WO2019088055A1 - Composé, composition, objet durci et procédé de production d'un objet durci - Google Patents

Composé, composition, objet durci et procédé de production d'un objet durci Download PDF

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Publication number
WO2019088055A1
WO2019088055A1 PCT/JP2018/040205 JP2018040205W WO2019088055A1 WO 2019088055 A1 WO2019088055 A1 WO 2019088055A1 JP 2018040205 W JP2018040205 W JP 2018040205W WO 2019088055 A1 WO2019088055 A1 WO 2019088055A1
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group
compound
carbon atoms
meth
mass
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PCT/JP2018/040205
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English (en)
Japanese (ja)
Inventor
光裕 岡田
大樹 三原
良智 竹内
木村　正樹
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株式会社Adeka
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Priority to KR1020207005559A priority Critical patent/KR20200078476A/ko
Priority to CN201880061861.7A priority patent/CN111132963B/zh
Priority to JP2019550389A priority patent/JPWO2019088055A1/ja
Publication of WO2019088055A1 publication Critical patent/WO2019088055A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

Definitions

  • the present invention relates to, for example, a compound capable of forming a cured product having excellent electrical properties.
  • spacers are used to maintain the distance between the upper and lower substrates of the cells.
  • a columnar spacer (hereinafter sometimes referred to as a column spacer) formed by applying a photosensitive composition onto a substrate, exposing it through a predetermined mask and developing it is known.
  • a black column spacer (BCS) having a light shielding property, in which a column spacer and a black matrix are integrated into one module, has been used (Patent Document 1).
  • the cured product of the conventional photosensitive composition has low electrical properties, and when it is used as a spacer, a display failure may occur when the display device is formed.
  • the present invention has been made in view of the above problems, and has as its main object to provide, for example, a compound capable of forming a cured product having excellent electrical properties.
  • the inventors of the present invention have found that the cured product of the photosensitive composition is deteriorated in the electrical properties by the decomposition product of the photopolymerization initiator and the photopolymerization initiator It has been found that a cured product having excellent electrical properties can be formed by introducing a hydroxyl group to the present invention, and the present invention has been completed.
  • the present invention provides a compound represented by the following general formula (I) (hereinafter sometimes referred to as compound I).
  • R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN
  • R 11 , R 12 and R 13 each independently represent R 11 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms
  • R 3 , R 4 , R 5 , R 6 and R 7 are each independently R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, a nitro group, CN or a halogen atom, and R 4 and R 5 , R 5 and R 6 and R 6 and R 7 respectively form a ring R 14 , R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
  • R 8 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms
  • the alkyl part of the group represented by R 8 may be branched side chain or cyclic alkyl
  • X is a direct bond or a group represented by CO, a represents an integer of 0 to 3; At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a group having a hydroxyl group.
  • R 1 , R 5 and R 8 are a group having a hydroxyl group.
  • R 1 and R 8 are a group having a hydroxyl group
  • R 1 is a group having a hydroxyl group
  • R 1 is a group represented by R 11
  • R 11 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom an arylalkyl group having 7 to 30, the alkyl group
  • the hydrogen atom of the aryl group and the aryl group is substituted with oR 21
  • hydrogen atoms in R 21 is substituted with a hydroxyl group
  • R 8 When R 8 is a group having a hydroxyl group, R 8 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and a hydrogen atom of the alkyl group or the aryl group is substituted with a carboxyl group Is preferred.
  • the present invention provides a composition comprising Compound I as described above.
  • the present invention provides a cured product of the above composition.
  • the present invention provides a method for producing a cured product comprising the step of irradiating the above-described composition with light.
  • a cured product having excellent electrical properties can be formed.
  • a cured product excellent in electrical characteristics such as the electrical retention can be easily obtained.
  • the cured product of the present invention is excellent in electrical characteristics such as electrical retention.
  • the method for producing a cured product of the present invention it is possible to easily obtain a cured product excellent in electrical properties such as the electrical retention.
  • the present invention relates to a compound, a composition, a cured product thereof and a method for producing the cured product.
  • a method for producing the compound, the composition, the cured product and the cured product of the present invention will be described in detail.
  • R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN
  • R 11 , R 12 and R 13 each independently represent R 11 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms
  • R 3 , R 4 , R 5 , R 6 and R 7 are each independently R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, a nitro group, CN or a halogen atom, and R 4 and R 5 , R 5 and R 6 and R 6 and R 7 respectively form a ring R 14 , R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
  • R 8 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms
  • the alkyl part of the group represented by R 8 may be branched side chain or cyclic alkyl
  • X is a direct bond or a group represented by CO, a represents an integer of 0 to 3; At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a group having a hydroxyl group.
  • the compound I of the present invention has, for example, a carbazole structure, an oxime ester group, and a hydroxyl group, which enables, for example, the formation of a cured product having excellent electrical properties.
  • the cured product is excellent in the electrical properties.
  • 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 voltage retention (VHR) of the liquid crystal composition is small.
  • VHR voltage retention
  • the conventionally known photoinitiator having a carbazole structure and an oxime ester group functions as a radical polymerization initiator by generating a radical by light irradiation.
  • the said photoinitiator produces a decomposition product as a result of a decomposition reaction occurring in an oxime ester group, when producing
  • 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.
  • the compound I of the present invention since the compound I of the present invention has a hydroxyl group together with a carbazole structure and an oxime ester group, the above-mentioned decomposed product also has a hydroxyl group. And since the said decomposition product has a hydroxyl group, the affinity with the liquid crystal material which generally shows hydrophobicity is low, for example, even when a hardened
  • the carbazole structure can absorb ultraviolet light of a wide wavelength, and the generation efficiency of radicals can be high in the oxime ester group. Furthermore, the carbazole structure tends to have a low migration to the liquid crystal layer relative to the radical generation efficiency. For this reason, the compound I of the present invention is excellent in the balance of the sensitivity and the effect of suppressing the transfer to the liquid crystal layer by having the carbazole structure and the oxime ester group. As a result, the compound I of the present invention can easily form a cured product because of its excellent electrical properties and excellent sensitivity. In addition, because of high sensitivity, for example, a thick cured product can be easily obtained where the film thickness is large at a portion where the exposure amount is large, and where the light exposure amount is small.
  • the compound I of the present invention is also a compound capable of forming a cured product having the above-mentioned structure and having excellent electrical properties.
  • a black column spacer may be formed on an element formed on a substrate or in a portion of the substrate paired with the substrate on which the element is opposed to the element. In such a case, it is necessary to change the height of the black column spacer between the portion where the device is formed and the other portions in consideration of the height of the device. At this time, if black column spacers of different heights can be formed at one time by performing exposure through a halftone mask, the manufacturing merit is large. Since the compound I of the present invention is highly sensitive as described above, it becomes easy to form black column spacers of different heights at one time using a halftone mask.
  • the compound I of the present invention is represented by the above general formula (I), and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and the like in the above general formula (I) At least one of R 8 is a group having a hydroxyl group.
  • the compound I is, for example, at least one of R 1 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8.
  • the group is preferably a group having the above-mentioned hydroxyl group, and it is particularly preferable that at least one of R 1 , R 5 and R 8 is a group having a hydroxyl group, and in particular, at least one of R 1 and R 8 is It is preferable that it is group which has the said hydroxyl group.
  • the compound I of the present invention can form a cured product having excellent electrical properties because the above-mentioned group is a group having the above-mentioned hydroxyl group. Moreover, it is because the compound I of this invention can be synthesize
  • the group having a hydroxyl group includes the hydroxyl group itself.
  • the number of hydroxyl groups contained in such a hydroxyl group-containing group can be one or more, and can be appropriately set according to the application of the compound I, the required electrical properties, the ease of synthesis, etc. For example, it is 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.
  • the compound represented by General formula (2) mentioned later shows the example of the compound containing the group which has two hydroxyl groups.
  • the type of hydroxyl group contained in the group having a hydroxyl group may be, for example, one in which the hydroxyl group is bonded to a carbon atom of a carbonyl group and is contained as a part of a carboxyl group, but from the viewpoint of improving electrical characteristics, a chain It is preferable to be contained as an alcoholic hydroxyl group bonded to a carbon atom of a cyclic hydrocarbon or a phenolic hydroxyl group bonded to a carbon atom of an aromatic hydrocarbon, and in particular, it is preferable to be contained as an alcoholic hydroxyl group.
  • the compound represented by General formula (1) mentioned later shows the example whose said hydroxyl group is alcoholic hydroxyl group
  • the compound represented by General formula (3) has one of the said hydroxyl groups of a carboxyl group. It shows an example included as a part.
