6 atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 further have a substituent, the number of the substituent is not limited to the extent that the object of the present invention is not impaired, 4 is preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^d3 in the formula (d1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ^d3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

The oxime ester compound represented by the formula (d1) can be synthesized according to the following Scheme 1 when p is 0, for example. Specifically, an aromatic compound represented by the following formula (d1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (d1-2) To obtain an oxime compound represented by the formula (d1-4) by oxytizing the obtained ketone compound (d1-3) with hydroxylamine to obtain an oxime compound represented by the formula (d1-4) , The oxime ester compound represented by the following formula (d1-7) is obtained. As the acylating agent, it is preferable to use an acid anhydride ((R ^d3 CO) ₂ O) represented by the following formula (d1-5) or an acid halide (R ^d3 COHal and Hal for a halogen) represented by the following formula (d1-6) . In the formula (d1-2), Hal is halogen and in the following formulas (d1-1), (d1-2), (d1-3), (d1-4) and (d1-7) ^{R d1, R d2, R d3} , and n1 is the same as the formula (d1).

<Scheme 1>

[43]

The oxime ester compound represented by formula (d1) can be synthesized according to the following scheme 2 when n2 is 1, for example. Specifically, a ketone compound represented by the following formula (d2-1) is reacted with a nitrite ester represented by the following formula (d2-2) (RONO, wherein R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid, (d2-3), and then the hydroxy group in the ketooxime compound represented by the following formula (d2-3) is acylated to obtain an oxime ester compound represented by the following formula (d2-6) . As the acylating agent, it is preferable to use an acid anhydride ((R ^d3 CO) ₂ O) represented by the following formula (d2-4) or an acid halide (R ^d3 COHal and Hal for a halogen) represented by the following formula (d2-5) . R ^d1 , R ^d2 , R ^d3 , and n1 in the following formulas (d2-1), (d2-3), (d2-4), (d2-5), and d1).

<Scheme 2>

[44]

When the oxime ester compound represented by formula (d1) has n2 of 1, ^Rd1 is a methyl group, and ^Rd1 is bonded to the para position with respect to the methyl group bonded to the benzene ring to which ^Rd1 is bonded, for example, The compound represented by the formula (d2-7) shown below can also be synthesized by oximation and acylation in the same manner as scheme 1. In the following formula (d2-7), R ^d2 is the same as in formula (d1).

[45]

Among the oxime ester compounds represented by the formula (d1), particularly preferred compounds are the following PI-1 to PI-42.

[46]

[47]

[48]

[49]

[50]

[51]

The oxime ester compound represented by the following formula (d4) is also preferable as a photopolymerization initiator.

[52]

(R ^d7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^d8 and R ^d9 are each a ^straight chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent or a hydrogen atom, R ^d8 and R ^d9 is to form a ring by combining to each other, R ^d10 is a monovalent organic group, R ^d11 is an aryl group which may have a number of carbon atoms which may have a hydrogen atom, an optionally substituted alkyl group of 1 to 11, or a substituent group, n4 Is an integer of 0 to 4, and n5 is 0 or 1.)

For this reason, as the oxime compound for producing the oxime ester compound of the formula (d4), a compound represented by the following formula (d5) is suitable.

[53]

(R ^d7 , R ^d8 , R ^d9 , R ^d10 , n4, and n5 are the same as in formula (d4).)

In formulas (d4) and (d5), ^Rd7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^d7 is bonded to a 6-membered aromatic ring which is different from a 6-membered aromatic ring bonded to a group represented by - (CO) _n5- , on a fluorene ring in formula (d4). In the formula (d4), the bonding position of R ^{d7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (d4) with one or more R ^d7, it is preferable that the expression, etc. that the synthesis is easy of a compound represented by the (d4), one of the one or more of R ^d7 is bonded to the fluorene ring 2-position of the . When R ^d7 is a plurality, the plurality of R ^d7 are may be the same or different.

When R ^d7 is an organic group, R ^d7 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. Suitable examples of R ^d7 in the 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, a phenyl group which may have a substituent, A phenoxycarbonyl 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, a naphthoxy group , A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, A heterocyclylcarbonyl group which may be substituted, an amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group, There may be mentioned 1-yl group and the like.

When R ^d7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 6. When R ^d7 is an alkyl group, it may be straight chain or branched chain. Specific examples of R ^d7 as 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- n-hexyl group, n-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- And an isodecyl group. When R ^d7 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 methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably from 1 to 20, more preferably from 1 to 6. When R ^d7 is an alkoxy group, it may be straight chain or branched chain. Specific examples of when R ^d7 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- N-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, isohexyloxy group, isopentyloxy group, sec- tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^d7 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 propoxyoxyethoxyethoxy group, and a methoxy Propyloxy group and the like.

When R ^d7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ^d7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of the case where R ^d7 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 ^d7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of 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 ^d7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanonyl group, a 2,2-dimethylpropanoyl group, Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, Decanoyl group, n-hexadecanoyl group, and the like. Specific examples of when R ^d7 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^d7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of when R ^d7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, Sec-butyloxycarbonyl, n-pentyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, iso-octyloxycarbonyl, sec-pentyloxycarbonyl, Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^d7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. When R ^d7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of when R ^d7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^d7 is a naphthylalkyl group include? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? - naphthyl) ethyl group. When R ^d7 is a phenylalkyl group or a naphthylalkyl group, R ^d7 may further have a substituent on the phenyl group or the naphthyl group.

