KR20200078476A - Compound, composition, cured product, and method for producing cured product - Google Patents

Abstract

An object of the present invention is to provide a compound capable of forming a cured product having excellent electrical properties, for example. The present invention achieves the above object by providing a compound represented by the following general formula (I) (see the specification for details of the substituents in general formula (I)). It is preferable that at least one of R ¹ , R ⁵ and R ⁸ in the following general formula (I) has a hydroxyl group, and at least one of R ¹ and R ⁸ is preferably a group having a hydroxyl group.

Description

Compound, composition, cured product, and method for producing cured product

The present invention relates to a compound capable of forming a cured product having excellent electrical properties, for example.

In display devices such as liquid crystal display devices and organic EL display devices, spacers are used to maintain the distance between the upper and lower substrates of the cell.

As a spacer, a columnar spacer (hereinafter, sometimes referred to as a column spacer) formed by applying a photosensitive composition to a substrate, exposing it through a predetermined mask, and then developing it is known. In addition, recently, a black column spacer (BCS) having a column spacer and a black matrix integrated into a single module and having light shielding properties has been used (Patent Document 1).

Japanese Patent Application Publication No. 2017-53942

However, the cured product of the conventional photosensitive composition has low electrical properties, and display defects may occur when a display device is formed using the spacer.

The present invention has been made in light of the above problems, and for example, it is a main task to provide a compound capable of forming a cured product having excellent electrical properties.

The present inventors have made extensive studies to solve the above problems, and as a result, the cured product of the photosensitive composition has a deterioration in electrical properties due to decomposition products of the photopolymerization initiator, and a cured product having excellent electrical properties is introduced by introducing a hydroxyl group into the photopolymerization initiator. It has been found that it can be formed and the present invention has been completed.

That is, the present invention provides a compound represented by the following general formula (I) (hereinafter, sometimes referred to as compound I).

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, It represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and is represented by R ¹¹ , R ¹² and R ¹³ . The hydrogen atom of the substituent represented is OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , -C(=N-OR ²¹ )- R ²² , -C(=N-OCOR ²¹ )-R ²² , CN, a halogen atom, or COOR ^{21 may} be substituted,

R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 represents a heterocyclic group, and the hydrogen atom of the substituent represented by R ²¹ , R ²² and R ^{23 may} be substituted with a CN, halogen atom, hydroxyl group or carboxyl group,

The alkylene portion of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ COO It may be interrupted 1 to 5 times by -, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-, R ²⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, carbon Represents an aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ The alkyl portion of the substituent may be a branched chain or a cyclic alkyl, and R ¹² and R ¹³ and R ²² and R ²³ may be one each to form a ring,

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl group, nitro group, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ and R ⁷ are each one to form a ring. , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. Represents a heterocyclic group of 20,

R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

The alkyl portion of the group represented by R ^{8 may} be a branched chain or a cyclic alkyl,

The hydrogen atom of the group represented by R ⁸ is furthermore R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , -C(=N-OR ²¹ )-R ²² , -C(=N-OCOR ²¹ )-R ²² , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, It may be substituted with CN, halogen atom, or COOR ²¹ ,

X is a group represented by a direct bond or CO,

a represents an integer from 0 to 3,

At least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a group having a hydroxyl group.)

In compound I of the present invention, it is preferable that at least one of R ¹ , R ⁵ and R ⁸ has a hydroxyl group.

In compound I of the present invention, at least one of R ¹ and R ⁸ is a group having a hydroxyl group,

When R ¹ is a group having a hydroxyl group, R ¹ is a group represented by R ¹¹ , R ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. , And when the hydrogen atom of the alkyl group, the aryl group, and the arylalkyl group is substituted with OR ²¹ , and the hydrogen atom of R ²¹ is substituted with a hydroxyl group, and R ⁸ is a group having a hydroxyl group, R ⁸ is 1 to 1 carbon atom. It is an alkyl group of 20 or an aryl group having 6 to 30 carbon atoms, and is preferably a group in which the hydrogen atom of the alkyl group or the aryl group is substituted with a carboxyl group.

The present invention provides a composition comprising Compound I described above.

The present invention provides a cured product of the composition described above.

The present invention provides a method for producing a cured product having a step of irradiating light with respect to the above-described composition.

According to the compound of the present invention, for example, a cured product having excellent electrical properties can be formed.

According to the composition of the present invention, it is possible to easily obtain a cured product excellent in electrical properties such as electrical retention.

The cured product of the present invention has excellent electrical properties such as electrical retention.

According to the method for producing a cured product of the present invention, it is possible to easily obtain a cured product having excellent electrical properties such as electrical retention.

The present invention relates to a compound, a composition, a cured product thereof and a method for producing the cured product.

Hereinafter, the compound, composition, cured product of the present invention and a method for producing the cured product will be described in detail.

A. Compound

First, the compound of the present invention will be described.

The compound of the present invention is represented by the following general formula (I).

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, carbon Represents an alkyl group having 1 to 20 atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, represented by R ¹¹ , R ¹² and R ¹³ The hydrogen atom of the substituent is OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , -C(=N-OR ²¹ )-R ²² , -C(=N-OCOR ²¹ )-R ²² , CN, halogen atom, or may be substituted with COOR ²¹ ,

R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 represents a heterocyclic group, and the hydrogen atom of the substituent represented by R ²¹ , R ²² and R ^{23 may} be substituted with a CN, halogen atom, hydroxyl group or carboxyl group,

The alkylene portion of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ COO It may be interrupted 1 to 5 times by -, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-, R ²⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, carbon Represents an aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ The alkyl portion of the substituent may be a branched chain or a cyclic alkyl, and R ¹² and R ¹³ and R ²² and R ²³ may be one each to form a ring,

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl group, nitro group, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ and R ⁷ are each one to form a ring. , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 carbon atoms. Represents a ~20 heterocyclic group,

R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

The alkyl portion of the group represented by R ⁸ may have a branched side chain or a cyclic alkyl,

The hydrogen atom of the group represented by R ⁸ is furthermore R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , -C(=N-OR ²¹ )-R ²² , -C(=N-OCOR ²¹ )-R ²² , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, It may be substituted with CN, a halogen atom, or COOR ²¹ ,

X is a group represented by direct bond or CO,

a represents the integer of 0-3,

At least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a group having a hydroxyl group.)

Since the compound I of the present invention has a carbazole structure, an oxime ester group, and a hydroxyl group, for example, it is possible to form a cured product having excellent electrical properties. When the influence of changes in the electrical properties of the member adjacent to the cured product is small, it can be said that the cured product has excellent electrical properties. For example, when the member adjacent to the cured product is a liquid crystal composition containing a liquid crystal material, it can be said that the cured product has excellent electrical properties when the drop in voltage retention (VHR) of the liquid crystal composition is small.

Here, the reason why the above-described effect is exhibited by the compound I of the present invention having the above structure or the like is estimated as follows.

That is, a conventionally known photopolymerization initiator having a carbazole structure and an oxime ester group functions as a radical polymerization initiator by generating radicals by light irradiation.

In addition, when the photopolymerization initiator generates a radical, a decomposition reaction occurs as an oxime ester group, and a decomposition product is generated. And when the decomposition product is transferred to the liquid crystal layer, the voltage retention of the liquid crystal composition containing the liquid crystal material is lowered. A decrease in the voltage retention rate of the liquid crystal composition causes, for example, poor display of the liquid crystal display device.

On the other hand, since the compound I of the present invention has a hydroxyl group together with a carbazole structure and an oxime ester group, the decomposition product also has a hydroxyl group.

In addition, since the decomposition product has a hydroxyl group, it has a low affinity with a liquid crystal material that generally exhibits hydrophobicity. For example, even when a cured product is used as a spacer for a liquid crystal layer, the voltage retention of the liquid crystal composition is lowered Transfer to the cause liquid crystal layer is suppressed.

From the above, the compound I of the present invention has a structure as described above, and thus becomes a compound capable of forming a cured product excellent in electrical properties.

In addition, the carbazole structure can absorb ultraviolet light of a wide wavelength, and it can be said that the generation efficiency of radicals in the oxime ester group is high.

Moreover, the carbazole structure tends to have a low shift to the liquid crystal layer with respect to radical generation efficiency.

For this reason, the compound I of the present invention has the above-described carbazole structure and an oxime ester group, thereby providing an excellent balance of sensitivity and effect of suppressing migration to the liquid crystal layer.

As a result, the compound I of the present invention has excellent electrical properties and excellent sensitivity, so that a cured product can be easily formed. Further, by being highly sensitive, for example, a cured product having a thick film thickness at a portion with a large exposure amount and a thin film thickness at a portion with a small exposure amount can be easily obtained.

Even in this respect, the compound I of the present invention is a compound capable of forming a cured product having excellent electrical properties having the above-described structure.

Moreover, in a display device such as a liquid crystal display device, a black column spacer may be formed on an element formed on a substrate or on a portion of the substrate on which the element is formed and opposite to an element of the substrate. In this case, it is necessary to change the height of the black column spacer in the portion where the element is formed and other portions in consideration of the height of the element. At this time, if the black column spacers of different heights can be formed at once by performing exposure through a halftone mask, the manufacturing merit is large. Since the compound I of the present invention has high sensitivity as described above, it becomes easy to form black column spacers of different heights at once using a halftone mask.

Hereinafter, the compound I of the present invention will be described in detail.

Compound I of the present invention is represented by the general formula (I), wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (I) is It is a group having a hydroxyl group.

1. Groups with hydroxyl groups

In view of the fact that the compound I can form a cured product having excellent electrical properties, for example, at least one group of R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is the hydroxyl group It is preferable that the branch is a group, and among these, at least one of R ¹ , R ⁵ and R ⁸ is preferably a group having a hydroxyl group, and particularly, at least one of R ¹ and R ⁸ is preferably a group having the hydroxyl group. Since the above-mentioned group is a group having the hydroxyl group, Compound I of the present invention can form a cured product having excellent electrical properties. Moreover, it is because the compound I of the present invention can be easily synthesized. In the present invention, the group having a hydroxyl group includes the hydroxyl group itself.

The number of hydroxyl groups included in the group having such a hydroxyl group may be 1 or more, and may be appropriately set according to the use of the compound I, required electrical properties, ease of synthesis, etc., for example, 1 or more 10 It is preferable to use the following, more preferably 1 or more and 5 or less, and more preferably 1 or more and 2 or less. This is because, as being the number of the hydroxyl group, the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

On the other hand, the compound represented by the general formula (2) to be described later shows an example of a compound containing a group having two hydroxyl groups.

The type of hydroxyl group included in the group having the hydroxyl group may be, for example, a hydroxyl group bound to a carbon atom of the carbonyl group and included as part of the carboxyl group. It is preferable to be included as a combined alcoholic hydroxyl group or a phenolic hydroxyl group bonded to a carbon atom of an aromatic hydrocarbon, and particularly preferably contained as an alcoholic hydroxyl group.

On the other hand, the compound represented by the general formula (1) to be described later shows an example in which the hydroxyl group is an alcoholic hydroxyl group, and the compound represented by the general formula (3) shows an example in which the hydroxyl group is included as part of the carboxyl group.

The bonding position of the hydroxyl group included in the group having the hydroxyl group is preferably the end of the group having the hydroxyl group. This is because the compound I can form a cured product having superior electrical properties and is easy to synthesize.

On the other hand, the term "terminal of the group having a hydroxyl group" means that the hydroxyl group included in the group having the hydroxyl group is bonded to the position farthest from the bonding position with the carbazole structure or the oxime ester group.

For example, the general formula (5) to be described later shows an example in which the bonding position of the hydroxyl group is the end of a group having a hydroxyl group, and the general formula (8) shows an example in which the bonding position of the hydroxyl group is not the end of a group having a hydroxyl group. To indicate.

