CN111132963A

CN111132963A - Compound, composition, cured product, and method for producing cured product

Info

Publication number: CN111132963A
Application number: CN201880061861.7A
Authority: CN
Inventors: 冈田光裕; 三原大树; 竹内良智; 木村正树
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2017-10-30
Filing date: 2018-10-29
Publication date: 2020-05-08
Anticipated expiration: 2038-10-29
Also published as: TW201922702A; KR20200078476A; JPWO2019088055A1; WO2019088055A1; CN111132963B; TWI793206B

Abstract

The main object of the present invention is to provide a compound capable of forming a cured product having excellent electrical characteristics, for example. The present invention provides a compound represented by the following general formula (I) to achieve the above object (the details of the substituents in the general formula (I) are referred to in the specification). R in the following general formula (I) is preferable¹、R⁵And R⁸At least 1 of them is a group having a hydroxyl group, preferably R¹And R⁸At least 1 of them is a group having a hydroxyl group.

Description

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

Technical Field

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

Background

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 cells.

As the spacer, a columnar spacer (hereinafter, may be referred to as a columnar spacer) formed by applying a photosensitive composition to a substrate, exposing the substrate through a predetermined mask, and then developing the substrate is known. In recent years, a black columnar spacer having a light-shielding property is used by integrating a columnar spacer and a black matrix into 1 Block (BCS) (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-53942

Disclosure of Invention

Problems to be solved by the invention

However, a cured product of a conventional photosensitive composition has low electrical characteristics, and display defects may occur when the cured product is used for a spacer to form a display device.

The present invention has been made in view of the above problems, and a main object thereof is to provide a compound capable of forming a cured product having excellent electrical characteristics, for example.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that a cured product of a photosensitive composition can be degraded in electrical characteristics by a decomposition product of a photopolymerization initiator and that a cured product having excellent electrical characteristics can be formed by introducing a hydroxyl group into the photopolymerization initiator, and have completed the present invention.

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

[ solution 1]

(in the formula, R¹And R²Each independently represents R¹¹、OR¹¹、COR¹¹、SR¹¹、CONR¹²R¹³Or CN, R¹¹、R¹²And R¹³Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R¹¹、R¹²And R¹³The hydrogen atoms of the substituents shown may be OR²¹、COR²¹、SR²¹、NR²²R²³、CONR²²R²³、-NR²²-OR²³、-NCOR²²-OCOR²³、-C(＝N-OR²¹)-R²²、-C(＝N-OCOR²¹)-R²²CN, halogen atom, or COOR²¹The substitution is carried out by the following steps,

R²¹、R²²and R²³Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R²¹、R²²And R²³The hydrogen atom of the substituent shown may be substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group,

R¹¹、R¹²、R¹³、R²¹、R²²and R²³The alkylene moiety of the substituents shown may be replaced by-O-, -S-, -COO-, -OCO-, -NR-²⁴-、-NR²⁴COO-、-OCONR²⁴-, -SCO-, -COS-, -OCS-or-CSO-are interrupted 1 to 5 times, R²⁴Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R¹¹、R¹²、R¹³、R²¹、R²²And R²³The alkyl moiety of the substituent may have a branched side chain or may be a cyclic alkyl group, and R is¹²And R¹³And R²²And R²³Or may be formed together as a ring,

R³、R⁴、R⁵、R⁶and R⁷Each independently represents R¹¹、OR¹¹、SR¹¹、COR¹⁴、CONR¹⁵R¹⁶、NR¹²COR¹¹、OCOR¹¹、COOR¹⁴、SCOR¹¹、OCSR¹¹、COSR¹⁴、CSOR¹¹Hydroxy, nitro, CN or halogen atom, R⁴And R⁵、R⁵And R⁶And R⁶And R⁷Or may each together form a ring, R¹⁴、R¹⁵And R¹⁶Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R⁸represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R⁸the alkyl portion of the groups shown may have branched side chains or may be cyclic alkyl,

R⁸the hydrogen atoms of the radicals indicated may also be further substituted by R²¹、OR²¹、COR²¹、SR²¹、NR²²R²³、CONR²²R²³、-NR²²-OR²³、-NCOR²²-OCOR²³、NR²²COR²¹、OCOR²¹、COOR²¹、-C(＝N-OR²¹)-R²²、-C(＝N-OCOR²¹)-R²²、SCOR²¹、OCSR²¹、COSR²¹、CSOR²¹Hydroxy, nitro, CN, halogen atom or COOR²¹The substitution is carried out by the following steps,

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

a represents an integer of 0 to 3,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸At least one of which is a group having a hydroxyl group. )

In the compounds I of the present invention, R is preferred¹、R⁵And R⁸At least 1 of them is a group having a hydroxyl group.

In the compounds I of the invention, R¹And R⁸At least 1 of which is a group having a hydroxyl group,

R¹when it is a group having a hydroxyl group, R¹Is R¹¹A group shown, R¹¹An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms OR an aralkyl group having 7 to 30 carbon atoms, wherein the hydrogen atoms of the alkyl group, the aryl group and the aralkyl group are OR²¹Substituted, R²¹Is substituted by a hydroxyl group, R⁸In the case of a group having a hydroxyl group, R is preferably⁸Is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, wherein a hydrogen atom of the alkyl group or the aryl group is substituted with a carboxyl group.

The present invention provides a composition containing the above compound I.

The present invention provides a cured product of the composition.

The present invention provides a method for producing a cured product having a step of irradiating the composition with light.

Effects of the invention

The compound of the present invention can form a cured product having excellent electrical characteristics, for example.

According to the composition of the present invention, a cured product having excellent electrical characteristics such as a power retention rate can be easily obtained.

The cured product of the present invention has excellent electrical characteristics such as electric retention rate.

According to the method for producing a cured product of the present invention, a cured product having excellent electrical characteristics such as a power retention rate can be easily obtained.

Detailed Description

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

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

A. Compound (I)

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

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

[ solution 2]

R¹¹、R¹²、R¹³、R²¹、R²²and R²³The alkylene moiety of the substituents shown may be replaced by-O-, -S-, -COO-, -OCO-, -NR-²⁴-、-NR²⁴COO-、-OCONR²⁴-, -SCO-, -COS-, -OCS-or-CSO-are interrupted 1 to 5 times, R²⁴Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atomsA group or a heterocyclic group having 2 to 20 carbon atoms, R¹¹、R¹²、R¹³、R²¹、R²²And R²³The alkyl moiety of the substituent may have a branched side chain or may be a cyclic alkyl group, and R is¹²And R¹³And R²²And R²³Or may be formed together as a ring,

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

a represents an integer of 0 to 3,

Since the compound I of the present invention has a carbazole structure, an oxime ester group, and a hydroxyl group, it can form a cured product having excellent electrical characteristics, for example. When the influence of the change in the electrical characteristics of the member adjacent to the cured product is small, the cured product can be said to have excellent electrical characteristics. For example, when the member adjacent to the cured product is a liquid crystal composition containing a liquid crystal material, the cured product can be said to have excellent electrical characteristics when the decrease in the Voltage Holding Ratio (VHR) of the liquid crystal composition is small.

Here, the reason why the compound I of the present invention has the above structure and the like and the above effect is obtained is presumed as follows.

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

In addition, the photopolymerization initiator generates a decomposed product as a result of decomposition reaction at an oxime ester group when generating a radical. Further, the decomposition product is transferred to the liquid crystal layer, thereby causing a decrease in the voltage holding ratio of the liquid crystal composition containing the liquid crystal material. The decrease in the voltage holding ratio of the liquid crystal composition causes, for example, display failure of the liquid crystal display device.

In contrast, in the compound I of the present invention, since the carbazole structure and the oxime ester group have a hydroxyl group, the decomposition product also has a hydroxyl group.

Further, since the above-mentioned decomposed product has a hydroxyl group, the affinity with a liquid crystal material which normally exhibits hydrophobicity is low, and even when a cured product is used as a spacer for a liquid crystal layer, for example, the transfer to the liquid crystal layer, which causes a decrease in the voltage holding ratio of the liquid crystal composition, can be suppressed.

As described above, it is understood that the compound I of the present invention has the above structure, and thus can form a cured product having excellent electrical characteristics.

The carbazole structure can absorb ultraviolet light having a wide range of wavelengths, and can generate radicals efficiently in the oxime ester group.

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

Therefore, the compound I of the present invention has the carbazole structure and the oxime ester group, and thus has an excellent balance between sensitivity and a transfer inhibition effect to a liquid crystal layer.

As a result, the compound I of the present invention has excellent electrical characteristics and excellent sensitivity, and thus a cured product can be easily formed. Further, by having high sensitivity, for example, a cured product having a large film thickness at a portion where the exposure amount is large and a small film thickness at a portion where the exposure amount is small can be easily obtained.

From this point of view, the compound I of the present invention is also a compound capable of forming a cured product having the above-described structure and excellent electrical characteristics.

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

The compound I of the present invention is described in detail below.

The compound I of the present invention is a compound represented by the above general formula (I), wherein R is represented by the above general formula (I)¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸At least one of them is a compound having a hydroxyl groupA group of (1).

1. Group having hydroxyl group

From the viewpoint of forming a cured product having excellent electrical characteristics, the compound I is preferably R, for example¹、R³、R⁴、R⁵、R⁶、R⁷And R⁸At least one group in (1) is a group having a hydroxyl group, and R is particularly preferred¹、R⁵And R⁸At least 1 of them is a group having a hydroxyl group, and R is particularly preferred¹And R⁸At least 1 of them is the above-mentioned group having a hydroxyl group. When the group is the group having a hydroxyl group, the compound I of the present invention can form a cured product having excellent electrical characteristics. In addition, this is because the compound I of the present invention can be easily synthesized. In the present invention, the group having a hydroxyl group includes a hydroxyl group itself.

The number of hydroxyl groups contained in such a group having a hydroxyl group may be 1 or more, and may be appropriately set according to the use of the compound I, required electrical characteristics, ease of synthesis, and the like, and is, for example, preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 2 or less. This is because the compound I can form a cured product having excellent electrical characteristics by the number of hydroxyl groups, and can be easily synthesized.

The compound represented by the general formula (2) described later is an example of a compound containing a group having 2 hydroxyl groups.

The kind of the hydroxyl group contained in the group having a hydroxyl group may be, for example, a hydroxyl group contained as a part of a carboxyl group bonded to a carbon atom of a carbonyl group, but from the viewpoint of improving electrical characteristics, it is preferably contained in the form of an alcoholic hydroxyl group bonded to a carbon atom of a chain hydrocarbon or a phenolic hydroxyl group bonded to a carbon atom of an aromatic hydrocarbon, and among these, it is preferably contained in the form of an alcoholic hydroxyl group.