  • the bonding position of the hydroxyl group contained in the group which has the said hydroxyl group is the terminal of the group which has the said hydroxyl group. While the said compound I becomes what can form the hardened
  • being the terminal of the group which has the said hydroxyl group means that the hydroxyl group contained in the group which has a hydroxyl group is couple
  • general formula (5) described later shows an example in which the bonding position of the hydroxyl group is an end of the group having a hydroxyl group
  • the bonding position of the hydroxyl group is an end of the group having a hydroxyl group
  • the number of carbon atoms of the group having a hydroxyl group may be 0, but is preferably 1 or more, more preferably 2 or more, and particularly preferably 4 or more. Is preferred.
  • the upper limit of the number of carbon atoms is not particularly limited as long as desired electrical characteristics can be obtained, but can be, for example, 20 or less, preferably 15 or less, and 10 or less. Is preferred. While the said compound I can form the hardened
  • the group having a hydroxyl group can be, for example, a hydroxyl group directly bonded to a carbazole structure or an oxime ester group.
  • the number of the group having a hydroxyl group in the compound I may be 1 or more, the use of the compound I, and the required electrical properties Can be appropriately set according to the easiness of synthesis etc., but can be, for example, 1 or more and 5 or less, preferably 1 or more and 3 or less, preferably 1 or more and 2 or less, 1 Is preferred.
  • the compound I can form a cured product excellent in the electric characteristics and is easy to synthesize.
  • the number of groups having a hydroxyl group is 2, for example, a case both the R 1 and R 5 is a group having a hydroxyl group. More specifically, the compounds represented by the general formulas (34) and (35) described later show examples in which the number of groups having a hydroxyl group is two.
  • the number of hydroxyl groups contained in the compound I can be 1 or more, but can be 1 or more and 10 or less, preferably 1 or more and 5 or less, and more preferably 1 or more and 2 or less. Is preferred. By being the number of the said hydroxyl groups, while the said compound I can form the hardened
  • aryl group of 30 examples include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl, an anthryl group and a phenanthrenyl group, and a phenyl group, a biphenylyl group and a naphthyl group substituted by one or more of the above alkyl groups. And anthryl groups and the like.
  • Examples of the arylalkyl group of 30 include a benzyl group, an ⁇ -methylbenzyl group, an ⁇ , ⁇ -dimethylbenzyl group and a phenylethyl group.
  • the heterocyclic group of 20 for example, pyridyl group, pyrimidyl group, furyl group, thienyl group, tetrahydrofuryl group, dioxolanyl group, benzoxazol-2-yl group, tetrahydropyranyl group, pyrrolidinyl group, imidazolidyl group, pyrazolidyl group
  • Preferred examples include 5- to 7-membered heterocyclic rings such as thiazolidyl group, isothiazolidyl group, oxazolidyl group, isoxazolidyl group, piperidyl group, piperazyl group and morpholinyl group.
  • halogen atom in the said general formula (I), a fluorine, chlorine, a bromine, and an iodine are mentioned, for example.
  • R 12 and R 13 and R 22 and R 23 in the general formula (I) may form together, for example, a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine
  • a cyclopentane ring for example, a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine
  • 5- to 7-membered rings such as rings, morpholine rings, lactone rings and lactam rings.
  • the alkylene moiety of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 in the general formula (I) is —O—, —S—, —COO—, — OCO -, - NR 24 -, - NR 24 CO -, - NR 24 COO -, - OCONR 24 -, - SCO -, - COS -, - OCS- or -CSO- by may be interrupted 1 to 5 times
  • the linking group to be interrupted may be one or more groups, and in the case of groups which can be interrupted successively, two or more groups may be interrupted successively.
  • the alkyl (alkylene) portion of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 in the above general formula (I) may have a branched side chain or a cyclic group. It may be alkyl (cyclic alkylene).
  • the number of carbon atoms in the group defines the number of carbon atoms in the group after the replacement.
  • the “1 to 20 carbon atoms” means that the alkylene group has been replaced It does not refer to the number of carbon atoms before the alkylene group is replaced.
  • the number of carbon atoms of the group after the substitution is defined.
  • the term "1 to 20 carbon atoms" refers to the number of carbon atoms after the hydrogen atom has been substituted, and the hydrogen atom is substituted Does not refer to the number of carbon atoms before the
  • the rings R 4 and R 5 , R 5 and R 6 and R 6 and R 7 in the general formula (I) can be formed together as the ring include the above R 12 and R 13 and R 22 and R 22 It may be the same as a ring which 23 can form together.
  • R 1 is a group having the above hydroxyl group
  • R 1 is a group represented by R 11
  • R 11 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom
  • It is preferably an arylalkyl group having 7 to 30 carbon atoms, more preferably an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and an aryl group having 6 to 15 carbon atoms
  • an arylalkyl group having 7 to 15 carbon atoms is more preferable
  • an arylalkyl group having 6 to 10 carbon atoms or 7 to 12 carbon atoms is particularly preferable.
  • R 1 is a group having the above-mentioned hydroxyl group
  • R 1 is a group represented by R 11
  • R 11 when R 11 is an alkyl group having 1 to 20 carbon atoms, R 11 has the number of carbon atoms It is preferably an alkyl group of 1 to 10, and more preferably an alkyl group of 1 to 5 carbon atoms, and particularly preferably an alkyl group of 1 to 3 carbon atoms. It is because while said compound I can form the hardened
  • R 11 used for R 1 is the above alkyl group, the above aryl group or the above aryl alkyl group, it is preferable that the hydrogen atom of the alkyl group, the aryl group and the aryl alkyl group is substituted by OR 21
  • R 21 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably R 21 is an alkyl group having 1 to 10 carbon atoms, and R 21 is an alkyl group having 1 to 5 carbon atoms. Is particularly preferred.
  • R 1 is a group having the above hydroxyl group
  • R 1 is a group represented by R 11
  • R 11 is the above alkyl group, the above aryl group or the above arylalkyl group
  • the hydrogens of these groups The atom can be substituted by a hydroxyl group. It is preferable that R 1 be one in which the hydrogen atom of the above-mentioned alkyl group, the above-mentioned aryl group and the above-mentioned arylalkyl group of R 11 is substituted by OR 21 and the hydrogen atom of R 21 is substituted by a hydroxyl group.
  • R 1 is a group having the above hydroxyl group
  • R 1 is a group represented by R 11
  • R 11 is the above alkyl group, the above aryl group or the above arylalkyl group
  • a hydrogen atom of the alkyl group, the aryl group and the arylalkyl group is substituted by OR 21
  • R 21 is an alkyl group
  • a hydrogen atom of R 21 is substituted by a hydroxyl group preferable.
  • R 1 is preferably the above alkyl group or an arylalkyl group.
  • R 1 is a group having a hydroxyl group and X is CO
  • R 1 is preferably the above-mentioned alkyl group, arylalkyl group or aryl group. It is because while said compound I can form the hardened
  • R 1 is a group having no hydroxyl group
  • R 1 is a group represented by R 11
  • R 11 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon It is preferably an arylalkyl group having 7 to 30 atoms
  • R 11 is preferably an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms
  • R 11 is a carbon atom.
  • R 11 is a carbon atom having an alkyl group having 1 to 10 carbon atoms or an alkylene moiety substituted by -OCO- more preferably an aryl alkyl group having 7 to 10 carbon which R 11 is alkylene group or oxime ester end having 1 to 10 carbon atoms is substituted with -OCO- And particularly preferably an arylalkyl group of atoms 7-10.
  • R 1 is a group having no hydroxyl group and X is a direct bond, it is preferably a water alkyl group or an arylalkyl group.
  • R 1 is a group having no hydroxyl group and X is CO, it is preferably an alkyl group, an arylalkyl group or an aryl group. It is because while said compound I can form the hardened
  • R 1 is a group having no hydroxyl group, it is easy to widen the absorption wavelength, and from the viewpoint of having excellent sensitivity, R 1 is a group represented by R 11 , R 11 is preferably 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.
  • R 5 is a group having the above hydroxyl group
  • R 5 is preferably a group represented by —COR 11 .
  • R 11 is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R 11 is more preferably an aryl group having 6 to 15 carbon atoms, and the above R 11 Is particularly preferably an aryl group having 6 to 10 carbon atoms.
  • R 11 used for R 5 is the above alkyl group, the above aryl group or the above aryl alkyl group, it is preferable that the hydrogen atom of the alkyl group, the aryl group and the aryl alkyl group is substituted by OR 21
  • R 21 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably R 21 is an alkyl group having 1 to 10 carbon atoms, and R 21 is an alkyl group having 1 to 5 carbon atoms. Is particularly preferred.
  • R 5 is a group having a hydroxyl group
  • R 5 is a group represented by —CO—R 11 and R 11 is the above alkyl group, the above aryl group or the above arylalkyl group, these groups Any of the hydrogen atoms of may be substituted with a hydroxyl group.
