Classifications

• • 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
  • 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
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters

Definitions

• the present invention relates to an oxime ester compound and a polymerization initiator containing the same.
• the polymerizable composition is obtained by adding a polymerization initiator to an ethylenically unsaturated compound and can be polymerized and cured by irradiating it with energy rays (light). It is used in various photoresists and the like.
• Patent Document 1 proposes an oxime ester photopolymerization initiator having a carbazole skeleton
• Patent Document 2 has an oxime ester compound having a triarylamine skeleton.
• Polymerization initiators have been proposed.
• the polymerizable composition containing a colorant such as a color filter is required to have high sensitivity, and it is necessary to increase the concentration of the polymerization initiator in the resist.
• an object to be solved by the present invention is to provide a polymerization initiator having excellent sensitivity, good solubility in a solvent, and high transmittance in the visible light region of the obtained cured product. .. Specifically, an object of the present invention is to provide an oxime ester compound useful as a polymerization initiator used in a polymerizable composition and a polymerization initiator containing the oxime ester compound.
• the present invention is a compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) in the same molecule.
• R 1 and R 2 each independently contain one or more of a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group.
• n 0 or 1 and represents * Represents a bond
• the plurality of R 1 , R 2 and n existing may be the same or different.
• ⁇ Group A>: -O-, -CO-, -COO-, -OCO-, -NR 3-, -NR 3 CO- , -S- R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
• R 4 is a group in which one or more of a hydrocarbon group having 1 to 20 carbon atoms or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following ⁇ Group B>, carbon.
• a heterocyclic group having 2 to 10 atoms, a heterocyclic group having 3 to 20 carbon atoms, or a methylene group in the heterocyclic group is composed of a divalent group selected from the following ⁇ Group B>.
• Represents a substituted group * Represents a bond
• the plurality of R4s present may be the same or different.
• ⁇ Group B>: -O-, -CO-, -COO-, -OCO-, -NR 5-, -NR 5 CO- , -S- R5 represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
• the compound of the present invention a polymerization initiator containing the same, a polymerizable composition containing the polymerization initiator, a cured product thereof, a color filter, and a method for producing the cured product will be described in detail based on preferred embodiments. explain.
• the compound of the present invention is a compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) in the same molecule.
• R 1 and R 2 each independently contain one or more of a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group.
• n 0 or 1 and represents * Represents a bond
• the plurality of R 1 , R 2 and n existing may be the same or different.
• ⁇ Group A>: -O-, -CO-, -COO-, -OCO-, -NR 3-, -NR 3 CO- , -S- R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
• R 4 is a group in which one or more of a hydrocarbon group having 1 to 20 carbon atoms or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following ⁇ Group B>, carbon.
• a heterocyclic group having 2 to 10 atoms, a heterocyclic group having 3 to 20 carbon atoms, or a methylene group in the heterocyclic group is composed of a divalent group selected from the following ⁇ Group B>.
• Represents a substituted group * Represents a bond
• the plurality of R4s present may be the same or different.
• ⁇ Group B>: -O-, -CO-, -COO-, -OCO-, -NR 5-, -NR 5 CO- , -S- R5 represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
• halogen atom in the above general formula (I) examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the hydrocarbon group having 1 to 20 carbon atoms in the general formula (I) and the general formula (II) may be a group having 1 to 20 carbon atoms composed of a carbon atom and a hydrogen atom, and is particularly limited. Examples thereof include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 20 carbon atoms is a hydrocarbon group that does not contain an aromatic hydrocarbon ring and a heterocyclic ring, and may have a substituent.
• An aliphatic hydrocarbon group having a substituent is a group having a structure in which one or more hydrogen atoms in the aliphatic hydrocarbon group are substituted with a substituent.
• the unsubstituted aliphatic hydrocarbon group includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cyclo having 4 to 20 carbon atoms. Alkylalkyl groups and the like can be mentioned.
• examples of the aliphatic hydrocarbon group having a substituent include a group in which one or more hydrogen atoms in the unsubstituted aliphatic hydrocarbon group are substituted with a substituent, and examples thereof include the substituent.
• Halogen atom cyano group, nitro group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group and the like.
• the alkyl group having 1 to 20 carbon atoms may be linear or branched.
• Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecylic, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
• the branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, and iso-heptyl. , Tert-Heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, isononyl and the like.
• the alkenyl group having 2 to 20 carbon atoms may be linear or branched. Further, it may be a terminal alkenyl group having an unsaturated bond at the end, or an internal alkenyl group having an unsaturated bond inside. Examples of the terminal alkenyl group include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl and the like.
• Examples of the internal alkenyl group include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, Examples thereof include 4-dodecenyl and 4,8,12-tetradecatorienylallyl.
• Examples of the cycloalkyl group having 3 to 20 carbon atoms include a saturated monocyclic alkyl group having 3 to 20 carbon atoms, a saturated polycyclic alkyl group having 3 to 20 carbon atoms, and rings of these groups. Examples thereof include groups having 4 to 20 carbon atoms in which one or more hydrogen atoms are substituted with alkyl groups.
• Examples of the saturated monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.
• Examples of the saturated polycyclic alkyl group include adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [11.1] pentanyl and the like.
• Examples of the alkyl group that replaces the hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified as the above-mentioned alkyl group having 1 to 20 carbon atoms.
• Examples of the group in which one or more hydrogen atoms in the ring of the saturated polycyclic alkyl group are substituted with an alkyl group include bornyl and the like.
• the cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with a cycloalkyl group.
• the cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of the cycloalkylalkyl group having a monocyclic cycloalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, and cyclooctylmethyl.
• Examples thereof include 2-cyclononylethyl and 2-cyclodecylethyl.
• Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms having a polycyclic cycloalkyl group include 3-adamantylpropyl and 3-decahydronaphthylpropyl.
• the aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms is a hydrocarbon group containing an aromatic hydrocarbon ring and not containing a heterocycle, and may have an aliphatic hydrocarbon group as a substituent. May have.
• the aromatic hydrocarbon ring-containing group having a substituent is a group having a structure in which one or more hydrogen atoms in the aromatic hydrocarbon ring-containing group are substituted with a substituent.