The compound represented by the general formula (1) described later represents an example in which the hydroxyl group is an alcoholic hydroxyl group, and the compound represented by the general formula (3) represents an example in which the hydroxyl group is contained as a part of a carboxyl group.

The bonding position of the hydroxyl group contained in the group having a hydroxyl group is preferably the terminal of the group having a hydroxyl group. This is because the compound I can form a cured product having more excellent electrical characteristics and can be easily synthesized.

The terminal of the group having a hydroxyl group means that the hydroxyl group contained in the group having a hydroxyl group is bonded to a position farthest from the bonding position with the carbazole structure or the oxime ester group.

For example, the general formula (5) described later shows an example in which the bonding position of the hydroxyl group is the terminal of the 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 terminal of the group having a hydroxyl group.

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

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 the above-mentioned groups having a hydroxyl group in the Compound I, namely, R¹～R⁸The number of the groups containing a group having a hydroxyl group in (b) may be 1 or more, and may be appropriately set according to the use of the compound I, the required electrical characteristics, the ease of synthesis, and the like, and for example, may be 1 or more and 5 or less, preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and preferably 1. This is because the compound I can form a cured product having excellent electrical characteristics and can be easily synthesized by setting the number of the groups having a hydroxyl group to the above range.

When the number of the groups having a hydroxyl group is 2, for example, the above-mentioned R is mentioned¹And R⁵In the case where both are groups having hydroxyl groups. More specifically, the compounds represented by the general formulae (34) and (35) described later represent examples in which the number of the groups having a hydroxyl group is 2.

The number of hydroxyl groups contained in the compound I may be 1 or more, may be 1 or more and 10 or less, is preferably 1 or more and 5 or less, and is particularly preferably 1 or more and 2 or less. This is because the compound I can form a cured product having excellent electrical characteristics by the number of hydroxyl groups, and can be easily synthesized.

2. Compound I

As R in the above general formula (I)⁸、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R²¹、R²²、R²³And R²⁴Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a.

As R in the above general formula (I)⁸、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R²¹、R²²、R²³And R²⁴Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, and phenanthryl, and phenyl, biphenyl, naphthyl, and anthryl groups substituted with 1 or more of the above alkyl groups.

As R in the above general formula (I)⁸、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R²¹、R²²、R²³And R²⁴Examples of the aralkyl group having 7 to 30 carbon atoms include benzyl, α -methylbenzyl, α -dimethylbenzyl and phenylethyl.

As R in the above general formula (I)⁸、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R²¹、R²²、R²³And R²⁴Examples of the heterocyclic group having 2 to 20 carbon atoms include, preferably, 5 to 7-membered heterocyclic rings such as pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolinyl, isothiazolinyl, oxazolidinyl, isoxazolidinyl, piperidyl, piperazinyl, and morpholinyl.

Examples of the halogen atom in the general formula (I) include fluorine, chlorine, bromine and iodine.

As R in the above general formula (I)¹²And R¹³And R²²And R²³Examples of the ring which may be formed together include a 5-to 7-membered ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring.

R in the above general formula (I)¹¹、R¹²、R¹³、R²¹、R²²And R²³The alkylene moiety of the substituents shown may be replaced by-O-, -S-, -COO-, -OCO-, -NR-²⁴-、-NR²⁴CO-、-NR²⁴COO-、-OCONR²⁴-, -SCO-, -COS-, -OCS-or-CSO-are interrupted 1 to 5 times, and the number of the interrupted bonding groups may be 1 or 2 or more, and in the case of groups capable of being interrupted continuously, 2 or more may be interrupted continuously.

In addition, R in the above general formula (I)¹¹、R¹²、R¹³、R²¹、R²²And R²³The alkyl (alkylene) moiety of the substituents shown may also have a branched side chain or may be a cyclic alkyl (cycloalkylene).

In the present invention, the number of carbon atoms in the group is defined as the number of carbon atoms in the group after substitution when the alkylene moiety in the group is substituted with the above-mentioned 2-valent group. For example, in the present specification, when an alkylene group in an alkyl group having 1 to 20 carbon atoms is substituted with the above-mentioned group having a valence of 2, the term "1 to 20 carbon atoms" refers to the number of carbon atoms after the substitution of the alkylene group and does not refer to the number of carbon atoms before the substitution of the alkylene group.

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

As R in the above general formula (I)⁴And R⁵、R⁵And R⁶And R⁶And R⁷Rings which may be formed together with R above¹²And R¹³And R²²And R²³The rings that may be formed together are identical.

R¹When the above group has a hydroxyl group, R¹Is R¹¹A group shown, R¹¹Preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, more preferably an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, still more preferably an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 15 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 12 carbon atoms.

In addition, R¹In the case of the above-mentioned group having a hydroxyl group, R¹Is R¹¹The group shown, further, R¹¹When it is an alkyl group having 1 to 20 carbon atoms, R¹¹The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms.

This is because of the passage of R¹As the above group, the compound I can form a cured product having excellent electrical characteristics, and can be easily synthesized. Further, the compound I can easily realize a wide absorption wavelength range, and can give a composition having excellent sensitivity.

R¹R used in (1)¹¹In the case where the above alkyl group, the above aryl group or the above aralkyl group is used, the alkyl groupThe hydrogen atoms of the aryl group and the aralkyl group are preferably OR²¹Substituted, R²¹Preferably an alkyl group having 1 to 20 carbon atoms, R²¹More preferably an alkyl group having 1 to 10 carbon atoms, R²¹Particularly preferably an alkyl group having 1 to 5 carbon atoms.

R¹Is the above-mentioned group having a hydroxyl group, R¹Is R¹¹A group shown, R¹¹In the case of the above alkyl group, the above aryl group or the above aralkyl group, the hydrogen atom of these groups may be substituted with a hydroxyl group.

R¹Preferably R¹¹The hydrogen atom of the above alkyl group, the above aryl group and the above aralkyl group is OR²¹Substituted, R²¹A group in which the hydrogen atom of (a) is substituted with a hydroxyl group.

R¹When the above group has a hydroxyl group, R¹More specifically, the following groups are preferred: r¹Is R¹¹A group shown, R¹¹Is the above alkyl group, the above aryl group OR the above aralkyl group, and a hydrogen atom of the above alkyl group, the above aryl group and the above aralkyl group is OR²¹Substituted, R²¹Is alkyl, R²¹Is substituted with a hydroxyl group.

R¹In the case where X is a group having a hydroxyl group and X is a direct bond, R¹The above alkyl group or aralkyl group is preferable. In addition, in R¹In the case where X is CO and is a group having a hydroxyl group, R¹The above alkyl group, aralkyl group or aryl group is preferable.

This is because of the passage of R¹As the above group, the compound I can form a cured product having excellent electrical characteristics, and can be easily synthesized.

R¹When it is a group having no hydroxyl group, R¹Is R¹¹The group shown, preferably R¹¹Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, preferably R¹¹Is an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, more preferably R¹¹Is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, more preferably R¹¹Is C1-10 alkyl or alkylene substituted by-OCO-Aralkyl having 7 to 10 carbon atoms, and R is particularly preferable¹¹An aralkyl group having 7 to 10 carbon atoms in which an alkylene group at the side of the alkyl group or oxime ester having 1 to 10 carbon atoms is substituted with-OCO-.

R¹When X is a group having no hydroxyl group and is a direct bond, an alkyl group or an aralkyl group is preferable. In addition, R¹When X is CO and is a group having no hydroxyl group, it is preferably an alkyl group, an aralkyl group or an aryl group.

In addition, R¹In the case of a group having no hydroxyl group, R is a group having a wide absorption wavelength range and is easy to form a compound having excellent sensitivity¹Is R¹¹A group shown, R¹¹Preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms.

R⁵When the above group has a hydroxyl group, R⁵Preferably made of-COR¹¹The group shown. R¹¹Preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, R¹¹More preferably an aryl group having 6 to 15 carbon atoms, R is¹¹Particularly preferably an aryl group having 6 to 10 carbon atoms.

R⁵R used in (1)¹¹In the case where the above alkyl group, the above aryl group OR the above aralkyl group is used, the hydrogen atom of the alkyl group, the aryl group OR the aralkyl group is preferably OR²¹Substituted, R²¹Preferably an alkyl group having 1 to 20 carbon atoms, R²¹More preferably an alkyl group having 1 to 10 carbon atoms, R²¹Particularly preferably an alkyl group having 1 to 5 carbon atoms.

R⁵Is a group having a hydroxyl group, R⁵is-CO-R¹¹A group shown, R¹¹In the case of the above alkyl group, the above aryl group or the above aralkyl group, any of the hydrogen atoms of these groups may be substituted with a hydroxyl group. R⁵Preferably in the range-CO-R¹¹R contained in (1)¹¹The above alkyl group, the aboveHydrogen atoms of aryl groups and aralkyl groups mentioned above being OR²¹Substituted, R²¹When it is an alkyl group, R²¹Is substituted with a hydroxyl group.

R⁵In the case of the above-mentioned group having a hydroxyl group, more specifically, R is preferable⁵is-CO-R¹¹A group shown, R¹¹Is the above alkyl group OR the above aryl group, the hydrogen atoms of the alkyl group and the aryl group being OR²¹Substituted, R²¹Is substituted with a hydroxyl group.

R⁵When the above group has a hydroxyl group, the group is R⁵The number of hydroxyl groups contained in (c) 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, and particularly preferably 2.

This is because of the passage of R⁵As the above group, the compound I can form a cured product having excellent electrical characteristics, and can be easily synthesized.

R⁵In the case of a group having no hydroxyl group, R is preferably⁵Is R¹¹A group shown or nitro, R¹¹Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, preferably R⁵Is R¹¹A group shown or nitro, R¹¹Is a hydrogen atom, particularly preferably R⁵Is nitro.

This is because of the passage of R⁵As the above group, the compound I can form a cured product having excellent electrical characteristics, and can be easily synthesized. In addition, this is because the sensitivity of the compound I is excellent.

R²When it is a group having no hydroxyl group, R²Is R¹¹A group shown, R¹¹Preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, 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.

R³、R⁴、R⁶And R⁷When it is a group having no hydroxyl group, R³、R⁴、R⁶And R⁷Is R¹¹A group shown, R¹¹Preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl 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.

This is because by making R²、R³、R⁴、R⁶And R⁷As the above group, the compound I can form a cured product having excellent electrical characteristics, and can be easily synthesized.

