WO2021200815A1 - Initiateur de polymérisation radicalaire, composition, produit durci et procédé de fabrication de produit durci - Google Patents

Initiateur de polymérisation radicalaire, composition, produit durci et procédé de fabrication de produit durci Download PDF

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Publication number
WO2021200815A1
WO2021200815A1 PCT/JP2021/013268 JP2021013268W WO2021200815A1 WO 2021200815 A1 WO2021200815 A1 WO 2021200815A1 JP 2021013268 W JP2021013268 W JP 2021013268W WO 2021200815 A1 WO2021200815 A1 WO 2021200815A1
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group
carbon atoms
substituent
ring
polymerization initiator
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PCT/JP2021/013268
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English (en)
Japanese (ja)
Inventor
貴之 伊香賀
洋大 横田
良智 竹内
直美 佐藤
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株式会社Adeka
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Priority to KR1020227026855A priority Critical patent/KR20220161262A/ko
Priority to JP2022512207A priority patent/JPWO2021200815A1/ja
Priority to CN202180015284.XA priority patent/CN115151579B/zh
Publication of WO2021200815A1 publication Critical patent/WO2021200815A1/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
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • 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 a radical polymerization initiator having excellent sensitivity and storage stability.
  • a photocurable composition in which a photopolymerization initiator is added to a polymerizable compound having an ethylenically unsaturated bond is known. Since such a photocurable composition can be cured by irradiating it with energy rays (light), it is used in photocurable inks, photosensitive printing plates, various photoresists, and the like.
  • Patent Documents 1 to 7 propose the use of an oxime ester compound.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a radical polymerization initiator having excellent sensitivity stability.
  • the present invention is a radical polymerization initiator containing a compound represented by the following general formula (A) and an acid component, and the content of the acid component is represented by the above general formula (A). It is a radical polymerization initiator which is 1 ppm or more and 400 ppm or less in the total of the compound and the acid component.
  • A represents an aromatic ring group having 6 to 20 carbon atoms.
  • R 31 represents a group represented by the following general formula (1).
  • R 32 is an unsubstituted or substituent having 1 to 20 carbon atoms in which the hydrogen atom in the group is substituted with a radical generating group other than the general formula (1) or a radical generating group other than the general formula (1). It has an unsubstituted or substituent having 6 to 20 carbon atoms in which the hydrogen atom in the group is substituted with a radical generating group other than the above general formula (1).
  • R 33 is a halogen atom, a nitro group, a cyano group, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , -SR 34 , -SOR 34 , -SO 2 R 34 , -NR 35 R 36 ,- NR 35 COR 36 , -CONR 35 R 36 , an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and an unsubstituted or substituent having 6 to 20 carbon atoms.
  • An aromatic hydrocarbon ring-containing group a heterocyclic ring-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms, an aliphatic hydrocarbon group, an aromatic hydrocarbon ring-containing group, or the above.
  • R 34 , R 35 and R 36 are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 20 carbon atoms substituted or substituents, and 6 to 20 carbon atoms unsubstituted or An aromatic hydrocarbon ring-containing group having a substituent, or a heterocyclic ring-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms, the above aliphatic hydrocarbon group, or the above aromatic A group in which one or more of the methylene groups in the group hydrocarbon ring-containing group or the heterocyclic ring-containing group is replaced with a divalent group selected from the following group I, and a plurality of R 34 , R 35 or R 36 are present.
  • the substituent which substitutes for is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group or -COOH.
  • a represents an integer from 1 to 20 and represents b represents an integer from 0 to 20 and represents c represents an integer from 0 to 20 The total of a, b and c is 20 or less.
  • R 1 is an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and an aromatic having an unsubstituted or substituent having 6 to 20 carbon atoms.
  • R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aliphatic hydrocarbon radical having an unsubstituted or substituted group having 1 to 20 carbon atoms, an unsubstituted or substituted 6 to 20 carbon atoms
  • the substituent which substitutes for is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group or -COOH.
  • n represents 0 or 1 and represents * Represents the joint location.
  • R 40 and R 41 each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and if a plurality of R 40 or R 41 are present, they may be the same. It may be different.
  • the radical polymerization initiator of the present invention has excellent sensitivity stability by containing a compound having the above structure and a predetermined amount of an acid component.