Although the number of carbon atoms of the group having a hydroxyl group may be 0, it is preferably 1 or more, particularly 2 or more, particularly preferably 4 or more, and preferably 6 or more. The upper limit of the number of carbon atoms is not particularly limited as long as the desired electrical properties can be obtained, but it can be, for example, 20 or less, preferably 15 or less, and preferably 10 or less. This is because the compound I can form a cured product having superior electrical properties and is easy to synthesize.

On the other hand, when the number of carbon atoms of the group having a hydroxyl group is 0, the group having a hydroxyl group may be, for example, a hydroxyl group directly bonded to a carbazole structure or an oxime ester group.

The number of groups having the hydroxyl group in compound I, that is, the number of groups having a hydroxyl group in R ¹ to R ⁸ may be one or more, depending on the use of compound I, required electrical properties, ease of synthesis, etc. Although it can be set appropriately, for example, it can be 1 or more and 5 or less, preferably 1 or more and 3 or less, preferably 1 or more and 2 or less, and preferably 1. This is because the number of groups having the hydroxyl group is within the above-mentioned range, and the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

On the other hand, the number of groups having a hydroxyl group is 2, for example, the case where both of R ¹ and R ⁵ are groups having a hydroxyl group can be mentioned. More specifically, the compounds represented by the general formulas (34) and (35), which will be described later, show an example in which the number of groups having the hydroxyl group is 2.

The number of hydroxyl groups included in the compound I may be 1 or more, and may be 1 or more and 10 or less, preferably 1 or more and 5 or less, and more preferably 1 or more and 2 or less. . This is because, as being the number of the hydroxyl group, the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

2. Compound I

An alkyl group having 1 to 20 carbon atoms represented by R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (I). For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, amyl group, isoamyl group, t-amyl group, hexyl group, heptyl group , Octyl group, isooctyl group, 2-ethylhexyl group, t-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, Icosyl group, cyclopentyl group, cyclopentyl methyl group, cyclopentyl ethyl group, cyclohexyl group, cyclohexyl methyl group, cyclohexyl ethyl group, etc. are mentioned.

An aryl group having 6 to 30 carbon atoms represented by R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (I). For example, phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl, anthryl group and phenanthrenyl group, and phenyl group substituted with one or more of the above alkyl groups, biphenylyl group, naphthyl group and anthryl group, etc. Can be lifted.

Arylalkyl groups having 7 to 30 carbon atoms represented by R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (I) Examples of the furnace include a benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.

A heterocyclic group having 2 to 20 carbon atoms represented by R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (I). Examples of the pyridyl group, pyrimidyl group, furyl group, thienyl group, tetrahydrofuryl group, dioxolanyl group, benzooxazol-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidil group, The 5-7 membered heterocycles, such as a pyrazolidil group, a thiazolidil group, an isothiazolidil group, an oxazolidil group, an isooxazolidil group, a piperidyl group, a piperazyl group, and a morpholinyl group, are mentioned preferably.

The halogen atom in the general formula (I) includes, for example, fluorine, chlorine, bromine and iodine.

In the general formula (I), R ¹² and R ¹³ , and R ²² and R ²³ may be formed as one, for example, cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, blood The 5-7 membered ring, such as a peridine ring, morpholine ring, lactone ring, and lactam ring, is mentioned preferably.

The alkylene portion of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the general formula (I) is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- may be interrupted 1 to 5 times. The linking group may be one or two or more groups, and in the case of groups that can be interrupted continuously, two or more may be interrupted continuously.

In addition, the alkyl (alkylene) portion of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the general formula (I) has a branched side chain or cyclic alkyl (cyclic alkylene). It may be.

In the present invention, the number of carbon atoms in the group defines the number of carbon atoms in the group after the substitution if the alkylene portion in the group is substituted with the divalent group. For example, in the present specification, when the alkylene group in the alkyl group having 1 to 20 carbon atoms is substituted with the divalent group, the "carbon number of 1 to 20" refers to the number of carbon atoms after the alkylene group is substituted. , It does not indicate the number of carbon atoms before the alkylene group is substituted.

Similarly, when the hydrogen atom in the group is substituted with a substituent, the number of carbon atoms in the group after the substitution is defined. For example, when the hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted, the number of carbon atoms 1 to 20 refers to the number of carbon atoms after the hydrogen atom is substituted, and indicates the number of carbon atoms before the hydrogen atom is substituted. It is not.

In the general formula (I), R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ and R ⁷ are each formed as one ring, and R ¹² and R ¹³ and R ²² and R ²³ are one. It can be made similarly to the ring which can be formed.

When R ¹ is a group having the hydroxyl group, R ¹ is a group represented by R ¹¹ , and R ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. It is preferably an alkyl group, more preferably an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 15 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms. It is more preferable that it is an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms.

Further, it is R ^1, if group having the hydroxyl group, the R group ¹ is represented by R ^11, Furthermore, the R ¹¹ In this case, an alkyl group of carbon atom 1 ~ 20, R ¹¹ is an alkyl group of a carbon atom number of 1 to 10 It is preferable, and it is preferable that it is a C1-C5 alkyl group especially, and it is especially preferable that it is a C1-C3 alkyl group.

This is because when R ¹ is the above-described group, the compound I can form a cured product having excellent electrical properties and is easy to synthesize. Moreover, it is because the above-mentioned compound I becomes easy to aim at broadening the absorption wavelength, and a composition having excellent sensitivity can be obtained.

The R ¹¹ that is used for R ¹ to be substituted with the alkyl group, if the aryl group or the aryl group, the alkyl group, the aryl group and the hydrogen atom is OR ²¹ of the arylalkyl group preferably, R ²¹ is the number of carbon atoms It is preferably an alkyl group having 1 to 20, more preferably R ²¹ is an alkyl group having 1 to 10 carbon atoms, and particularly preferably R ²¹ is an alkyl group having 1 to 5 carbon atoms.

When R ¹ is a group having the hydroxyl group, R ¹ is a group represented by R ¹¹ , and R ¹¹ is the alkyl group, the aryl group, or the arylalkyl group, it can be said that the hydrogen atom of these groups is substituted with a hydroxyl group.

R ¹ is preferably a hydrogen atom of the alkyl group, the aryl group, and the arylalkyl group of R ¹¹ is substituted with OR ²¹ , and the hydrogen atom of R ²¹ is substituted with a hydroxyl group.

When R ¹ is a group having the hydroxyl group, R ¹ is more specifically a group represented by R ¹¹ , R ¹¹ is the alkyl group, the aryl group, or the arylalkyl group, and the alkyl group, the aryl group, and the arylalkyl group It is preferable that the hydrogen atom is substituted with OR ²¹ , R ²¹ is an alkyl group, and that the hydrogen atom of R ²¹ is a hydroxyl group.

When R ¹ is a group having a hydroxyl group and X is a direct bond, R ¹ is preferably the alkyl group or an arylalkyl group. In addition, when R ¹ is a group having a hydroxyl group and X is CO, R ¹ is preferably the alkyl group, arylalkyl group, or aryl group.

This is because when R ¹ is the above-described group, the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

When R ¹ is a group having no hydroxyl group, R ¹ is a group represented by R ¹¹ , and R ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. It is preferable that it is an alkyl group, R ¹¹ is preferably an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and R ¹¹ is an alkyl group having 1 to 10 carbon atoms or 7 to 10 carbon atoms. It is more preferable that it is an arylalkyl group, and R ¹¹ is more preferably an alkyl group having 1 to 10 carbon atoms or an arylalkyl group having 7 to 10 carbon atoms in which the alkylene portion is substituted with -OCO-, and R ¹¹ is carbon. It is particularly preferable that the alkyl group having 1 to 10 atoms or the alkylene at the side end of the oxime ester is an arylalkyl group having 7 to 10 carbon atoms substituted with -OCO-.

R ¹ is a group having no hydroxyl group, and when X is a direct bond, preferably an alkyl group or an arylalkyl group. Moreover, it is preferable that R<^1> is a group which does not have a hydroxyl group, and when X is CO, it is an alkyl group, an arylalkyl group, or an aryl group.

This is because when R ¹ is the above-described group, the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

Further, when R group ¹ does not have a hydroxyl group, a group in it is easy to reduce the wide screen of the absorption wavelength, and the viewpoint of that the superior sensitivity R ¹ is represented by R ^11, R ¹¹ can be from 6 to 30 carbon atoms Is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.

When R ⁵ is a group having the hydroxyl group, R ⁵ is preferably a group represented by -COR ¹¹ . R ¹¹ is an aryl group of carbon atoms of 1 to 20 alkyl group or a carbon atom number of 6 to 30 is preferable, and, R ¹¹ is more preferably a number from 6 to 15 carbon atoms, an aryl group, wherein R ¹¹ carbon atom 6 It is particularly preferable that it is an aryl group of ~10.

When R ¹¹ used in R ⁵ is the alkyl group, the aryl group, or the arylalkyl group, it is preferable that the hydrogen atom of the alkyl group, the aryl group, and the arylalkyl group is substituted with OR ²¹ , and R ²¹ is the number of carbon atoms. It is preferably an alkyl group having 1 to 20, more preferably R ²¹ is an alkyl group having 1 to 10 carbon atoms, and particularly preferably R ²¹ is an alkyl group having 1 to 5 carbon atoms.

When R ⁵ is a group having a hydroxyl group, R ⁵ is a group represented by -CO-R ¹¹ , and when R ¹¹ is the alkyl group, the aryl group, or the arylalkyl group, a hydrogen atom in any one of these groups is substituted with a hydroxyl group It can be said. In R ⁵ , the hydrogen atom of the alkyl group, the aryl group, and the arylalkyl group represented by R ¹¹ in -CO-R ¹¹ is substituted with OR ²¹ , and when R ²¹ is an alkyl group, the hydrogen atom of R ²¹ is substituted with a hydroxyl group. Is preferred.

When R ⁵ is a group having the hydroxyl group, more specifically R ⁵ is a group represented by -CO-R ¹¹ , R ¹¹ is the alkyl group or the aryl group, and the hydrogen atom of the alkyl group and the aryl group is OR ²¹ It is preferable that the hydrogen atom of R ²¹ is substituted with a hydroxyl group.

When R ⁵ is a group having the above hydroxyl group, the number of hydroxyl groups included in R ⁵ is preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, particularly preferably 1 or more and 2 or less. In particular, it is particularly preferable to use two.

This is because R ⁵ is the above-described group, and the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

When R ⁵ is a group having no hydroxyl group, R ⁵ is a group represented by R ¹¹ or a nitro group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom It is preferably an arylalkyl group having a number of 7 to 30, a group represented by R ¹¹ or a nitro group, preferably R ¹¹ is a hydrogen atom, particularly preferably a nitro group.

This is because R ⁵ is the above-described group, and the compound I can form a cured product having excellent electrical properties and is easy to synthesize. Moreover, it is because the said compound I becomes excellent in sensitivity.

When R ² is a group having no hydroxyl group, R ² is a group represented by R ¹¹ , and R ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. It is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms. Do.

When R ³ , R ⁴ , R ⁶ and R ⁷ are groups having no hydroxyl group, R ³ , R ⁴ , R ⁶ and R ⁷ are groups represented by R ¹¹ , R ¹¹ is a hydrogen atom, and 1 to 20 carbon atoms It is preferably an alkyl group, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom. Do.

This is because R ² , R ³ , R ⁴ , R ⁶ and R ⁷ are the groups described above, and the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

When R ⁸ is a group having the hydroxyl group, R ⁸ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and carbon It is particularly preferable that it is an alkyl group having 1 to 10 atoms.

When R ⁸ is a group having the hydroxyl group, and R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, any one of these groups can be said substituted by a hydrogen atom is a hydroxyl group, particularly (and COOR ^21, R ²¹ is one of a hydrogen atom), the alkyl group, the aryl group, and hydrogen atom is a hydroxyl group or a carboxyl group of the aryl group, and preferably will substituted with, It is preferable that the hydrogen atom of the alkyl group, the aryl group, and the arylalkyl group is substituted with a carboxyl group (COOR ²¹ and R ²¹ is a hydrogen atom).