R⁸When the above group has a hydroxyl group, R⁸Preferably 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 particularly preferably an alkyl group having 1 to 10 carbon atoms.

R⁸Is the above-mentioned group having a hydroxyl group, R⁸When the alkyl group has 1 to 20 carbon atoms, the aryl group has 6 to 30 carbon atoms, or the aralkyl group has 7 to 30 carbon atoms, any one of these groups may be substituted with a hydroxyl group, and among them, the hydrogen atom of the alkyl group, the aryl group, and the aralkyl group is preferably substituted with a hydroxyl group or a carboxyl group (COOR)²¹，R²¹Hydrogen atom), preferably a hydrogen atom of the above alkyl group, the above aryl group and the above aralkyl group is substituted with a carboxyl group (COOR)²¹，R²¹Hydrogen atom) is substituted.

R⁸When the group having a hydroxyl group is mentioned above, more specifically, R⁸Preferably, the alkyl group or the aryl group, and the hydrogen atom of the alkyl group or the aryl group is substituted by a carboxyl group (COOR)²¹，R²¹Is a hydrogen atom).

This is because of the passage of R⁸As the above group, the compound I can form a cured product having excellent electrical characteristics, and can be easily synthesized.

R⁸When it is a group having no hydroxyl group, R⁸Preferably 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, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

This is because of the passage of R⁸Is the above groupThe compound I can form a cured product having excellent electrical characteristics, and can be easily synthesized.

In the above compound I, a represents R³The number of the functional group(s) of (b) may be an integer of 0 to 3, preferably an integer of 0 to 2, particularly preferably an integer of 0 to 1, and particularly preferably 0. This is because when a is in the above range, the compound I can form a cured product having excellent electrical characteristics and can be easily synthesized.

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

In the compound I, the bonding position of the oxime ester group is not particularly limited as long as it is a position capable of bonding to the benzene ring contained in the carbazole structure, and for example, a position at the 6-position of the carbazole structure is preferable as shown in the following general formula (Ia). This is because the compound I can form a cured product having excellent electrical characteristics and can be easily synthesized.

[ solution 3]

(in the formula, R¹、R²、R⁵And R⁸And X represents the same group as the above general formula (I). )

The compound I is preferably a compound represented by the 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 characteristics and can be easily synthesized.

Specific examples of the compound I represented by the above general formula (I) include the following compounds (1) to (14), (21) to (35), (41) to (54), and (61) to (79). These compounds can form a cured product having excellent electrical characteristics and can be easily synthesized.

[ solution 4]

[ solution 5]

[ solution 6]

[ solution 7]

[ solution 7A ]

The molecular weight of the compound I can be set according to the use of the compound I. The molecular weight of the compound I may be, for example, 250 or more and 2000 or less, 300 or more and 2000 or less, or 350 or more and 1000 or less. This is because a cured product having excellent electrical characteristics can be formed by adjusting the molecular weight of compound I to the above range.

The method for producing the compound I represented by the above general formula (I) is not particularly limited as long as the compound I having the above structure can be obtained, and for example, the method described in japanese patent No. 4223071 and the like can be used. Specifically, the production can be carried out by the following reaction scheme.

The following methods may be mentioned: first, a carbazole compound (I-0) and an acid chloride (I-1) are reacted in the presence of aluminum chloride to obtain an acyl base (I-2). Next, the acyl base (I-2) and hydroxylamine hydrochloride are reacted in the presence of DMF to give an oxime compound (I-3). Next, the oxime compound (I-3) is reacted with an acid anhydride (I-4) or an acid chloride (I-5) to obtain an oxime ester compound (I-6) of the present invention corresponding to the above general formula (I).

In addition, the above-mentioned production method may use R²～R⁸At least 1 of them is a carbazole compound (I-0) having a group having a hydroxyl group. In addition, R may be used²～R⁸To hydrogen atomsA method in which the carbazole compound (I-0) is reacted with the acid anhydride (I-4) or the acid chloride (I-5), and then an alkyl group having a hydroxyl group or the like is introduced thereto according to a conventional method.

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

In the production of the above-mentioned compound I wherein X is-CO-, the oxime compound may be formed by the same method as the above-mentioned production method except that the method of reacting the acyl group (I-3) with nitrite in the presence of hydrochloric acid is used.

[ solution 8]

(in the formula, R¹、R²、R⁵、R⁶、R⁷、R⁸And a represents the same group as the above general formula (I). )

The compound I can be used, for example, as a photopolymerization initiator component that generates radicals by irradiation with light.

The compound I can be used by being added to a composition such as a photocurable composition.

Examples of the applications of the composition include a photocurable coating or varnish, a photocurable adhesive, a printed board, a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a portable information terminal, and a digital camera, an electrode material for a plasma display panel, a powder coating, a printing ink, a printing plate, an adhesive, a dental composition, a gel coat, a photoresist for electronic engineering, a plating resist, an etching resist, both a liquid and a dry film, a solder resist, a resist for manufacturing a color filter for various display applications or a resist for forming a structure in a manufacturing process of a plasma display panel, an electroluminescent display device, and an LCD, a composition for encapsulating electric and electronic parts, a magnetic recording material, a micromachine component, a waveguide, an optical switch, a mask for plating, a light-emitting diode, a light-emitting, Various applications such as etching masks, color test systems, stencils for glass fiber cable coating, screen printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, fine electronic circuits, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, and photoresist materials or protective films used for dielectric layer formation in successive lamination of printed circuit boards are not particularly limited.

Among them, the use of the compound I is preferably, for example, the use of an alignment layer, a spacer for a liquid crystal layer, an insulating film, an overcoat layer, a sealant for sealing the periphery of the liquid crystal layer, and a member in contact with a liquid crystal material such as a color filter or a black matrix, and particularly preferably the use of a spacer for a liquid crystal layer, from the viewpoint of more effectively exhibiting an effect of forming a cured product having excellent electrical characteristics.

In the present invention, by using the compound I, for example, a liquid crystal layer spacer characterized by having a cured product of a composition containing the compound I, a liquid crystal display device characterized by containing the liquid crystal layer spacer, and the like can be obtained.

The liquid crystal layer spacer may be used as a black columnar spacer having a function as a black matrix, for example.

B. Photopolymerization initiator

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

The photopolymerization initiator of the present invention is characterized by containing the compound I.

The photopolymerization initiator of the present invention can form a cured product having excellent electrical characteristics, for example, by containing the compound I.

The photopolymerization initiator contains the compound I.

The respective components of the photopolymerization initiator are described below.

The content of the compound I in the photopolymerization initiator of the present invention may be appropriately set according to the use of the photopolymerization initiator, as long as the desired photopolymerization curability can be imparted. The content of the compound I in the photopolymerization initiator may be 100 parts by mass in 100 parts by mass of the photopolymerization initiator, that is, the photopolymerization initiator may be composed of only the compound I. This is because the content of the compound I in the above range is useful as a photopolymerization initiator which can easily form a cured product having excellent electrical characteristics.

The content of the compound I in the photopolymerization initiator of the present invention may be less than 100 parts by mass based on 100 parts by mass of the photopolymerization initiator, that is, the photopolymerization initiator may be a composition containing the compound I and other components. In this case, the content of the compound I may 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 in the above range is useful as a photopolymerization initiator which can easily form a cured product having excellent electrical characteristics.

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

The number of the compounds I contained in the photopolymerization initiator may be only 1, or may be 2 or more. The types of the above-mentioned substances may be set to 2 or more and 5 or less, for example.

The compound I may be the same as that described in the section "compound a", and therefore, the description thereof will be omitted.

As the other components, components that do not inhibit the function as a photopolymerization initiator can be used, and examples thereof include components described in the section of "2. other components" of "c. composition" described later, and polymer components described in the section of "e. cured product" described later.

Among them, the photopolymerization initiator of the present invention preferably contains the above-mentioned polymer component as the above-mentioned other component.

The photopolymerization initiator may be in the form of a powder or a pellet.

When the photopolymerization initiator is in the form of pellets, for example, a method of mixing the compound I and the polymer component with an extruder or the like and molding the mixture into pellets can be used as a production method thereof.

C. Composition comprising a metal oxide and a metal oxide

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

The composition of the present invention is characterized by containing the above-mentioned compound I.

By containing the compound I, the composition of the present invention can easily obtain a cured product having excellent electrical characteristics.

The composition of the present invention comprises the above 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 or the like to the composition.

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

The solid component means a component containing all components except the solvent.

The content of the compound I may be 0.001 part by mass or more and 30 parts by mass or less, and preferably 0.005 part by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the composition. This is because a cured product having excellent electrical characteristics can be obtained more easily.

The content of the compound I may be set to 0.01 part by mass or more and 30 parts by mass or less, particularly preferably 0.1 part by mass or more and 25 parts by mass or less, further preferably 0.5 part 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, 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 the polymerizable compound or the polymer having a hydrophilic group. This is because a cured product having excellent electrical characteristics can be obtained more easily.

The number of the compounds I contained in the composition may be only 1, or may be 2 or more. The types of the above-mentioned substances may be set to 2 or more and 5 or less, for example. This is because the type of compound I in the above range facilitates formation of a cured product having excellent electrical characteristics.

2. Others

The composition contains the compound I, but may contain other components as needed.

Examples of the other components include a polymerizable compound, a polymer having a hydrophilic group, a colorant, a solvent, an inorganic compound used as a filler, an antireflection agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength enhancer, a special wavelength absorber, an ink repellent, and the like, a dispersant for dispersing a colorant, an inorganic compound, and the like, a polymerizable compound other than the polymerizable compound and the polymer a used for improving the characteristics of a cured product, an organic polymer other than the polymer having a hydrophilic group, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine, and the like.

(1) Polymerizable compound

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

The polymerizable compound may be any compound as long as it can form a polymer, and may be, for example, a compound having a radical polymerizable group.

As the polymerizable compound, a compound having an ethylenically unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be used, for example.

The term (meth) acrylic acid is used in the meaning including acrylic acid and methacrylic acid. In addition, (meth) acrylate is used in the meaning including acrylate and methacrylate.

Examples of such polymerizable compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene fluoride, tetrafluoroethylene, and the like, (meth) acrylic acid, α -chloropropenoic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, norbornene diacid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl ester ], phthalic acid mono [2- (meth) acryloyloxyethyl ester ], omega-carboxy mono (meth) acrylic ester of a polymer having carboxyl groups and hydroxyl groups at both ends, mono (meth) acrylic acid esters such as maleic acid hydroxyethyl, maleic acid (meth) acrylate, maleic acid hydroxypropyl ester, dicyclopentadiene maleic acid, or polyfunctional (meth) acrylic esters having 1 carboxyl group and 2 or more (meth) acryloyl groups, such as poly (meth) acrylic acid esters, maleic anhydride, ethylene glycol mono (meth) acrylic acid, maleic anhydride, maleic.