  • the acid component is an organic acid. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the compound represented by the general formula (A) is preferably a compound represented by the following formula (A1). This is because the radical polymerization initiator has more excellent sensitivity stability.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom, a group represented by R 31 in the general formula (A), and the above. It is a group represented by R 32 in the general formula (A) or a group represented by R 33 in the above general formula (A), and is R 11 and R 12 , R 12 and R 13 , R 14 and R 15. , R 15 and R 16 or R 16 and R 17 may be coupled to each other to form a ring. At least one of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is a group represented by R 31 in the above general formula (A). )
  • R 11 is R 31 in the general formula (A). This is because the radical polymerization initiator has more excellent sensitivity stability.
  • R 13 and R 16 are R 33 in the general formula (A). This is because the radical polymerization initiator has more excellent sensitivity stability.
  • R 13 is a R 33 in the general formula (A), R 33 for use in R 13 is a unsubstituted or substituted group having 6 to 20 carbon atoms It is preferable that one or more of the aromatic hydrocarbon ring-containing group or the methylene group in the aromatic hydrocarbon ring-containing group is replaced with a divalent group selected from the above group I. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the content of the compound represented by the general formula (A) is preferably 90 parts by mass or more in 100 parts by mass of the radical polymerization initiator. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the present invention is a composition containing the above radical polymerization initiator and a radically polymerizable compound.
  • the composition of the present invention has excellent sensitivity stability.
  • the present invention is a cured product of the above composition. Since the cured product of the present invention uses the above composition, the durability of the cured product can be easily adjusted.
  • the present invention is a method for producing a cured product, which comprises a polymerization step of polymerizing radically polymerizable compounds in the above composition. According to the method for producing a cured product of the present invention, since the above composition is used in the polymerization step, a cured product having desired durability and the like can be easily obtained.
  • the present invention relates to a radical polymerization initiator, a composition, a cured product, and a method for producing a cured product.
  • a radical polymerization initiator the radical polymerization initiator, the composition, the cured product, and the method for producing the cured product of the present invention will be described in detail.
  • the radical polymerization initiator of the present invention is a radical polymerization initiator containing a compound (Compound A) represented by the following general formula (A) and an acid component, and the content of the acid component is the above general formula ( The total of the compound represented by A) and the acid component is 1 ppm or more and 400 ppm or less.
  • A represents an aromatic ring group having 6 to 20 carbon atoms.
  • R 31 represents a group represented by the following general formula (1).
  • R 32 is an unsubstituted or substituent having 1 to 20 carbon atoms in which the hydrogen atom in the group is substituted with a radical generating group other than the general formula (1) or a radical generating group other than the general formula (1). It has an unsubstituted or substituent having 6 to 20 carbon atoms in which the hydrogen atom in the group is substituted with a radical generating group other than the above general formula (1).
  • R 33 is a halogen atom, a nitro group, a cyano group, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , -SR 34 , -SOR 34 , -SO 2 R 34 , -NR 35 R 36 ,- NR 35 COR 36 , -CONR 35 R 36 , an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and an unsubstituted or substituent having 6 to 20 carbon atoms.
  • An aromatic hydrocarbon ring-containing group a heterocyclic ring-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms, an aliphatic hydrocarbon group, an aromatic hydrocarbon ring-containing group, or the above.
  • R 34 , R 35 and R 36 are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 20 carbon atoms substituted or substituents, and 6 to 20 carbon atoms unsubstituted or An aromatic hydrocarbon ring-containing group having a substituent, or a heterocyclic ring-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms, the above aliphatic hydrocarbon group, or the above aromatic A group in which one or more of the methylene groups in the group hydrocarbon ring-containing group or the heterocyclic ring-containing group is replaced with a divalent group selected from the following group I, and a plurality of R 34 , R 35 or R 36 are present.
  • the substituent which substitutes for is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group or -COOH.
  • a represents an integer from 1 to 20 and represents b represents an integer from 0 to 20 and represents c represents an integer from 0 to 20 The total of a, b and c is 20 or less.
  • R 1 is an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, and an aromatic having an unsubstituted or substituent having 6 to 20 carbon atoms.
  • R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aliphatic hydrocarbon radical having an unsubstituted or substituted group having 1 to 20 carbon atoms, an unsubstituted or substituted 6 to 20 carbon atoms
  • the substituent which substitutes for is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group or -COOH.