When R ^d7 is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing one or more N, S or O, or a heterocyclyl group formed by condensation of such monocyclic ring and benzene ring. And in the case where the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group can be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl 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, Quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. When R ^d7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^d7 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as the case that R ^d7 is a heterocyclyl group.

When R ^d7 is an amino group substituted with 1 or 2 organic groups, suitable 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 group having 2 to 21 carbon atoms 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 naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, and heterocyclyl group. Specific examples of these suitable organic ^groups are the same as R ^d7 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, Naphthoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, .

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^d7 have further substituents, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 2 to 7 carbon atoms A saturated 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 A morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d7 further have a substituent, the number of the substituent is not limited within the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^d7 is preferably a nitro group or a group represented by R ^d12 -CO- since sensitivity tends to be improved. R ^d12 is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various kinds of organic devices. Examples of a group suitable as R ^d12 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 ^d12 , among these groups, a 2-methylphenyl group, a thiophen-2-yl group and an a-naphthyl group are particularly preferable.

When R ^d7 is a hydrogen atom, transparency tends to be good, which is preferable. Furthermore, when R ^d7 is a hydrogen atom and R ^d10 is a group represented by the formula (d4b) described later, the transparency tends to be better.

In the formula (d4), R ^d8 and R ^d9 each are a straight chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^d8 and R ^d9 may be bonded to each other to form a ring. Of these groups, R ^d8 and R ^d9 are preferably chain alkyl groups which may have a substituent. When R ^d8 and R ^d9 are a straight chain alkyl group which may have a substituent, the straight chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^d8 and R ^d9 are a ^straight chain alkyl group having no substituent, the number of carbon atoms of the straight chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6. Specific examples of R ^d8 and R ^d9 in the case of a ^straight chain 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- N-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl , n-decyl group, and isodecyl group. When R ^d8 and R ^d9 are alkyl groups, 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 methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d8 and R ^d9 are a ^straight chain alkyl group having a substituent, the number of carbon atoms of the straight chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The straight chain alkyl group having a substituent is preferably a straight chain.

The substituent that the alkyl group may have is not particularly limited within the scope of not impairing the object of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of 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 those in the case where R ^d7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as those in the case where R ^d7 is a heterocyclyl group. When R ^d7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear, branched or straight-chain. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably from 1 to 10, more preferably from 1 to 6.

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

When R ^d8 and R ^d9 are cyclic organic groups, the cyclic organic group may have alicyclic or aromatic groups. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^d8 and R ^d9 are cyclic organic groups, the substituent that the cyclic organic group may have is the same as when R ^d8 and R ^d9 are chain alkyl groups.

When R ^d8 and R ^d9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group may be a phenyl group, or a group in which a plurality of benzene rings are bonded through a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed to form. When the aromatic hydrocarbon group is a phenyl group or a group in which a plurality of benzene rings are formed by bonding or condensation, the number of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited and is preferably 3 or less, more preferably 2 or less, desirable. Specific preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^d8 and R ^d9 are aliphatic cyclic hydrocarbon groups, aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10. Examples of the monocyclic cyclic 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 isobonyl group, a tricyclodecyl group, Tetradecyldodecyl group, adamantyl group, and the like.

When R ^d8 and R ^d9 are a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or a monocyclic or bicyclic monocyclic ring containing one or more of these monocyclic rings, . And in the case where the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group can be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl 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, Quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like.

R ^d8 and R ^d9 may be bonded to each other to form a ring. The group consisting of rings formed by R ^d8 and R ^d9 is preferably a cycloalkylidene group. When R ^d8 and R ^d9 are combined to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ^d8 and R ^d9 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 a 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, And pyrimidine rings, and the like.

Examples of suitable groups among R ^d8 and R ^d9 described above include groups represented by the formula -A ¹ -A ² . 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.

The number of carbon atoms of the straight chain alkylene group of A ¹ is preferably from 1 to 10, more preferably from 1 to 6. When A ² is an alkoxy group, the alkoxy group may be linear or branched or straight-chain. The number of carbon atoms of the alkoxy group is preferably from 1 to 10, more preferably from 1 to 6. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. 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, more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be straight chain or branched chain, and straight chain is preferable. When A ² is a cyclic organic group, examples of cyclic organic groups are the same as cyclic organic groups having R ^d8 and R ^d9 as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group having R ^d8 and R ^d9 as a substituent.

Suitable examples of R ^d8 and R ^d9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group and n-octyl group; Methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, Ethoxy-n-hexyl group, 7-ethoxy-n-heptyl group, and 8-ethoxy-n-octyl group; N-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano- n-heptyl group, and 8-cyano-n-octyl group; 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; Cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl n-hexyl group, 7-cyclohexyl cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, Cycloalkylalkyl groups such as a t-butyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group and an 8-cyclopentyl-n-octyl group; Methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl- Ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, An alkoxycarbonylalkyl group such as an ethoxycarbonyl-n-octyl group; Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro- n-heptyl group, Propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5, And a 5-heptafluoro-n-pentyl group.