Among them, from the viewpoint of curability and chromaticity characteristics, mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polyfunctional (meth) acrylates having 1 carboxyl group and 2 or more (meth) acryloyl groups, esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols are preferable.

The polymerizable compounds can be used alone or in combination of 2 or more.

[ solution 9]

Compound No. A1

[ solution 10]

Compound No. A2

[ chemical 11 ]

Compound No. A3

[ solution 12]

Compound No. A4

The molecular weight of the polymerizable compound is not particularly limited as long as a desired cured product can be obtained, and may be, for example, less than 2000, preferably 1500 or less, particularly preferably 1000 or less, and particularly preferably less than 1000. This is because the curability is excellent.

When the polymerizable compound is a polymer containing a repeating structure as its structure, the molecular weight is represented by a weight average molecular weight (Mw).

The weight average molecular weight can be determined as a standard polystyrene equivalent by Gel Permeation Chromatography (GPC) as follows.

The weight average molecular weight Mw can be measured, for example, using GPC (LC-2000plus series) manufactured by Nippon spectral Co., Ltd., tetrahydrofuran as an elution solvent, polystyrene standards for calibration curves Mw1110000, 707000, 397000, 189000, 98900, 37200, 13700, 9490, 5430, 3120, 1010, 589 (TSKgel standard polystyrene manufactured by Tosoh Co., Ltd.), and KF-804, KF-803, KF-802 (manufactured by Showa Denko K.K.) as measurement columns.

The measurement temperature was set to 40 ℃ and the flow rate was set to 1.0 mL/min.

The content of the polymerizable compound is not particularly limited as long as a desired cured product can be obtained, and for example, may be 1 part by mass or more and 50 parts by mass or less, particularly preferably 5 parts by mass or more and 40 parts by mass or less, 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, with respect to 100 parts by mass of the solid content of the composition. This is because the composition has excellent curability when the content is in the above range.

The content of the resin component containing the polymerizable compound may be appropriately set according to the use of the composition, and for example, may be 1 part by mass or more and 99 parts by mass or less, preferably 10 parts by mass or more and 80 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less, with respect to 100 parts by mass of the solid content. This is because, when the content is in the above range, the composition can easily impart various functions to a cured product. The resin component may be any component used for retaining the decomposition product of the compound I, the colorant, and the like by being contained in the cured product of the composition, and may be a component containing the polymerizable compound, a hydrophilic group-containing polymer described later, and another organic polymer, for example.

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

(2) Polymers having hydrophilic groups

By containing the polymer having a hydrophilic group (hereinafter, sometimes referred to as polymer a), the composition can be easily used 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 conventionally used organic polymers can be used.

The hydrophilic group is not particularly limited as long as it can impart desired alkali solubility to the polymer a, and examples thereof include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group, and salts thereof.

The preferred functional group equivalent of the hydrophilic group in the polymer a (the mass of the polymer a containing 1 equivalent of the hydrophilic group) may be appropriately set according to the desired alkali solubility, and may be set to, for example, 50 or more and 10000 or less. This is because when the functional group equivalent is in the above range, the alkali developability of the polymer a is excellent.

The weight average molecular weight (Mw) of the polymer a may be appropriately set according to the desired alkali solubility, and may be 1000 or more and 500000 or less, preferably more than 1000 and 100000 or less, and particularly preferably 2000 or more and 30000 or less. This is because when the weight average molecular weight is in the above range, the alkali developability of the polymer a is excellent.

The acid value of the polymer a may be appropriately set according to the desired alkali solubility, and may be set to 10mgKOH/g or more and 200mgKOH/g or less, and preferably 30mgKOH/g or more and 150mgKOH/g or less. This is because when the acid value is in the above range, the polymer a is excellent in alkali developability.

Here, the acid value represents the mass (mg) of potassium hydroxide required for neutralizing the acidic component contained in 1g of the solid content of the polymer, and can be a value measured by the method described in JIS K0070.

The polymer a may have a repeating unit, and specifically, a copolymer of acrylic acid ester, phenol and/or cresol novolac epoxy resin, polyphenylmethane-type epoxy resin having a polyfunctional epoxy group, epoxy acrylate resin, a compound having a structure obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (V), or a resin having a structure obtained by allowing a polybasic acid anhydride to further act on the compound may be used.

The polymer a preferably has an unsaturated group, and particularly preferably an epoxy adduct compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following general formula (V), or an ethylenically unsaturated compound having a structure obtained by esterification of the epoxy adduct compound with a polybasic acid anhydride. This is because the composition is excellent in patterning property.

In order to obtain the epoxy addition compound, an unsaturated monobasic acid may be subjected to an addition reaction with an epoxy compound represented by the following general formula (V). In order to obtain the above ethylenically unsaturated compound, the epoxy adduct compound obtained by the addition reaction may be subjected to an esterification reaction with a polybasic acid anhydride.

The ethylenically unsaturated compound preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

The unsaturated group may be the same as the above-mentioned ethylenically unsaturated double bond group.

[ solution 13]

(wherein M represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO₂SS, SO, CO, OCO, a substituent selected from the group represented by the following formula (V-1), (V-2) or (V-3), R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷And R¹⁰⁸Each independently represents a hydrogen 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 of 0 to 10. )

[ solution 14]

(R¹⁰⁹、R¹¹⁰、R¹¹¹、R¹¹²、R¹¹³、R¹¹⁴、R¹¹⁵、R¹¹⁶、R¹¹⁷、R¹¹⁸、R¹¹⁹、R¹²⁰、R¹²¹、R¹²²、R¹²³、R¹²⁴、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R¹³¹And R¹³²Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, wherein the methylene chain constituting the alkylene moiety in the alkyl group and the aralkyl group may be substituted by an unsaturated bond, -O-or-S-, and R is¹⁰⁹、R¹¹⁰、R¹¹¹、R¹¹²、R¹¹⁷、R¹¹⁸、R¹¹⁹、R¹²⁰、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R¹³¹And R¹³²Through adjacent R¹⁰⁹、R¹¹⁰、R¹¹¹、R¹¹²、R¹¹⁷、R¹¹⁸、R¹¹⁹、R¹²⁰、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R¹³¹And R¹³²Form a loop with each other ＊ represents a bond end)

Examples of the alkyl group, aryl group, aralkyl group, heterocyclic group and halogen atom in the general formula (V) include various groups exemplified for the alkyl group, aryl group, aralkyl group, heterocyclic group and halogen atom in the description of the general formula (I). Examples of the alkoxy group in the general formula (V) include groups corresponding to the alkyl groups exemplified in the description of the general formula (I).

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

As the unsaturated monobasic acid to be reacted on the epoxy compound, a compound having 1 unsaturated group and 1 carboxyl group can be used, and examples thereof include 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.

Further, as the polybasic acid anhydride which acts after the unsaturated monobasic acid acts, carboxylic acid anhydrides may be used, and examples thereof include: biphenyl tetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, diphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2 '-3, 3' -benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methylnadic 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, the epoxy adduct compound is preferably added so that the carboxyl group of the unsaturated monobasic acid is in a ratio of 0.1 to 1.0 relative to 1 epoxy group of the epoxy compound, and the ethylenically unsaturated compound is preferably reacted so that the acid anhydride structure of the polybasic acid anhydride is in a ratio of 0.1 to 1.0 relative to 1 hydroxyl group of the epoxy adduct compound.

The reaction of the above epoxy compound, the above unsaturated monobasic acid and the above polybasic acid anhydride can be carried out according to a 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 1 epoxy group can be used, and examples thereof include: glycidyl methacrylate, methylglycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxypropyl glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyltolyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2, 3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1, 2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following compounds No. E1, No. E2 and the like.

[ solution 15]

Compound No. E1

[ solution 16]

Compound No. E2

As the polyfunctional epoxy compound, a compound having 2 or more epoxy groups can be used, and for example, one or more compounds selected from bisphenol type epoxy compounds and glycidyl ethers can be used.

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

As the glycidyl ethers, there can be used: 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-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-tris (glycidoxymethyl) propane, 1, 1, 1-tris (glycidoxymethyl) ethane, 1, 1, 1-tris (glycidoxymethyl) methane, 1, 1-tetrakis (glycidoxymethyl) methane, and the like.

Further, there may be mentioned novolak type epoxy compounds such as phenol novolak type epoxy compounds, biphenol novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol a novolak type epoxy compounds, dicyclopentadiene novolak type epoxy compounds and the like; alicyclic epoxy compounds such as 3, 4-epoxy-6-methylcyclohexylmethyl-3, 4-epoxy-6-methylcyclohexanecarboxylate, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, and 1-epoxyethyl-3, 4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer acid; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl-p-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; a naphthalene type epoxy compound; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds, and the like.

The polymer a preferably contains a polymer having a carboxyl group from the viewpoint of excellent developability. This is because the composition has more excellent patterning accuracy by containing the polymer.

The polymer having a carboxyl group is not particularly limited as long as it contains a structural unit having a carboxyl group (hereinafter referred to as "structural unit (U1)"), and more preferably contains a structural unit selected from a structural unit having a crosslinkable group such as a methacryloyl group, an acryloyl group, a vinyl group, an epoxy group, an oxetanyl group, a vinyl ether group, a mercapto group, an isocyanate group, and the like (hereinafter referred to as "structural unit (U2)") and a structural unit having a silyl group (hereinafter referred to as "structural unit (U3)").

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

The structural unit (U1) is preferably at least 1 type (hereinafter referred to as "compound (U1)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.

Examples of the compound (u1) include: monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, and the like. Examples of the monocarboxylic acid include: acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and the like;

examples of the dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, and the like;

examples of the anhydrides of the dicarboxylic acids include anhydrides of the dicarboxylic acids.

Among them, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in a developer.

The compound (u1) can be used alone or in combination of 2 or more.

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

The compound (u2) is preferably at least 1 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 an ethylene oxide (cyclo) alkyl (meth) acrylate, an ethylene oxide (cyclo) alkyl (α -alkylacrylate), and a glycidyl ether compound having a polymerizable unsaturated bond;

examples of the polymerizable unsaturated compound having an oxetanyl group include (meth) acrylates having an oxetanyl group and the like.