  • R 5 is a hydrogen atom of the above-mentioned alkyl group, the above-mentioned aryl group and the above-mentioned arylalkyl group represented by R 11 contained in —CO—R 11 substituted with OR 21 and R 21 is an alkyl group And R 21 is preferably substituted by a hydroxyl group.
  • R 5 is a group having the above hydroxyl group
  • R 5 is a group represented by —CO—R 11 and R 11 is the above alkyl group or the above aryl group, and the alkyl group
  • the hydrogen atom of the aryl group is preferably substituted by OR 21
  • the hydrogen atom of R 21 is preferably substituted by a hydroxyl group.
  • R 5 is a group having a hydroxyl group
  • the number of hydroxyl groups contained in R 5 is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less, and particularly preferably 1 or more.
  • the number is preferably 2 or less, and particularly preferably 2. It is because while said compound I can form the hardened
  • R 5 is a group having no hydroxyl group
  • R 5 is a group represented by R 11 or a nitro group
  • R 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 to 6 carbon atoms It is preferably a 30 aryl group or an arylalkyl group having 7 to 30 carbon atoms, a group represented by R 11 or a nitro group, and it is preferable that R 11 be a hydrogen atom, especially a nitro group.
  • R 2 is a group having no hydroxyl group
  • R 2 is a group represented by R 11
  • R 11 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon It is preferably an arylalkyl group having 7 to 30 atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms Or an aryl group having 6 to 15 carbon atoms is particularly preferred.
  • R 3, R 4, R 6 and R 7 are a radical having no hydroxyl group
  • R 3, R 4, R 6 and R 7 is a group represented by R 11,
  • R 11 is a hydrogen atom, It is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Is more preferable, and a hydrogen atom is particularly preferable.
  • R 2 , R 3 , R 4 , R 6 and R 7 are the above-mentioned groups, the compound I can form a cured product having excellent electrical properties and is easy to synthesize.
  • R 8 is a group having the above hydroxyl group
  • R 8 is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and is an alkyl group having 1 to 15 carbon atoms. And more preferably an alkyl group having 1 to 10 carbon atoms.
  • R 8 is a group having the above hydroxyl group
  • R 8 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms
  • Any hydrogen atom of these groups may be substituted with a hydroxyl group, and among them, the hydrogen atoms of the above alkyl group, the above aryl group and the above arylalkyl group are a hydroxyl group or a carboxyl group (COOR 21)
  • R 21 is preferably a hydrogen atom, and the hydrogen atom of the alkyl group, the aryl group and the arylalkyl group is a carboxyl group (COOR 21 and R 21 is a hydrogen atom).
  • R 8 is a group having the above hydroxyl group, more specifically, R 8 is the above alkyl group or the above aryl group, and the hydrogen atom of the alkyl group or the aryl group is a carboxyl group (COOR 21) , It is preferable that R 21 be a group substituted with a hydrogen atom. It is because while said compound I can form the hardened
  • R 8 is a group having no hydroxyl group
  • R 8 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • An alkyl group having 1 to 5 carbon atoms is particularly preferable. It is because while said compound I can form the hardened
  • a in the compound I represents the number of functional groups of R 3 and may be an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably an integer of 0 to 1 It is preferable that it be 0, in particular.
  • the compound I can form a cured product having excellent electrical properties and can be easily synthesized.
  • X in the compound I is a direct bond or a group represented by CO, it is preferably CO from the viewpoint of obtaining a cured product which is excellent in sensitivity and sufficiently cured.
  • the bonding position of the oxime ester group may be a bondable position among benzene rings contained in the carbazole structure, for example, as represented by the following general formula (Ia), the 6-position of the carbazole structure It is preferred that The compound I can form a cured product having excellent electrical properties and is easy to synthesize.
  • the compound I is preferably a compound represented by the general formula (Ia). This is because a compound having a hydroxyl group represented by the above general formula (Ia) can form a cured product excellent in electrical properties and is easy to synthesize.
  • 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) can be preferably used. These compounds can form a cured product having excellent electrical properties and are easy to synthesize.
  • the molecular weight of the compound I can be set according to the use of the compound I and the like.
  • the molecular weight of the compound I can be, for example, 250 or more and 2000 or less, can be 300 or more and 2000 or less, and can be 350 or more and 1000 or less.
  • a cured product having excellent electrical properties can be formed.
  • the method for producing the compound I represented by the above general formula (I) is not particularly limited as long as it is a method which can obtain the compound I having the above-mentioned structure, but for example, using the method described in Japanese Patent No. 4223071 etc. Can. Specifically, it can be produced by the following reaction scheme. First, carbazole compound (I-0) and acid chloride (I-1) are reacted in the presence of aluminum chloride to obtain acyl compound (I-2). Then, the acyl compound (I-2) and hydroxylamine hydrochloride are reacted in the presence of DMF to obtain an oxime compound (I-3).
  • the oxime compound (I-3) is reacted with the acid anhydride (I-4) or the acid chloride (I-5) to obtain the oxime ester compound (I-6) of the present invention corresponding to the above general formula (I) Can be mentioned.
  • carbazole compound (I-0) in which at least one of R 2 to R 8 is a group having a hydroxyl group can be used.
  • carbazole compound (I-0) in which R 2 to R 8 are hydrogen atoms alkyl having a hydroxyl group according to a conventional method It may be a method of introducing a group or the like.
  • the following reaction scheme shows a method for producing the above-mentioned compound I in which X is a direct bond.
  • the said compound I can use as a photoinitiator component which generate
  • it can be added and used for compositions, such as a photocurable composition, for example.
  • a color filter in a liquid crystal display element for color display such as a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color television, a PC monitor, a portable information terminal, a digital camera
  • Electrode materials for plasma display panels powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solders Compositions for forming resists, color filters for various display applications or for forming structures in plasma display panels, electroluminescent displays, and LCD manufacturing processes, compositions for encapsulating electrical and electronic components , Magnetic recording materials, micro mechanical parts, waveguides, optical switches, masks for plating, Etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, microelectronic circuits, bleaching materials, image
  • a liquid crystal layer spacer characterized by having, for example, a cured product of a composition containing the compound I by using the compound I, and a liquid crystal display device characterized by including the liquid crystal layer spacer Etc can be obtained.
  • the liquid crystal layer spacer can also be used, for example, as a black column spacer which also has a function as a black matrix.
  • the photopolymerization initiator of the present invention is characterized by containing the above-mentioned compound I.
  • the photoinitiator of this invention can form the hardened
  • the said photoinitiator contains the above-mentioned compound I.
  • each component of the said photoinitiator is demonstrated.
  • the content of the compound I in the photopolymerization initiator of the present invention may be any as long as it can impart desired photopolymerization curability, and can be appropriately set according to the application of the photopolymerization initiator and the like.
  • 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. It is because it is useful as a photoinitiator which can form easily the hardened
  • the content of Compound I in the photopolymerization initiator of the present invention is less than 100 parts by mass in 100 parts by mass of the photopolymerization initiator, that is, a composition containing the compound I and other components. can do.
  • the content of the compound I can be, for example, more than 30 parts by mass and 99 parts by mass or less, and preferably 50 parts by mass or more and 75 parts by mass or less. It is because it is useful as a photoinitiator which can form easily the hardened
  • the content is on a mass basis unless otherwise specified.
  • the type of the compound I contained in the photopolymerization initiator may be only one type or two or more types.
  • the type can be, for example, two or more and five or less.
  • the photoinitiator of this invention contains the said polymer component as said other component.
  • the shape of the photopolymerization initiator may be powdery or pelletized.
  • the photopolymerization initiator is in the form of pellets, for example, after mixing the compound I and the polymer component using an extruder or the like, a method of molding into pellets can be used. .
  • composition of the present invention is characterized by containing the above-mentioned compound I.
  • composition of this invention can obtain easily the hardened
  • composition of the present invention contains the above-mentioned compound I.
  • each component contained in the composition of this invention is demonstrated in detail.
  • the content of the compound I in the composition of the present invention is not particularly limited as long as it can impart desired curability and the like to the composition.
  • the content of the compound I in the composition of the present invention can be, for example, 0.001 to 30 parts by mass in 100 parts by mass of the solid content of the composition, and 0.005 to 10 parts by mass It is preferable that it is less than part. It is because the hardened
  • solid content is what contains all the components other than a solvent.
  • the content of the compound I can be 0.001 to 30 parts by mass in 100 parts by mass of the composition, and is preferably 0.005 to 10 parts by mass.