When R ⁸ is a group having the hydroxyl group, more specifically, R ⁸ is the alkyl group or the aryl group, and the hydrogen atom of the alkyl group or the aryl group is substituted with a carboxyl group (COOR ²¹ , where R ²¹ is a hydrogen atom). It is preferable that it is a group.

This is because R ⁸ is the above-mentioned group, and the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

When R ⁸ is a group having no hydroxyl group, R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably 1 carbon atom. It is particularly preferable that it is an alkyl group of ~5.

This is because R ⁸ is the above-mentioned group, and the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

A in the compound I represents the number of functional groups of R ³ , and may be an integer from 0 to 3, preferably an integer from 0 to 2, particularly preferably an integer from 0 to 1, particularly preferably 0. This is because the compound I is capable of forming a cured product having excellent electrical properties, and is easy to synthesize because the a is within the above-mentioned range.

X in the compound I is a group represented by a direct bond or CO, and is preferably CO from the viewpoint of excellent sensitivity and obtaining a cured product sufficiently cured.

In the compound I, the bonding position of the oxime ester group may be any part of the benzene ring contained in the carbazole structure, for example, as represented by the following general formula (Ia), which is the 6th position of the carbazole structure. It is preferred. This is because the compound I can form a cured product having excellent electrical properties and is easy to synthesize.

(In the formula, R ¹ , R ² , R ⁵ and R ⁸ and X represent the same group as the general formula (I).)

It is preferable that the compound I is a compound represented by the above general formula (Ia). This is because the compound having a hydroxyl group represented by the general formula (Ia) can form a cured product having excellent electrical properties and is easy to synthesize.

As specific examples of the compound I represented by the general formula (I), the following compounds (1) to (14), (21) to (35), (41) to (54), (61) to (79) It can be preferably used. It is because these compounds can form a hardened|cured material excellent in electrical properties, and are easy to synthesize|combine.

The molecular weight of the compound I can be set according to the use of the compound I and the like. The molecular weight of the compound I can be, for example, 250 or more and 2000 or less, 300 or more and 2000 or less, and 350 or more and 1000 or less. This is because a cured product having excellent electrical properties can be formed when the molecular weight of Compound I is within the above-mentioned range.

The method for producing the compound I represented by the general formula (I) is not particularly limited as long as it is a method for obtaining the compound I having the above structure. For example, a method described in Japanese Patent Publication No. 4223071 can be used. Specifically, it can be produced by the following reaction scheme.

First, an acyl body (I-2) is obtained by reacting a carbazole compound (I-0) and an acid chloride (I-1) in the presence of aluminum chloride. Subsequently, the acyl body (I-2) and hydroxylamine hydrochloride are reacted in the presence of DMF to obtain an oxime compound (I-3). Subsequently, an oxime compound (I-3) and an acid anhydride (I-4) or an acid chloride (I-5) are reacted to obtain an oxime ester compound (I-6) of the present invention corresponding to the general formula (I). And a method.

On the other hand, in the production method, at least one of R ² to R ⁸ may be a carbazole compound (I-0), which is a group having a hydroxyl group. Moreover, after reaction with an acid anhydride (I-4) or an acid chloride (I-5) using a carbazole compound (I-0) in which R ² to R ⁸ are hydrogen atoms, an alkyl group having a hydroxyl group according to a conventional method, etc. It may be a method of introducing.

The following reaction scheme shows a method for preparing the compound I in which X is a direct bond.

When preparing the compound I in which X is -CO-, the same method as the above production method can be used, except that a method of reacting an acyl body (I-3) and a nitrite ester in the presence of hydrochloric acid is used as a method for forming an oxime compound. Can.

(In the formula, R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ and a represent the same group as the general formula (I).)

As the use of the compound I, for example, it can be used as a photopolymerization initiator component that generates radicals by light irradiation.

In addition, the use of the compound I can be used, for example, by adding to a composition such as a photocurable composition.

Examples of the use of the composition include, for example, photo-curable paints or varnishes, photo-curable adhesives, printed boards, or color filters and plasmas in color display liquid crystal display elements such as color TVs, PC monitors, portable information terminals, digital cameras, etc. Electrode materials for display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solder resists, color filters for various display applications A composition for manufacturing or encapsulating a resist for forming a structure in the manufacturing process of a plasma display panel, an electroluminescent display device, and an LCD, an electrical and electronic component, a magnetic recording material, and a micro machine Components, waveguides, optical switches, masks for plating, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, microelectronic circuits , Decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, in sequential lamination of printed circuit boards It can be used for various uses, such as a photoresist material or a protective film used to form a dielectric layer of, there is no particular limitation on the use.

Among the uses of the compound I, for example, from the viewpoint of more effectively exerting the effect that a cured product having excellent electrical properties can be formed, for example, the alignment layer, the spacer of the liquid crystal layer, the insulating film, the overcoating layer, and the surroundings of the liquid crystal layer It is preferable to be a member for contact with a liquid crystal material such as a sealing agent to be sealed, a color filter, or a black matrix, and particularly, it is preferable for a spacer for a liquid crystal layer.

In the present invention, by using the compound I, for example, a liquid crystal layer spacer characterized in that it has a cured product of a composition containing the compound I, a liquid crystal display device characterized in that it comprises the liquid crystal layer spacer, etc. Can be obtained.

Meanwhile, the liquid crystal layer spacer may be used, for example, as a black column spacer which also has a function as a black matrix.

B. Photopolymerization initiator

Next, the photopolymerization initiator of the present invention will be described.

The photopolymerization initiator of the present invention is characterized by including the compound I described above.

When the photopolymerization initiator of the present invention contains the compound I, for example, a cured product having excellent electrical properties can be formed.

The photopolymerization initiator includes compound I described above.

Hereinafter, each component of the said photoinitiator is demonstrated.

The content of the compound I in the photopolymerization initiator of the present invention may be any one that can impart desired photopolymerization curability, and can be appropriately set depending on the use of the photopolymerization initiator and the like. It can be said that the content of the compound I in the photopolymerization initiator is 100 parts by mass in 100 parts by mass of the photopolymerization initiator, that is, the photopolymerization initiator is composed of only the compound I. This is because the content of the compound I is useful as a photopolymerization initiator that is easy to form a cured product having excellent electrical properties because it is within the above-described range.

In addition, the content of the compound I in the photopolymerization initiator of the present invention is less than 100 parts by mass in 100 parts by mass of the photopolymerization initiator, that is, the photopolymerization initiator can be a composition containing the compound I and other components. In that case, the content of compound I can be, for example, more than 30 parts by mass and 99 parts by mass or less, and preferably 50 parts by mass or more and 75 parts by mass or less. This is because the content of the compound I is useful as a photopolymerization initiator that is easy to form a cured product having excellent electrical properties because it is within the above-described range.

In the present invention, the content is based on mass unless otherwise specified.

As for the type of the compound I contained in the photopolymerization initiator, only one type may be used, or two or more types may be used. The said kind can be made into two or more types and five or less types, for example.

On the other hand, for Compound I described above, the contents described in the section "A. Compound" can be carried out in the same way, and thus descriptions thereof will be omitted.

As the other components, those that do not impair the function as a photopolymerization initiator can be used, for example, the components described in the item "2. Other components" of "C. Composition" to be described later, "E. Cured product" to be described later. The polymer component etc. which were described in the item of are mentioned.

Especially, it is preferable that the photoinitiator of this invention contains the said polymer component as said other component.

The photopolymerization initiator may have a powder shape or a pellet shape.

When the photopolymerization initiator is in the form of pellets, for example, a method of mixing the compound I and the polymer component using an extruder or the like and then molding into a pellet may be used.

C. Composition

Next, the composition of the present invention will be described.

The composition of the present invention is characterized by including the compound I described above.

By including the compound I, the composition of the present invention can easily obtain a cured product excellent in the above properties.

The composition of the present invention comprises Compound I.

Hereinafter, each component contained in the composition of the present invention will be described in detail.

1.Compound I

The content of the compound I in the composition of the present invention is not particularly limited as long as it can impart desired curability and the like to the composition.

The content of the compound I in the composition of the present invention can be, for example, 0.001 part by mass or more and 30 parts by mass or less in 100 parts by mass of the solid content of the composition, and is preferably 0.005 parts by mass or more and 10 parts by mass or less. This is because a cured product having excellent electrical properties can be more easily obtained.

On the other hand, the solid content includes all components other than the solvent.

Content of the said compound I can be 0.001 mass part or more and 30 mass parts or less in 100 mass parts of compositions, and it is preferable that it is 0.005 mass parts or more and 10 mass parts or less. This is because a cured product having excellent electrical properties can be more easily obtained.

The content of the compound I is 0.01 to 30 parts by mass in 100 parts by mass of the total of the compound I, the polymerizable compound and the polymer having a hydrophilic group, when the composition contains a polymerizable compound or a polymer having a hydrophilic group It is preferable that it is 0.1 parts by mass or more and 25 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and particularly preferably 1 part by mass or more and 15 parts by mass or less. This is because a cured product having excellent electrical properties can be more easily obtained.

The compound I contained in the composition may be of only one type, or may be of two or more types. The said kind can be made into two or more types and five or less types, for example. This is because it is easy to form a cured product having excellent electrical properties because the type of compound I is within the above-mentioned range.

On the other hand, for Compound I described above, the contents described in the section "A. Compound" can be carried out in the same way, and thus descriptions thereof will be omitted.

2. Other

The composition is to include the compound I, may contain other components as necessary.

The other components include polymerizable compounds, polymers having hydrophilic groups, colorants, solvents, fillers, anti-reflective agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellent agents, etc. Dispersants for dispersing inorganic compounds, colorants, inorganic compounds, and the like, the polymerizable compound used to improve the properties of the cured product, a polymer different from the polymer A, and a polymerizable compound obtained by improving the properties of the cured product, other than a polymer having a hydrophilic group And other organic polymers, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine, and the like.

(1) polymerizable compounds

The composition of the present invention can be easily used as a photocurable composition by including the polymerizable compound.

The polymerizable compound may be any one capable of forming a polymer, and for example, it may be said to have a radically polymerizable group.

The polymerizable compound may be a radical polymerizable group, for example, a compound having an ethylenically unsaturated double bond such as a (meth)acrylic group or a vinyl group.

On the other hand, (meth)acrylic is used in a sense including acrylic and methacryl. In addition, (meth)acrylate is used in the sense containing acrylate and methacrylate.

Examples of such polymerizable compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene, (meth)acrylic acid, α-chloroacrylic acid, and ita Conic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono succinate [2-(meth)acryloyloxyethyl] , Mono(meth)acrylate, hydroxyethyl of polymers having carboxyl groups and hydroxyl groups at both ends, such as mono phthalate [2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate (Meth)acrylate, maleate, hydroxypropyl (meth)acrylate, maleate, dicyclopentadiene, maleate or polyfunctional (meth)acrylic having one or more carboxyl groups and two or more (meth)acryloyl groups Unsaturated polybasic acids such as rate, (meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid glycidyl, the following compounds No.A1 to No.A4, (meth)acrylic acid Methyl, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Isononyl, (meth)acrylic acid stearyl, (meth)acrylic acid lauryl, (meth)methoxyethyl acrylate, (meth)dimethyl acrylate aminomethyl, (meth)acrylic acid dimethylaminoethyl, (meth)acrylic acid aminopropyl, ( Dimethylaminopropyl methacrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate , (Meth)acrylic acid tetrahydrofuryl, (meth)acrylic acid vinyl, (meth)acrylic acid allyl, (meth)acrylate benzyl, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di (Meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) Ta)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritolpenta(meth)acrylate, pentaerythritol Tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecanedimethyloldi(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester(meth)acrylate Unsaturated monobasic acids such as oligomers and esters of polyhydric alcohols or polyphenols, metal salts of unsaturated polybasic acids such as zinc (meth)acrylate, magnesium (meth)acrylate, maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydro Phthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyl Tetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl anhydride, methyl anhydride, and other unsaturated polybasic acid anhydrides, (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris( Unsaturated monobasic acids such as meta)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide, and amides of polyvalent amines, unsaturated aldehydes such as acrolein , Unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide, styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, Unsaturated aromatic compounds such as 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether, methyl vinyl ketone, etc. Unsaturated amine compounds such as unsaturated ketone, vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine, vinyl alcohols such as allyl alcohol and crotyl alcohol; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether, unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide, Indens such as indene and 1-methylindene, aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene, polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, polysiloxane Macromonomers having a mono(meth)acryloyl group at the end of a polymer molecular chain such as vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl Thioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound vinyl urethane compound, hydroxyl group-containing vinyl monomer and polyepoxy compound vinyl epoxy compound Can be lifted.