  • n represents 0 or 1 and represents * Represents the joint location.
  • R'and R independently represent hydrogen atoms or unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and if a plurality of R'or R'are present, they may be the same. It may be different.
  • the radical polymerization initiator of the present invention exerts the above-mentioned effect by containing a predetermined amount of an acid component together with the above-mentioned compound A is presumed as follows.
  • the radical polymerization initiator has a predetermined amount of the acid component used in combination with the compound A, so that the group represented by the general formula (1) is suppressed from being decomposed by the acid component during storage. can.
  • the radical polymerization initiator can generate a predetermined amount of radicals at a desired timing, and has excellent sensitivity stability.
  • the radical polymerization initiator contains a predetermined amount of an acid component together with the compound A, the dissolution rate with each component of the curable composition is improved, and the curable composition can be easily prepared. ..
  • the radical polymerization initiator of the present invention contains compound A and an acid component.
  • each component of the radical polymerization initiator of the present invention will be described in detail.
  • the compound A has an oxime ester group which is a group represented by the general formula (1), and specifically, R 31 is a group represented by the general formula (1).
  • halogen atom in the general formula (A) and the general formula (1) examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms in the general formula (A) and the general formula (1) is a hydrocarbon group containing no aromatic hydrocarbon ring or heterocycle and has a substituent. May be.
  • 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.
  • Examples of the unsubstituted aliphatic hydrocarbon group include 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 4 to 20 carbon atoms. Cycloalkylalkyl groups of.
  • 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 the like. , Halogen atom, cyano group, nitro group, hydroxyl group, thiol group, -COOH and the like.
  • the alkyl group having 1 to 20 carbon atoms may be linear or branched.
  • Linear alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl and octyl.
  • 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, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, octadecyl 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-. Examples thereof include undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienylallyl.
  • 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 [1.1.1] 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 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 the alkyl group include a Bornyl group 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 cyclooctyl.
  • Examples thereof include methyl, 2-cyclononylethyl and 2-cyclodecylethyl.
  • Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms in which the cycloalkyl group is polycyclic include 3-3-adamantylpropyl and decahydronaphthylpropyl.
  • the aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms in the general formula (A) and the general formula (1) is a hydrocarbon group containing an aromatic hydrocarbon ring and not containing a heterocycle, and is a fat. It may have a group hydrocarbon group or a substituent.
  • An 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 unsubstituted aromatic hydrocarbon ring-containing group are substituted with a substituent.
  • Examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH and the like.
  • 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.
  • the aryl group in which two aromatic hydrocarbon rings are linked may be one in which two monocyclic aromatic hydrocarbon rings are linked, and has a monocyclic aromatic hydrocarbon ring and a fused ring structure.
  • the aromatic 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.
  • the linking group connecting the two aromatic hydrocarbon rings may be any as long as it can have aromaticity as a whole aryl group, such as a single bond, a sulfide group (—S—) and a carbonyl group.
  • a sulfide group —S—
  • Examples of the aryl group having a monocyclic structure include phenyl, trill, xsilyl, ethylphenyl, 2,4,6-trimethylphenyl and the like.
  • Examples of the aryl group of the fused ring structure include naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.
  • 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 means 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 having 2 to 20 carbon atoms in the general formula (A) and the general formula (1) is a hydrocarbon group containing a heterocycle, and even if it has an aromatic hydrocarbon ring-containing group. Often, it may have an aliphatic hydrocarbon group or a substituent.
  • a heterocycle-containing group having a substituent is a group having a structure in which one or more hydrogen atoms in the heterocycle-containing group are substituted with a substituent.
  • Examples of the unsubstituted heterocycle-containing group 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, a benzothiophene group and a pyrrole group.
  • Pyrrolidine group imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperidine group, piperazine group, pyrimidyl group, frill group, thienyl group, benzoxazole-2-yl group, thiazole group, isothiazole group, oxazole
  • Examples thereof include a heterocyclic group such as a group, an isooxazole group and a morphornyl group, and a group in which one or more hydrogen atoms of an alkyl group are substituted with a heterocycle.
  • heterocyclic-containing group having a substituent examples include a group in which one or more hydrogen atoms in the unsubstituted heterocyclic-containing group are substituted with a substituent, and the like. Examples thereof include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group or -COOH.