Suitable groups among R ^d8 and R ^d9 among the above groups are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, A 2-chloroethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, and a 3,3,4,4,5,5,5-heptafluoro- pentyl group.

Of R ^d10 suitable organic group for example in the same manner as R ^d7, an alkyl 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, 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, a substituent A naphthoyl group which may have a substituent, a naphthoylcarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent A heterocyclylcarbonyl group which may have a substituent, an amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group, And a piperazin-1-yl group. Specific examples of these groups are the same as those described for R ^d7 . R ^{d10 is} also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R ^d7 may have.

Among the organic groups, R ^{d10 is preferably an} alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group or a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably 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. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, and particularly preferably 2. [ Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, the 2- (4-chlorophenylthio) ethyl group is preferred.

R ^d10 is preferably a group represented by -A ³ -CO-OA ⁴ . A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and is preferably an alkylene group. A ⁴ is a monovalent organic group and is preferably a monovalent hydrocarbon group.

When A &lt; ³ &gt; is an alkylene group, the alkylene group may be straight chain, branched chain or straight chain. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 4.

Suitable examples of A ⁴ include an alkyl group of 1 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, and an aromatic hydrocarbon group of 6 to 20 carbon atoms. Suitable examples of A ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Naphthyl group, benzyl group, phenethyl group,? -Naphthylmethyl group, and? -Naphthylmethyl group.

Specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxycarbonylethyl group , 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl- 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, and 3-phenoxycarbonyl-n-propyl group.

Above has been described for R ^d10, is preferably a group represented by the following formula as the R ^d10 (d4a) or (d4b).

[54]

(In the formulas (d4a) and (d4b), R ^d13 and R ^d14 are each an organic group, n6 is an integer of 0 to 4, and when R ^d13 and R ⁸ are present at adjacent positions on the benzene ring, R ^d13 And R ^d14 may bond together to form a ring. N7 is an integer of 1 to 8, n8 is an integer of 1 to 5, n9 is an integer of 0 to (n8 + 3), and ^Rd15 is an organic group.

An example of an organic group for R ^d13 and R ^d14 in formula (d4a) is the same as R ^d7 . R ^d13 is preferably an alkyl group or a phenyl group. When R ^d13 is an alkyl group, the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, most preferably 1. In other words, R ^d13 is most preferably a methyl group. When R ^d13 and R ^d14 are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (d4a) in which R ^d13 and R ^d14 form a ring include a naphthalene-1-yl group and a 1,2,3,4-tetrahydronaphthalen-5-yl group have. In the formula (d4a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula (d4b), R ^d15 is an organic group. The organic group may be the same group as the organic group described for R ^d7 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. As R ^d15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the formula (d4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the formula (d4b), n9 is 0 to (n8 + 3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the formula (d4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the formula (d4), R ^d11 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. As the substituent which R ^d11 may be an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. The substituent which may be taken when R ^d7 is an aryl group is preferably an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms.

In the formula (d4), R ^{d11 is preferably a} hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group or a naphthyl group. Or a phenyl group is more preferable.

The compound represented by formula (d4) includes a step of converting the oxime group (> C = N-OH) contained in the compound represented by formula (d5) described above into oxime ester group represented by> ^C═NO -COR ^d11 &Lt; / RTI &gt; R ^d11 and R ^d11 are the same as in the formula (d4).

Conversion of the oxime group (> C = N-OH) to an oxime ester group represented by> ^C═NO -COR ^d11 is carried out by reacting the compound represented by the formula (d5) with an acylating agent.

Acylating agents giving an acyl group represented by -COR ^d11 include an acid anhydride represented by (R ^d11 CO) ₂ O and an acid halide represented by R ^d11 COHal (Hal is a halogen atom).

The compound represented by formula (d4) can be synthesized according to the following scheme 3 when n5 is 0, for example. In Scheme 3, a fluorene derivative represented by the following formula (d3-1) is used as a raw material. When R ^d7 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (d3-1) can be obtained by subjecting a fluorene derivative in which the 9-position is substituted with R ^d8 and R ^d9 to a substituent R ^d7 Can be obtained. If the 9-position is substituted by R ^d8 and R ^d9 fluorene derivative is, for example, the R ^d8 and R ^d9 is an alkyl group, as described in Japanese Patent Laid-Open No. Hei-06-234668, in the presence of an alkali metal hydroxide, Can be obtained by reacting fluorene with an alkylating agent in an aprotic polar organic solvent. An alkylation reaction such as an alkyl halide such as an alkyl halide, an aqueous solution of an alkali metal hydroxide and an interphase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide iodide is added to an organic solvent solution of fluorene, 9-alkyl substituted fluorene can be obtained.