Among these, a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, a polyfunctional (meth)acrylate having one carboxyl group and two or more (meth)acryloyl groups, unsaturated monobasic acid and polyhydric alcohol, or Esters of polyphenols are preferred from the viewpoints of curability and chromaticity properties.

The polymerizable compounds may be used alone or in combination of two or more.

The molecular weight of the polymerizable compound is not particularly limited as long as the desired cured product can be obtained, but can be, for example, less than 2000, preferably 1500 or less, particularly preferably 1000 or less, and less than 1000 Especially preferred. It is because it becomes the thing excellent in hardenability.

On the other hand, the molecular weight is expressed by the weight average molecular weight (Mw) when the polymerizable compound is a polymer containing a repeating structure as its structure.

In addition, below, the weight average molecular weight can be calculated|required as a standard polystyrene conversion value by gel permeation chromatography (GPC).

The weight average molecular weight Mw, for example, using GPC (LC-2000plus series) manufactured by Nippon Bunko Co., Ltd., the eluent is tetrahydrofuran, and the polystyrene standard for the calibration curve is Mw1110000, 707000, 397000, 189000 , 98900, 37200, 13700, 9490, 5430, 3120, 1010, 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and the measurement columns were KF-804, KF-803, KF-802 (Showa Denko Co., Ltd. ) Product).

In addition, the measurement temperature can be 40°C, and the flow rate can be 1.0 ml/min.

The content of the polymerizable compound is not particularly limited as long as a desired cured product can be obtained. For example, it can be 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. It is preferable that it is 40 parts by mass or more, and particularly preferably 8 parts by mass or more and 30 parts by mass or less, and preferably 10 parts by mass or more and 20 parts by mass or less. It is because the said composition becomes the composition excellent in curability by the said content being the said range.

In addition, the content of the resin component containing the polymerizable compound can be appropriately set depending on the use of the composition and the like. For example, it can be 1 part by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the solid content, and 10 It is preferable that it is 80 mass parts or more by mass part, and it is preferable that it is 40 mass parts or more and 60 mass parts or less among them. It is because the said content is the said range, and it is easy for the said composition to provide various functions to a hardened|cured material. On the other hand, the resin component is contained in the cured product of the composition, so long as it is used to maintain the decomposition product of the compound I, a colorant, etc., for example, the polymerizable compound, a polymer having a hydrophilic group to be described later and other organic polymers It can be said to include.

The content of the polymerizable compound may be 0.1 parts by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, It is particularly preferable that it is 1.5 parts by mass or more and 10 parts by mass or less. This is because a cured product having excellent electrical properties can be more easily obtained.

(2) Polymers with hydrophilic groups

By including the polymer having the hydrophilic group (hereinafter, sometimes referred to as polymer A), the composition becomes easy to use as a curable composition having alkali developability.

The polymer A is not particularly limited as long as it is a polymer capable of imparting alkali developability, and an organic polymer conventionally used can be used.

The hydrophilic group may be any one that can impart desired alkali solubility to polymer A, and examples thereof include hydroxyl groups, thiol groups, carboxyl groups, sulfo groups, amino groups, amide groups, or salts thereof, and hydroxyl groups and carboxyl groups are polymer A Is preferred because of its high solubility in alkalis.

The preferable functional group equivalent of the hydrophilic group in the polymer A (mass of the polymer A containing one equivalent of the hydrophilic group) can be appropriately set depending on the desired alkali solubility, for example, may be 50 or more and 10000 or less. It is because polymer A becomes excellent in alkali developability by the said functional group equivalent being the said range.

The weight average molecular weight (Mw) of the polymer A may be appropriately set depending on the desired alkali solubility, and may be 1000 or more and 500000 or less, preferably 1000 or more and 100000 or less, particularly preferably 2000 or more and 30000 or less. It is because polymer A becomes excellent in alkali developability when the said weight average molecular weight is the said range.

The acid value of the polymer A can be appropriately set depending on the desired alkali solubility, and can be 10 mgKOH/g or more and 200 mgKOH/g or less, and preferably 30 mgKOH/g or more and 150 mgKOH/g or less. It is because polymer A becomes excellent in alkali developability because the said acid value is the said range.

Here, the acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the polymer, and can be a value measured by the method described in JIS K 0070.

The polymer A may be one having a repeating unit, specifically, a copolymer of an acrylic acid ester, a phenol and/or cresol novolac epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, an epoxy acrylate resin, and the following general A compound having a structure in which an unsaturated monobasic acid is applied to an epoxy compound such as an epoxy compound represented by Formula (V), or a resin having a structure obtained by further reacting a polybasic anhydride with the compound can be used.

It is preferable that the polymer A has an unsaturated group, and among them, an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the following general formula (V), or the epoxy addition compound and polybasic acid anhydride are esterified. An ethylenically unsaturated compound having a reacted structure is preferred. It is because the said composition becomes excellent in patterning property.

Meanwhile, in order to obtain the epoxy addition compound, an unsaturated monobasic acid may be added to the epoxy compound represented by the following general formula (V). Moreover, in order to obtain the said ethylenically unsaturated compound, it is sufficient to esterify the epoxy addition compound obtained by the said addition reaction and polybasic acid anhydride.

Moreover, it is preferable that the said ethylenically unsaturated compound contains 0.2 equivalent or more and 1.0 equivalent or less of an unsaturated group.

On the other hand, for the unsaturated group, the same can be done for the ethylenically unsaturated double bond group.

(In the formula, M is a direct bond, methylene group, alkylidene group having 1 to 4 carbon atoms, alicyclic hydrocarbon group, O, S, SO ₂ , SS, SO, CO, OCO, the following formula (V-1), (V-2) or (V-3) represents a substituent selected from the group represented by, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are each independently hydrogen Represents an atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and s is a number from 0 to 10.)

(R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, carbon An aryl group having 6 to 20 atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene portion in the alkyl group and the arylalkyl group is a methylene chain constituting it. May be substituted with an unsaturated bond, -O- or -S-, R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² are adjacent R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² may form a ring between each other. * represents the number of bonds.)

Examples of each of the alkyl group, aryl group, arylalkyl group, heterocyclic group, and halogen atom in the general formula (V) are the alkyl group, aryl group, arylalkyl group, heterocyclic group, and halogen atom in the description of the general formula (I). Various groups illustrated for are mentioned. Moreover, as said alkoxy group in general formula (V), the group corresponding to the alkyl group illustrated in the description of said general formula (I) is mentioned.

Examples of the alkylidene group having 1 to 4 carbon atoms include methylidene, ethylidene, propylidene and butylidene.

As the unsaturated monobasic acid acting on the epoxy compound, a compound having one unsaturated group and one carboxyl group can be used. Acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate, maleate , Hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, and the like.

In addition, as the polybasic acid anhydride which acts after the unsaturated monobasic acid is applied, a carboxylic acid anhydride can be used, for example, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, Biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bis-anhydrotrimellitate, glycerol trisanthane hydrotri Mellitate, hexahydrophthalic anhydride, methyltetrahydro phthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydro phthalic anhydride, hexahydro phthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3 -Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydro phthalic anhydride-maleic anhydride adduct, dodecenyl anhydride succinic acid, methylhymic anhydride and the like.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride is preferably as follows.

That is, it is preferable that the epoxy addition compound is added so that the ratio of the carboxyl group of the unsaturated monobasic acid to 0.1 or more and 1.0 or less relative to one epoxy group of the epoxy compound, and the ethylenically unsaturated compound is the epoxy It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride to 0.1 or more and 1.0 or less with respect to one hydroxyl group of the additional compound.

The reaction of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to the conventional method.

The polymer A may be used after further adjusting the acid value by reacting a monofunctional or polyfunctional epoxy compound. The polymer A can improve the alkali developability of the composition by adjusting the acid value.

As the monofunctional epoxy compound, a compound having one epoxy group may be used, glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl Glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, Decylglycidyl ether, undecylglycidyl ether, dodecylglycidyl ether, tridecylglycidyl ether, tetradecylglycidyl ether, pentadecylglycidyl ether, hexadecylglycidyl ether, 2- Ethyl hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol Glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycyl Diether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide , Methyl styrene oxide, cyclohexene oxide, propylene oxide, the following compounds No.E1, No.E2 and the like.

As the polyfunctional epoxy compound, a compound having two or more epoxy groups may be used, for example, one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers.

As the bisphenol-type epoxy compound, in addition to the epoxy compound represented by the general formula (V), bisphenol-type epoxy compounds such as hydrogenated bisphenol-type epoxy compounds can also be used.

In addition, the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1 ,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, Triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycine Cydyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, 1,1,1,1-tetra(glycylate) Cidyloxymethyl)methane and the like can be used.

In addition, novolak-type epoxy compounds such as phenol novolak-type epoxy compounds, biphenyl novolak-type epoxy compounds, cresol novolak-type epoxy compounds, bisphenol A novolak-type epoxy compounds, and dicyclopentadiene novolak-type epoxy compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1- Alicyclic epoxy compounds such as epoxyethyl-3,4-epoxycyclohexane; Glycidyl esters such as diglycidyl phthalate, diglycidyl ester tetrahydro, and glycidyl dimer acid; Glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylP-aminophenol, and N,N-diglycidylaniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds, such as dicyclopentadiene dioxide; Naphthalene type epoxy compounds; Triphenylmethane type epoxy compound; Dicyclopentadiene type epoxy compounds and the like can also be used.

It is preferable that the polymer A includes a polymer having a carboxyl group from the viewpoint of being excellent in developability. It is because the composition becomes more excellent in patterning precision by including the said polymer.

The polymer having a carboxyl group may be one having a structural unit having a carboxyl group (hereinafter referred to as "structural unit (U1)"), and is not particularly limited, and further includes methacryloyl group, acryloyl group, vinyl group, Structural unit having a crosslinkable group such as an epoxy group, oxetanyl group, vinyl ether group, mercapto group, isocyanate group (hereinafter referred to as "structural unit (U2)"), and a structural unit having a silyl group (hereinafter "structural unit" It is desirable to have a structural unit selected from (U3)".

The polymer having the carboxyl group may have structural units other than the structural units (U1) to (U3) (hereinafter referred to as "structural units (U4)").

The structural unit (U1) is preferably a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (u1)").

As said compound (u1), monocarboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, etc. are mentioned, for example. Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, and 2-acryloyloxyethyl hexahydro. Phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, and the like;

Examples of the dicarboxylic acid include maleic acid, fumaric acid and citraconic acid;

The anhydride of the above-mentioned dicarboxylic acid etc. are mentioned as anhydride of the said dicarboxylic acid, respectively.

Of these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, or maleic anhydride is preferred from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in a developer.

The compound (u1) may be used alone or in combination of two or more.