  • the unsubstituted heterocycle-containing group may be one in which a heterocycle and an aromatic hydrocarbon ring having a monocyclic structure are linked, and the heterocycle and an aromatic hydrocarbon ring having a fused ring structure are linked. It may be a thing.
  • the linking group connecting the two aromatic hydrocarbon rings include a single bond and a carbonyl group.
  • the heterocyclic-containing group in which a heterocycle and an aromatic hydrocarbon ring having a monocyclic structure are linked include benzothiophene and the like.
  • One or more of the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the methylene group in the heterocyclic ring-containing group in the general formula (A) and the general formula (1) is selected from the above group I.
  • a group replaced by a divalent group does not have a structure in which a plurality of divalent groups are adjacent to each other.
  • the plurality of divalent groups may be the same or different.
  • 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. Does not refer to the number of carbon atoms before is replaced.
  • 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 after the substitution.
  • the carbon atom number 1 to 20 means that the methylene group is replaced with a divalent group. It refers to the number of carbon atoms, not the number of carbon atoms before they are replaced.
  • aromatic ring group A has 6 carbon atoms containing an aromatic ring. It means a structure of up to 20 and contains at least one of an aromatic hydrocarbon ring and an aromatic heterocycle. Further, the "carbon atom number 6 to 20" of the aromatic ring group A having 6 to 20 carbon atoms refers to the number of carbon atoms forming the ring skeleton of the aromatic ring contained in the aromatic ring group. When the aromatic ring group has a linked structure, it refers to the total number of carbon atoms forming the ring skeleton of the aromatic ring.
  • the tolyl group, the indole ring group, and the diphenylsulfide group correspond to aromatic ring groups having 6, 8 and 12, respectively.
  • the aromatic ring contained in the aromatic ring group A may have a monocyclic structure or a polycyclic structure. In the case of a polycyclic structure, it may have a fused ring structure, an aromatic ring having a monocyclic structure and an aromatic ring having a monocyclic structure may be linked, and the aromatic ring having a monocyclic structure may be used.
  • the linking group that connects the aromatic ring and the aromatic ring may be any one that can have aromaticity as a whole aryl group, and is a single bond, a sulfide group (—S—), and a carbonyl group. And so on.
  • the aromatic ring group A preferably has a polycyclic structure. This is because the radical polymerization initiator can more effectively exert the effect of being excellent in sensitivity stability.
  • the aromatic hydrocarbon ring means a structure containing an aromatic hydrocarbon ring without containing a heterocycle, and for example, a cyclobutadiene ring, a benzene ring, a cyclooctatetraene ring, a cyclotetradecaheptaene ring, and a cyclo.
  • Examples thereof include a monocyclic structure or a fused ring structure such as an octadecanonaene ring, a naphthalene ring, and an anthracene ring, a triphenylamine structure, a diphenylsulfide structure, and a linked structure such as a fluorene ring.
  • the aromatic hydrocarbon ring preferably has a polycyclic structure, and more preferably has a linked structure or a condensed ring structure.
  • the linking structure is preferably a diphenyl sulfide structure in which the linking group is a sulfide group. This is because the radical polymerization initiator can more effectively exert the effect of being excellent in sensitivity stability.
  • the fused ring structure may be one in which two or more ring structures are condensed, but preferably two or more and four or less ring structures are condensed, and two or more and three or less ring structures are condensed. It is preferable that the ring structure is condensed, and the fluorene ring is particularly preferable. This is because the radical polymerization initiator can more effectively exert the effect of being excellent in sensitivity stability.
  • the aromatic heterocycle means a structure containing an aromatic heterocycle, for example, a furan ring, a thiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a carbazole.
  • an aromatic heterocycle for example, a furan ring, a thiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a carbazole.
  • Examples thereof include a monocyclic structure such as a ring and an indole ring, a fused ring structure, and the like.
  • the aromatic heterocycle preferably has a
  • the fused ring structure may be one in which two or more ring structures are condensed, but preferably two or more and four or less ring structures are condensed, and two or more and three or less ring structures are condensed. It is preferable that the two ring structures are condensed. This is because the radical polymerization initiator can more effectively exert the effect of being excellent in sensitivity stability.
  • the indole ring is preferable as the condensed product of the two ring structures. This is because the radical polymerization initiator can more effectively exert the effect of being excellent in sensitivity stability.