Specific examples of the above compound (u2) include the following:

examples of the oxirane (cyclo) alkyl (meth) acrylate include: glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3, 4-epoxytricyclo [5.2.1.02.6] decyl (meth) acrylate, and the like;

examples of the α -alkyl ethylene oxide (cyclo) alkyl acrylate include α -glycidyl ethacrylate, α -glycidyl n-propylacrylate, α -glycidyl n-butylacrylate, α -6-ethyl acrylate, 7-epoxyheptyl ester, α -3, 4-epoxycyclohexyl ethacrylate, and the like;

examples of the glycidyl ether compound having a polymerizable unsaturated bond include: o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.;

examples of the (meth) acrylate having an oxetanyl group include: 3- ((meth) acryloyloxymethyl) oxetane, 3- ((meth) acryloyloxymethyl) -3-ethyloxetane, 3- ((meth) acryloyloxymethyl) -2-methyloxetane, 3- ((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- ((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane and the like.

Among these specific examples, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxytricyclo [5.2.1.02.6] decyl acrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane are particularly preferable from the viewpoint of polymerizability.

The compound (u2) can be used alone or in combination of 2 or more.

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

The structural unit having a (meth) acryloyloxy group is obtained by reacting a carboxyl group in a polymer with a (meth) acrylate having an epoxy group. The structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U2-1).

[ formulation 16A ]

(in the formula, R¹⁰⁰⁰And R¹⁰⁰¹Each independently being a hydrogen atom or a methyl group, R¹⁰⁰²Is a 2-valent group represented by the following formula (α) or the following formula (β), c is an integer of 1 to 6, and represents a bonding position

[ formulation 16B ]

(in the formula, R¹⁰⁰³Is a hydrogen atom or a methyl group, and represents a bonding position. )

Regarding the structural unit represented by the above formula (U2-1), for example, when a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate is reacted with a copolymer having a carboxyl group, R in the formula (U2-1)¹⁰⁰²Is of the formula (α). on the other hand, in the case of reacting 3, 4-epoxycyclohexylmethyl methacrylate with a copolymer having a carboxyl group, R in the formula (U2-1)¹⁰⁰²Is formula (β).

In the reaction between the carboxyl group in the polymer and the unsaturated compound such as (meth) acrylate having an epoxy group, it is preferable to add the unsaturated compound having an epoxy group to a solution of the polymer containing a polymerization inhibitor in the presence of an appropriate catalyst, if necessary, and stir the mixture for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably 70-100 ℃. The reaction time is preferably 8 to 12 hours.

In the above-mentioned ratio of the structural units 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 to 70 mol%, more preferably 20 to 50 mol%, of the total structural units of the polymer having a carboxyl group.

When the ratio of the structural unit having a (meth) acryloyloxy group is in the above range, heat resistance and development failure during development are reduced, and generation of development residue 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) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and the like.

The above-mentioned compound (u3) may be used alone or in combination of 2 or more.

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

Examples of the compound (u4) include: alkyl (meth) acrylates, cycloalkyl (meth) acrylates, aryl (meth) acrylates, aralkyl (meth) acrylates, dialkyl unsaturated dicarboxylates, (meth) acrylates having an oxygen-containing five-membered heterocyclic ring or an oxygen-containing six-membered heterocyclic ring, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds. Specific examples of the alkyl (meth) acrylate include methyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and the like;

examples of the cycloalkyl (meth) acrylate include: cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02, 6] decan-8-yl (meth) acrylate, 2- (tricyclo [5.2.1.02, 6] decan-8-yloxy) ethyl (meth) acrylate, isobornyl (meth) acrylate, and the like;

examples of the aryl (meth) acrylate include phenyl acrylate and the like;

examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate and the like;

examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate, diethyl fumarate, and the like;

examples of the (meth) acrylate having an oxygen-containing five-membered heterocyclic ring or an oxygen-containing six-membered heterocyclic ring include tetrahydrofuran-2-yl (meth) acrylate, tetrahydropyran-2-yl (meth) acrylate, 2-methyltetrahydropyran-2-yl (meth) acrylate, and the like;

examples of the vinyl aromatic compound include styrene, α -methylstyrene and the like;

examples of the conjugated diene compound include 1, 3-butadiene, isoprene, and the like;

examples of the other polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

The compound (u4) is preferably n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.02, 6] decan-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1, 3-butadiene or the like, from the viewpoint of copolymerization reactivity.

The above-mentioned compound (u4) may be used alone or in combination of 2 or more.

The polymer having a carboxyl group can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the compounds (u1) to (u4) in the following proportions.

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

Compound (u 2): preferably 1 to 95 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 30 mol%

Compound (u 3): preferably 50 mol% or less, more preferably 1 to 40 mol%, and still more preferably 10 to 30 mol%

Compound (u 4): preferably 80 mol% or less, more preferably 1 to 60 mol%, and still more preferably 25 to 50 mol%

In addition, a polymer containing a structural unit having a (meth) acryloyloxy group can be formed by reacting a carboxyl group in a structural unit derived from the compound (u1) in the obtained copolymer with a (meth) acrylate having an epoxy group.

A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture containing polymerizable unsaturated compounds of the compounds (u1) to (u4) in the above-described range is preferable because high resolution can be achieved without impairing good coatability, and a cured film having a highly adjusted balance of characteristics can be provided even in a highly fine pattern.

The weight average molecular weight (Mw) of the polymer having a carboxyl group may be the same as the molecular weight of the high molecular weight compound in the "radical polymerizable component having 2. thiol reactivity" (1) radical polymerizable component ", for example, as long as the desired developability can be obtained. By using the above polymer, high resolution can be achieved without impairing good coatability, and therefore, even with a high-definition pattern, a cured film with a highly-adjusted balance of characteristics can be provided.

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

Examples of the solvent used in 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, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol, and the like. These solvents may be used alone or in combination of 2 or more.

The radical polymerization initiator is not particularly limited, and examples thereof include: azo compounds such as 2, 2 '-azobisisobutyronitrile, 2' -azobis- (2, 4-dimethylvaleronitrile), 2 '-azobis- (4-methoxy-2, 4-dimethylvaleronitrile), 4' -azo (4-cyanovaleric acid), dimethyl-2, 2 '-azobis (2-methylpropionate), and 2, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of 2 or more.

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

[ Polymer U-1]

An example of the polymerization method is a polymer U-1 having a weight average molecular weight of 9000, which is obtained by adding 4 parts by mass of 2, 2' -azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate to a flask equipped with a cooling tube and a stirrer, then adding 55 parts by mass of methacrylic acid, 45 parts by mass of benzyl methacrylate, and 2 parts by mass of α -methylstyrene dimer as a molecular weight modifier, gradually stirring the mixture, raising the temperature of the solution to 80 ℃ and maintaining the temperature at 80 ℃ for 4 hours, then raising the temperature of the solution to 100 ℃ and maintaining the temperature for 1 hour to polymerize the polymer, then adding 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor to the solution containing the copolymer, stirring the mixture at 90 ℃ for 30 minutes in an air atmosphere, then adding 74 parts by mass of glycidyl methacrylate, and reacting the mixture at 90 ℃ for 10 hours.

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

[ Polymer U-2]

The polymer U-2 obtained by the following method can be mentioned. 5 parts by mass of 2, 2' -azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added to a flask equipped with a cooling tube and a stirrer, and 18 parts by mass of methacrylic acid, 25 parts by mass of tricyclo [5.2.1.02.6] decan-8-yl methacrylate, 5 parts by mass of styrene, 20 parts by mass of 3-acryloxypropyltrimethoxysilane and 32 parts by mass of glycidyl methacrylate were further added thereto, and after nitrogen substitution, the temperature of the solution was raised to 80 ℃ while slowly stirring. The polymerization was carried out while maintaining the temperature for 5 hours to obtain polymer U-2 having a weight average molecular weight Mw of 12000.

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 a carboxyl group is appropriately selected depending on the purpose of use thereof, and is not particularly limited, and may be set to 10 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the solid content of the composition, for example.

The total content of the polymer having a carboxyl group and the polymerizable component B may be appropriately selected depending on the purpose of use, and is not particularly limited, and for example, may be 10 parts by mass or more and 99 parts by mass or less in total in 100 parts by mass of the solid content of the composition.

The content of the polymer a may be appropriately set according to the desired alkali solubility, and may 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, particularly preferably 15 parts by mass or more and 70 parts by mass or less, and particularly preferably 20 parts by mass or more and 60 parts by mass or less, with respect to 100 parts by mass of the solid content of the composition. This is because when the content is in the above range, the composition has excellent alkali developability.

The epoxy adduct compound having a structure obtained by adding an epoxy compound represented by the general formula (V) to an unsaturated monobasic acid and the ethylenically unsaturated compound having a structure obtained by esterification of the epoxy adduct compound with a polybasic acid anhydride are preferably contained in total in an amount of 25 parts by mass or more and 100 parts by mass or less, more preferably 40 parts by mass or more and 100 parts by mass or less, based on 100 parts by mass of the polymer a.

The content of the polymer a may be 0.1 part by mass or more and 99 parts by mass or less, preferably 0.5 part 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, and particularly preferably 2 parts by mass or more and 20 parts by mass or less, with respect to 100 parts by mass of the composition.

This is because when the content of the polymer a is in the above range, the composition has excellent alkali developability. This is because the composition can more easily give a pattern-like cured product having excellent electrical characteristics.

(3) Coloring agent

By containing the colorant, a colored composition, a colored cured product, and the like can be obtained from the composition.

Such a colorant is not particularly limited as long as it can impart a desired coloring to the composition, cured product, or the like, and examples thereof include pigments, dyes, natural pigments, and the like. They may be used alone or in combination of 2 or more.

As the above-mentioned pigment, for example, a nitroso compound; a nitro compound; an azo compound; a diazo compound; a xanthene compound; a quinoline compound; an anthraquinone compound; a coumarin compound; a phthalocyanine compound; isoindolinone compounds; isoindoline compounds; a quinacridone compound; an anthanthrone dione compound; a perinone compound; a perylene compound; diketopyrrolopyrrole compounds; a thioindigo compound; a dioxazine compound; a triphenylmethane compound; a quinophthalone compound; naphthalene tetracarboxylic acid;metal complex compounds of azo dyes, cyanine dyes; a lake pigment; carbon black obtained by a furnace method, a tunnel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black; carbon black obtained by adjusting or coating the carbon black with an epoxy resin, carbon black obtained by dispersing the carbon black in a solvent in advance with a resin and adsorbing the resin in an amount of 20 to 200mg/g, carbon black obtained by subjecting the carbon black to an acidic or basic surface treatment, carbon black having an average particle diameter of 8nm or more and a DBP oil absorption of 90ml/100g or less, carbon black having a molecular weight of 950 ℃ or less, carbon dioxide having a molecular weight of carbon black adjusted or coated with an epoxy₂The calculated total oxygen amount is per 100m²A carbon black-treated product such as carbon black having a carbon black surface area of 9mg or more; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; nigrosine, pigment black 7, titanium black; organic or inorganic pigments such as chromium oxide green, milori blue, cobalt green, cobalt blue, manganese-based, ferrocyanide, ultramarine, prussian blue, ultramarine, viridian (viridian), emerald green, lead sulfate, chrome yellow, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, synthetic iron black, and umber. These pigments may be used alone or in combination of two or more.