The structural unit (U2) is preferably a structural unit derived from a polymerizable unsaturated compound (hereinafter referred to as "compound (u2)") having an epoxy group or an oxetanyl group.

The compound (u2) is preferably at least one member selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.

Examples of the polymerizable unsaturated compound having an epoxy group include (meth)acrylic acid oxiranyl (cyclo) alkyl ester, α-alkyl acrylate oxyranyl (cyclo) alkyl ester, and polymerizable unsaturated glycidyl ether compounds. ;

As a polymerizable unsaturated compound which has an oxetanyl group, (meth)acrylic acid ester etc. which have an oxetanyl group are mentioned, for example.

As a specific example of the compound (u2),

As (meth)acrylic acid oxiranyl (cyclo) alkyl ester, for example, (meth)acrylic acid glycidyl, (meth)acrylic acid 2-methylglycidyl, 4-hydroxybutyl (meth)acrylate glycidyl ether , (Meth)acrylic acid3,4-epoxybutyl, (meth)acrylic acid 6,7-epoxyheptyl, (meth)acrylic acid3,4-epoxycyclohexyl, (meth)acrylic acid3,4-epoxycyclohexylmethyl, 3, 4-epoxycitricyclo[5.2.1.02.6]decyl(meth)acrylate, etc.;

As an α-alkylacrylic acid oxiranyl (cyclo)alkyl ester, for example, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylic acid 6 ,7-epoxyheptyl, α-ethylacrylic acid3,4-epoxycyclohexyl, and the like;

As a glycidyl ether compound having a polymerizable unsaturated bond, for example, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc.;

As a (meth)acrylic acid ester having an oxetanyl group, for example, 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acrylo Iloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, etc. are mentioned, respectively.

Among these specific examples, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxy Tricyclo[5.2.1.02.6]decylmethacrylate, 3,4-epoxycitricyclo[5.2.1.02.6]decylacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl -3-methacryloyloxymethyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane is preferred from the viewpoint of polymerizability.

The compound (u2) may be used alone or in combination of two or more.

As the crosslinkable group among the structural units (U2), a structural unit having a (meth)acryloyloxy group can be preferably used as a structural unit having a methacryloyl group or an acryloyl group.

The structural unit having the (meth)acryloyloxy group is obtained by reacting a (meth)acrylic acid ester having an epoxy group with a carboxyl group in the polymer. It is preferable that the structural unit which has (meth)acryloyloxy group after reaction is a structural unit represented by following formula (U2-1).

(In the formula, R ¹⁰⁰⁰ and R ¹⁰⁰¹ are each independently a hydrogen atom or a methyl group, R ¹⁰⁰² is a divalent group represented by the following formula (α) or the following formula (β), c is an integer from 1 to 6, * is Indicates the bonding portion.)

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

When the structural unit represented by the formula (U2-1) is reacted with, for example, a compound having a carboxyl group, such as glycidyl methacrylate or 2-methylglycidyl methacrylate, the formula ( R ¹⁰⁰² in U2-1) becomes formula (α). On the other hand, when methacrylic acid 3,4-epoxycyclohexylmethyl is reacted with a copolymer having a carboxyl group, R ¹⁰⁰² in formula (U2-1) becomes formula (β).

In the reaction of an unsaturated compound such as a (meth)acrylic acid ester having a carboxyl group and an epoxy group in the above-described polymer, an unsaturated compound having an epoxy group is preferably added to a solution of a polymer containing a polymerization inhibitor, preferably in the presence of a suitable catalyst, if necessary. It is added and stirred for a predetermined time under warming. As said catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As said polymerization inhibitor, p-methoxyphenol etc. are mentioned, for example. The reaction temperature is preferably 70°C to 100°C. The reaction time is preferably 8 hours to 12 hours.

In the proportion of the structural unit of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth)acryloyloxy group as a crosslinkable group is preferably 10 mol% to 70 mol% of all the polymer structural units having a carboxyl group, It is more preferable that it is 20 mol%-50 mol%.

When the ratio of the structural unit having a (meth)acryloyloxy group is within the above range, heat resistance and development defects during development can be reduced, and development residues can be suppressed.

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

Examples of the compound (u3) include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyl dimethoxysilane, 3-(meth)acryloyloxypropyl And trimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, and the like.

The compound (u3) may be used alone or in combination of two or more.

The structural unit (U4) is a structural unit other than (U1) to (U3), and is derived from a polymerizable unsaturated compound (hereinafter referred to as "compound (u4)") other than (u1) to (u3). It is preferably a structural unit.

Examples of the compound (u4) include (meth)acrylic acid alkyl ester, (meth)acrylic acid cycloalkyl ester, (meth)acrylic acid aryl ester, (meth)acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, and oxygen-containing And (meth)acrylic acid esters having a complex 5-membered ring or an oxygen-containing complex 6-membered ring, a vinyl aromatic compound, a conjugated diene compound, and other polymerizable unsaturated compounds. As these specific examples, (meth)acrylic acid alkyl ester, for example, methyl acrylate, (meth)acrylic acid n-propyl, (meth)acrylic acid i-propyl, (meth)acrylic acid n-butyl, (meth)acrylic acid sec -Butyl, (meth)acrylic acid t-butyl, and the like;

As (meth)acrylic acid cycloalkyl ester, for example, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-methylcyclohexyl, (meth)acrylic acid tricyclo[5.2.1.02,6]decane-8-yl, ( Meta)acrylic acid 2-(tricyclo[5.2.1.02,6]decane-8-yloxy)ethyl, (meth)isobornyl acrylate, and the like;

As the (meth)acrylic acid aryl ester, for example, phenyl acrylate;

As the (meth)acrylic acid aralkyl ester, for example, (meth)benzyl acrylate, etc.;

As an unsaturated dicarboxylic acid dialkyl ester, diethyl maleate, diethyl fumarate, etc. are mentioned, for example;

As a (meth)acrylic acid ester having an oxygen-containing complex 5-membered ring or an oxygen-containing complex 6-membered ring, for example, (meth)acrylic acid tetrahydrofuran-2-yl, (meth)acrylic acid tetrahydropyran-2-yl, (meth) 2-methyltetrahydropyran-2-yl acrylic acid, etc.;

Examples of the vinyl aromatic compound include styrene and α-methylstyrene;

As conjugated diene compounds, for example, 1,3-butadiene, isoprene, and the like;

Examples of the other polymerizable unsaturated compound include (meth)acrylic acid 2-hydroxyethyl, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide, respectively.

In terms of copolymerization reactivity as the compound (u4), n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, and tricyclo methacrylate[5.2.1.02,6]decane-8- Preference is given to mono, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, and the like.

The compound (u4) may be used alone or in combination of two or more.

The polymer having the carboxyl group can be synthesized by copolymerizing a mixture of the polymerizable unsaturated compounds each containing the compounds (u1) to (u4) as described above.

Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, more preferably 5 mol% to 15 mol%

Compound (u2): Preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, more preferably 20 mol% to 30 mol%

Compound (u3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, more preferably 10 mol% to 30 mol%

Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, more preferably 25 mol% to 50 mol%

Moreover, it can be set as having a structural unit which has a (meth)acryloyloxy group by reacting the (meth)acrylic acid ester which has an epoxy group with the carboxyl group in the structural unit derived from the compound (u1) in the obtained copolymer.

The polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing compounds (u1) to (u4) within the above range does not impair good coatability and achieves high resolution. A high-definition pattern is preferable because it is possible to provide a cured film having a highly balanced balance of properties.

As long as the weight average molecular weight (Mw) of the polymer having a carboxyl group can be obtained, a desired developability can be obtained. For example, "2. Polymeric component having thiol reactivity" in "(1) radical polymerization component" It can be made similar to the molecular weight of the molecular weight compound. By using the above polymer, good coating properties are not impaired and high resolution is achieved, so that even if it is a high-fine pattern, it is possible to impart a cured film with a high balance of properties.

The polymer having a carboxyl group can be prepared by polymerizing the mixture of the polymerizable unsaturated compounds as described above in a suitable solvent, preferably in the presence of a radical polymerization initiator.

Examples of the solvent used for the polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, and ethylene glycol monobutyl And ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, and 3-methoxybutanol. These solvents may be used alone or in combination of two or more.

The radical polymerization initiator is not particularly limited, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2 '-Azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methyl And azo compounds such as propionate) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

Preferred examples of the polymer having the carboxyl group include the following polymers U-1 and U-2.

[Polymer U-1]

To a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate were added, followed by 55 parts by mass of methacrylic acid and 45 parts of benzyl methacrylate The mass of the solution and 2 parts by mass of the α-methylstyrene dimer as a molecular weight modifier were added and the mixture was slowly stirred, and the temperature of the solution was raised to 80°C. After maintaining at 80°C for 4 hours, the temperature of the solution was raised to 100°C, and the temperature was maintained for 1 hour to polymerize to obtain a solution containing the copolymer. Subsequently, to the solution containing this copolymer, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added, and after stirring at 90°C for 30 minutes in an air atmosphere, glycidyl methacrylate And polymer U-1 having a weight average molecular weight of Mw9000 obtained by reacting for 10 hours while adding 90 parts by mass of dill at 90°C.

The polymer U-1 has a structural unit (U1), a structural unit (U2), and a structural unit (U4).

[Polymer U-2]

Into a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added, and 18 parts by mass of methacrylic acid and trimethacrylate Cyclo[5.2.1.02.6] decane-8-day 25 parts by mass, styrene 5 parts by mass, 3-acryloxypropyl trimethoxysilane 20 parts by mass and 32 parts by mass of glycidyl methacrylate were substituted for nitrogen. , While stirring slowly, the temperature of the solution was raised to 80°C. And polymer U-2 having a weight average molecular weight Mw12000 obtained by polymerizing by maintaining this temperature for 5 hours.

The polymer U-2 has a structural unit (U1), a structural unit (U2), a structural unit (U3), and a structural unit (U4).

The content of the polymer having the carboxyl group is appropriately selected depending on the intended use, and is not particularly limited, but can be, for example, 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the solid content of the composition.

Further, the total content of the polymer having the carboxyl group and the polymerizable component B is appropriately selected depending on the intended use, and is not particularly limited. For example, the total content of the solid content of the composition is 10 parts by mass or more and 99 parts by mass or less. can do.

The content of the polymer A can be appropriately set depending on the desired alkali solubility. The content of the composition can be 5 parts by mass or more and 90 parts by mass or less, preferably 10 parts by mass or more and 75 parts by mass or less, with respect to 100 parts by mass of the solid content of the composition, Especially, it is preferable that it is 15 mass parts or more and 70 mass parts or less, and it is especially preferable that it is 20 mass parts or more and 60 mass parts or less. It is because the said composition becomes the composition excellent in alkali developability when the said content is the said range.

In addition, the epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (V), and the ethylenically unsaturated compound having a structure in which the epoxy addition compound and a polybasic anhydride are subjected to esterification reaction, In total, it is preferable to occupy 25 parts by mass or more and 100 parts by mass or less out of 100 parts by mass of the polymer A, and more preferably 40 parts by mass or more and 100 parts by mass or less.

The content of the polymer A can be 0.1 parts by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, 2 It is especially preferable that it is 20 parts by mass or more by mass.

It is because the content of the said polymer A is the range mentioned above, and the said composition becomes excellent in alkali developability. In addition, the composition is because it is possible to more easily obtain a cured product of a pattern shape excellent in electrical properties.

(3) Coloring agent

By including the coloring agent, the composition can obtain a coloring composition, a colored cured product, and the like.

As such a colorant, any color can be given to a desired color such as a composition, a cured product, and examples thereof include pigments, dyes, and natural pigments. These may be used alone or in combination of two or more.