• Examples of the unsubstituted aromatic hydrocarbon ring-containing group include an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.
• Examples of the aromatic hydrocarbon ring-containing group having a substituent include a group in which one or more hydrogen atoms in the above-mentioned unsubstituted aromatic hydrocarbon ring-containing group are substituted with a substituent, and the like.
• Examples of the group include a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group or an isocyanate group.
• the aryl group having 6 to 20 carbon atoms may have a monocyclic structure, a condensed ring structure, or a chain of two aromatic hydrocarbon rings.
• aryl group having a monocyclic structure examples include phenyl, trill, xsilyl, ethylphenyl, 2,4,6-trimethylphenyl and the like.
• aryl group of the fused ring structure examples include naphthyl, anthrasenyl, phenanthryl, pyrenyl and the like.
• the aryl group in which two aromatic hydrocarbon rings are linked may be one in which two aromatic hydrocarbon rings having a monocyclic structure are linked, and the aromatic hydrocarbon ring having a monocyclic structure and the aromatic having a fused ring structure are aromatic.
• the group hydrocarbon ring may be linked, or the aromatic hydrocarbon ring having a fused ring structure and the aromatic hydrocarbon ring having a fused ring structure may be linked.
• Examples of the linking group connecting the two aromatic hydrocarbon rings include a single bond, a sulfide group (—S—) and a carbonyl group.
• Examples of the aryl group in which two aromatic hydrocarbon rings having a monocyclic structure are linked include biphenyl, diphenyl sulfide, benzoyl phenyl and the like.
• the arylalkyl group having 7 to 20 carbon atoms is a group in which one or more hydrogen atoms in the alkyl group are substituted with an aryl group.
• Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and naphthylpropyl groups.
• the heterocyclic group in the above general formula (I) and the above general formula (II) is a group obtained by removing one hydrogen atom from the heterocyclic compound.
• heterocyclic group having 2 to 10 carbon atoms examples include a pyridyl group, a quinolyl group, a thiazolyl group, a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group, a morpholylfuran group, a methylthiophene group, a hexylthiophene group, and a benzothiophene group.
• the heterocyclic group having 2 to 10 carbon atoms may have a substituent, and the substituents include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH and -SO 2 H. And so on.
• the heterocyclic-containing group in the general formula (I) and the above general formula (II) is a group in which a hydrogen atom in a hydrocarbon group is substituted with a heterocyclic group.
• heterocyclic group having 3 to 20 carbon atoms examples include a group in which one or more hydrogen atoms of an alkyl group are replaced with a heterocycle, and the heterocyclic group has 2 to 10 carbon atoms. Examples of the heterocyclic group of the above are mentioned.
• the heterocyclic ring-containing group having 3 to 20 carbon atoms may have an aromatic hydrocarbon ring-containing group, an aliphatic hydrocarbon group, or a substituent. good.
• substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH and -SO 2H .
• the "carbon atom number 3 to 20" of the heterocyclic ring-containing group having 3 to 20 carbon atoms is the total number of carbon atoms of the heterocyclic ring-containing group.
• the heterocyclic-containing group may be a heterocyclic ring in which a heterocyclic ring and an aromatic hydrocarbon ring having a monocyclic structure are linked, or a heterocyclic ring in which an aromatic hydrocarbon ring having a fused ring structure is linked.
• the linking group connecting the two aromatic hydrocarbon rings include a single bond and a carbonyl group.
• the heterocyclic-containing group in which the heterocycle and the aromatic hydrocarbon ring having a monocyclic structure are linked include benzothiophene and the like.
• a group in which two or more of the hydrocarbon group and the methylene group in the heterocyclic ring-containing group in the general formula (I) are substituted with a divalent group selected from the above ⁇ Group A> includes a plurality of divalent groups. It does not have an adjacent structure.
• the plurality of divalent groups may be the same or different. The same applies to a group in which two or more of the hydrocarbon group and the heterocyclic-containing group in the general formula (II) are substituted with a divalent group selected from the above ⁇ Group B>.
• the number of carbon atoms of a group defines the number of carbon atoms of the group after the hydrogen atom in the group is substituted with a substituent.
• the carbon atom number 1 to 20 refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the number of carbon atoms before.
• the number of carbon atoms of a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group defines the number of carbon atoms of the group before the replacement.
• the methylene group in the alkyl group having 1 to 20 carbon atoms is replaced with a divalent group
• the methylene group in the alkyl group is replaced with a divalent group in 1 to 20 carbon atoms. It refers to the number of carbon atoms before being replaced, not the number of carbon atoms after being replaced.
• n in the general formula (I) is 1 is preferable because it has high sensitivity, excellent solubility in a solvent, and the obtained cured product has excellent transparency.
• R 1 in the general formula (I) is a cycloalkylalkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable because of its high sensitivity, and particularly 4 to 4 carbon atoms.
• Compounds that are 10 cycloalkylalkyl groups or phenyl groups are preferred.
• R 2 in the general formula (I) is an alkyl group having 1 to 10 carbon atoms is preferable because of its high sensitivity, and a compound having an alkyl group having 1 to 4 carbon atoms is more preferable, particularly methyl.
• the underlying compound is preferred.
• R 2 in the general formula (I) is a branched alkyl group because it has excellent solubility in a solvent.
• R 4 in the general formula (II) is an alkoxy group having 1 to 10 carbon atoms is preferable because of its high sensitivity, and a compound having an alkoxy group having 1 to 4 carbon atoms is more preferable, and methoxy is particularly preferable.
• the underlying compound is preferred.
• the compound of the present invention has high sensitivity and excellent solubility in a solvent, it is preferable that the compound has a structure represented by the following general formula (III).
• a 1 represents an aromatic ring having 6 to 20 carbon atoms.
• R 11 represents a group represented by the above general formula (I).
• R 12 is a group represented by the above general formula (II), a hydrocarbon group having 1 to 20 carbon atoms substituted with the group represented by the above general formula (II), or a methylene group in the hydrocarbon group.
• a group in which one or more of the above is substituted with a divalent group selected from the following ⁇ Group C>, a heterocyclic group having 2 to 10 carbon atoms substituted with a group represented by the above general formula (II), or a heterocyclic group having 2 to 10 carbon atoms.