As the pigment, a commercially available pigment may be used, and 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.

Examples of the dye include: azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and a plurality of these may be mixed and used.

The colorant preferably contains a black pigment, for example, when the composition is used for a black matrix, the colorant is used as a spacer of a liquid crystal layer, and when the composition is used for a black columnar spacer having a light-shielding property.

The black pigment may be any black pigment as long as it can impart a desired light-shielding property, and examples thereof include the various carbon blacks, carbon black-treated materials, graphitized carbon blacks, activated carbons, carbon fibers, carbon nanotubes, carbon microcoils, carbon nanohorns, carbon aerogels, fullerenes, aniline black, pigment black 7, titanium black, lactam black, perylene black, and cyanine black described above.

The content of the colorant is not particularly limited as long as a composition, a cured product, or the like having a desired coloring can be obtained, and for example, may be 1 part 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, particularly preferably 20 parts by mass or more and 60 parts by mass or less, and particularly preferably 25 parts by mass or more and 60 parts by mass or less, with respect to 100 parts by mass of the solid content of the composition. This is because a desired colored cured product can be obtained by setting the content to the above range.

The content of the colorant may be 0.5 part by mass or more and 90 parts by mass or less, 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 particularly preferably 3 parts by mass or more and 15 parts by mass or less, with respect to 100 parts by mass of the composition. This is because a cured product having excellent electrical characteristics can be obtained more easily.

(4) Solvent(s)

The solvent is not particularly limited as long as it can disperse or dissolve each component of the composition, and examples thereof include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based 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 pentanol; ether ester solvents such as 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, and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene and pinene; paraffin solvents such as mineral spirits, Swasol #310(Cosmo pine mountain Petroleum Co.), Solvesso #100(Exxon chemical Co.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; a carbitol-based solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; n, N-dimethylformamide; n, N-dimethylacetamide; n-methyl pyrrolidone; dimethyl sulfoxide; water, etc., and 1 or 2 or more kinds of these solvents can be used as a mixed solvent.

Among them, ketones, ether ester solvents and the like are preferable from the viewpoint of good compatibility with the compound I, the polymer a and the like, and propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as "PGMEA" or "propylene glycol monomethyl ether acetate"), cyclohexanone and the like are particularly preferable.

The content of the solvent may be appropriately set according to the coatability and the like, and for example, may 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. This is because the viscosity of the composition can be easily adjusted by setting the content to the above range.

(5) Inorganic compound

The inorganic compound is appropriately selected depending on the use of the filler, mechanical strength improver, and the like, and examples thereof include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, milori blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder (particularly glass powder), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, and the like.

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

The content of the inorganic compound varies depending on the performance required for the inorganic compound, and may be, for example, 1 part by mass or more and 90 parts by mass or less, preferably 5 parts by mass or more and 70 parts by mass or less, and particularly preferably 5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the solid content of the composition. This is because, for example, by using the above-mentioned content, a cured product having excellent mechanical strength can be obtained from the above-mentioned composition.

Further, 1 or 2 or more of these inorganic compounds may be used.

(6) Dispersing agent

The dispersant is not limited as long as it can disperse and stabilize the colorant, inorganic compound, and the like in the composition, and a commercially available dispersant, for example, BYK series manufactured by BYK Chemie, and the like can be used. The above-mentioned dispersant is particularly preferably a polymeric dispersant composed of a polyester, polyether or polyurethane having a basic functional group, a dispersant having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom being an amine and/or a quaternary salt thereof, and an amine value of 1mgKOH/g or more and 100mgKOH/g or less.

(7) Other organic polymers

The other organic polymer may be any polymer that is different from the polymerizable compound and the polymer a and improves the characteristics of the cured product.

Examples of such other organic polymer include polymers containing no polymerizable group or hydrophilic group, such as 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, polyurethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin, and among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, polyamide, polyvinyl butyral, cellulose ester, and epoxy resin are preferable, And (3) epoxy resin.

The weight average molecular weight of the organic polymer may be the same as that of the polymer a.

The content of the other organic polymer may be appropriately set according to the use of the composition, and may be, for example, 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 a compound containing a sulfur atom, as long as the sensitivity of the composition can be adjusted. Examples thereof include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptobutanoic 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-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, and mixtures thereof, Mercapto compounds such as mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodinated alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, 1, 4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolate, Trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, diethyl thioxanthone, diisopropyl thioxanthone, the following aliphatic polyfunctional thiol compounds such as compound No. C1 and tris (2-hydroxyethyl) isocyanurate of trimercaptopropionic acid, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko K.K., and the like.

[ solution 17]

Compound No. C1

(9) Surface active agent

As the surfactant, a surfactant capable of improving dispersion stability, coatability, and the like of the composition can be used, and for example, a fluorine-based surfactant such as perfluoroalkyl phosphate ester, perfluoroalkyl carboxylate, and the like; anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates, and alkyl sulfates; cationic surfactants such as higher amine halides and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; an amphoteric surfactant; surfactants such as silicone surfactants, and the like may be used in combination.

(10) Silane coupling agent

As the silane coupling agent, a silane compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material such as a synthetic resin, a silane coupling agent capable of improving the adhesion of a cured product, and the like can be used. As the silane coupling agent, for example, a silane coupling agent manufactured by shin-Etsu chemical Co., Ltd is used, and among them, silane coupling agents having an isocyanate group, a methacryloyl group or an epoxy group such as KBE-9007, KBM-502 and KBE-403 are preferably used.

(11) Melamine compound

As the melamine compound, compounds capable of improving curability can be used, and examples thereof include active methylol groups (CH) in nitrogen compounds such as (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, and (poly) methylolurea₂OH group) or a part (at least 2) of them are etherified with an alkyl group, and the like.

Examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, and they may be the same or different from each other. The methylol group not etherified with an alkyl group may be self-condensed in one molecule or condensed between two molecules, and as a result, an oligomer component is formed.

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

Among them, alkyl-etherified melamines such as hexamethoxy methyl melamine and hexabutoxy methyl melamine are preferable.

(12) Others

Examples of the other components include: thermal polymerization inhibitors such as hydroquinone, catechol, t-butyl catechol, phenothiazine, and the like; a plasticizer; an adhesion promoter; a filler; defoaming agents; leveling agent; a surface conditioner; an antioxidant; an ultraviolet absorber; a dispersing aid; an anti-agglomerating agent; a catalyst; an effect-promoting agent; a crosslinking agent; thickening agents and the like.

The content of the additive is not particularly limited, and may be appropriately selected depending on the purpose of use, and may be, for example, 50 parts by mass or less in total per 100 parts by mass of the solid components of the composition.

4. Composition comprising a metal oxide and a metal oxide

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

The composition can be used, for example, as a photocurable composition that is cured by light irradiation.

The specific use may be the same as that described in the above item "a.

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 above composition.

The cured product of the present invention and the above composition are used, and therefore have excellent electrical characteristics.

The cured product of the present invention uses the above composition.

The cured product of the present invention will be described in detail below.

The composition may be the same as that described in the section "c composition". The composition usually contains a polymerizable compound, a polymer a having an unsaturated group, and the like in order to form a cured product.

The cured product usually contains a polymer component.

Examples of such a polymer component include the polymer of the polymerizable compound described in the above item "c composition", and the polymer of the polymer a having an unsaturated group.

The polymer of the polymerizable compound may contain the polymerizable compound as a constituent unit, and is not limited to a polymer of polymerizable compounds, and includes a polymer of the polymerizable compound and the polymer a.

The content of each of the polymer of the polymerizable compound and the polymer of the polymer a having an unsaturated group may be the same as the content of the polymerizable compound, the polymer a, and the like described in the above "c.

The polymer component may contain other organic polymers described in the above "c composition".

The content of the entire polymer component may be appropriately set according to the use of the composition 2, and may be, for example, the same as the content of the resin component described in the above "c.

The cured product may be substantially free of a solvent.

The content of the solvent contained in the cured product may be, for example, 1 part by mass or less, and preferably 0.5 part by mass or less, based on 100 parts by mass of the cured product. This is because the cured product has excellent stability with time when the content is in the above range.

The shape of the cured product of the present invention in a plan view can be appropriately set according to the use of the cured product and the like. For example, when the cured product is used as a spacer or the like of a liquid crystal layer, the cured product may be in a pattern such as a dot or a line.

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 of a liquid crystal layer or the like.

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

The production method can be, for example, the same as that described in the section "method for producing an e cured product" to be described later, and therefore, the description thereof is omitted.

The use of the cured product may be the same as that described in the section "compound a".

E. Method for producing cured product

Next, a method for producing a cured product of the present invention will be described.

The method for producing a cured product of the present invention is characterized by comprising a step of irradiating the composition with light.

The method for producing an effect product of the present invention includes a step of irradiating a composition containing the compound I with light, and thus a cured product having excellent electrical characteristics can be easily obtained.

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

Hereinafter, each step of the production method of the present invention will be described in detail.

1. Step of light irradiation

This step is a step of curing the composition by irradiating the composition with light.

In the present step, the light to be irradiated to the composition may be any light as long as the compound I can generate radicals, and may be light including light having a wavelength of 250nm to 450nm, for example.

The irradiation amount of the light to be irradiated may be adjusted as appropriate depending on the thickness of the coating film of the composition, as long as a cured product having a desired hardness can be formed.

Examples of the light source for the light irradiation include ultrahigh-pressure mercury, mercury vapor arc, carbon arc, and xenon arc.

As the light to be irradiated, laser light may be used. The laser light may be a laser light including light having a wavelength of 340nm to 430 nm.

As the light source of the laser, a light source emitting light in a range from visible light to infrared light, such as an argon ion laser, a helium neon laser, a YAG laser, or a semiconductor laser, may be used.

When these lasers are used, the composition may contain a sensitizing dye that absorbs light in the visible to infrared region.

The light irradiation may be performed by irradiating the entire surface of the coating film of the composition in a plan view, or may be performed by irradiating a part of the coating film.

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

The composition may be the same as that described in the section "b. The composition usually contains a polymerizable compound, a polymer a having an unsaturated group, and the like in order to form a cured product.