  • the content of the compound I is 100 parts by mass in total of the compound I, the polymerizing compound and the polymer having a hydrophilic group. And 0.01 to 30 parts by mass, and more preferably 0.1 to 25 parts by mass, and preferably 0.5 to 20 parts by mass More preferably, it is particularly preferably 1 part by mass or more and 15 parts by mass or less. It is because the hardened
  • the number of types of the above-mentioned compound I contained in the above-mentioned composition may be one, or two or more.
  • the type can be, for example, two or more and five or less. It is because it becomes easy to form the hardened
  • the above composition contains the above-mentioned compound I, it can contain other components as needed.
  • a polymerizable compound a polymer having a hydrophilic group, a colorant, a solvent, a filler, an antireflective agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber
  • An inorganic compound used as an ink repellent agent, a dispersing agent for dispersing an inorganic compound, a coloring agent, an inorganic compound, etc., the above-mentioned polymerizable compound used to improve the properties of a cured product, a polymer different from Polymer A Mention may be made of polymerizable compounds, organic polymers other than polymers having a hydrophilic group, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine, etc. which can improve the properties of cured products. Can.
  • the composition of the present invention can be easily used as a photocurable composition by including the above-described polymerizable compound.
  • the polymerizable compound may be any one capable of forming a polymer, and for example, it may have a radically polymerizable group.
  • the said polymeric compound can use the compound which has ethylenic unsaturated double bonds, such as a (meth) acryl group and a vinyl group, as a radically polymerizable group, for example.
  • (meth) acryl is used by the meaning containing acryl and methacryl.
  • (meth) acrylate is used in the meaning including acrylate and methacrylate.
  • unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, (meth) acrylic acid, ⁇ -chloroacrylic acid , Itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl ester , Hydroxyethyl (mono) (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as phthalic acid mono [2- (meth) acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono (
  • A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxye
  • mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends polyfunctional (meth) acrylates having one carboxy group and two or more (meth) acryloyl groups, Saturated monobasic acids and polyhydric alcohols or esters of polyhydric phenols are preferred from the viewpoint of curability and chromaticity characteristics.
  • the said polymeric compound can be used individually or in mixture of 2 or more types.
  • the molecular weight of the polymerizable compound is not particularly limited as long as a desired cured product can be obtained, but may be, for example, less than 2000, preferably 1500 or less, among which It is preferably 1000 or less, and particularly preferably less than 1000. It is because it will be excellent in curability.
  • said molecular weight is represented by a weight average molecular weight (Mw), when a polymeric compound is a polymer which contains a repeating structure as the structure.
  • Mw weight average molecular weight
  • the weight average molecular weight can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
  • the weight average molecular weight Mw is, for example, GPC (LC-2000 plus series) manufactured by JASCO Corporation, and the elution solvent is tetrahydrofuran, and polystyrene standards for calibration curve are Mw 110000, 707000, 397000, 189000, 98900, 37200 13700, 9490, 5430, 3120, 1010, 589 (TSKgel standard polystyrene manufactured by Tosoh Corp.) and measuring columns as KF-804, KF-803, KF-802 (manufactured by Showa Denko KK) You can get it. Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.
  • the content of the polymerizable compound is not particularly limited as long as a desired cured product can be obtained.
  • 1 part by mass or more and 50 parts by mass with respect to 100 parts by mass of the solid content of the composition It can be made as follows, and in particular, it is 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 10 parts by mass or more and 20 parts by mass or less Is preferred.
  • the content becomes a composition having excellent curability.
  • content of the resin component containing the said polymeric compound although it can set suitably according to the use etc.
  • the amount can be set to 10 parts by mass or more and 80 parts by mass or less, and preferably 40 parts by mass or more and 60 parts by mass or less. It is because it is easy for the above-mentioned composition to give various functions to a hardened material because the above-mentioned content is the above-mentioned range.
  • the resin component may be contained in the cured product of the composition to be used for retaining the decomposition product of the compound I, the colorant, and the like, and, for example, the above-mentioned polymerizable compound, which will be described later Polymers having hydrophilic groups and other organic polymers can be included.
  • the content of the polymerizable compound can be 0.1 parts by mass or more and 99 parts by mass or less, and is preferably 0.5 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the composition, and 1 It is further more preferable that it is a mass part or more and 30 mass parts or less, and it is especially preferable that it is 1.5 mass parts or more and 10 mass parts or less. It is because the hardened
  • the composition described above is a curable composition having alkali developability. It becomes easy to use as The polymer A is not particularly limited as long as it is a polymer that can impart alkali developability, and conventionally used organic polymers can be used.
  • the hydrophilic group may be any group 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 or a salt thereof A hydroxyl group and a carboxyl group are preferable because the solubility of the polymer A in alkali is high.
  • the preferable functional group equivalent (mass of the polymer A containing one hydrophilic group equivalent) of the hydrophilic group in the above-mentioned polymer A can be suitably set according to desired alkali solubility, for example, 50 or more and 10,000 The following can be made.
  • the weight average molecular weight (Mw) of the polymer A can be appropriately set depending on the desired alkali solubility, but can be 1000 or more and 500000 or less, and preferably 1000 or more and 100000 or less, It is particularly preferable that the number is 2000 or more and 30000 or less. When the weight average molecular weight is in the above range, the polymer A becomes excellent in alkali developability.
  • the acid value of the polymer A can be appropriately set depending on the desired alkali solubility, but can be 10 mg KOH / g or more and 200 mg KOH / g or less, and is 30 mg KOH / g or more and 150 mg KOH / g or less Is preferred.
  • the acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of solid content of the polymer, and the value measured by the method described in JIS K 0070 and can do.
  • the polymer A may be one having a repeating unit, and specifically, a copolymer of an acrylic ester, a phenol and / or cresol novolac epoxy resin, and a polyphenylmethane type having a polyfunctional epoxy group.
  • a compound having a structure in which an unsaturated monobasic acid is allowed to act on an epoxy compound such as an epoxy resin, an epoxy acrylate resin, or an epoxy compound represented by the following general formula (V), or a polybasic acid anhydride is further added to the compound
  • the resin which has a structure obtained by making it act can be used.
  • the polymer A is preferably one having an unsaturated group, and in particular, an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (V)
  • an ethylenically unsaturated compound having a structure in which the epoxy addition compound and the polybasic acid anhydride are subjected to an esterification reaction is preferable. It is because the said composition becomes what was excellent in the patterning property.
  • what is necessary is just to carry out addition reaction of unsaturated monobasic acid to the epoxy compound represented by the following general formula (V), in order to obtain the said epoxy addition compound.
  • the epoxy addition compound obtained by the addition reaction and the polybasic acid anhydride may be subjected to an esterification reaction.
  • the said ethylenically unsaturated compound contains 0.2 equivalent or more and 1.0 equivalent or less of unsaturated groups.
  • the unsaturated group can be the same as the above-mentioned ethylenically unsaturated double bond group.
  • V- 1 represents a substituent selected from the group represented by (V-2) or (V-3), and R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 Each 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.
  • R109 , R110 , R111 , R112 , R113 , R114 , R115 , R116 , R117 , R118 , R119 , R120 , R121 , R122 , R123 , R124 , R124) 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 and R 132 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms And an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the above alkyl group and arylalkyl group are methylene chains constituting it, unsaturated bonds may be substituted by -O- or -S-, R 109, R 110, R
  • alkyl group examples include aryl group, arylalkyl group, heterocyclic group and halogen atom in the general formula (V), in the description of the above general formula (I), an alkyl group, an aryl group, an arylalkyl group And various groups exemplified for each of the heterocyclic group and the halogen atom.
  • alkoxy group in general formula (V) the group corresponding to the alkyl group illustrated in description of said general formula (I) is mentioned.
  • alkylidene group having 1 to 4 carbon atoms examples include methylidene, ethylidene, propylidene and butylidene.
  • the compound which has one unsaturated group and one carboxyl group can be used, and acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, Examples include hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate and the like.
  • a carboxylic acid anhydride can be used as the polybasic acid anhydride which is allowed to act after the action of the unsaturated monobasic acid.
  • a carboxylic acid anhydride can be used.
  • the reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride be as follows. That is, it is preferable to add the above-mentioned epoxy addition compound so that the carboxyl group of the above-mentioned unsaturated monobasic acid becomes a ratio of 0.1 or more and 1.0 or less to 1 epoxy group of the above-mentioned epoxy compound. Also, the above-mentioned ethylenically unsaturated compound has a ratio such that the acid anhydride structure of the above polybasic acid anhydride is 0.1 or more and 1.0 or less per 1 hydroxyl group of the above-mentioned epoxy addition compound. It is preferable to do.
  • the reaction of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.
  • the above-mentioned polymer A can also be used after 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.
  • a compound having one epoxy group can be used, and glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t- Butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycid
  • the compound which has an epoxy group 2 or more can be used,
  • 1 or more types of compounds selected from the group which consists of a bisphenol type epoxy compound and glycidyl ethers can be used.