• One or more of the heterocyclic group having 3 to 20 carbon atoms substituted with the group represented by the general formula (II) or the methylene group in the heterocyclic group is selected from the following ⁇ Group C> 2 Represents a group substituted with a valence group, In R 13 , one or more of a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is independently selected from the following ⁇ Group C> 2
• One or more of a group substituted with a valent group, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, or a methylene group in the heterocycle-containing group is described in the following ⁇ group.
• a represents an integer of 1 to 20, and when a is an integer of 2 or more, a plurality of existing R 11s may be the same or different.
• b represents an integer of 1 to 20, and when b is an integer of 2 or more, a plurality of existing R 12s may be the same or different.
• c represents an integer of 0 to 20, and when c is an integer of 2 or more, a plurality of R 13s existing may be the same or different.
• a + b + c is 20 or less.
• ⁇ Group C>: -O-, -CO-, -COO-, -OCO-, -NR 14- , -NR 14 CO-, -S- R 14 represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
• Examples of the aromatic ring having 6 to 20 carbon atoms in the general formula (III) include an aromatic hydrocarbon ring and an aromatic heterocycle, and specifically, indole, carbazole, diphenylsulfide, fluorene, and triarylamine. , Cmarin, benzene, diphenyl, naphthalene, anthracene and the like.
• the hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, and the heterocyclic group having 3 to 20 carbon atoms in the general formula (III) are described in the general formula (I). It is the same as a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, and a heterocycle-containing group having 3 to 20 carbon atoms.
• a compound in which c in the general formula (III) is an integer of 1 to 20 is preferable, and since the compound has excellent solubility in a solvent, a compound having a branched alkyl group or a cycloalkyl group having 3 to 20 carbon atoms in the molecule is preferable.
• a compound in which one or more of R 13 is a branched alkyl group or a cycloalkyl group having 3 to 20 carbon atoms is more preferable, and a compound in which a branched alkyl group having 3 to 20 carbon atoms is more preferable, particularly a carbon atom.
• a compound having a number of 3 to 10 branched alkyl groups is preferable.
• a compound having a structure in which A 1 of the general formula (III) is represented by the following general formula (IV ⁇ ) or the following general formula (IV ⁇ ) is preferable because of its high sensitivity, and is particularly represented by the following general formula (IV ⁇ ).
• Compounds having a structure are preferable.
• the above general formula (IV ⁇ ) represents the structure when the groups represented by R 11 , R 12 and R 13 in the above general formula (III) are replaced with hydrogen atoms, and X 1 in the formula.
• X 2 represents a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CH 2 , CO, NH or PH.
• the general formula (IV ⁇ ) represents the structure when the groups represented by R 11 , R 12 and R 13 in the general formula (III) are replaced with hydrogen atoms.
• a compound in which A 1 is represented by the above general formula (IV ⁇ ), X 1 is NR 13 , and X 2 is a single bond is particularly preferable because of its excellent sensitivity.
• R 13 is a branched alkyl group or a cycloalkyl group having 3 to 20 carbon atoms is preferable because it has excellent solubility in a solvent, and a compound having a branched alkyl group having 3 to 20 carbon atoms is more preferable.
• a compound which is a branched alkyl group having 3 to 10 carbon atoms is preferable.
• a compound in which a is an integer of 1 to 3 is preferable because it is excellent in solubility in a solvent and sensitivity, and a compound in which a is 1 is particularly preferable.
• a compound in which b is an integer of 1 to 3 is preferable because it is excellent in solubility in a solvent and sensitivity, and a compound in which b is 1 is particularly preferable.
• a compound in which c is an integer of 1 to 3 is preferable because it is excellent in solubility in a solvent and sensitivity, and a compound in which c is 1 is particularly preferable.
• Preferred specific examples of the compound of the present invention include the following compounds.
• the compound of the present invention can be produced by a known method.
• the compound represented by the above general formula (III) can be produced by the method shown below.
• the ketone compound 1 is obtained by reacting a known aromatic ring-containing compound with an acid chloride, and the ketone compound 1 is reacted with a chloride having a diketonyl group.
• the ketone compound 1' is obtained in 1', and the ketone compound 1'is reacted with hydroxylamine hydrochloride to obtain the oxime compound 1.
• the oxime compound 1 is reacted with an acid anhydride or an acid chloride in the presence of triethylamine (TEA) to obtain a group represented by the general formula (I) and a group represented by the general formula (II).
• TAA triethylamine
• a compound having the same molecule can be produced. It can also be manufactured by the method described in Japanese Patent No. 4223071.
• a ketone compound 2 is obtained by reacting a known aromatic ring-containing compound with an acid chloride, and the ketone compound 2 is reacted with a chloride having a diketonyl group.
• the ketone compound 2' is obtained in 1
• the oxime compound 2 is obtained by reacting the ketone compound 2'with isobutyl nitrite.
• the group represented by the general formula (I) and the group represented by the general formula (II) are contained in the same molecule. The compound having the above can be produced.
• the compound of the present invention described above is useful as a polymerization initiator, specifically a radical polymerization initiator, particularly a photopolymerization initiator or a thermal polymerization initiator. Furthermore, the compound of the present invention can also be suitably used as a base generator and a sensitizer.
• the polymerization initiator of the present invention contains at least one compound having the group represented by the general formula (I) and the group represented by the general formula (II) in the same molecule.
• the content of the compound in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass, because the sensitivity is high and the obtained cured product is excellent in transparency.
• the polymerizable composition of the present invention contains the polymerization initiator (A) and the ethylenically unsaturated compound (B) of the present invention, and as optional components, a colorant (C), an alkali-developable compound (D), and an inorganic substance. It may be contained in combination of components such as a compound and a solvent.
• the polymerization initiator (A) contains at least one compound having a group represented by the general formula (I) and a group represented by the general formula (II) in the same molecule, and is ethylene. It is useful as a radical polymerization initiator of the sex unsaturated compound (B).
• the above-mentioned polymerization initiator (A) may be used in combination with another polymerization initiator.
• the other polymerization initiator is not particularly limited as long as it generates radicals by light irradiation or heating, and conventionally known compounds can be used.
• oxime ester compounds, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds and the like are preferable.