2. Other procedures

The above-described production method includes a step of performing light irradiation, but may include other steps as necessary.

Examples of the other steps include a step of forming a coating film of the composition before the step of irradiating light, a step of developing after the step of irradiating light, a step of removing a solvent after the step of forming the coating film, and a step of heating after the step of irradiating light.

The step of forming the coating film may be any method as long as it can obtain a coating film of a composition having a desired thickness, and for example, known methods such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, a slit coater, various printing, and dipping may be used.

The substrate 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 substrates made of soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like.

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

The developing method in the above-mentioned developing step may be any method as long as it can remove the uncured composition, and for example, a known developing method such as a method of removing by an alkaline aqueous solution can be used.

The solvent in the step of removing the solvent may be removed by any method as long as the solvent content in the cured product can be set to a desired amount, and examples thereof include a method of heating, that is, a method of performing a pre-baking step as the step of removing.

The heating temperature in the heating step (post-baking step) performed after the light irradiation step may be set as appropriate depending on the type and use of the cured product, as long as the temperature can improve the mechanical strength of the cured product.

3. Others

The cured product produced by the above production method, the use thereof, and the like may be the same as those described in the above "c.

The present invention is not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same operational effects are included in the technical scope of the present invention.

Examples

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

[ example 1-1]

Under a nitrogen atmosphere, 78 mmol of aluminum chloride and 33.0g of dichloroethane were added, 36 mmol of 4-fluoro-o-toluyl chloride was slowly dropped under ice cooling, 30 mmol of 9-ethyl-3-nitrocarbazole (carbazole compound) was then slowly dropped, and the mixture was stirred at 5 ℃ for 30 minutes. Pouring the reaction solution into ice water for oil-water separation. Desolventizing to obtain the acyl matrix.

Then, 45.0g of ethylene glycol, 40 mmol of the obtained acylate and 80 mmol of potassium carbonate were added thereto, and the mixture was reacted at 100 ℃ for 5 hours. After cooling to room temperature, ion-exchanged water was added to the reaction solution, and the precipitate was filtered. Drying under reduced pressure to obtain ketone body with hydroxyl.

Then, 20 mmol of the obtained ketone body, 40 mmol of hydroxylamine hydrochloride and 25.0g of pyridine were added thereto, and the mixture was stirred at 100 ℃ for 3 hours. Ion-exchanged water was added thereto, and the precipitate was filtered. Drying under reduced pressure to obtain oxime.

Then, 10 mmol of the obtained oxime and 15.0g of dimethylformamide were added thereto, and triethylamine and acetyl chloride were slowly added dropwise under ice cooling, followed by stirring at 5 ℃ for 1 hour. Ion-exchanged water and ethyl acetate were added to the reaction mixture to remove the solvent. The organic layer was washed with water 3 times and desolventized. The compound I was applied to a silica gel column (ethyl acetate/hexane: 50/50) to obtain a target compound represented by the following general formula (24).

The obtained compound was confirmed to be the target by H-NMR.

[ examples 1-2]

50g of 10 mmol of compound No.1 synthesized according to the disclosure of paragraphs [0072] to [0080] of International publication No. 2006/018973 and 60% acetic acid water was added thereto, and the mixture was stirred at 45 ℃ for 1 hour. The reaction mixture was poured into 60g of ice water, and 100g of ethyl acetate was added thereto to conduct extraction. The organic layer was washed 4 times with 100g of ion-exchanged water, and then desolventized. The compound I was applied to a silica gel column (chloroform/ethanol: 95/5) to obtain a compound represented by the following general formula (13).

The obtained compound was confirmed to be the target by H-NMR.

[ examples 1 to 3]

93 mmol of 60% sodium hydride and 40g of dimethylformamide were added thereto, and 62 mmol of carbazole dissolved in 50g of dimethylformamide was added dropwise under ice cooling. Further, 124 mmol of ethyl bromoheptanoate dissolved in 50g of dimethylformamide was added dropwise thereto, and the reaction was carried out for 30 minutes. The reaction mixture was poured into ice water containing hydrochloric acid, and ethyl acetate was added to separate the reaction mixture into oil and water. The organic layer was washed with water 3 times, then, the solvent was removed, and recrystallization was performed with methanol to obtain an ester.

Then, 44 mmol of the ester and 200g of dichloroethane were added, and 46 mmol of aluminum chloride and 46 mmol of octanoyl chloride were added in this order under ice cooling. After reacting at room temperature for 15 hours, the reaction mixture was poured into ice water, and 200g of chloroform was added thereto to conduct extraction. The organic layer was washed with water 3 times, desolvated, and then applied to a silica gel column (hexane/ethyl acetate: 85/15) to obtain an acyl group.

Then, 30 mmol of an acyl base and 80.8g of acetic anhydride were added thereto, and 6.4g of 60% nitric acid was slowly dropped at 10 to 12 ℃. The reaction solution was poured into ice water, and chloroform was added thereto to conduct extraction. The organic layer was washed with water 3 times, desolventized, and applied to a silica gel column (hexane/ethyl acetate 70/30) to obtain a nitro compound.

Then, 18 mmol of nitro compound and 60.0g of acetic acid were added, and 17.0g of 35% hydrochloric acid was added dropwise. After reacting at 50 ℃ for 2 hours, the reaction mixture was poured into ice water, and 85g of chloroform was added thereto to conduct extraction. The organic layer was washed with water 3 times, and then desolventized to obtain a ketone body having a hydroxyl group.

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

The obtained compound was confirmed to be the target by H-NMR.

[ examples 1 to 4]

22 mmol of a hydroxyl group-containing ketone obtained in the same manner as in example 1-3, 33g of dimethylformamide, 24 mmol of isobutyl nitrite, and 2.3g of 35% hydrochloric acid were added, and the mixture was reacted at room temperature for 24 hours. Ion exchange water and chloroform were added to separate oil from water. The organic layer was washed with water 3 times to obtain an oxime.

Next, 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.

The obtained compound was confirmed to be the target by H-NMR.

[ examples 1 to 5]

Under a nitrogen atmosphere, 78 mmol of aluminum chloride and 33.0g of dichloroethane were added, 36 mmol of 4-chlorobutyryl chloride was slowly dropped under ice cooling, 30 mmol of 9-ethyl-3-nitrocarbazole (carbazole compound) was then slowly dropped, and the mixture was stirred at 5 ℃ for 30 minutes. Pouring the reaction solution into ice water for oil-water separation. Desolventizing to obtain the acyl matrix.

Then, 120 mmol of sodium formate, 1.5 mmol of tetrabutylammonium bromide and 30.0g of dimethylformamide were added thereto, and the mixture was stirred at 100 ℃ for 2 hours. Then, 5.2g of a 48% aqueous sodium hydroxide solution was slowly added at room temperature and stirred. Adding ion exchange water, extracting with ethyl acetate, and removing solvent to obtain ketone body.

Then, a compound represented by the following general formula (76) was obtained as the target compound of compound I in the same manner as in [ example 1-1] except that the obtained ketone body was used. The obtained compound was confirmed to be the target by H-NMR.

[ examples 1 to 6]

Examples 1 to 5 ketone bodies having hydroxyl groups were obtained in the same manner as described above. In the same manner as in [ examples 1 to 4] except for using the obtained ketone body, compound I as a target compound was obtained as a compound represented by general formula (77). The obtained compound was confirmed to be the target by H-NMR.

[ examples 1 to 7]

In the same manner as in example [1-1] except that phenylacetyl chloride was used as an acid chloride, a compound represented by the general formula (78) was obtained as the target compound I. The obtained compound was confirmed to be the target by H-NMR.

[ examples 1 to 8]

In the same manner as in [ examples 1 to 7], a ketone body having a hydroxyl group was obtained. In the same manner as in [ examples 1 to 4] except for using the obtained ketone body, a compound represented by the general formula (79) was obtained as the target compound I. The obtained compound was confirmed to be the target by H-NMR.

[ solution 18]

[ solution 18A ]

TABLE 1

TABLE 1A

Production example 1 preparation of Polymer B-1 having hydrophilic group

184g of 1, 1-bis [4- (2, 3-epoxypropoxy) phenyl ] indane, 58g of acrylic acid, 0.26g of 2, 6-di-t-butyl-p-cresol, 0.11g of tetra-n-butylammonium bromide and PGMEA105g were added thereto, and the mixture was stirred at 120 ℃ for 16 hours. The reaction mixture was cooled to room temperature, 160g of PGMEA, 59g of phthalic anhydride and 0.24g of tetra-n-butylammonium bromide were added thereto, and the mixture was stirred at 120 ℃ for 4 hours. Further, 20g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ℃ for 4 hours, at 100 ℃ for 3 hours, at 80 ℃ for 4 hours, at 60 ℃ for 6 hours, and at 40 ℃ for 11 hours, followed by addition of 128g of PGMEA to obtain a PGMEA solution as a PGMEA solution, thereby obtaining a polymer B-1 having a hydrophilic group (Mw: 5000, Mn: 2100, acid value (solid content) 92.7mgKOH/g, solid content 44.5 mass%).

Production example 2 preparation of carbon Black Dispersion D-1

A carbon black dispersion D-1 was prepared by mixing 15 parts by mass of MA100 (manufactured by Mitsubishi chemical corporation) as carbon black, 11.25 parts by mass of BYK161 (manufactured by BYKChemie (BYK)) as a dispersant (solid content concentration: 40 mass%) and 73.75 parts by mass of PGMEA as a solvent, and treating the mixture with a bead mill.

Production example 3 Synthesis of comparative Compound (A' -1)

10 mmol of 4-hydroxythiophenol, 11 mmol of 4' -chlorophenylacetone, and 10.0g of dimethylacetamide were added thereto, and 15 mmol of sodium hydroxide was added thereto, followed by stirring at 50 ℃ for 1 hour. Cooled to room temperature, and subjected to oil-water separation in an ethyl acetate/water system. The solvent was distilled off to obtain a target diphenylphenol.

Then, 10 mmol of the obtained diphenylphenol, 20 mmol of potassium carbonate, 2-chloroethanol as an alcohol, 20.0g of acetonitrile, and 20 mmol of potassium carbonate were added thereto, and the mixture was refluxed for 5 hours. After cooling to room temperature, ethyl acetate and ion-exchanged water were added to separate oil from water. The organic layer was washed with water 5 times, and after removal of the solvent, ketone bodies having hydroxyl groups were obtained.

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

The obtained compound was confirmed to be the target by H-NMR.

Production example 4 Synthesis of comparative Compound (A' -2)

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

The obtained compound was confirmed to be the target by H-NMR.