  • a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
  • glycidyl ethers ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxy
  • novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, etc .
  • Alicyclic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compounds
  • Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester
  • tetraglycidyl diamino acid Glycidyl amines such as phenylmethane, triglycidyl P-aminophenol, N, N-digly
  • the polymer A preferably contains a carboxyl group-containing polymer from the viewpoint of achieving excellent developability. By including the polymer, the composition becomes more excellent in patterning accuracy.
  • the polymer having a carboxyl group is not particularly limited as long as it has a carboxyl-containing structural unit (hereinafter referred to as “structural unit (U1)”), and is not particularly limited, but a methacryloyl group, an acryloyl group, vinyl Structural unit having a crosslinkable group such as epoxy group, oxetanyl group, vinyl ether group, mercapto group, isocyanate group (hereinafter referred to as “structural unit (U2)”), and structural unit having a silyl group (hereinafter referred to as "structural unit It is preferable to have a structural unit selected from units (U3).
  • the polymer having a carboxyl group may have a structural unit other than the structural units (U1) to (U3) (hereinafter referred to as “structural unit (U4)").
  • the structural unit (U1) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (u1)"). Is preferred. 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-methacryloyloxyethyl hexahydrate Hydrophthalic acid etc;
  • Examples of the dicarboxylic acids include maleic acid, fumaric acid, citraconic acid and the like;
  • Examples of the above-mentioned anhydrides of dicarboxylic acids include the above-mentioned anhydrides of dicarboxylic acids and the like.
  • acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid or maleic anhydride are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained copolymer in a developer.
  • the compounds (u1) can be used alone or in combination of two or more.
  • the structural unit (U2) is preferably a structural unit derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter referred to as "compound (u2)").
  • the compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.
  • Examples of the polymerizable unsaturated compound having an epoxy group include (meth) acrylic acid oxiranyl (cyclo) alkyl ester, ⁇ -alkyl acrylic acid oxiranyl (cyclo) alkyl ester, glycidyl ether compound having a polymerizable unsaturated bond, and the like. ;
  • As a polymerizable unsaturated compound which has oxetanyl group the (meth) acrylic acid ester etc. which have oxetanyl group can be mentioned, for example.
  • (meth) acrylic acid oxiranyl (cyclo) alkyl ester for example, glycidyl (meth) acrylic acid, 2-methyl glycidyl (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid 3, 4-epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) acrylic acid 3,4-epoxycyclohexyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 3,4-epoxytricyclo [4] 5.2.1.02.6] decyl (meth) acrylate, etc .;
  • ⁇ -alkyl acrylic acid oxiranyl (cyclo) alkyl esters such as glycidyl ⁇ -ethyl acrylic acid, glycidyl ⁇ -n-propyl acrylic acid, glycidyl
  • the compounds (u2) can be used alone or in combination of two or more.
  • a structural unit having a (meth) acryloyloxy group can be preferably used as a structural unit having a methacryloyl group or an acryloyl group as a crosslinkable group.
  • the structural unit having a (meth) acryloyloxy group is obtained by reacting a carboxyl group in a polymer with a (meth) acrylic acid ester 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).
  • R 1000 and R 1001 each independently represent a hydrogen atom or a methyl group
  • R 1002 represents a divalent group represented by the following formula ( ⁇ ) or the following formula ( ⁇ )
  • * represents a bonding point.
  • R 1003 represents a hydrogen atom or a methyl group, and * represents a bonding site
  • a heavy catalyst containing a polymerization inhibitor is preferably added, if necessary, in the presence of a suitable catalyst.
  • the unsaturated compound which has an epoxy group is thrown into the solution of a combination, and it stirs under heating for a predetermined time.
  • the catalyst include tetrabutyl ammonium bromide and the like.
  • the polymerization inhibitor include p-methoxyphenol and the like.
  • the reaction temperature is preferably 70 ° C to 100 ° C.
  • the reaction time is preferably 8 hours to 12 hours.
  • the content ratio of the structural unit having a (meth) acryloyloxy group as a crosslinkable group is 10 mol% to 70 mol of the total structural units of the polymer having a carboxyl group. % Is preferable, and 20 mol% to 50 mol% is more preferable.
  • the ratio of the structural unit having a (meth) acryloyloxy group is in the above range, heat resistance and development failure at the time of 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) And acryloyloxypropyltriethoxysilane etc. can be mentioned.
  • the compounds (u3) can be used alone or in combination of two or more.
  • the structural unit (U4) is a structural unit other than the above (U1) to (U3), and a polymerizable unsaturated compound other than the above (u1) to (u3) (hereinafter referred to as "the compound (u4)"). It is preferable that it is a structural unit derived from As the above compound (u4), for example, (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, Mention may be made of (meth) acrylic esters having an oxygen-containing five-membered ring or an oxygen-containing six-membered ring, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds.
  • (meth) acrylic acid alkyl esters such as methyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, Meta) acrylic acid sec-butyl, (meth) acrylic acid t-butyl etc .
  • (meth) acrylic acid cycloalkyl ester for example, cyclohexyl (meth) acrylic acid, 2-methylcyclohexyl (meth) acrylic acid, tricyclo [5.2.1.
  • the above compound (u4) includes n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, and tricyclo methacrylate [5.2.1. -Yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.
  • the compounds (u4) can be used alone or in combination of two 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) as described above in the following proportions.
  • Compound (u1) preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, still more preferably 5 mol% to 15 mol%
  • Compound (u2) preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 30 mol%
  • Compound (u3) preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, still more preferably 10 mol% to 30 mol%
  • Compound (u4) preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, still more preferably 25 mol% to 50 mol%
  • a (meth) acryloyloxy group is obtained by reacting a (meth) acrylic acid ester having an epoxy group with a carboxyl group in a structural unit derived from the compound (u1) in the obtained copolymer. It can have the structural unit which it has.
  • a polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of a polymerizable unsaturated compound containing the compound (u1) to the compound (u4) in the above range has good coatability
  • high resolution can be achieved without loss, so that even a high-definition pattern is preferable because a cured film with a highly balanced property can be provided.
  • a polymer having a carboxyl group can be produced by polymerizing a mixture of polymerizable unsaturated compounds as described above, preferably in a suitable solvent, preferably in the presence of a radical polymerization initiator.
  • Examples of the solvent used for the above 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 can be mentioned. These solvents can be used alone or in combination of two or more.
  • the radical polymerization initiator is not particularly limited, and, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2 '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, Mention may be made of azo compounds such as 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used alone or in combination of two or more.
  • polymer U-1 and polymer U-2 can be mentioned as a preferable example of the polymer which has the said carboxyl group.
  • the temperature of the solution is raised to 100 ° C., and the temperature is held for 1 hour to polymerize to obtain a solution containing a copolymer.
  • 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor are added to a solution containing this copolymer, and the mixture is stirred at 90 ° C. for 30 minutes in an air atmosphere, and then methacrylic.
  • the polymer U-1 of the weight average molecular weight Mw 9000 obtained by adding 74 mass parts of acid glycidyls and making it react at 90 degreeC for 10 hours can be mentioned.
  • the polymer U-1 has a structural unit (U1), a structural unit (U2) and a structural unit (U4).
  • maintaining this temperature for 5 hours can be mentioned.
  • 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 carboxyl group-containing polymer is appropriately selected according to the purpose of use and is not particularly limited. Can.
  • the total content of the carboxyl group-containing polymer and the polymerizable component B is appropriately selected according to the intended purpose and is not particularly limited. It can be made to be not less than mass part and not more than 99 parts by mass.
  • content of the said polymer A can be suitably set according to desired alkali solubility, it can be 5 mass parts or more and 90 mass or less with respect to 100 mass parts of solid content of a composition,
  • the amount is preferably 10 parts by mass to 75 parts by mass, and more preferably 15 parts by mass to 70 parts by mass, and particularly preferably 20 parts by mass to 60 parts by mass. It is because the said composition turns into a composition excellent in alkali developability because the said content is the above-mentioned range.
  • the total amount of the above-mentioned ethylenically unsaturated compounds having the same structure is preferably 25 parts by mass or more and 100 parts by mass or less, and more preferably 40 parts by mass or more and 100 parts by mass or less in 100 parts by mass of the polymer A.
  • the content of the polymer A can be 0.1 to 99 parts by mass in 100 parts by mass of the composition, and is preferably 0.5 to 50 parts by mass, and 1 It is further more preferable that it is mass part or more and 30 mass parts or less, and it is especially preferable that it is 2 mass parts or more and 20 mass parts or less.
  • the content of the polymer A is in the above-described range, the composition becomes excellent in alkali developability. Moreover, it is because the said composition can obtain the hardened
  • the composition can obtain a colored composition, a colored cured product, and the like.