An acyl group represented by -CO-R ^d10 is introduced into a fluorene derivative represented by the formula (d3-1) by a Friedel-Crafts acylation reaction to obtain a fluorene derivative represented by the formula (d3-3). The acylating agent for introducing an acyl group represented by -CO-R ^d10 may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by formula (d3-2) is preferable. In the formula (d3-2), Hal is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected from a method of appropriately changing the conditions of the Friedel-Crafts reaction or a method of protecting and deprotecting other positions in the position to be acylated.

Then, a group represented by -CO-R ^d10 in the fluorene derivative represented by the formula (d3-3) to be obtained is converted into a group represented by -C (= N-OH) -R ^d10 , To obtain an oxime compound. The method of converting a group represented by -CO-R ^d10 into a group represented by -C (= N-OH) -R ^d10 is not particularly limited, but oxydation with hydroxylamine is preferable. An oxime compound of the formula (d3-4) and an acid anhydride ((R ^d11 CO) ₂ O) represented by the following formula (d3-5) or an acid halide (R ^d11 COHal, Hal Is a halogen atom) to obtain a compound represented by the following formula (d3-7).

Further, in the formula (d3-1), (d3-2), (d3-3), (d3-4), (d3-5), (d3-6), and (d3-7), R ^d7, R ^d8 , R ^d9 , R ^d10 , and R ^d11 are the same as in formula (d4).

In Scheme 3, R ^d10 included in each of formulas (d3-2), (d3-3) and (d3-4) may be the same or different. That is, R ^d10 in the formulas (d3-2), (d3-3) and (d3-4) may be chemically modified in the course of synthesis shown as Scheme 3. Examples of the chemical formula include esterification, etherification, acylation, amidation, halogenation, and substitution of hydrogen atoms in an amino group by an organic group. The chemical formulas acceptable for R ^d10 are not limited to these.

<Scheme 3>

[55]

The compound represented by formula (d4) can be synthesized according to the following Scheme 4 when n5 is 1, for example. In Scheme 4, a fluorene derivative represented by the following formula (d4-1) is used as a raw material. The fluorene derivative represented by the formula (d4-1) can be produced by introducing an acyl group represented by -CO-CH ₂ -R ^d10 into the compound represented by the formula (d3-1) by the Friedel-Crafts reaction, . As the acylating agent, a carboxylic acid halide represented by the formula (d3-8): Hal-CO-CH ₂ -R ^d10 is preferable. Next, the methylene group present between R ^d10 and the carbonyl group in the compound represented by the formula (d4-1) is oximized to obtain a ketooxime compound represented by the following formula (d4-3). The method of oxymering the methylene group is not particularly limited, but a method of reacting a nitrite ester represented by the following general formula (d4-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid is preferred. Then, the ketooxime compound represented by the following formula (d4-3), the acid anhydride ((R ^d11 CO) ₂ O) represented by the following formula (d4-4) A compound represented by the following formula (d4-6) can be obtained by reacting a halide (R ^d11 COHal, Hal being a halogen atom). In the following formulas (d4-1), (d4-3), (d4-4), (d4-5) and (d4-6), R ^d7 , R ^d8 , R ^d9 , R ^d10 , and R ^d11 is the same as the formula (d4).

When n5 is 1, generation of foreign matter in a pattern formed by using the photosensitive resin composition containing the compound represented by the formula (d4) tends to be further reduced.

In Scheme 4, R ^d10 included in each of formulas (d3-8), (d4-1) and (d4-3) may be the same or different. That is, R ^d10 in the formulas (d3-8), (d4-1) and (d4-3) may be chemically modified in the course of the synthesis represented by the scheme 4. Examples of the chemical formula include esterification, etherification, acylation, amidation, halogenation, and substitution of hydrogen atoms in an amino group by an organic group. The chemical formulas acceptable for R ^d10 are not limited to these.

<Scheme 4>

[56]

Suitable specific examples of the compound represented by the formula (d4) include the following PI-43 to PI-82.

[57]

[58]

(III) The content of the photopolymerization initiator is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass with respect to the solid content of the composition. By setting the content of the (III) photopolymerization initiator in the above range, it is possible to obtain a photosensitive composition hardly causing defects in the pattern shape.

As the photopolymerization initiator (III), a photo initiator auxiliary may be used in combination. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, benzoic acid Dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10 Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2- mercaptobenzooxazole, 2- mercaptobenzoimidazole, 2- Thiol compounds such as benzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiators may be used alone or in combination of two or more.

((IV) colorant)

The colorant (IV) contained in the composition is not particularly limited. For example, the color index (CI) (published by The Society of Dyers and Colourists) is a compound classified as a pigment, It is preferable to use those having the same color index (CI) number.

Examples of suitable yellow pigments include C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, .

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

Examples of suitable purple pigments include C.I. Pigment Violet 1 (hereinafter, the same is true of C. I. Pigment Violet), and only numbers are given), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40,

Examples of suitable red pigments include C.I. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 49: 1, 49: 1, 48: 2, 48: 3, 48: 4, 49: 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264 and 265.

Examples of suitable blue pigments include C.I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only numbers are listed), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, .

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 Brown 23, 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. Pigment Black 7 and the like.