• Examples of the oxime ester compound include compounds having a group represented by the above general formula (I), and since they have good sensitivity, they can be preferably used in the polymerizable composition of the present invention.
• acetophenone compound examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2-.
• benzyl compound examples include benzyl and the like.
• benzophenone compound examples include benzophenone, methyl o-benzoylbenzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenylsulfide.
• thioxanthone-based compound examples include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.
• polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1-).
• phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1-).
• titanium can be mentioned.
• radical initiators include ADEKA PTOMER N-1414, N-1717, N-1919, ADEKA ARCLUS NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE. 01, IRGACURE OXE 02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, manufactured by TRONLY); and the like.
• the content of the polymerization initiator (A) is not particularly limited, but the sensitivity of the polymerizable composition to 100 parts by mass of the radically polymerizable compound having an ethylenically unsaturated group. It is preferably 0.1 to 70 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 1 to 5 parts by mass.
• the ethylenically unsaturated compound (B) may be any compound having an ethylenically unsaturated bond and no acidic group.
• the ethylenically unsaturated compound (B) is not particularly limited, and those conventionally used in polymerizable compositions can be used.
• ethylene, propylene, butylene, isobutylene, vinyl chloride and vinylidene chloride can be used.
• Vinylidene fluoride unsaturated aliphatic hydrocarbons such as tetrafluoroethylene; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more.
• Unsaturated polybasic acids such as polyfunctional (meth) acrylates having (meth) acryloyl groups; (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid Glycidyl, the following compound No. A1 to No.
• A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl acrylate, (meth) isononyl acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, (meth) aminopropyl acrylate, (meth) dimethylaminopropyl acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth)
• Lipid-conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; mono (meth) at the end of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
• Macromonomers having an acryloyl group vinyl chloride, vinylidene chloride, divinylsuccinate, diallylphthalate, triallyl phosphate, triallyl isocyanurate, vinylthioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, Examples thereof include vinyl pyridine, a vinyl urethane compound of a hydroxyl group-containing vinyl monomer and a polyisocyanate compound, and a vinyl epoxy compound of a hydroxyl group-containing vinyl monomer and a polyepoxy compound.
• a commercially available product can also be used as the ethylenically unsaturated compound (B).
• Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 manufactured by Nippon Kayaku Co., Ltd.
• Aronix M-140, M-215, M-350 manufactured by Toagosei Co., Ltd.
• NK examples thereof include esters A-DPHA-TMPT, A-DCP, A-HD-N, A-9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
• the ethylenically unsaturated compound can be used alone or in combination of two or more kinds, and when two or more kinds are mixed and used, they are copolymerized in advance and used as a copolymer. You may.
• the polymerizable composition of the present invention may further contain a colorant (C) to form a colored polymerizable composition.
• a colorant (C) examples include pigments, dyes, natural pigments and the like. These colorants (C) can be used alone or in combination of two or more.
• Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolin compounds; quinacridone compounds; antanthrone compounds; perinone compounds.
• Perylene compound Diketopyrrolopyrrole compound; Thioindigo compound; Dioxazine compound; Triphenylmethane compound; Kinophthalone compound; Naphthalenetetracarboxylic acid; Azo dye, cyanine dye metal complex compound; Lake pigment; Furness method, channel method or thermal method
• Carbon black obtained by, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin, the above carbon black is previously dispersed in a resin in a solvent, and 20 to 20 to A compound adsorbed with a resin of 200 mg / g, an acidic or alkaline surface treatment of the above carbon black, a compound having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO and CO in the volatile matter at 950 ° C.
• the total amount of oxygen calculated from CO 2 is 9 mg or more per 100 m 2 of the surface area of carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; Aniline Black, Pigment Black 7, Titanium Black; Chromium Oxide Green, Milori Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrosinate, Phosphate Ultramarine, Navy Blue, Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate, Organic or inorganic pigments such as yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, and amber can be used. These pigments can be used alone or in combination of two or more.
• pigment a commercially available pigment can also be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97. , 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223.
• Dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, aclysine dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxadin dyes, phthalocyanine dyes, Examples thereof include dyes such as cyanine dyes, and these may be used as a mixture of a plurality of dyes.
• the content of the colorant (C) in the polymerizable composition is preferably 5 to 5 to 100 parts by mass of the radically polymerizable compound having an ethylenically unsaturated group because the balance between curability and colorability is good. It is 350 parts by mass, more preferably 10 to 50 parts by mass.
• the polymerizable composition according to the present invention may further contain the alkali-developable compound (D) to prepare an alkali-developable photosensitive resin composition.
• Those containing the colorant (C) and the alkali-developable compound (D) at the same time are also referred to as a colored alkali-developable photosensitive resin composition.
• the alkali developable compound (D) is not particularly limited as long as it is a compound having an acidic group, and examples thereof include the resin described in JP-A-2004-264414.
• the alkali developable compound (D) may have an ethylenically unsaturated bond.
• a polymer having a carboxyl group is preferable because it is excellent in developability and compatibility with an ethylenically unsaturated compound and the like.
• the alkali developable compound (D) includes a copolymer of an acrylic acid ester, a phenol and / or a cresol novolak epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy compound such as an epoxy acrylate resin.
• a resin obtained by allowing an unsaturated monobasic acid to act on the epoxy group of the above and further allowing a polybasic acid anhydride to act can be used.
• the epoxy acrylate resin referred to here is an epoxy compound on which (meth) acrylic acid is allowed to act, and examples thereof include Ripoxy SPC-1000, SPC-2000, SPC-3000, and DIC manufactured by Showa Denko KK.
• Dicklite UE-777 manufactured by Japan U-Pica Company, Yupica 4015 manufactured by Japan U-Pica Company, and the like can be mentioned.
• a compound having an ethylenically unsaturated bond is preferable because the obtained polymerizable composition has excellent sensitivity.
• acrylic groups and methacrylic groups are preferable, and acrylic groups are particularly preferable.
• the polymer having a carboxyl group may be any one having a structural unit having a carboxyl group (hereinafter referred to as “structural unit (U1)”), and is not particularly limited, but is limited to a methacryloyl group, an acryloyl group, an epoxy group, and the like.