  • a coloring agent what is necessary is just to give a desired color to a composition, hardened
  • the pigment examples include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthrone compounds, perinones Compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, lake pigments, furnace method, channel method or thermal Black obtained by the above method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared or coated with an epoxy resin, the above carbon black previously dispersed in a solvent with a resin, and adsorbed with a resin of 20 to 200 mg / g, the above carbon black
  • pigments can also be used as the pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 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, Pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 9 , 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 137, 138, 139, 147, 148, 150, 151, 152,
  • the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes And dyes such as cyanine dyes, and the like, and these may be used as a mixture of two or more.
  • the colorant is preferably used as a spacer of a liquid crystal layer, for example, when the composition is for a black matrix, and preferably contains a black pigment when it is for a black column spacer having a light shielding property.
  • the black pigment may be any pigment capable of imparting a desired light shielding property, and, for example, the above-mentioned various carbon blacks and carbon black-treated products, graphitized carbon black, activated carbon, carbon fibers, carbon nanotubes, carbon micro coils, carbon Nanohorn, carbon airgel, fullerene, aniline black, pigment black 7, titanium black, lactam black, perylene black, cyanine black can be mentioned.
  • the content of the coloring agent is not particularly limited as long as a composition having a desired color, a cured product or the like can be obtained, and for example, 1 part relative to 100 parts by mass of the solid content of the composition It can be made to be not less than 10 parts by mass and not more than 90 parts by mass, preferably not less than 10 parts by mass and not more than 75 parts by mass, and more preferably 20 parts by mass to 60 parts by mass, It is preferable that it is below a mass part. It is because a desired colored cured product can be obtained because the said content is the above-mentioned range.
  • the content of the coloring agent can be 0.5 parts 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, and 2 parts by mass or more in 100 parts by mass of the composition.
  • the content is more preferably 30 parts by mass or less, particularly preferably 3 parts by mass or more and 15 parts by mass or less. It is because the hardened
  • the solvent may be any solvent as long as it can disperse or dissolve each component of the composition.
  • solvents can be used as one or more mixed solvents.
  • ketones, ether ester solvents and the like particularly propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as "PGMEA” or “propylene glycol monomethyl ether acetate”), cyclohexanone etc. It is preferable from the viewpoint of good compatibility with I, polymer A and the like.
  • the content of the above-mentioned solvent can be suitably set up according to coating nature etc., it can be 5 mass parts or more and 90 mass parts or less with respect to 100 mass parts of compositions, for example, and 10 mass parts It is preferable that it is 80 mass parts or less. It is because adjustment of the viscosity of a composition is easy because the said content is the above-mentioned range.
  • Inorganic Compound The above-mentioned inorganic compound can be appropriately selected according to the application such as a filler, mechanical strength improver, etc.
  • nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide Metal oxides such as magnesium oxide, calcium oxide, potassium oxide, silica and alumina; layered clay mineral, miloli blue, calcium carbonate, magnesium carbonate, cobalt based, manganese based, glass powder (especially glass frit), mica, talc, kaolin, Ferrocyanides, various metal sulfates, sulfides, selenides, aluminum silicates, calcium silicates, aluminum hydroxide, platinum, gold, silver, copper and the like can be mentioned.
  • the inorganic compounds for example, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable, for example, from the viewpoint of mechanical strength improvement.
  • the content of the inorganic compound varies depending on the performance required of the inorganic compound, but can be, for example, 1 to 90 parts by mass with respect to 100 parts by mass of the solid content of the composition
  • the content is preferably 70 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less. It is because the said composition can obtain the hardened
  • These inorganic compounds can be used alone or in combination of two or more.
  • Dispersant is not particularly limited as long as it can disperse and stabilize a colorant, an inorganic compound and the like in the composition, and a commercially available dispersant, such as BYK series manufactured by Bick Chemie, etc. It can be used.
  • a polymer dispersant comprising polyester, polyether or polyurethane having a basic functional group, an amine having a nitrogen atom as a basic functional group and a functional group having a nitrogen atom, and /
  • a quaternary salt thereof having an amine value of 1 mg KOH / g or more and 100 mg KOH / g or less is preferably used.
  • the other organic polymer may be a polymer different from the above-mentioned polymerizable compound and the polymer A, as long as it is a polymer which can improve the properties of the cured product.
  • Such other organic polymers can be polymers not containing a polymerizable group and a hydrophilic group, and examples thereof include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) Acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamidoimide resin, polyamic
  • the weight average molecular weight of the organic polymer can be the same as that of the polymer A.
  • content of another organic polymer is suitably set according to the use etc. of the said composition, for example, 1 mass part or more and 90 mass parts with respect to 100 mass parts of solid content of a composition The following can be made.
  • chain transfer agent or sensitizer any compound capable of adjusting the sensitivity of the composition, etc. may be used, and a sulfur atom-containing compound is generally used.
  • surfactant those which can improve the dispersion stability, coatability and the like of the composition can be used.
  • perfluoroalkyl phosphate, perfluoroalkyl carboxylate and the like Fluorinated surfactants; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; cationic surfactants such as higher amine halides and quaternary ammonium salts; polyethylene glycol alkyl ethers
  • Nonionic surfactants such as polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; amphoteric surfactants; surfactants such as silicone surfactants can be used, and these may be used in combination.
  • the above silane coupling agent is 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, which is cured What can improve the adhesiveness etc. of a thing can be used.
  • a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, isocyanate group such as KBE-9007, KBM-502, KBE-403, methacryloyl group or epoxy group
  • the silane coupling agent which has these is used suitably.
  • meltamine Compound As the above-mentioned melamine compound, those which can improve the curability can be used, and examples thereof include (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, (poly) methylolurea and the like. of active methylol groups of the nitrogen compound (CH 2 OH groups) of all or part (at least two) can be exemplified compounds which is alkyl-etherified.
  • examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group or a butyl group, which may be identical to or different from each other.
  • the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
  • hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
  • alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.
  • thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, phenothiazine, etc .; plasticizers; adhesion promoters; fillers; antifoaming agents; leveling agents; Antioxidants; UV absorbers; dispersing aids; aggregation inhibitors; catalysts; effect accelerators; crosslinking agents; conventional additives such as thickeners can be added.
  • the content of the additive is appropriately selected according to the purpose of use and is not particularly limited. For example, the total content of 100 parts by mass of the composition can be 50 parts by mass or less.
  • composition As a method for producing the above composition, any known mixing method can be used as long as it can be mixed so as to achieve the desired content of each of the above components. As a use of the said composition, it can be used as a photocurable composition hardened
  • the cured product of the present invention is a cured product of the above-mentioned composition.
  • the cured product of the present invention uses the composition described above.
  • the cured product of the present invention will be described in detail.
  • the said composition it can be made the same as the content as described in the term of the said "C. composition”.
  • the above composition usually contains a polymerizable compound, a polymer A having an unsaturated group, and the like to form a cured product.
  • the cured product usually contains a polymer component.
  • a polymer component the polymer of the polymeric compound as described in the term of said "C. composition", the polymer of the polymer A which has an unsaturated group, etc. can be mentioned, for example.
  • the polymer of a polymeric compound should just contain a polymeric compound as a structural unit, and not only the polymer of polymeric compounds but the polymer of a polymeric compound and the polymer A is included.
  • the respective contents of the polymer of the polymerizable compound and the polymer of the polymer A having an unsaturated group are the contents of the polymerizable compound and the polymer A described in the section of "C. composition” and the like. It can be the same.
  • the other organic polymer as described in the term of the said "C. composition” can also be included.
  • the total content of the polymer component can be appropriately set according to the application of the second composition, and, for example, the content of the resin component described in the above "C. composition” It can be the same as
  • the cured product may be substantially free of a solvent.
  • the content of the solvent contained in the cured product can be, for example, 1 part by mass or less in 100 parts by mass of the cured product, and preferably 0.5 parts by mass or less. It is because the said hardened
  • cured material of this invention can set suitably according to the use etc. of the said hardened
  • the above-mentioned cured product when used as a spacer or the like of a liquid crystal layer, it can be formed into a dot or line pattern or the like.
  • the thickness of the cured product can be, for example, 0.1 ⁇ m or more and 100 ⁇ m 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.
  • a manufacturing method for example, since it can be made to be the same as the contents described in the section of “E.
  • the method for producing a cured product of the present invention is characterized by comprising the step of irradiating the above-mentioned composition with light.
  • the method for producing the effect of the present invention comprises the step of irradiating the composition containing the compound I with light, so that a cured product having excellent electrical properties can be easily obtained.
  • the production method of the present invention includes the step of light irradiation.
  • each process of the manufacturing method of this invention is demonstrated in detail.