Examples of the pigment include nitroso compounds; Nitro compounds; Azo compounds; Diazo compounds; Xanthene compounds; Quinoline compounds; Anthraquinone compounds; Coumarin compounds; Phthalocyanine compounds; Isoindolinone compound; Isoindoline compounds; Quinacridone compound; Anthrone compounds; Perinone compounds; Perylene compounds; Diketopyrrolopyrrole compound; Thioindigo compounds; Dioxazine compounds; Triphenylmethane compound; Quinophthalone compounds; Naphthalene tetracarboxylic acid; Metal complex compounds of azo dyes and cyanine dyes; Lake pigments; Carbon black obtained by the furnace method, channel method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black; The carbon black is adjusted or coated with an epoxy resin, the carbon black is previously dispersed with a resin in a solvent, and 20 to 200 mg/g of resin is adsorbed, and the carbon black is treated with an acidic or alkaline surface , Carbon black treatment such as having an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less, and a total oxygen amount calculated from CO and CO ₂ in volatile matter at 950° C. of 9 mg or more per 100 m 2 of carbon black water; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nanohorn, carbon airgel, fullerene; Aniline black, pigment black 7, titanium black; Chromium Green, Millory Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine, Ultramarine, Ultramarine, Cerulean Blue, Viridian, Emerald Green, Lead Sulfate, Yellow Lead, Zinc Sulfur, Bengala ( Organic or inorganic pigments such as red iron oxide (III)), cadmium red, synthetic iron black, and umber can be used. These pigments can be used singly or in combination.

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

Examples of the dye include azo dye, anthraquinone dye, indigo dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, inda And dyes such as amine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These may be used by mixing a plurality.

The colorant may be used as a spacer of a liquid crystal layer, for example, when the composition is for a black matrix, and preferably contains a black pigment in the case of a black column spacer having light shielding properties.

The black pigment may be any one that can impart desired light shielding properties. For example, the various carbon black or carbon black products, graphitized carbon black, activated carbon, carbon fibers, carbon nanotubes, carbon micro coils, and carbon Nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black, perylene black, and cyanine black.

The content of the colorant is not particularly limited as long as a composition having a desired color, a cured product, or the like can be obtained. For example, it can be 1 part by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. , It is preferably 10 parts by mass or more and 75 parts by mass or less, particularly preferably 20 parts by mass or more and 60 parts by mass or less, particularly preferably 25 parts by mass or more and 60 parts by mass or less. It is because a desired colored hardened|cured material can be obtained by said content being the said range.

The content of the colorant may be 0.5 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the composition, preferably 1 part by mass or more and 50 parts by mass or less, more preferably 2 parts by mass or more and 30 parts by mass or less, and 3 masses Particularly, it is particularly preferable to be 15 parts by mass or less. This is because a cured product having excellent electrical properties can be more easily obtained.

(4) Solvent

The solvent may be one that can disperse or dissolve each component of the composition, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, Ketones such as 2-heptanone; Ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate Ether ester solvents such as; BTX-based solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon-based solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; Paraffinic solvents such as mineral spirits, Suwasol #310 (Cosmo Matsuyama Sekiyu), and Solvesso #100 (Exxon Gakuaku); Halogenated aliphatic hydrocarbon-based solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; Halogenated aromatic hydrocarbon-based solvents such as chlorobenzene; Carbitol solvents; aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; Dimethyl sulfoxide; Water, etc. are mentioned, These solvents can be used as 1 type or 2 or more types of mixed solvents.

Among them, ketones, ether ester solvents, etc., in particular, propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as "PGMEA" or "propylene glycol monomethyl ether acetate"), cyclohexanone, etc. It is preferable from the viewpoint of good compatibility with polymer A and the like.

The content of the solvent can be appropriately set depending on coating properties and the like. For example, it can be 5 parts by mass or more and 90 parts by mass or less, and preferably 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the composition. It is because viscosity adjustment of a composition is easy because the said content is the said range.

(5) Inorganic compounds

The inorganic compound may be appropriately selected according to uses such as fillers and mechanical strength improvers, for example, nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, alumina Metal oxides such as; Layered clay minerals, milori blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder (especially glass fleet), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides , Aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, and the like.

Among the inorganic compounds, for example, from the viewpoint of improving mechanical strength, glass frit, titanium oxide, silica, layered clay mineral, silver, and the like are preferable.

The content of the inorganic compound varies depending on the required performance of the inorganic compound, but may be, for example, 1 part by mass or more and 90 parts by mass or less, and 5 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. It is preferable that it is 5 mass parts or more and 50 mass parts or less especially. It is because the said content, for example, the said composition can obtain the hardened|cured material excellent in mechanical strength.

Meanwhile, one or two or more of these inorganic compounds may be used.

(6) Dispersant

The dispersant is not limited as long as it is capable of dispersing and stabilizing a colorant, an inorganic compound, or the like in the composition, and a commercially available dispersant, for example, BYK series manufactured by BIC Chemie, can be used. The dispersing agent is a polymer dispersing agent consisting of a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as a basic functional group, a functional group having a nitrogen atom is an amine, and/or a quaternary salt thereof, and an amine value of 1 What is suitable is MGKOH/g or more and 100 mgKOH/g or less.

(7) Other organic polymers

As said other organic polymer, it is a polymer different from the said polymerizable compound and polymer A, and it is good if it is a polymer from which the property improvement of hardened|cured material is obtained.

As such other organic polymers, polymers that do not contain a polymerizable group and a hydrophilic group can be used. For example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid , Styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin, etc., among these, polystyrene , (Meth)acrylic acid-methyl methacrylate copolymer, epoxy resin is preferred.

The weight average molecular weight of the organic polymer can be the same as that of the polymer A.

On the other hand, the content of the other organic polymer is appropriately set depending on the use of the composition and the like. For example, it can be 1 part by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the solid content of the composition.

(8) Chain transfer agent and sensitizer

The chain transfer agent or sensitizer may be any one that can adjust the sensitivity and the like of the composition, and a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3 -[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethane Sulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1- Mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3- Mercapto compounds such as pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and Disulfide compounds obtained by oxidizing mercapto compounds, alkyl iodide compounds such as iodine acetic acid, iodine propionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, trimethylolpropanetris (3-mercaptoy Sobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycol bisthio Glycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis Thioglycolate, trishydroxyethyl tristhiopropionate, diethyl thioxanthone, diisopropyl thioxanthone, compound No. C1 below, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, etc. Aliphatic polyfunctional thiol compound, Carens MT BD1, PE1, NR1 by Showa Denko Corporation, etc. are mentioned.

(9) surfactant

The surfactant may be used to improve the dispersion stability, coating properties, etc. of the composition, for example, fluorine surfactants such as perfluoroalkyl phosphate ester, perfluoroalkylcarboxylate; Anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; Cationic surfactants such as higher amine halide salts and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, and fatty acid monoglyceride; Amphoteric surfactants; Surfactants such as silicone surfactants can be used, and these may be used in combination.

(10) Silane coupling agent

The silane coupling agent is a silane compound having a reactor for chemically bonding with an inorganic material such as glass, and a reactor for chemically bonding with an organic material such as synthetic resin, and can be used to improve adhesion of a cured product or the like. As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, having an isocyanate group, methacryloyl group or epoxy group such as KBE-9007, KBM-502, KBE-403, etc. Silane coupling agents are suitably used.

(11) Melamine compound

The melamine compound may be used to improve the curability, for example, (poly)methylolmelamine, (poly)methylolglycoluril, (poly)methylolbenzoguanamine, (poly)methylolurea And compounds in which all or part (at least two) of the active methylol group (CH ₂ OH group) in the nitrogen compound is alkyl ether.

Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, or a butyl group, and may be the same or different from each other. Further, the methylol group that is not alkyl etherified may be self-condensing within one molecule, or condensing between two molecules, and as a result, an oligomer component may be formed.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, and the like can be used.

Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred.

(12) Other

Examples of the other components include thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol and phenothiazine; Plasticizers; Adhesion promoters; Fillers; Antifoaming agent; Leveling agents; Surface modifiers; Antioxidants; Ultraviolet absorbers; Dispersion aids; Anti-agglomeration agents; catalyst; Effect accelerator; Crosslinking agents; Conventional additives, such as a thickener, can be added.

The content of the additive is appropriately selected depending on the intended use, and is not particularly limited. For example, the total content of the composition may be 50 parts by mass or less based on 100 parts by mass.

4. Composition

As a method for producing the composition, any method may be used so long as each component can be mixed to a desired content, and a known mixing method can be used.

As the use of the composition, for example, it can be used as a photocurable composition that is cured by light irradiation.

Moreover, as a specific use, it can be made similar to the content described in the item of "A. Compound" above.

D. Cured product

Next, the cured product of the present invention will be described.

The cured product of the present invention is a cured product of the aforementioned composition.

Since the cured product of the present invention and the composition described above are used, it becomes excellent in electrical properties.

The cured product of the present invention is to use the composition described above.

Hereinafter, the cured product of the present invention will be described in detail.

On the other hand, about the said composition, it can carry out similarly to what was described in the item of "C. composition" above. For the formation of the cured product, the composition usually contains a polymerizable compound, polymer A having an unsaturated group, and the like.

The cured product usually contains a polymer component.

Examples of such a polymer component include a polymerized product of the polymerizable compound described in the section "C. Composition" above, a polymerized product of polymer A having an unsaturated group, and the like.

On the other hand, the polymerized product of the polymerizable compound may be any one that contains a polymerizable compound as a structural unit, and is not limited to polymerized products of polymerizable compounds, and also includes polymerizable compounds and polymerized products of Polymer A.

The content of each of the polymerized product of the polymerizable compound and the polymerized product of the polymer A having an unsaturated group may be the same as the content of the polymerizable compound and the polymer A and the like described in the section "C. Composition" above.

In addition, the polymer component may also include other organic polymers described in the section "C. Composition" above.

The total content of the polymer component can be appropriately set depending on the use of the second composition, and the like, for example, it can be the same as the content of the resin component described in the section "C. Composition".

It can be said that the hardened|cured material does not contain a solvent substantially.

The content of the solvent contained in the cured product can be, for example, 1 part by mass or less in 100 parts by mass of the cured product, and preferably 0.5 part by mass or less. This is because the cured product has excellent stability over time when the content is within the above-mentioned range.

The shape seen from the plane of the cured product of the present invention can be appropriately set according to the use of the cured product or the like. For example, when the cured product is used as a spacer or the like of the liquid crystal layer, it may be formed into a pattern shape such as a dot shape or a line shape.

The thickness of the cured product may be, for example, 0.1 μm or more and 100 μm or less when the cured product is used as a spacer or the like in the liquid crystal layer.

The method for producing the cured product is not particularly limited as long as it can be formed so that the cured product of the composition has a desired shape.

As such a manufacturing method, for example, it can be carried out in the same manner as described in the section "E. Manufacturing Method of Cured Product", which will be described later, and thus description thereof is omitted.

The use of the cured product or the like can be performed in the same manner as described in the item "A. Compound" above.

E. Manufacturing method of cured product

Next, the manufacturing method of the cured product of this invention is demonstrated.

The manufacturing method of the cured product of this invention is characterized by having the process of irradiating light with respect to the above-mentioned composition.

Since the method for producing the effect product of the present invention has a step of irradiating light to the composition containing the compound I, a cured product having excellent electrical properties can be easily obtained.

The manufacturing method of the present invention includes a step of irradiating light.

Hereinafter, each process of the manufacturing method of this invention is demonstrated in detail.

1. Light irradiation process

This step is a step of irradiating light with the composition described above and curing the composition.

The light irradiated to the composition in this step may be any compound I can generate a radical, for example, it can be assumed to contain light having a wavelength of 250 to 450 nm.

The irradiation amount of light to be irradiated may be one that can form a cured product having a desired hardness, and is appropriately adjusted according to the thickness of the coating film of the composition.

Examples of the light source of the light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, and the like.

As the light to be irradiated, laser light may be used. As the laser light, one containing light having a wavelength of 340 nm to 430 nm can be used.