When a colorant is used as a light shielding agent, a black pigment or a purple pigment is preferably used as the light shielding agent. Examples of the black pigments and the purple pigments include metal oxides, complex oxides, metal sulfides, metal sulfides such as carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, Sulphates, metal carbonates, organic, and inorganic pigments. Among these, it is preferable to use carbon black having high light shielding properties.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used. Resin-coated carbon black may also be used.

As the carbon black, carbon black to which an acidic group is introduced is also preferable. The acid group introduced into the carbon black is a functional group which indicates acidity by definition of Bronsted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acid group introduced into the carbon black may form a salt. The cation forming the acidic group and the salt is not particularly limited within the range not hindering the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ion are preferable.

Among the carbon black to which the acidic groups have been introduced as described above, it is preferable that the carbon black containing the carboxylic acid group, the carboxylic acid group, the sulfonic acid group, and the sulfonic acid group is selected from the group consisting of carboxylic acid group, sulfonic acid group, and sulfonic acid group in view of low relative dielectric constant of the light-shielding cured film formed by using the photosensitive resin composition Carbon black having at least one functional group selected is preferable.

The method of introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.

1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using a sulfite or a bisulfite hydrogen salt.

2) A method of diazotizing a carbon black with an organic compound having an amino group and an acidic group.

3) A method of reacting an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group by the Williamson etherification method.

4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.

5) A method in which carbonyl black is subjected to a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acid group protected by a protecting group, followed by deprotection.

Among these methods, the method 2) is preferable in that the acidic group introduction treatment is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The molar number of the acid group introduced into the carbon black is not particularly limited within the range not hindering the object of the present invention. The number of moles of acid groups introduced into the carbon black is preferably 1 to 200 mmol, more preferably 5 to 100 mmol, per 100 g of carbon black.

The carbon black into which the acidic group has been introduced may be coated with a resin. When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light shielding properties and insulation properties and a low surface reflectance. In addition, the coating treatment with a resin does not particularly adversely affect the dielectric constant of the light-shielding cured film formed by using the photosensitive resin composition. Examples of the resin that can be used for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glidant resin, epoxy resin and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, Polyether sulfone, polyether sulfone, polyether sulfone, polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, And a thermoplastic resin such as ketone. The covering amount of the resin with respect to the carbon black is preferably from 1 to 30 mass% with respect to the sum of the mass of the carbon black and the mass of the resin.

As the light-shielding agent, a perylene pigment is also preferable. Specific examples of the perylene pigments include perylene pigments represented by the following formula (e-1), perylene pigments represented by the following formula (e-2), and perylene pigments represented by the following formula (e-3). In the case of commercially available products, the products K0084 and K0086, Pigment Black 21, 30, 31, 32, 33 and 34, etc., which are products of BASF, can be suitably used as a perylene pigment.

[59]

In the formula (e-1), R ^e1 and R ^e2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^e3 and R ^e4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, .

[60]

In the formula (e-2), R ^e5 and R ^e6 each independently represent an alkylene group having 1 to 7 carbon atoms.

[61]

In the formula (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain a hetero atom of N, O, S, or P. When R ^e7 and R ^e8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the above formula (e-1), the compound represented by the formula (e-2) and the compound represented by the formula (e-3) are described in, for example, Japanese Patent Laid- Can be synthesized by the method described in Japanese Patent Application Laid-Open No. 266784/1990. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydrides and amines are used as raw materials, and heating reaction is carried out in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained preparation in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

In order to disperse the perylene pigment in the composition well, the average particle diameter of the perylene pigment is preferably 10 to 1000 nm.

The light-shielding agent may contain a color pigment such as red, blue, green, and sulfur together with the black pigment or the purple pigment described above for the purpose of preparing a color tone. The pigments of other colors such as black pigments and purple pigments can be appropriately selected from known pigments. For example, various pigments described above can be used as pigments of other colors such as black pigments and purple pigments. The amount of the coloring matter other than the black pigment or the purple pigment to be used is preferably 15 mass% or less, more preferably 10 mass% or less, with respect to the total mass of the light-shielding agent.

In order to uniformly disperse the colorant in the composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of a polyethylene imine type, a urethane resin type or an acrylic resin type. Particularly, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

The inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used in combination, the organic pigments are preferably used in an amount of from 10 to 80 parts by mass per 100 parts by mass of the total amount of the inorganic pigments and the organic pigments, And more preferably in the range of 20 to 40 parts by mass.

The amount of the colorant (IV) to be used in the composition may be appropriately selected so as not to impair the object of the present invention. Typically, the amount is preferably 5 to 70 parts by mass, more preferably 25 to 60 parts by mass with respect to 100 parts by mass of the total solid content of the composition The mass addition is more preferred.

(IV) The colorant is preferably added to the photosensitive resin composition after preparing a dispersion in which the colorant is dispersed at a suitable concentration using a dispersant.

((V) organic solvent)

The composition preferably contains (V) an organic solvent in order to improve the coating property and adjust the viscosity.

Specific examples of the organic solvent (V) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether , Tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. Kylene glycol monoalkyl ethers; (Propylene glycol monomethyl ether acetate), 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 (PGMEA) Alkylene 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; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, Butyl acetate, n-butyl acetate, n-butyl acetate, n-propyl acetate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate , Ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; N, N-dimethylacetamide, N, N-dimethylisobutylamide, N, N-diethylacetamide, N, N-diethyl Nitrogen-containing polar organic solvents such as formamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and N, N, N ', N'-tetramethylurea; And the like.