  • Step of Irradiating Light This step is a step of irradiating the above composition with light to cure the composition.
  • any light can be used as long as Compound I can generate a radical, and for example, light having a wavelength of 250 nm to 450 nm can be included.
  • the irradiation amount of the light to be irradiated may be any as long as it can form a cured product having a desired hardness, and is appropriately adjusted in accordance with the thickness of the coating film of the composition and the like.
  • an ultra-high pressure mercury, a mercury vapor arc, a carbon arc, a xenon arc etc. can be mentioned, for example.
  • Laser light may be used as the light to be irradiated.
  • the laser light one containing light with a wavelength of 340 nm to 430 nm can be used.
  • a light source of laser light those emitting light in the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser can also be used.
  • the said composition can contain the sensitizing dye which absorbs the said area
  • the light irradiation method may be a method of irradiating light to the entire surface of the coating film of the composition in plan view, or a method of irradiating light to a part of the coating film.
  • the method of light irradiation may be, for example, a method of irradiating light through a mask or the like, or a method of irradiating light only to a region where the composition cures. .
  • composition usually contains a polymerizable compound, a polymer A having an unsaturated group, and the like to form a cured product.
  • the above-mentioned manufacturing method includes the step of light irradiation, but may include other steps as necessary.
  • steps for example, a step of forming a coating film of the composition, which is carried out before the step of irradiating light, a step of developing which is carried out after the step of irradiating light, and the coating is formed
  • the step of removing the solvent, which is carried out after the step of conducting, the step of heating which is carried out after the step of irradiating light, and the like can be mentioned.
  • the above-mentioned coat it may be a method which can obtain a coat of composition of desired thickness, for example, a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, a slit coater, Various known methods such as printing and immersion can be used.
  • the substrate on which the coating film of the above composition is formed can be appropriately set according to the application of the cured product and the like, and includes, for example, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic and the like Can be mentioned.
  • the cured product after the cured product is formed on a substrate, it may be peeled off from the substrate, or may be transferred from the substrate to another substrate.
  • the developing method in the step of developing may be any method as long as the uncured composition can be removed.
  • a known developing method such as a method of removing using an aqueous alkaline solution can be used.
  • the method of removing the solvent in the step of removing the solvent may be any method as long as the content of the solvent contained in the cured product can be made a desired amount.
  • a method of heating, that is, prebaking as a removing step The method etc. which implement a process can be mentioned.
  • the heating temperature in the heating step (post-baking step), which is carried out after the light irradiation step, may be a temperature at which the mechanical strength of the cured product can be improved, depending on the type of the cured product, use, etc. It can be set appropriately.
  • the present invention is not limited to the above embodiment.
  • the above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.
  • Example 1-1 In a nitrogen atmosphere, 78 mmol of aluminum chloride and 33.0 g of ethane dichloride are charged, and under ice cooling, 36 mmol of 4-fluoro-O-toluoyl chloride and then 30 mmol of 9-ethyl-3-nitrocarbazole (carbazole compound) was gradually added dropwise and stirred at 5 ° C. for 30 minutes. The reaction solution was poured into ice water, and oil / water separation was performed. The solvent was removed to obtain an acyl. Then, 45.0 g of ethylene glycol, 40 mmol of the obtained acyl compound, and 80 mmol of potassium carbonate were charged, and reacted at 100 ° C. for 5 hours.
  • Embodiment 1-2 The compound No. 1 described in paragraph [0022] of the same document synthesized based on the description of paragraphs [0072] to [0080] of WO 2006/018973. 10 mmol of 1 and 50 g of 60% aqueous acetic acid were charged, and stirred at 45 ° C. for 1 hour. The reaction solution was poured into 60 g of ice water, and 100 g of ethyl acetate was added and extraction was performed. The organic layer was washed four times with 100 g of ion-exchanged water, and the solvent was removed.
  • Embodiment 1-3 93 mmol of 60% sodium hydride and 40 g of dimethylformamide were charged, and 62 mmol of carbazole dissolved in 50 g of dimethylformamide was added dropwise under ice-cooling. Further, 124 mmol of ethyl bromoheptanoate dissolved in 50 g of dimmerformamide was added dropwise and reacted for 30 minutes. The reaction solution was poured into ice water containing hydrochloric acid, ethyl acetate was added, and oil-water separation was performed. The organic layer was washed three times with water, desolvated, and recrystallized with methanol to obtain an ester.
  • Embodiment 1-4 After charging 22 mmol of a ketone body having a hydroxyl group, 33 g of dimethylformacetamide, 24 g of isobutyl nitrite, and 2.3 g of 35% hydrochloric acid obtained in the same manner as in [Example 1-3], the reaction is carried out at room temperature for 24 hours. I did. Ion-exchanged water and chloroform were charged and oil-water separation was performed. The organic layer was washed three times with water to obtain an oxime. Subsequently, a compound represented by the following general formula (47) was obtained as a target compound I, in the same manner as in [Example 1-1] except that benzoyl chloride was used as the acid chloride. It was confirmed by H-NMR that the obtained compound was the desired product.
  • Example 1-5 Under nitrogen atmosphere, 78 mmol of aluminum chloride and 33.0 g of ethane dichloride are charged, and 36 mmol of 4-chlorobutyryl chloride and then 30 mmol of 9-ethyl-3-nitrocarbazole (carbazole compound) are gradually added under ice cooling. It was added dropwise and stirred at 5 ° C. for 30 minutes. The reaction solution was poured into ice water, and oil / water separation was performed. The solvent was removed to obtain an acyl. Then, 120 millimoles of sodium formate, 1.5 millimoles of tetrabutylammonium bromide and 30.0 g of dimethylformamide were charged and the mixture was stirred at 100 ° C.
  • Example 1-6 In the same manner as in [Example 1-5], a ketone having a hydroxyl group was obtained. A compound represented by the general formula (77) was obtained as a target compound I in the same manner as in [Example 1-4] except that the obtained ketone body was used. It was confirmed by H-NMR that the obtained compound was the desired product.
  • Example 1-7 A compound represented by the general formula (78) was obtained as a target compound I in the same manner as in Example [1-1] except that phenylacetyl chloride was used as the acid chloride. It was confirmed by H-NMR that the obtained compound was the desired product.
  • Example 1-8 In the same manner as in [Example 1-7], a ketone having a hydroxyl group was obtained. A compound represented by the general formula (79) was obtained as a target compound I in the same manner as in [Example 1-4] except that the obtained ketone body was used. It was confirmed by H-NMR that the obtained compound was the desired product.
  • Preparation Example 2 Preparation of Carbon Black Dispersion D-1 15 parts by mass of MA100 (manufactured by Mitsubishi Chemical Corporation) as carbon black, and 11.25 parts by mass (solid content concentration) of BYK 161 (manufactured by BIC Chemie (BYK)) as a dispersing agent 40% by mass) and 73.75 parts by mass of PGMEA as a solvent were mixed and treated by a bead mill to prepare carbon black dispersion liquid D-1.
  • MA100 manufactured by Mitsubishi Chemical Corporation
  • BYK 161 manufactured by BIC Chemie (BYK)
  • Examples 2-1 to 2-63 and Comparative Examples 1 to 12 The composition was prepared by mixing the components according to the formulations in Tables 2 to 4 below. In addition, a number represents a mass part.
  • A-1 Compound (24) (Compound I, obtained in Example 1-1)
  • A-2 Compound (13) (Compound I, obtained in Example 1-2)
  • A-3 Compound (3) (Compound I, obtained in Example 1-3)
  • A-4 Compound (76) (Compound I, obtained in Example 1-5)
  • A-5 Compound (77) (Compound I, obtained in Example 1-6)
  • A-6 Compound (78) (Compound I, obtained in Example 1-7)
  • A′-1 Compound A′-2 represented by the above-mentioned compound (A′-1): Compound A′-3 represented by the above-mentioned compound (A′-2): With the above-mentioned compound (A′-3)
  • Compound A′-4 represented: Compound represented by the above-described compound (A′-4) (photopolymerization initiator, IRGACURE-OXE02 manufactured by BASF Corp.)
  • B-1 Polymer obtained in the above Production Example 1 (polymer having a hydrophilic group)
  • B-2 SPC-3000 (polymer having a hydrophilic group; 42.7% solid content, PGMEA solution manufactured by Showa Denko KK)
  • D-1 Carbon black pigment dispersion (obtained in the above-mentioned Production Example 2)
  • D-2 Lactam black dispersion (solid content concentration 19.5% by mass, pigment concentration in solid content 76.9% by mass, solvent PGMEA)
  • E-1 KBE-403 (Coupling agent, Shin-Etsu Chemical Co., Ltd.)