As the light source of the laser light, it is also possible to use light emitting from the visible region to the infrared region, such as an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser.

On the other hand, when using these lasers, the composition may include a sensitizing dye that absorbs the corresponding region from visible to infrared.

The method of light irradiation may be a method of irradiating light to the entire surface of the coating film of the composition when viewed from a plane, or a method of light irradiation of a part of the coating film.

When the object of light irradiation is a part of the coating film, for example, a method of irradiating light through a mask or the like, a method of irradiating light only to a portion to be cured of the composition, or the like can be used.

On the other hand, about the said composition, it can carry out similarly to what was described in the item of "B. composition" above. For the formation of the cured product, the composition usually contains a polymerizable compound, polymer A having an unsaturated group, and the like.

2. Other processes

The manufacturing method includes a step of irradiating light, but may include other steps as necessary.

The other processes include, for example, a step of forming a coating film of the composition, a step of developing after the step of light irradiation, a step of forming a coating film of the composition, and a solvent to be performed after the step of forming the coating film. And a removing step, a heating step performed after the light irradiation step, and the like.

The step of forming the coating film may be any method that can obtain a coating film of a desired thickness composition, for example, spin coater, roll coater, bar coater, die coater, curtain coater, slit coater, various types of printing, dipping, etc. Known methods can be used.

The base material on which the coating film of the composition is formed can be appropriately set according to the use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like.

Further, the cured product may be used after being formed on a substrate, peeled from the substrate, or transferred from the substrate to another substrate.

As the developing method in the developing step, any method that can remove the uncured composition may be used. For example, a known developing method such as a method of removing using an aqueous alkali solution can be used.

The method of removing the solvent in the step of removing the solvent may be any method capable of setting the content of the solvent contained in the cured product to a desired amount, for example, a heating method, that is, a prebaking step as a removing step. And a method of carrying out.

The heating temperature in the heating step (post-baking step) performed after the step of irradiating the light may be any temperature that can improve the mechanical strength of the cured product, and may be appropriately set according to the type, use, or the like of the cured product.

3. Other

The cured product produced by the above-mentioned manufacturing method and the use thereof can be made in the same manner as described in the item "C. Cured product" above.

The present invention is not limited to the above embodiment. The above-mentioned embodiment is an example, and it has substantially the same structure as the technical idea described in the claims of the present invention, and anything that exhibits the same working effect is included in the technical scope of the present invention.

Example

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

[Example 1-1]

Under nitrogen atmosphere, 78 mmol of aluminum chloride and 33.0 g of ethane dichloride were added, and 36 mmol of 4-fluoro-O-toluic acid chloride under ice cooling, followed by 30 mmol of 9-ethyl-3-nitrocarbazole (carbazole compound) Was slowly added dropwise, and stirred at 5°C for 30 minutes. The reaction solution was poured into ice water, and oil-water separation was performed. Desolvation gave an acyl body.

Subsequently, 45.0 g of ethylene glycol, 40 mmol of the obtained acyl body, and 80 mmol of potassium carbonate were added and reacted at 100°C for 5 hours. After cooling to room temperature, ion-exchanged water was added, and the precipitate was filtered off. It dried under reduced pressure and obtained the ketone body which has a hydroxyl group.

Subsequently, 20 mmol of the obtained ketone body, 40 mmol of hydroxylamine hydrochloride, and 25.0 g of pyridine were added and stirred at 100°C for 3 hours. Ion-exchanged water was added, and the precipitate was filtered off. It dried under reduced pressure to obtain an oxime body.

Subsequently, 10 millimoles of the obtained oxime body and 15.0 g of dimethylformamide were added, and triethylamine and acetyl chloride were slowly added dropwise under ice cooling and stirred at 5°C for 1 hour. Ion-exchanged water and ethyl acetate were added to the reaction solution, and desolvation was performed. The organic layer was washed three times, and desolvation was performed. Passed on a silica gel column (ethyl acetate/hexane=50/50), the compound represented by the following general formula (24) was obtained as the target compound I.

It was confirmed by H-NMR that the obtained compound was the target product.

[Example 1-2]

10 millimoles of compound No. 1 described in paragraph [0022] of the same document, synthesized based on the description of paragraphs [0072] to [0080] of international publication WO2006/018973, and 50 g of 60% acetic acid water were added. And stirred at 45°C for 1 hour. The reaction solution was poured into 60 g of ice water, 100 g of ethyl acetate was added, and extraction was performed. The organic layer was washed 4 times with 100 g of ion-exchanged water, and desolvation was performed. It was put on a silica gel column (chloroform/ethanol=95/5), and the compound represented by the following general formula (13) was obtained as the target compound I.

It was confirmed by H-NMR that the obtained compound was the target product.

[Example 1-3]

93 mmol of 60% sodium hydride and 40 g of dimethylformamide were added, and under ice-cooling, 62 mmol of carbazole dissolved in 50 g of dimethylformamide was added dropwise. Further, 124 millimoles of ethyl bromoheptanoate dissolved in 50 g of dimethylformamide was added dropwise and reacted for 30 minutes. The reaction solution was poured into ice water containing hydrochloric acid, ethyl acetate was added, and oil-water separation was performed. After washing the organic layer three times, the solvent was desolvated and recrystallized with methanol to obtain an ester body.

Subsequently, 44 millimoles of the ester body and 200 g of dichloroethane were added, and under ice cooling, 46 millimoles of aluminum chloride and 46 millimoles of octanoyl chloride were added. After reacting at room temperature for 15 hours, the reaction solution was poured into ice water, 200 g of chloroform was added and extraction was performed. The organic layer was washed three times, and after desolvation, it was put on a silica gel column (hexane/ethyl acetate = 85/15) to obtain an acyl body.

Subsequently, 30 mmol of the acyl body and 80.8 g of acetic anhydride were added, and 6.4 g of 60% nitric acid was slowly added dropwise at 10 to 12°C. The reaction solution was poured into ice water, chloroform was added and extraction was performed. The organic layer was washed three times, and after desolvation, it was put on a silica gel column (hexane/ethyl acetate = 70/30) to obtain a nitro body.

Subsequently, 18 millimoles of nitro bodies and 60.0 g of acetic acid were added, followed by dropwise addition of 17.0 g of 35% hydrochloric acid. After reacting at 50°C for 2 hours, the reaction solution was poured into ice water, and 85 g of chloroform was added and extraction was performed. After washing the organic layer three times, the solvent was desolvated to obtain a ketone body having a hydroxyl group.

Subsequently, in the same manner as in [Example 1-1], the compound represented by the following general formula (3) was obtained as the target compound I.

It was confirmed by H-NMR that the obtained compound was the target product.

[Example 1-4]

After adding the hydroxyl group obtained in the same manner as in [Example 1-3], 22 millimoles of ketone bodies, 33 g of dimethylformacetamide, 24 millimoles of isobutyl nitrite, and 2.3 g of 35% hydrochloric acid were added and reacted at room temperature for 24 hours. Ion-exchanged water and chloroform were added, and oil-water separation was performed. The organic layer was washed 3 times to obtain an oxime body.

Subsequently, a compound represented by the following general formula (47) was obtained as the target compound I in the same manner as in [Example 1-1], except that benzoyl chloride was used as the acid chloride.

It was confirmed by H-NMR that the obtained compound was the target product.

[Example 1-5]

Under nitrogen atmosphere, 78 mmol of aluminum chloride and 33.0 g of ethane dichloride were added, and 36 mmol of 4-chlorobutyryl chloride and then 30 mmol of 9-ethyl-3-nitrocarbazole (carbazole compound) were slowly added dropwise under ice cooling. , And stirred at 5°C for 30 minutes. The reaction solution was poured into ice water, and oil-water separation was performed. Desolvation gave an acyl body.

Subsequently, 120 mmol of sodium formate, 1.5 mmol of tetrabutylammonium bromide, and 30.0 g of dimethylformamide were added and stirred at 100°C for 2 hours. Then, 5.2 g of a 48% aqueous sodium hydroxide solution was slowly added at room temperature and stirred. Ion-exchanged water was added, extracted with ethyl acetate, and desolvated to obtain a ketone body.

Subsequently, a compound represented by the following general formula (76) was obtained as the target compound I in the same manner as in [Example 1-1], except that the obtained ketone body was used. It was confirmed by H-NMR that the obtained compound was the target product.

[Example 1-6]

In the same manner as in [Example 1-5], a ketone body having a hydroxyl group was obtained. A compound represented by the general formula (77) was obtained as the target compound I in the same manner as in [Example 1-4], except that the obtained ketone body was used. It was confirmed by H-NMR that the obtained compound was the target product.

[Example 1-7]

A compound represented by the general formula (78) was obtained as the target compound I in the same manner as in Example [1-1], except that phenylacetyl chloride was used as the acid chloride. It was confirmed by H-NMR that the obtained compound was the target product.

[Example 1-8]

In the same manner as in [Example 1-7], a ketone body having a hydroxyl group was obtained. A compound represented by the general formula (79) was obtained as the target compound I in the same manner as in [Example 1-4], except that the obtained ketone body was used. It was confirmed by H-NMR that the obtained compound was the target product.

[Table 1]

[Table 1A]

[Production Example 1] Preparation of polymer B-1 having a hydrophilic group

1,1-bis [4-(2,3-epoxypropyloxy)phenyl] indan 184 g, acrylic acid 58 g, 2,6-di-tert-butyl-p-cresol 0.26 g, tetra-n-butylammonium bromide 0.11 g and 105 g of PGMEA were added and stirred at 120° C. for 16 hours. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of non-phthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added and stirred at 120°C for 4 hours. In addition, 20 g of tetrahydrophthalic anhydride was added, stirred at 120°C for 4 hours, 100°C for 3 hours, 80°C for 4 hours, 60°C for 6 hours, and 40°C for 11 hours, and then 128 g of PGMEA was added. , Polymer B-1 having a hydrophilic group as a PGMEA solution (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH/g, solid content 44.5 mass%).

[Production Example 2] Preparation of carbon black dispersion D-1

15 parts by mass of MA100 (manufactured by Mitsubishi Chemical Co., Ltd.) as carbon black, 11.25 parts by mass of BYK161 (manufactured by Bicke (BYK)) as a dispersant (40% by mass of solid content), 73.75 parts by mass of PGMEA as a solvent, and bead mill The carbon black dispersion liquid D-1 was prepared by processing by.

[Production Example 3] Synthesis of Comparative Compound (A'-1)

10 mmol of 4-hydroxybenzenethiol, 11 mmol of 4'-chloropropiophenone, and 10.0 g of dimethylacetamide were added, and 15 mmol of sodium hydroxide was added, followed by stirring at 50°C for 1 hour. It cooled to room temperature, and oil-water separation was performed with ethyl acetate/aqueous system. The solvent was distilled off to obtain the target product, diphenylphenol.

Subsequently, 10 mmol of the obtained diphenylphenol body, 20 mmol of potassium carbonate, 2-chloroethanol, 20.0 g of acetonitrile, and 20 mmol of potassium carbonate were added as an alcohol, and reflux was performed for 5 hours. After cooling to room temperature, ethyl acetate and ion-exchanged water were added, and oil-water separation was performed. The organic layer was washed 5 times, and after desolvation, a ketone body having a hydroxyl group was obtained.

Subsequently, in the same manner as in [Example 1-4], a comparative compound (A'-1) represented by the following general formula (A'-1) was obtained.

It was confirmed by H-NMR that the obtained compound was the target product.

[Production Example 4] Synthesis of Comparative Compound (A'-2)

(A'-2) was obtained in the same manner as in the preparation of (A'-1), except that 1-chloro-2-propanol was used as the alcohol.

It was confirmed by H-NMR that the obtained compound was the target product.