• a structural unit having a crosslinkable group such as a vinyl group, a vinyl ether group, a mercapto group, an oxetanyl group or an isocyanate group (hereinafter referred to as “structural unit (U2)”), and a structural unit having a silyl group (hereinafter referred to as “structural unit (U3)”).
• the polymer having a carboxyl group may have a structural unit other than the structural units (U1) to (U3) (hereinafter, referred to as“ structural unit (U4) ”).
• the structural unit (U1) may be a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter referred to as “compound (u1)”). preferable.
• Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids.
• Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloxyethyl hexahydro.
• dicarboxylic acid examples include maleic acid, fumaric acid, citraconic acid and the like; and as the anhydride of the dicarboxylic acid, the above-mentioned anhydride of the dicarboxylic acid and the like can be mentioned.
• acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride are selected from the viewpoints of copolymerizability and solubility of the obtained copolymer in the developing solution.
• the compound (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 oxylanyl (cyclo) alkyl ester, ⁇ -alkylacrylic acid oxylanyl (cyclo) alkyl ester, and a glycidyl ether compound having a polymerizable unsaturated bond;
• Examples of the polymerizable unsaturated compound having an oxetanyl group include (meth) acrylic acid esters having an oxetanyl group.
• the compound (u2) include oxylanyl (meth) acrylate (cyclo) alkyl ester, for example, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 4-hydroxybutyl.
• Examples of the ⁇ -alkylacrylic acid oxylanyl (cyclo) alkyl ester include ⁇ -ethylacrylic acid glycidyl, ⁇ -n-propylacrylic acid glycidyl, ⁇ -n-butylacrylic acid glycidyl, and ⁇ -ethylacrylic acid 6,7-.
• Examples thereof include epoxy heptyl and ⁇ -ethylacrylic acid 3,4-epoxycyclohexyl.
• Examples of the glycidyl ether compound having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.
• Examples of the (meth) acrylic acid ester having an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxy).
• These compounds (u2) can be used alone or in admixture of two or more.
• the structural unit having a (meth) acryloyloxy group can be preferably used as the structural unit having a methacryloyl group or an acryloyl group.
• the structural unit having a (meth) acryloyloxy group is obtained by reacting a (meth) acrylic acid ester having an epoxy group with a carboxyl group in a polymer.
• the structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following general formula (U).
• R 1000 and R 1001 are independently hydrogen atoms or methyl groups, respectively.
• u is an integer from 1 to 6.
• R 1002 is a divalent group represented by the following general formula (U ⁇ ) or the following general formula (U ⁇ ), and * represents a bond.
• R1003 is a hydrogen atom or a methyl group.
• * indicates a bond.
• R 1002 has a general formula (U ⁇ ).
• R 1002 in the general formula (U) becomes the general formula (U ⁇ ).
• a weight containing a polymerization inhibitor is preferable in the presence of a suitable catalyst, if necessary.
• An unsaturated compound having an epoxy group is added to the combined solution, and the mixture is stirred under heating for a predetermined time.
• the catalyst include tetrabutylammonium 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 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 all the structural units of the polymer having a carboxyl group. It is preferably 20 mol% to 50 mol%, and more preferably 20 mol% to 50 mol%.
• 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, and 3- (meth). Acryloyloxypropyltriethoxysilane and the like can be mentioned.
• the above-mentioned compound (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 is a polymerizable unsaturated compound other than the above (u1) to (u3) (hereinafter referred to as “compound (u4)”). It is preferably a structural unit from which it is derived.
• the compound (u4) include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, and unsaturated dicarboxylic acid dialkyl ester.
• examples thereof include (meth) acrylic acid esters having an oxygen-containing complex 5-membered ring or an oxygen-containing complex 6-membered ring, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds.
• Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, n-propyl (meth) acrylic acid, i-propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and sec-butyl (meth) acrylic acid. , (Meta) t-butyl acrylate and the like.
• Examples of the (meth) acrylic acid cycloalkyl ester include (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, and (meth) acrylic acid tricyclo [5.2.1.0 2,6 ] decane-8. -Il, 2- (tricyclo [5.2.1.0 2,6 ] decane-8-yloxy) ethyl (meth) acrylate, isoboronyl (meth) acrylate and the like can be mentioned.
• Examples of the (meth) acrylic acid aryl ester include phenyl acrylic acid, and examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylic acid.
• Examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate and diethyl fumaric acid.
• Examples of the (meth) acrylic acid ester having an oxygen-containing complex 5-membered ring or an oxygen-containing complex 6-membered ring include (meth) acrylate tetrahydropyran-2-yl, (meth) acrylate tetrahydropyran-2-yl, (meth). ) 2-Methyltetrahydropyran-2-yl acrylate and the like can be mentioned.
• vinyl aromatic compound examples include styrene and ⁇ -methylstyrene.
• conjugated diene compound examples include 1,3-butadiene, isoprene and the like.
• Examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.
• Decane-8-yl, styrene, p-methoxystyrene, methacrylic acid tetrahydrofuran-2-yl, 1,3-butadiene and the like are preferable.
• the compound (u4) can be used alone or in combination of two or more.
• the polymer having a preferable carboxyl group according to the present invention is synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the above compounds (u1) to (u4) in the following ratios, respectively. be able to.
• the (meth) acryloyloxy group is obtained by reacting the carboxyl group in the structural unit derived from the compound (u1) in the obtained copolymer with the (meth) acrylic acid ester having an epoxy group. It can have a structural unit to have.
• the compounds (u1) to (u4) are preferably used in the following ranges.
• 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 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. Since high resolution is achieved without impairing the above, it is preferable because a cured film having a highly balanced characteristic balance can be provided even with a high-definition pattern.
• the weight average molecular weight (Mw) of the polymer having a carboxyl group is preferably 2000 to 100,000, more preferably 5000 to 50,000.
• Mw weight average molecular weight
• the method for measuring the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).
• the polymer having a carboxyl group can be produced by polymerizing a mixture of the above-mentioned polymerizable unsaturated compound in a suitable solvent, preferably in the presence of a radical polymerization initiator.
• Examples of the solvent used for the polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and dipropylene.
• Examples thereof include glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol and the like. These solvents can be used alone or in admixture of two or more.