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.

The obtained compound was confirmed to be the target by H-NMR.

[ solution 19]

Examples 2-1 to 2-63 and comparative examples 1 to 12

The compositions were prepared by mixing the components in accordance with the formulation shown in tables 2 to 4 below.

In addition, the numbers indicate parts by mass.

A-1: compound (24) (Compound I, the Compound obtained in example 1-1)

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

A-3: compound (3) (Compound I, the Compound obtained in example 1-3)

A-4: compound (76) (Compound I, the Compound obtained in example 1-5)

A-5: compound (77) (Compound I, the Compounds obtained in examples 1 to 6)

A-6: compound (78) (Compound I, the Compounds obtained in examples 1 to 7)

A-7: compound (79) (Compound I, Compound obtained in examples 1 to 8)

A' -1: the compound represented by the above-mentioned compound (A' -1)

A' -2: the compound represented by the above-mentioned compound (A' -2)

A' -3: the compound represented by the above-mentioned compound (A' -3)

A' -4: a compound represented by the above-mentioned compound (A' -4) (photopolymerization initiator, IRGACURE-OXE02 manufactured by BASF Co., Ltd.)

B-1: the Polymer obtained in production example 1 (Polymer having hydrophilic group)

B-2: SPC-3000 (Polymer having hydrophilic group; 42.7% solid content, PGMEA solution, manufactured by Showa Denko K.K.)

C-1: KAYARAD DPHA (polymerizable compound (polyfunctional acrylate); manufactured by Nippon chemical Co., Ltd.)

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, product of shin-Etsu chemical Co., Ltd.)

F-1: propylene glycol-1-monomethyl ether-2-acetate (solvent)

[ evaluation method ]

(1) Sensitivity of the device

The compositions obtained in examples 2-1 to 2-63 and comparative examples 1 to 12 were applied onto a glass substrate (100 mm. times.100 mm) by a spin coater, and prebaked at 90 ℃ for 100 seconds.

Next, the coating film was irradiated with ultraviolet light through a negative mask having a line pattern of 30 μm, with an exposure gap of 150 μm using a mirror projection aligner (product name: TME-150RTO, TOPCON, Inc.).

The exposure amount was set at 25, 50, 75, 100mJ/cm²These 4 levels.

Then, a developer solution containing 0.04 mass% potassium hydroxide aqueous solution was discharged at 23 ℃ to the substrate, and shower development was performed.

The developing time was 1.5 times as long as that of BT, based on the time until the unexposed portion was completely dissolved (BT: developing time).

Then, post-baking was performed at 230 ℃ for 30 minutes.

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

Then, the width (line width) of the pattern at a portion of 30 μm after post-baking was obtained and evaluated as an index of sensitivity characteristics. The results are shown in table 2 below.

◎ the exposure dose with line width of more than 30 μm is less than 25mJ/cm²

○ the exposure dose is 25mJ/cm with line width of more than 30 μm²More than and less than 50mJ/cm²

△ the exposure dose is 50mJ/cm with line width of more than 30 μm²Above and less than 100mJ/cm²

X: the exposure dose is 100mJ/cm with line width of more than 30 μm²The above

The smaller the exposure amount required for the line width to be the predetermined width, the more excellent the sensitivity can be judged, and particularly, the better the evaluation criteria are, and the better the sensitivity is ◎.

(2) Half tone property

Next, the coating film was irradiated with ultraviolet light through a halftone negative mask having a halftone portion (transmittance of 50% for light (transmittance at 365nm of the full-tone portion is 100%)) and a full-tone portion (transmittance of 100% for light) in which a10 μm arc pattern was formed, with an exposure gap of 150 μm using a mirror projection alignment exposure machine (product name: TME-150RTO, manufactured by TOPCON, Inc.).

The exposure amount was 50mJ/cm². Then, a developer solution containing 0.04 mass% potassium hydroxide aqueous solution was discharged at 23 ℃ to the substrate, and shower development was performed.

Then, post-baking was performed at 230 ℃ for 30 minutes.

The film thickness of the coating film in the full tone portion after the post-baking was 3.0. mu.m.

Then, the difference in film thickness between the full tone portion and the halftone portion of the 10 μm circular arc pattern after post-baking was obtained and evaluated as an index of halftone characteristics. The results are shown in table 2 below.

○ film thickness difference of 0.5-1.0 μm

△, the difference in film thickness is more than 1.0 μm and 2.9 μm or less

X: the difference in film thickness exceeded 2.9 μm, no pattern was obtained, and it was not possible to measure

When the difference in film thickness is too large, it can be determined that it is difficult to adjust the film thickness of the obtained cured product according to the exposure amount, and particularly, when the evaluation criterion is good, spacers having different heights can be easily formed.

(3)VHR

Next, a mirror projection aligner (product name: TME-150RTO, TOPCON, Inc.) was used to align the exposure apparatus at 200mJ/cm without passing through a mask²The coating film is irradiated with ultraviolet rays.

Then, post-baking was performed at 230 ℃ for 30 minutes.

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

1 part by mass of the post-baked coating film was mixed with 40 parts by mass of liquid crystal "RS-182" manufactured by ADEKA, and stored at 120 ℃ for 1 hour. After taking it out to room temperature and standing, a supernatant was collected. The sampled liquid crystal compositions were compared with VHR (voltage holding ratio) before and after mixing the liquid crystal and the coating film, and the holding ratio of VHR was obtained by the following formula and evaluated according to the following criteria. The results are shown in table 2 below.

The liquid crystal composition was injected into a TN cell (cell thickness 5 μm, electrode area 8 mm. times.8 mm alignment film JALS2096) for liquid crystal evaluation, and VHR was measured using VHR-1A (manufactured by Toyo technical Corporation) (measurement conditions: pulse voltage width 60 μ s, frame period 16.7ms, wave height. + -. 5V, measurement temperature 60 ℃ C.).

The retention ratio (%) of VHR { (VHR of liquid crystal "RS-182" before mixing with a coating film) - (VHR of liquid crystal composition obtained by mixing with a coating film) }/(VHR of liquid crystal "RS-182" before mixing with a coating film) × 100

◎ VHR retention rate over 96.0%

○ VHR retention ratio of 93.0% or more and less than 96.0%

△ VHR retention ratio is more than 90.0% and less than 93.0%

X: VHR retention less than 90.0%

The electrical characteristics can be determined to be more excellent as the VHR holding ratio is higher, and particularly, the electrical characteristics can be determined to be excellent when the evaluation criteria are ○ and ◎.

(4) Residual film rate

The compositions obtained in examples 2-1 to 2-63 and comparative examples 1 to 12 were applied to glass substrates (100 mm. times.100 mm) by a spin coater to form coating films. The formed coating film was prebaked at 90 ℃ for 100 seconds. The film thickness of the pre-baked coating film was measured using DEKTAKXT manufactured by Bruker corporation. The film thickness of the pre-baked coating film was 3.0. mu.m. Subsequently, the prebaked coating film was irradiated with ultraviolet light through a halftone negative mask having a halftone portion (light transmittance of 50%) and a full-color portion (light transmittance of 100%) in which a10 μm arc pattern was formed, with an exposure gap of 150 μm using a mirror projection alignment exposure machine (product name: TME-150RTO, TOPCON). The exposure amount was 50mJ/cm². Then, a developing solution of 0.04 mass% potassium hydroxide aqueous solution at 23 ℃ was discharged from the glass substrate, and the glass substrate was subjected to shower development. The developing time was 1.5 times as long as that of BT, based on the time until the unexposed portion was completely dissolved (BT: developing time). Then, the coating film was post-baked at 230 ℃ for 30 minutes. The film thickness of the coating film after the post-baking was measured using DEKTAKXT manufactured by Bruker corporation. The residual film ratio was calculated by the following equation using the measured film thickness of the pre-baked coating film and the measured film thickness of the post-baked coating film. By determining after prebaking and after-bakingThe film thickness of the full tone portion of the baked 10 μm circular pattern was varied, and the sensitivity was evaluated using the residual film ratio as an index. The results are shown in tables 2 to 4 below.

Residual film ratio (%) (film thickness after post-baking/film thickness after pre-baking) × 100

◎ residual film rate is over 85%

○ residual film rate is more than 80.0% and less than 85.0%

△ residual film rate is above 75.0% and less than 80.0%

X: the residual film rate is less than 75.0 percent

The higher the residual film ratio, the higher the crosslinking density of the resist film, and the less shrinkage during post baking, indicating good sensitivity.

TABLE 2

TABLE 3

TABLE 3A

TABLE 3B

TABLE 3C

TABLE 4

As can be seen from tables 2 to 4, in the examples, cured products having excellent VHR and residual rate were formed.

From this, it was confirmed that a cured product having excellent electrical characteristics can be formed by using compound I.

In addition, it was confirmed that in the examples, even at a high optical concentration where the content of the pigment such as D-1 or D-2 is high, a composition having excellent sensitivity and halftone characteristics together with the electrical characteristics can be formed.

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

Claims

1. A compound represented by the following general formula (I),

in the formula, R¹And R²Each independently represents R¹¹、OR¹¹、COR¹¹、SR¹¹、CONR¹²R¹³Or CN, R¹¹、R¹²And R¹³Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R¹¹、R¹²And R¹³The hydrogen atoms of the substituents shown may be OR²¹、COR²¹、SR²¹、NR²²R²³、CONR²²R²³、-NR²²-OR²³、-NCOR²²-OCOR²³、-C(＝N-OR²¹)-R²²、-C(＝N-OCOR²¹)-R²²CN, halogen atom, or COOR²¹The substitution is carried out by the following steps,

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

a represents an integer of 0 to 3,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸At least one of which is a group having a hydroxyl group.

2. The compound of claim 1, wherein R¹、R⁵And R⁸At least 1 of them is a group having a hydroxyl group.

3. The compound of claim 2, wherein R¹And R⁸At least one of which is a group having a hydroxyl group,

R¹when it is a group having a hydroxyl group, R¹Is R¹¹A group shown, R¹¹An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms OR an aralkyl group having 7 to 30 carbon atoms, wherein the hydrogen atoms of the alkyl group, the aryl group and the aralkyl group are OR²¹Substituted, R²¹Is substituted with a hydroxyl group,

R⁸when it is a group having a hydroxyl group, R⁸Is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, wherein a hydrogen atom of the alkyl group or the aryl group is substituted with a carboxyl group.

4. A composition comprising a compound of any one of claims 1-3.

5. A cured product of the composition according to claim 4.

6. A method for producing a cured product, comprising a step of irradiating the composition according to claim 4 with light.