[Production Example 5] Synthesis of Comparative Compound (A'-3)

(A'-3) was obtained in the same manner as in the production of (A'-1), except that 1-bromo-2-butanol was used as the alcohol.

It was confirmed by H-NMR that the obtained compound was the target product.

[Examples 2-1 to 2-63 and Comparative Examples 1 to 12]

Each component was mixed according to the formulations of Tables 2 to 4 below to prepare a composition.

Meanwhile, the numbers indicate parts by mass.

A-1: Compound (24) (Compound I, obtained in Example 1-1)

A-2: Compound (13) (Compound I, obtained in Example 1-2)

A-3: Compound (3) (Compound I, obtained in Example 1-3)

A-4: Compound (76) (Compound I, obtained in Example 1-5)

A-5: Compound (77) (Compound I, obtained in Example 1-6)

A-6: Compound (78) (Compound I, obtained in Example 1-7)

A-7: Compound (79) (Compound I, obtained in Example 1-8)

A'-1: Compound represented by the compound (A'-1)

A'-2: Compound represented by the compound (A'-2)

A'-3: Compound represented by the compound (A'-3)

A'-4: Compound represented by the compound (A'-4) (photopolymerization initiator, IRGACURE-OXE02 manufactured by BASF)

B-1: Polymer obtained in Production Example 1 (polymer having a hydrophilic group)

B-2: SPC-3000 (polymer having a hydrophilic group; Showa Denko Corporation, solid content 42.7%, PGMEA solution)

C-1: Kayard DPHA (polymerizable compound (polyfunctional acrylate); manufactured by Nippon Kayakusa)

D-1: Carbon black pigment dispersion (obtained in Production Example 2 above)

D-2: lactam black dispersion (solid content concentration 19.5 mass%, pigment concentration in solid content 76.9 mass%, solvent PGMEA)

E-1: KBE-403 (Coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

F-1: Propylene glycol-1-monomethyl ether-2-acetate

(solvent)

[Assessment Methods]

(1) Sensitivity

The compositions obtained in Examples 2-1 to 2-63 and Comparative Examples 1 to 12 were applied onto a glass substrate (100 mm×100 mm) using a spin coater, and prebaking was performed at 90° C. for 100 seconds.

Subsequently, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 150 μm, and the coating film was irradiated with ultraviolet light through a negative mask having a line pattern of 30 μm. .

The exposure doses were 4 steps of 25, 50, 75 and 100 mJ/cm 2.

Then, shower development was performed by discharging the developing solution which consists of 0.04 mass% aqueous potassium hydroxide solution at 23 degreeC with respect to this board|substrate.

The development time was set to 1.5 times the BT, based on the time until the unexposed portion was completely dissolved (BT: break time).

Thereafter, post-baking was performed at 230°C for 30 minutes.

The thickness of the coating film after post-baking was 3.0 µm.

Then, the width (line width) of the pattern of 30 µm after post-baking was determined, and evaluation was performed as an index of sensitivity characteristics. The results are shown in Table 2 below.

◎: The exposure amount with a line width of 30 µm or more is less than 25 mJ/㎠

○: The exposure amount with a line width of 30 μm or more is 25 mJ/cm 2 or more and less than 50 mJ/cm 2

△: The exposure amount with a line width of 30 µm or more is 50 mJ/cm 2 or more and less than 100 mJ/cm 2

X: The exposure amount with a line width of 30 µm or more is 100 mJ/cm 2 or more

On the other hand, it can be judged that the sensitivity is excellent as the exposure amount required for the line width to be a predetermined width is small. In particular, when the evaluation criteria are ○ and ◎, it can be determined that the sensitivity is excellent.

(2) Halftone

The compositions obtained in Examples 2-1 to 2-63 and Comparative Examples 1 to 12 were applied onto a glass substrate (100 mm×100 mm) using a spin coater, and prebaking was performed at 90° C. for 100 seconds.

Subsequently, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 150 µm, and a halftone portion in which a circle pattern of 10 µm was formed (light transmittance 50% (of the fulltone portion) The coating film was irradiated with ultraviolet light through a halftone negative mask having a transmittance at 365 nm of 100%) and a fulton portion (100% of light transmittance).

The exposure amount was 50 mJ/cm 2. Then, shower development was performed by discharging the developing solution which consists of 0.04 mass% aqueous potassium hydroxide solution at 23 degreeC with respect to this board|substrate.

The development time was 1.5 times of BT based on the time until the unexposed portion was completely dissolved (BT: break time).

Thereafter, post-baking was performed at 230°C for 30 minutes.

The thickness of the coating film of the Fulton portion after post-baking was 3.0 µm.

Then, the difference between the thicknesses of the fulltone portion and the halftone portion of the 10 µm circle pattern after post-baking was determined, and evaluation was performed as an index of halftone characteristics. The results are shown in Table 2 below.

○: The difference in film thickness was 0.5 µm or more to 1.0 µm or less.

△: The film thickness difference was more than 1.0 µm and less than 2.9 µm.

X: The film thickness difference was more than 2.9 µm, and no pattern was obtained, so measurement was impossible.

On the other hand, if the difference in film thickness is too large, it can be judged that it is difficult to adjust the film thickness of the cured product obtained according to the exposure amount, and in particular, when the evaluation criterion is ○, spacers having different heights can be easily formed.

(3) VHR

The compositions obtained in Examples 2-1 to 2-63 and Comparative Examples 1 to 12 were applied onto a glass substrate (100 mm×100 mm) using a spin coater, and prebaking was performed at 90° C. for 100 seconds.

Subsequently, a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used, and the coating film was irradiated with ultraviolet radiation at a dose of 200 mJ/cm 2 without interposing a mask.

Thereafter, post-baking was performed at 230°C for 30 minutes.

The thickness of the coating film after post-baking was 3.0 µm.

1 part by mass of the post-baking coating film was mixed with 40 parts by mass of liquid crystal "RS-182" manufactured by ADEKA, and stored at 120°C for 1 hour. This was taken out to room temperature, and after standing, the supernatant was collected. About the collected liquid crystal composition, VHR (voltage retention ratio) before and after mixing the said liquid crystal with a coating film was compared, the retention ratio of VHR was calculated|required by the following formula|equation, and evaluated according to the following criteria. The results are shown in Table 2 below.

On the other hand, in the evaluation, the liquid crystal composition was injected into a liquid crystal evaluation TN cell (cell thickness of 5 µm, electrode area 8 mm×8 mm alignment film JALS2096), and VHR was measured using VHR-1A (manufactured by Toyo Technica) (measurement conditions). : Pulse voltage width 60μs, frame period 16.7ms, wave height ±5V, measurement temperature 60℃).

Retention rate of VHR (%) = {((VHR of liquid crystal "RS-182" before mixing with film)-(VHR of liquid crystal composition obtained by mixing with film)}/(VHR of liquid crystal "RS-182" before mixing with film) ×100

◎: VHR retention rate exceeds 96.0%

○: VHR retention rate is more than 93.0% and less than 96.0%

△: VHR retention rate is more than 90.0% and less than 93.0%

×: VHR retention rate was less than 90.0%

On the other hand, it can be determined that the higher the VHR retention rate, the better the electrical properties, and particularly, when the evaluation criteria are ○ and ◎, it can be determined that the electrical properties are excellent.

(4) Residual rate

The compositions obtained in Examples 2-1 to 2-63 and Comparative Examples 1 to 12 were respectively applied onto a glass substrate (100 mm×100 mm) using a spin coater to form coating films. The formed coating film was prebaked at 90°C for 100 seconds. The film thickness of the pre-baked coating film was measured using DEKTAKXT manufactured by Bruker. The film thickness of the pre-baked coating film was 3.0 µm. Subsequently, a halftone portion (light transmittance 50) of a 10 μm circle pattern was formed on the coating film which had been pre-baked using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) with an exposure gap of 150 μm. %) and a halftone negative mask having a Fulton portion (light transmittance of 100%) was irradiated with ultraviolet light. The exposure amount was 50 mJ/cm 2. Subsequently, a developing solution at 23° C. consisting of an aqueous 0.04 mass% potassium hydroxide solution was discharged to the glass substrate to perform shower development. The development time was 1.5 times the BT based on the time until the unexposed portion was completely dissolved (BT: break time). Thereafter, the coating film was post-baked at 230°C for 30 minutes. The film thickness of the coating film after post-baking was measured using DEKTAKXT manufactured by Bruker. Using the measured film thickness of the pre-baking coating film and the post-baking coating film, the residual film ratio was calculated by the following equation. Sensitivity was evaluated using the residual film rate as an index by obtaining a change in the film thickness of the Fulton portion of the 10 µm circle pattern after pre-baking and post-baking. The results are shown in Tables 2-4 below.

Residual film rate (%) = (film thickness after post-baking / film thickness after pre-baking) x 100

◎: residual film ratio exceeds 85%

○: Residual rate is more than 80.0% and less than 85.0%

△: Residual rate is more than 75.0% and less than 80.0%

×: residual film ratio was less than 75.0%

The larger the residual film ratio, the higher the crosslink density of the resist film, the less shrinkage during post-baking, and the better the sensitivity.

[Table 2]

[Table 3]

Table 3A

Table 3B

Table 3C

[Table 4]

From Tables 2 to 4, it was confirmed that in Examples, a cured product having excellent VHR and residual ratio could be formed.

Thus, it was confirmed that the use of Compound I can form a cured product having excellent electrical properties.

In addition, in the Examples, it was confirmed that, even at high optical concentrations with high pigment contents such as D-1 and D-2, a composition having excellent electrical properties and sensitivity and halftone properties can be formed.

From this point, it was confirmed that the compound I is useful for a member in contact with a liquid crystal material, such as a spacer of a liquid crystal layer.

Claims (6)

Compound represented by the following general formula (I).

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, It represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and is represented by R ¹¹ , R ¹² and R ¹³ . The hydrogen atom of the substituent represented is OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , -C(=N-OR ²¹ )- R ²² , -C(=N-OCOR ²¹ )-R ²² , CN, a halogen atom, or COOR ^{21 may} be substituted,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 represents a heterocyclic group, and the hydrogen atom of the substituent represented by R ²¹ , R ²² and R ^{23 may} be substituted with a CN, halogen atom, hydroxyl group or carboxyl group,
The alkylene portion of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ COO It may be interrupted 1 to 5 times by -, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-, R ²⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, carbon Represents an aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ The alkyl portion of the substituent may be a branched chain or a cyclic alkyl, and R ¹² and R ¹³ and R ²² and R ²³ may be one each to form a ring,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl group, nitro group, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ and R ⁷ are each one to form a ring. , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. Represents a heterocyclic group of 20,
R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,
The alkyl portion of the group represented by R ⁸ may have a branched chain or a cyclic alkyl,
The hydrogen atom of the group represented by R ⁸ is furthermore R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , -C(=N-OR ²¹ )-R ²² , -C(=N-OCOR ²¹ )-R ²² , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, It may be substituted with CN, halogen atom, or COOR ²¹ ,
X is a group represented by a direct bond or CO,
a represents an integer from 0 to 3,
At least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a group having a hydroxyl group.) According to claim 1,
A compound in which at least one of R ¹ , R ⁵ and R ⁸ is a group having a hydroxyl group. According to claim 2,
At least one of R ¹ and R ⁸ is a group having a hydroxyl group,
When R ¹ is a group having a hydroxyl group, R ¹ is a group represented by R ¹¹ , R ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. Is, the hydrogen atom of the alkyl group, the aryl group and the arylalkyl group is substituted with OR ²¹ , the hydrogen atom of R ²¹ is substituted with a hydroxyl group,
When R ⁸ is a group having a hydroxyl group, R ⁸ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and the hydrogen atom of the alkyl group or the aryl group is substituted with a carboxyl group. A composition comprising the compound according to any one of claims 1 to 3. Hardened|cured material of the composition of Claim 4. A method for producing a cured product having a step of irradiating light to the composition according to claim 4.