Of these, alkylene glycol monoalkyl ether acetates, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, lactic acid alkyl esters and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates, One other ether, and the other esters described above are more preferable.

From the viewpoints of the solubility of each component, (IV) the dispersibility of the colorant, etc., it is also preferable that the organic solvent (V) contains a nitrogen-containing polar organic solvent. As the nitrogen-containing polar organic solvent, N, N, N ', N'-tetramethylurea is preferable.

These solvents may be used alone or in combination of two or more.

The content of the organic solvent (V) is not particularly limited and is appropriately set in accordance with the thickness of the coating film at a concentration applicable to a substrate or the like. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and even more preferably 20 to 30 cp. The solid concentration is preferably 5 to 100% by mass, and more preferably 20 to 50% by mass.

(Other components)

The composition may contain, if necessary, additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, a defoaming agent, and a silane coupling agent. Any additive may be any conventionally known one.

The composition preferably includes a silane coupling agent in that it has a good shape and is easy to form a film having excellent adhesion to a substrate. As the silane coupling agent, those conventionally known can be used without particular limitation.

Examples of the surfactant include anionic, cationic and nonionic surfactants. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples of the defoaming agent include silicon compounds and fluorine compounds.

&Quot; Second Composition &quot;

The second composition is a composition containing a carboxylic acid ester having a structure represented by the following formula (A1-a).

In the structure represented by the following formula (A1-a), the carboxylic acid ester having a structure represented by the formula (A1-a) has a high alkali solubility because the number of carboxyl groups bonded to the acid anhydride residue represented by Q is 1 to 7.

Therefore, a carboxylic acid ester having a structure represented by the following formula (A1-a) is suitably used as a component of a photoresist composition or the like to be developed with, for example, an alkaline developer.

[62]

... (A1-a)

(In the formula (A1-a), R ^c1 and R ^c2 are each independently a hydrogen atom or a hydroxy group, X is a tetravalent organic group represented by the following formula (A2), Y ¹ to Y ³ are each a hydrogen atom, Wherein j is an integer of 1 to 7, m1 is an integer of 1 to 7, k1 is an integer of 1 to 6, k is an integer of 1 to 6, is an integer of 0 ~ 7, j1 is at least m1, j1 + 1k is an integer of 0 ~ 7, Gi is a group represented by the formula (A3-a) or (A4), p of ₁ ~ p ₃ is 0-4 It is an integer.)

[0065]

(In the formula (A2), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 * Represents a binding position)

[0065]

... (A3-a)

[65]

(Formula (A3-a) and (A4) ^{of, R c1, R c2, X} , Y 1 ~ Y 3, Q, Z, and p ₁ ~ p ₃ are as defined above and, G _{i +1} are G _i and the same carboxylic acid is an ester structure [However, in G _{i +1,} j _i, m _i, k _i and G _{i +1} of the G _i is a j _{i +1,} m _{i + 1,} k _{i +1,} and is represented by G _{i +2,} j _{i +1,} m _{i + 1,} k _{i +1} and the G _{i +2} is j _i, m _i, each independently and k _i and G _{i + 1} j _i, m _i, k _i and G _{i + 1} corresponding in independently and G _i to each other (This applies equally to G _{i + 2} and so on.

Expression acid ester having the structure represented by (A1-a) is H- [OY ² -] are contained in the carboxylic acid ester having the structure represented by the above formula (A1) all or part of the group represented by -O- _p2, With a carboxylic acid anhydride represented by the following formula (C1). (C1), Q is an acid anhydride residue and is a divalent organic group. The organic group as Q may contain at least one carboxylic acid anhydride group. In this case, (C1) is a polycarboxylic anhydride, and an acid anhydride residue containing a carboxylic anhydride group is present in the structure represented by formula (A1-a).

[66]

Specific examples of the carboxylic acid anhydride represented by the formula (C1) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 3,6-endo-methylene tetrahydrophthalic anhydride, methyl alicyclic dibasic acid anhydrides such as -endo-methylene tetrahydrophthalic anhydride and tetrabromophthalic anhydride; Aliphatic or aromatic aliphatic or tricarboxylic acid anhydrides such as maleic anhydride, maleic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl anhydridesuccinate, phthalic anhydride, and trimellitic anhydride, or biphenyltetracarboxylic dianhydride , Aliphatic or aromatic tetrabasic acid dianhydrides such as diphenyl ether tetracarboxylic acid dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, anhydrous pyromellitic acid, and benzophenonetetracarboxylic dianhydride. One or more of them may be used. Among them, alicyclic dibasic acid anhydride is particularly preferable.

A suitable example of the carboxylic acid ester having the structure represented by the formula (A1-a) is a mixture of at least a part of the hydroxyl groups contained in the carboxylic acid ester represented by the aforementioned formulas (Z1) to (Z4) and a carboxylic acid anhydride represented by the formula (C1) Lt; / RTI &gt;

The second composition is the same as the first composition except that the carboxylic acid ester having a structure represented by formula (A1) is replaced with a carboxylic acid ester having a structure represented by formula (A1-a).