• the radical polymerization initiator is not particularly limited, and is, 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), 2,2 '-Azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds can be mentioned. These radical polymerization initiators can be used alone or in admixture of two or more.
• An unsaturated monobasic acid is allowed to act on the epoxy group of the polymer described in JP-A-2005-234362, which is a polymer having a carboxyl group, and the epoxy compound represented by the following general formula (VI). Further, a polymer obtained by allowing a polybasic acid anhydride to act is preferable.
• X 21 is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, and -SO. 2- , -SS-, -SO-, -CO-, -OCO- or the group represented by the following (VI ⁇ ), (VI ⁇ ) or the following (VI ⁇ ), and the alkylidene group is substituted with a halogen atom.
• R 61 and R 62 may independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom.
• the above-mentioned alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and when a plurality of R 61 and R 62 are present, they may be the same or different, and f is 0. It is an integer of 4 to 4, g is an integer of 0 to 4, m is an integer of 0 to 10, and the optical isomer present when m is not 0 may be any isomer.
• Z 1 is a hydrogen atom, a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or a phenyl group having 1 to 10 carbon atoms. It represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and Y 1 is an alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms.
• alkoxy group of 10 and an alkenyl group or a halogen atom having 2 to 10 carbon atoms are shown, and the above-mentioned alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and j represents an integer of 0 to 5. * Represents a bond.
• Y 2 and Z 2 are independently substituted with an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and may be substituted with a halogen atom.
• the methylene group in the group representing the heterocyclic group or halogen atom of 20 and represented by Y 2 may be substituted with an unsaturated bond, —O— or —S—, and Z 2 is adjacent.
• Z 2 may form a ring with each other, where k represents an integer of 0 to 4, r represents an integer of 0 to 8, s represents an integer of 0 to 4, and t represents an integer of 0 to 4. , The total number of s and t is an integer of 2 to 4, and * represents a bond.
• Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, and hydroxypropyl acrylate.
• -Malate, dicyclopentadiene malate, etc. can be mentioned.
• polybasic acid anhydride examples include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, and trimellitic acid.
• Anhydride Pyromellitic Anhydride, 2,2'-3,3'-Benzophenone Tetracarboxylic Acid Anhydride, Ethylene Glycolbisanhydrotrimeritate, Gglycerol Trisanhydrotrimeritate, Hexahydroanophthalic Acid, Methyltetrahydro Phthalic anhydride, nagic acid anhydride, methyl nagic acid anhydride, trialkyltetrahydroanhydride, hexahydroanhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, Examples thereof include 2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl anhydride succinic acid, and methylhymic acid anhydride.
• the reaction molar ratio of the epoxy compound, unsaturated monobasic acid and polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of unsaturated monobasic acid are added to one epoxy group of the epoxy compound, one hydroxyl group of the epoxy adduct is used. It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0.
• the reaction of the epoxy compound, unsaturated monobasic acid and polybasic acid anhydride can be carried out according to a conventional method.
• Preferred examples of the polymer having a carboxyl group include the following [Polymer U1] and [Polymer U2].
• a polymer U1 having a weight average molecular weight Mw of 9000 was obtained by adding 74 parts by mass of glycidyl acid acid and reacting at 90 ° C. for 10 hours.
• the polymer U1 has a structural unit (U1), a structural unit (U2), and a structural unit (U4).
• a polymer U2 having a weight average molecular weight Mw of 12000 obtained by maintaining this temperature for 5 hours and polymerizing was obtained.
• the polymer U2 has a structural unit (U1), a structural unit (U2), a structural unit (U3), and a structural unit (U4).
• the alkali-developable photosensitive resin composition of the present invention which is one of the embodiments of the polymerizable composition according to the present invention, contains a polymerization initiator (A) and an ethylenically unsaturated compound (B) as essential components. And the alkali-developable compound (D), and as an optional component, a component such as an inorganic compound or a solvent is contained in combination.
• a component such as an inorganic compound or a solvent is contained in combination.
• those containing the colorant (C) are also referred to as the colored alkali-developable photosensitive resin composition according to the present invention.
• the ethylenically unsaturated compound (B) and the alkali-developable compound (D) may be the same compound, may be different, or may be used alone or in combination of two or more. ..
• the compound further has an alkali-developable property which may have an ethylenically unsaturated bond.
• Monofunctional or polyfunctional epoxy compounds can be used.
• the alkali-developable compound which may have an ethylenically unsaturated bond preferably has an acid value of a solid content in the range of 5 to 120 mgKOH / g, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably. , It is preferable to select so as to satisfy the above acid value.
• Examples of the monofunctional epoxy compound include 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, and heptyl glycidyl.
• Ether octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl.
• Glycyzyl ether propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, Benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized flaxseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4 -Vinylcyclohexane, styrene oxide
• the polyfunctional epoxy compound one or more compounds selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers can be used to obtain a (colored) alkali-developable photosensitive resin composition having better characteristics. It is preferable because it can be done.
• the bisphenol type epoxy compound an epoxy compound represented by the general formula (VI) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
• glycidyl ethers examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,8-octanediol diglycidyl ether.
• novolak type epoxy compounds such as phenol novolac type epoxy compound, biphenyl novolac type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, dicyclopentadiene novolac type epoxy compound; 3,4-epoxy-6-methyl.
• 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; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiened
• the polymerizable composition according to the present invention is an alkali-developable photosensitive resin composition
• the content of the compound having an alkali-developable property which may have an ethylenically unsaturated bond is according to the present invention.
• the alkali-developed photosensitive resin composition 1 to 20% by mass, particularly 3 to 12% by mass is preferable.
• a solvent can be further added to the polymerizable composition according to the present invention.
• a solvent capable of dissolving or dispersing each of the above components (polymerization initiator (A), ethylenically unsaturated compound (B), etc.) as needed, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, etc.
• Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Cellosolve-based solvents such as: methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol and other alcohol-based solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1- Ether ester solvents such as monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; BTX solvents
• ketones, ether ester solvents and the like particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like have good compatibility between the resist and the polymerization initiator (A) in the polymerizable composition. preferable.