  • F-1 Propylene glycol-1-monomethyl ether-2-acetate (solvent)
  • shower development was performed by discharging the developing solution which consists of 0.04 mass% potassium hydroxide aqueous solution at 23 degreeC with respect to this board
  • the development time was 1.5 times that of BT based on the time (BT: break time) until the unexposed area was completely dissolved.
  • post-baking was performed at 230 ° C. for 30 minutes.
  • the film thickness of the post-baking coating was 3.0 ⁇ m.
  • the width (line width) of the pattern in the 30 ⁇ m portion after post-baking was evaluated to evaluate it as an index of sensitivity characteristics. The results are shown in Table 2 below.
  • the exposure dose was 50 mJ / cm 2 .
  • shower development was performed by discharging the developing solution which consists of 0.04 mass% potassium hydroxide aqueous solution at 23 degreeC with respect to this board
  • the development time was 1.5 times that of BT based on the time (BT: break time) until the unexposed area was completely dissolved.
  • post-baking was performed at 230 ° C. for 30 minutes.
  • the film thickness of the film of the full tone portion after post-baking was 3.0 ⁇ m.
  • the film thickness difference between the full tone portion and the halftone portion of the 10 ⁇ m circle pattern after post-baking was evaluated to evaluate it as an index of halftone characteristics. The results are shown in Table 2 below.
  • film thickness difference is 0.5 ⁇ m or more to 1.0 ⁇ m or less
  • film thickness difference is more than 1.0 ⁇ m to 2.9 um or less
  • film thickness difference is more than 2.9 ⁇ m, no pattern can be obtained
  • the film thickness difference is too large, it can be judged that the film thickness of the cured product obtained according to the exposure amount is difficult to adjust.
  • the evaluation criterion is ⁇ , spacers with different heights are easily formed. can do.
  • the liquid crystal composition was injected into a TN cell for liquid crystal evaluation (cell thickness 5 ⁇ m, electrode area 8 mm ⁇ 8 mm alignment film JALS 2096), and VHR was measured using VHR-1A (manufactured by Toyo Corporation) (measurement conditions: Pulse voltage width 60 ⁇ s, frame period 16.7 ms, wave height ⁇ 5 V, measurement temperature 60 ° C.).
  • VHR retention (%) ⁇ (VHR of liquid crystal “RS-182” before mixing with coating film) ⁇ (VHR of liquid crystal composition obtained by mixing with coating film) ⁇ / (before mixing with coating film) Liquid Crystal “RS-182” VHR) ⁇ 100 :: VHR retention rate is more than 96.0% ⁇ : VHR retention rate is 93.0% or more and less than 96.0% ⁇ : VHR retention rate is 90.0% or more and less than 93.0% ⁇ : VHR retention rate is 90 Less than 0% It can be determined that the higher the VHR retention, the better the electrical characteristics, and particularly, when the evaluation criteria are ⁇ and ⁇ , it can be determined that the electrical characteristics are superior.
  • a half tone portion (light of light) in which a circle pattern of 10 ⁇ m was formed with an exposure gap of 150 ⁇ m
  • the ultraviolet light was irradiated through a halftone negative mask having a transmittance of 50%) and a full tone portion (light transmittance of 100%).
  • the exposure dose was 50 mJ / cm 2 .
  • a shower liquid was developed on the glass substrate by discharging a 23 ° C. developer composed of a 0.04 mass% aqueous potassium hydroxide solution.
  • the development time was 1.5 times that of BT based on the time (BT: break time) until the unexposed area was completely dissolved. Thereafter, the coating was post-baked at 230 ° C. for 30 minutes.
  • the film thickness of the coating film after post-baking was measured using DEKTAKXT manufactured by Bruker. Using the measured film thickness of the coating film after prebaking and the film thickness of the coating film after postbaking, the residual film ratio was calculated by the following equation. By determining the film thickness change of the full tone portion of the 10 ⁇ m circle pattern after prebaking and after postbaking, 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 80.0% to 85.0% ⁇ : Residual film rate is 75.0% to 80.0% ⁇ : Residual film rate is 75.0 Less than% The higher the residual film rate, the higher the crosslinking density of the resist film, the less the shrinkage at post-baking, and the better the sensitivity.

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Abstract

Le but principal de la présente invention est de fournir un composé capable de former, par exemple, des objets durcis ayant d'excellentes propriétés électriques. La présente invention concerne un composé représenté par la formule générale (I) (les substituants dans la formule générale (I) sont tels que définis dans la description). Dans la formule générale (I), au moins l'un de R1, R5 et R8 est de préférence un groupe ayant un groupe hydroxyle, et R1 et/ou R8 est de préférence un groupe ayant un groupe hydroxyle.
PCT/JP2018/040205 2017-10-30 2018-10-29 Composé, composition, objet durci et procédé de production d'un objet durci WO2019088055A1 (fr)

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KR1020207005559A KR20200078476A (ko) 2017-10-30 2018-10-29 화합물, 조성물, 경화물 및 경화물의 제조 방법
CN201880061861.7A CN111132963B (zh) 2017-10-30 2018-10-29 化合物、组合物、固化物及固化物的制造方法
JP2019550389A JPWO2019088055A1 (ja) 2017-10-30 2018-10-29 化合物、組成物、硬化物及び硬化物の製造方法

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WO2022065006A1 (fr) 2020-09-28 2022-03-31 富士フイルム株式会社 Procédé de fabrication de stratifié, procédé de fabrication de boîtier d'antenne, stratifié et composition
WO2022131191A1 (fr) 2020-12-16 2022-06-23 富士フイルム株式会社 Composition, membrane, filtre optique, élément de capture d'image solide, appareil d'affichage d'image et capteur de rayons infrarouges
WO2022130773A1 (fr) 2020-12-17 2022-06-23 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge
WO2022196599A1 (fr) 2021-03-19 2022-09-22 富士フイルム株式会社 Film et photocapteur
WO2022202647A1 (fr) 2021-03-22 2022-09-29 富士フイルム株式会社 Composition de résine photosensible négative, produit durci, stratifié, procédé de production d'un produit durci et dispositif à semi-conducteur
WO2022210175A1 (fr) 2021-03-29 2022-10-06 富士フイルム株式会社 Composition photosensible noire, procédé de fabrication de composition photosensible noire, film durci, filtre coloré, film de protection contre la lumière, élément optique, élément de capture d'image à semi-conducteurs et unité de phare
WO2023032545A1 (fr) 2021-08-31 2023-03-09 富士フイルム株式会社 Procédé de production de produit durci, procédé de production de stratifié, procédé de fabrication de dispositif à semi-conducteur et liquide de traitement
WO2023054142A1 (fr) 2021-09-29 2023-04-06 富士フイルム株式会社 Composition, résine, film et capteur optique

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WO2021193543A1 (fr) * 2020-03-24 2021-09-30 株式会社Adeka Composé, composition, produit durci et procédé de production de produit durci
CN115052861A (zh) * 2020-03-24 2022-09-13 株式会社艾迪科 化合物、组合物、固化物及固化物的制造方法
KR20220157365A (ko) 2020-03-24 2022-11-29 가부시키가이샤 아데카 화합물, 조성물, 경화물 및 경화물의 제조 방법
WO2022065006A1 (fr) 2020-09-28 2022-03-31 富士フイルム株式会社 Procédé de fabrication de stratifié, procédé de fabrication de boîtier d'antenne, stratifié et composition
WO2022131191A1 (fr) 2020-12-16 2022-06-23 富士フイルム株式会社 Composition, membrane, filtre optique, élément de capture d'image solide, appareil d'affichage d'image et capteur de rayons infrarouges
WO2022130773A1 (fr) 2020-12-17 2022-06-23 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge
WO2022196599A1 (fr) 2021-03-19 2022-09-22 富士フイルム株式会社 Film et photocapteur
WO2022202647A1 (fr) 2021-03-22 2022-09-29 富士フイルム株式会社 Composition de résine photosensible négative, produit durci, stratifié, procédé de production d'un produit durci et dispositif à semi-conducteur
WO2022210175A1 (fr) 2021-03-29 2022-10-06 富士フイルム株式会社 Composition photosensible noire, procédé de fabrication de composition photosensible noire, film durci, filtre coloré, film de protection contre la lumière, élément optique, élément de capture d'image à semi-conducteurs et unité de phare
WO2023032545A1 (fr) 2021-08-31 2023-03-09 富士フイルム株式会社 Procédé de production de produit durci, procédé de production de stratifié, procédé de fabrication de dispositif à semi-conducteur et liquide de traitement
WO2023054142A1 (fr) 2021-09-29 2023-04-06 富士フイルム株式会社 Composition, résine, film et capteur optique

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CN111132963B (zh) 2023-11-24
KR20200078476A (ko) 2020-07-01

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