[ Example ]

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

[Example 1]

275 g of the epoxy compound represented by the following formula (0.5 mole, epoxy equivalent 292), 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72 g of acrylic acid were introduced into a 1500 mL four- , And the mixture was heated and melted at 90 to 100 ° C while blowing air at a rate of 25 mL / min.

[67]

Then, the temperature of the solution was gradually elevated while the solution was cloudy, and the solution was completely dissolved by heating at 120 ° C. The solution gradually became a clear viscous solution, but stirring was continued. In the meantime, the acid value was measured, and heating stirring was continued until it was less than 1.0 mg KOH / g. It took 12 hours for the mountain to reach its goal. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate of a colorless transparent solid phase structure of the following formula.

[68]

Then, 650 g of propylene glycol monomethyl ether acetate was added to and dissolved in 347.4 g (0.5 mol) of the bisphenol fluorene type epoxy acrylate thus obtained, and then the compound of the following formula (b1) -1 (b1) -1) (0.25 mol) were mixed together with the catalyst, the temperature was gradually raised, and the reaction was carried out at 130 DEG C for 4 hours.

The compound (b1) -1 is a tetracarboxylic acid dianhydride (norbornane-2-spiro-a-cyclopentanone-a'-spiro-2 &quot; -norbornane- , 6,6 &quot; -tetracarboxylic dianhydride).

[69]

After confirming disappearance of the acid anhydride group, 30 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a bisphenol fluorene-type epoxy acrylate and an acid anhydride (compound b1 ) -1). &Lt; / RTI &gt; The disappearance of the acid anhydride was confirmed by IR spectrum.

[Comparative Synthesis Example 1]

Comparative carboxylic acid ester 1 was obtained in the same manner as in Example 1 except that cis-4-cyclohexene-1,2-dicarboxylic acid anhydride was used in place of compound (b1) -1 in the same molar amount.

[Comparative Synthesis Example 2]

Comparative carboxylic acid ester 2 was obtained in the same manner as in Example 1 except that 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was used in the same mole instead of the compound (b1) -1.

[Example 2, Comparative Examples 1 and 2]

A photosensitive resin composition was prepared by using the carboxylic acid ester obtained in Example 1, Comparative Synthesis Example 1, and Comparative Synthesis Example 2 according to the following method. In Example 2, the carboxylic acid ester obtained in Example 1 was used. In Comparative Example 1, the carboxylic acid ester obtained in Comparative Synthesis Example 1 was used. In Comparative Example 2, the carboxylic acid ester obtained in Comparative Synthesis Example 2 was used.

As alkali-soluble resins, 50 parts by mass of the respective carboxylic acid esters obtained in Example 1 and Comparative Synthesis Examples 1 and 2, and 15 parts by mass of dipentaerythritol hexaacrylate as a photopolymerizable monomer,

[70]

(Solid content concentration: 25 mass%) and 29 mass parts (in terms of solid content) as a pigment dispersion were dispersed and dissolved in a solvent so as to have a solid content of 20 mass% To prepare a photosensitive resin composition. The solvent component in the composition was adjusted so that 3-methoxybutyl acetate (MA) and tetramethyl urea (TMU) had an MA / TMU of 20/80 (by mass ratio).

[evaluation]

A photosensitive resin composition of each of the Examples and Comparative Examples was coated on a glass substrate of 10 cm x 10 cm and dried at 100 캜 for 120 seconds to form a photosensitive resin layer having a thickness of 2 탆.

Then, this photosensitive resin layer was subjected to selective exposure at an exposure amount of 300 mJ / cm ² through an exposure apparatus using a high-pressure mercury lamp through a negative mask with a mask size of 25 μm.

The exposed photosensitive resin layer was developed at 25 占 폚 using a KOH aqueous solution having a concentration of 0.04 mass% to obtain a photosensitive resin pattern. The developing time was 1.5 times the time for the unexposed portions of each composition to dissolve.

The obtained photosensitive resin pattern was subjected to post-baking at 230 DEG C for 20 minutes to obtain a patterned black film. The sectional shape of the pattern was confirmed from the cross-sectional SEM photograph of each pattern.

As a result, it was confirmed that the undercut shape of the photosensitive resin pattern obtained using the composition of Example 2 was the most suppressed, and the margin of the developing time was large. The photosensitive resin pattern obtained by using the composition of Comparative Example 2 had a larger undercut portion than that of Example 2, and the photosensitive resin pattern obtained by using the composition of Comparative Example 1 had a larger undercut portion than that of Comparative Example 2, It was confirmed that the developing margin is small.

Since the carboxylic acid ester obtained in Example 1 contains a skeleton derived from the tetracarboxylic dianhydride represented by the formula (b1), it is excellent in transparency and can be cured to the lower side of the photosensitive resin layer even when a pigment is contained as the photosensitive resin composition It is considered that the reaction proceeds satisfactorily.

Claims (7)

A composition containing a carboxylic acid ester having a structure represented by the following formula (A1).