• the polymerizable composition according to the present invention may contain p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, an inorganic compound, a latent additive, an organic polymer, a chain transfer agent, and a sensitization, if necessary.
• Conventional additives such as anti-aggregation agents; catalysts; effect promoters; cross-linking agents; thickeners can be added.
• a dispersant for dispersing the colorant (C) and / or the inorganic compound can be added to the polymerizable composition according to the present invention.
• the dispersant is not limited as long as it can disperse and stabilize the colorant (C) or the inorganic compound, and a commercially available dispersant, for example, the BYK series manufactured by Big Chemie can be used.
• the latent additive is represented by the following general formulas (A) to (C).
• the ring A 2 is a six-membered alidal ring, an aromatic ring or a heterocyclic ring, and R 81 , R 82 , R 83 , R 84 and R 85 are hydrogen atom, halogen atom and cyano.
• R 81 , R 82 , R 83 , R 84 and R 85 is not a hydrogen atom.
• R 86 has an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and 2 to 2 carbon atoms. Represents 20 heterocyclic-containing groups or trialkylsilyl groups.
• R 92 , R 93 , R 94 and R 95 are an alkyl group having 1 to 40 carbon atoms and carbon which may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group and a substituent. Represents an aryl group having 6 to 20 atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group containing 2 to 20 carbon atoms. At least one of R 92 , R 93 , R 94 and R 95 is not a hydrogen atom.
• X8 is -CR 97 R 98- , -NR 99- , a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, and an aromatic hydrocarbon having 6 to 35 carbon atoms.
• the methylene group in the aliphatic hydrocarbon group is -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a bonding group in which oxygen atoms are combined without being adjacent to each other.
• R 97 and R 98 represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl alkyl group having 7 to 20 carbon atoms.
• Z 5 and Z 6 are independently bonded, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO 2- , -SS-, -SO- or >
• R 99 and R 100 are hydrogen atoms, aliphatic hydrocarbon groups having 1 to 35 carbon atoms which may have substituents, and aromatics having 6 to 35 carbon atoms which may have substituents. It represents a heterocyclic group having 2 to 35 carbon atoms which may have a hydrocarbon group or a substituent, and * represents a bond.
• Y 11 is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, and an aromatic group having 6 to 35 carbon atoms.
• Z 11 , Z 12 and Z 13 are independently directly bonded, -O-, -S-,> CO, -CO-O-, respectively.
• Y 12 is a carbon atom, an aliphatic hydrocarbon group having a tetravalent carbon atom number of 1 to 35, an aromatic hydrocarbon group having a carbon atom number of 6 to 35, or a carbon atom number of 2 to 2. Representing 35 heterocyclic groups, the methylene group in the aliphatic hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-.
• Z 11 to Z 14 are independently groups having the same range as the groups represented by Z 11 to Z 13 in the general formula (3).
• Y 13 is a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms.
• the methylene group in the aliphatic hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z 11 to Z 15 Are independently the groups in the same range as the groups represented by Z 11 to Z 13 in the general formula (3).
• Y 14 is a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms.
• the methylene group in the aliphatic hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z 11 to Z 16 may be substituted.
• Z 11 to Z 16 may be substituted.
• examples of the organic polymer capable of improving the characteristics of the cured product by using an organic polymer include polystyrene and polymethyl.
• a sulfur atom-containing compound is generally used.
• Alkyl iodide compounds trimethylolpropanetris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopro Pionate, Butanediol Bisthioglycolate, Ethylene Glycol Bisthioglycolate, Trimethylol Propantristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanetristhiopropionate, Trimethylol Propantristhiopropionate, Trimethylol Propantristhioglycolate, Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate
• Examples thereof include aliphatic polyfunctional thiol compounds such as C1, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, and Karenz MT BD1, PE1, NR1 manufactured by Showa Denko KK.
• the surfactant examples include fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher amine halogens. Cationic surfactants such as acid salts and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; Amphoteric surfactants; Silicone surfactants Such surfactants can be used, and these may be used in combination.
• fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
• anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher
• silane coupling agent for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, among which isocyanate groups, acryloyl groups, and methacryloyl groups such as KBE-9007, KBM-5103, KBM-502, and KBE-403 can be used.
• a silane coupling agent having a group or an epoxy group is preferably used.
• Examples of the melamine compound include all or part of the active trimethylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) trimethylol melamine, (poly) trimethylol glycol uryl, (poly) trimethylol benzoguanamine, and (poly) trimethylol urea. Examples thereof include compounds in which at least two) are alkyl etherified.
• examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, which may be the same or different from each other. Further, the methylol group which has not been alkyl etherified may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
• hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycol uryl, tetrabutoxymethyl glycol uryl and the like can be used.
• alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.
• an existing leveling agent can be used as long as it has a leveling effect, and among them, a silicone-based leveling agent and a fluorine-based leveling agent can be particularly preferably used.
• silicone-based leveling agent a commercially available silicone-based leveling agent can be used, for example, BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322.
• fluorine-based leveling agent a commercially available fluorine-based leveling agent can be used, for example, Optool DSX, Optool DAC-HP (all manufactured by Daikin Industries); Surflon S-242, Surflon S-243, Surflon S-420, Surflon.
• any component excluding the polymerization initiator (A), the ethylenically unsaturated compound (B), the colorant (C), the alkali-developable compound (D), the solvent, the inorganic compound, and the organic polymer is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the ethylenically unsaturated compound (B).
• the cured product of the present invention is obtained by curing the above-mentioned polymerizable composition or alkaline developable photosensitive resin composition.
• the polymerizable composition, alkali-developable photosensitive resin composition or cured product according to the present invention is a photocurable paint or varnish; a photocurable adhesive; a printed substrate; a display device (color television, PC monitor, mobile information terminal). , Digital camera, etc.) Color filter in liquid crystal display element of color display; Color filter of CCD image sensor; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Dental composition; Gel coat; Photoresists for electronic engineering; Electroplated resists; Etching resists; Dry films; Solder resists; Resistors for forming structures of various display devices; Compositions for encapsulating electrical and electronic components; Solder resists; Magnetic recording Materials; Micromechanical parts; Waveguides; Optical switches; Plating masks; Etching masks; Color test systems; Glass fiber cable coatings; Screen printing stencil; Materials for manufacturing three-dimensional objects by stereolithography; For holographic recording Materials; Image recording materials; Microelectronic circuits; Decolorizing
• the polymerizable composition or the alkali-developable photosensitive resin composition according to the present invention is useful as a polymerizable composition for a color filter because it can form a high-luminance cured product.