(A1)
(Formula (A1) of, R ^c1 and R ^c2 are each independently a hydrogen atom or a hydroxy group, X is a tetravalent organic group represented by the formula ^{(A2), Y 1 ~ Y} 3 is a carbon atom number of 1 to 20 Wherein j1 is an integer of 0 to 7, k1 is an integer of 0 to 7, j1 + k1 is an integer of 0 to 7, and Gi is an integer of 0 to 7, and Z is an organic group of j1 + A group represented by the following formula (A3) or (A4), and p ₁ to p ₃ are integers from 0 to 4.)

(In the formula (A2), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 * Represents a binding position.)

(A3)

(Formula (A3) and (A4) ^{of, R c1, R c2, X} , Y 1 ~ Y 3, Z, and p ₁ ~ p ₃ are as defined above and, G _{i +1} are the same carboxylic acid ester structure, and G _i a [However, in G _{i +1,} j _i, k _i and G _{i +1} of the G _i denotes a j _{i +1,} k _{i +1,} and G _{i +2,} j _{i +1,} k _{i +1} and the G _{i +2} is be the same as each other independently, and G _i j _i, k _i and G _{i +} each independently represents a j _i, k _i and G _{i +1} and ₁ corresponding in, and this applies in the same manner after the G _{i + 2.].)} A composition containing a carboxylic acid ester having a structure represented by the following formula (A1-a).

... (A1-a)
(In the formula (A1-a), R ^c1 and R ^c2 are each independently a hydrogen atom or a hydroxy group, X is a tetravalent organic group represented by the following formula (A2), Y ¹ to Y ³ are each a hydrogen atom, Wherein j is an integer of 1 to 7, m1 is an integer of 1 to 7, k1 is an integer of 1 to 6, k is an integer of 1 to 6, is an integer of 0 ~ 7, j1 is at least m1, j1 + 1k is an integer of 0 ~ 7, Gi is a group represented by the formula (A3-a) or (A4), p of ₁ ~ p ₃ is 0-4 It is an integer.)

(In the formula (A2), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 * Represents a binding position)

... (A3-a)

(Formula (A3-a) and (A4) ^{of, R c1, R c2, X} , Y 1 ~ Y 3, Q, Z, and p ₁ ~ p ₃ are as defined above and, G _{i +1} are G _i and the same carboxylic acid is an ester structure [However, in G _{i +1,} j _i, m _i, k _i and G _{i +1} of the G _i is a j _{i +1,} m _{i + 1,} k _{i +1,} and is represented by G _{i +2,} j _{i +1,} m _{i + 1,} k _{i +1} and the G _{i +2} is j _i, m _i, each independently and k _i and G _{i + 1} j _i, m _i, k _i and G _{i + 1} corresponding in independently and G _i to each other (This applies equally to G _{i + 2} and so on. The method according to claim 1,
Further comprising at least one selected from the group consisting of a photopolymerization initiator, an acid generator, and a base generator. (A) at least one hydroxyl group-providing compound selected from the group consisting of a phenol compound and an alcohol,
(B) a norbornane-2-spiro-? -Cycloalkanone-? '- spiro-2 "-norbornane-5,5'',6,6" Reacting carboxylic acid dianhydrides to produce a carboxylic acid ester.

(In the formula (b1), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 Lt; / RTI &gt; The method of claim 4,
Wherein the hydroxy group-providing compound (A) is a carboxylic acid ester represented by the following formula (5).

(In the formula (5), Z, Y ¹ to Y ³ , p ₁ to p ₃ , j ₁ , and k 1 are as defined above.) The method of claim 4,
Wherein the carboxylic acid ester has a structure represented by Formula (1).

···(One)
(1), R ^c1 and R ^c2 are each independently a hydrogen atom or a hydroxy group, X is a tetravalent organic group represented by the following formula (2), Y ¹ to Y ³ are each an alkyl group having 1 to 20 carbon atoms Wherein j1 is an integer of 0 to 7, k1 is an integer of 0 to 7, j1 + k1 is an integer of 0 to 7, and Gi is an integer of 0 to 7, and Z is an organic group of j1 + (3) or (4), and p ₁ to p ₃ are integers of 0 to 4.

(In the formula (2), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 * Represents a binding position)

(3)

(Formula (3) and (4) ^{of, R c1, R c2, X} , Y 1 ~ Y 3, Z, and p ₁ ~ p ₃ are as defined above and, G _{i +1} are the same carboxylic acid ester structure, and G _i a [Note each other in G _{i +1,} j _i, k _i and G _{i +1} of the G _i is a j _{i + 1,} k _{i +1,} and G _i is represented by _+2, j _{i +1,} k _{i +1} and the G _{i +2} independently the same as G _i and a j _i, k _i and G _{i + 1} and j independently represent _i, k _i and G _{i + 1} respectively corresponding in, and this equally applied even after the G _{i +2.].)} Spiro-? -Cycloalkanone? '- spiro-2''-norbornane-5,5'', 6,6 "-tetracarboxylic acid 2 anhydride represented by the following formula (b1) Logistics of the acid anhydride ring opening esterification.

(In the formula (b1), R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m is 0 to 12 Lt; / RTI &gt;