• the polymerizable composition or the alkali-developable photosensitive resin composition according to the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for the purpose of forming a protrusion for a vertically oriented liquid crystal display element.
• it is useful as a polymerizable composition for simultaneously forming protrusions and spacers for a vertically oriented liquid crystal display element.
• the polymerizable composition or the alkali-developable photosensitive resin composition is obtained by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, etc., and is used for soda glass, quartz glass, and semiconductors. It can be applied on a supporting substrate such as a substrate, metal, paper, or plastic. Further, it is also possible to apply it once on a support substrate such as a film and then transfer it onto another support substrate, and there is no limitation on the application method thereof.
• the method for producing a cured product of the above-mentioned polymerizable composition includes a step of curing the polymerizable composition by light irradiation or a step of curing by heating.
• Light sources used in the process of curing by light irradiation include ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury steam arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, etc. It is possible to use electromagnetic energy having a wavelength of 2000 to 7000 angstroms obtained from tungsten lamps, excimer lamps, sterilizing lamps, light emitting diodes, CRT light sources, etc., and high energy rays such as electron beams, X-rays, and radiation. Preferred examples thereof include ultra-high pressure mercury lamps, mercury steam arc lamps, carbon arc lamps, xenon arc lamps and the like that emit light having a wavelength of 300 to 450 nm.
• the laser direct drawing method which forms an image directly from digital information of a computer or the like without using a mask by using a laser beam as an exposure light source, improves not only productivity but also resolution and position accuracy.
• the laser light light having a wavelength of 340 to 430 nm is preferably used, but an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, and a krypton ion laser are used.
• Various semiconductor lasers, YAG lasers and the like that emit light in the visible to infrared region are also used. When these lasers are used, a sensitizing dye that absorbs the visible to infrared region is added.
• the heating temperature is appropriately set according to the thickness of the coating film or the cured product of the composition to be treated, the polymerization initiation temperature of the thermal polymerization initiator, etc., and is, for example, 50 ° C. or higher and 250 ° C. or lower.
• the temperature is preferably 100 ° C. or higher and 200 ° C. or lower, and particularly preferably 100 ° C. or higher and 150 ° C. or lower.
• the heating temperature indicates, for example, the surface temperature of the polymerizable composition or the cured product.
• the heating time can be 10 minutes or more and 2 hours or less.
• the heating time indicates the time for maintaining the temperature after the composition or the cured product reaches a predetermined temperature.
• the above spacer for a liquid crystal display panel is obtained by (1) a step of forming a coating film of the polymerizable composition according to the present invention on a substrate, and (2) irradiating the coating film with radiation through a mask having a predetermined pattern shape. It is preferably formed by the steps of (3) baking after exposure, (4) developing the film after exposure, and (5) heating the film after development.
• the polymerizable composition according to the present invention to which an ink repellent agent is added is useful as a partition wall forming resin composition for an inkjet method, and the composition is used for a color filter, and in particular, an inkjet method having a profile angle of 50 ° or more. It is preferably used for color filter partition walls.
• an ink repellent a composition composed of a fluorine-based surfactant and a fluorine-based surfactant is preferably used.
• An optical element is formed by a method in which a partition wall formed from the polymerizable composition according to the present invention partitions the transferred body, and droplets are applied to the recesses on the partitioned transferred body by an inkjet method to form an image region. Is manufactured. At this time, it is preferable that the droplets contain a colorant and the image region is colored, and at least a partition wall separating the pixel group consisting of a plurality of colored regions and each colored region of the pixel group is provided on the substrate.
• An optical element having and manufactured by the above-mentioned method for manufacturing an optical element is preferably used.
• Example 2 Synthesis of compound 2> Compound 2 was obtained in the same manner as in Example 1 except that the bromocyclopentane used for the production of Intermediate 1-A was changed to 1-bromo-2-ethylhexane. The obtained compound was dissolved in deuterated chloroform and 1 1 H-NMR measurement was carried out. The results are shown in Table 1.
• Example 3 Synthesis of compound 3> Compound 3 was obtained in the same manner as in Example 1 except that the bromocyclopentane used for the production of Intermediate 1-A was changed to 1-bromo-2-methylpropane. The obtained compound was dissolved in deuterated chloroform and 1 1 H-NMR measurement was carried out. The results are shown in Table 1.
• Example 4 Synthesis of compound 4> Example 1 except that the bromocyclopentane used for the production of intermediate 1-A was changed to 1-bromo-2-ethylhexane and the cyclohexylpropionyl chloride used for the production of compound 1-B was changed to phenylacetyl chloride.
• Compound 4 was obtained in the same manner as in the above. The obtained compound was dissolved in deuterated chloroform and 1 1 H-NMR measurement was carried out. The results are shown in Table 1.
• the polymerizable composition was prepared according to the formulations shown in Table 3.
• A-1 Compound 1 A-2: Compound 2 A-3: Compound 3 A-4: Compound 4 A'-1: Comparative compound A'-1
• B-1 Kayarad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku Co., Ltd.)
• C-1 Blue pigment dispersion liquid No. 1
• D-1 SPC-3000 (alkali developable compound; polymer having acrylic group and carboxy group; manufactured by Showa Denko KK, solid content 42.7%, PGMEA solution)
• E-1 KBE-403 (Coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)
• F-1 PGMEA (solvent)
• the compound of the present invention has excellent solubility in a solvent. Further, as shown in Table 3, it was confirmed that the polymerizable composition using the polymerization initiator containing the compound of the present invention has excellent sensitivity, and a cured product having high brightness and high transmittance in the visible light region can be obtained. did it.
• the compound of the present invention is useful as a polymerization initiator because it has high sensitivity and excellent solubility in a solvent. Further, the polymerizable composition using the polymerization initiator containing the compound of the present invention is particularly useful as a polymerizable composition for a color filter because a cured product having a high transmittance in the visible light region can be obtained.

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• 2021
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