  • the carbazole ring is preferable as the condensed product of the three ring structures. This is because the radical polymerization initiator can more effectively exert the effect of being excellent in sensitivity stability.
  • a represents an integer of 1 to 19, when a is an integer of 2 or more, R 31 there are a plurality may be the same or different.
  • b represents an integer of 0 to 19, and when b is an integer of 2 or more, a plurality of R 32s existing may be the same or different.
  • c represents an integer of 0 to 19, and when c is an integer of 2 or more, a plurality of R 33s existing may be the same or different.
  • a + b + c is 20 or less. However, a + b + c is limited to the number that can be bonded to the aromatic ring group A.
  • the a may be any as long as it can obtain the stability of the desired sensitivity, but is preferably 1 to 3, preferably 1 to 2, and preferably 1. This is because when a is in the above range, the radical polymerization initiator can effectively exert the effect of being excellent in sensitivity stability.
  • b may be any as long as it can obtain the desired stability of sensitivity, but is preferably 0 to 3, preferably 0 to 2, and preferably 0 to 1. This is because when b is in the above range, the radical polymerization initiator can effectively exert the effect of being excellent in sensitivity stability.
  • c may be any one that can obtain the desired stability of sensitivity, but is preferably 0 to 3, preferably 0 to 2, and preferably 0 to 1. This is because when c is in the above range, the radical polymerization initiator can effectively exert the effect of being excellent in sensitivity stability.
  • the group represented by the general formula (1) is a group bonded to the aromatic ring group A, and substitutes a hydrogen atom bonded to an atom constituting the ring structure of the aromatic ring in the aromatic ring group.
  • an aliphatic hydrocarbon group has an unsubstituted or substituted group having 1 to 20 carbon atoms, or a methylene in the radical of the aliphatic hydrocarbon group It is preferable that one or more of the groups is a group substituted with the group represented by the above group I, and the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or the above aliphatic hydrocarbon group.
  • one or more of the methylene groups in the group are substituted with the group represented by the above group I, and in particular, it is an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms. preferable. This is because when R 1 is the above-mentioned group, the above-mentioned radical polymerization initiator can effectively exert the effect of being excellent in sensitivity stability.
  • the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms used in R 1 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has 2 to 10 carbon atoms. It is more preferably a straight chain or branched alkyl group, and further preferably a straight chain or branched alkyl group having 4 to 8 carbon atoms, particularly a straight chain alkyl group having 4 to 8 carbon atoms. It is preferable to have. This is because the radical polymerization initiator can effectively exert the effect of being excellent in sensitivity stability.
  • the R 2 used in the general formula (1) is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and is a linear or branched alkyl group having 1 to 20 carbon atoms. It is more preferable to have a linear or branched alkyl group having 1 to 10 carbon atoms, and particularly preferably a straight chain alkyl group having 1 to 3 carbon atoms. This is because the radical polymerization initiator can effectively exert the effect of being excellent in sensitivity stability.
  • the radical generating group other than the general formula (1) in the general formula (A) means a radical generating group having no oxime ester group, and for example, the following general formulas (IVa), (IVb) and (IVc). , (IVd), (IVe), (IVf), (IVg) and (IVh).
  • the radical generating group other than the general formula (1) is a group bonded to the aromatic ring group A, and substitutes a hydrogen atom bonded to an atom constituting the ring structure of the aromatic ring in the aromatic ring group. To combine.
  • R 51 represents an OR 81 , NR 82 R 83, or a heterocycle-containing group having an unsubstituted or substituent having 2 to 20 carbon atoms.
  • R 52 and R 53 independently represent R 81 or OR 81 , respectively, and R 52 and R 53 may be combined to form a ring.
  • R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 , R 71 and R 73 are aryl groups having an unsubstituted or substituent having 6 to 20 carbon atoms.
  • R 54 , R 57 , R 60 , R 63 , R 66 , R 67 and R 72 each independently represent an arylene group or a single bond having an unsubstituted or substituent having 6 to 20 carbon atoms.
  • R 68 represents a hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms.
  • R 69 and R 70 independently represent R 81 or OR 81 , respectively.
  • R 81 , R 82 and R 83 each independently represent a hydrogen atom or a hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms. * Represents a bond. )
  • hydrocarbon group having 1 to 20 carbon atoms used in the above general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh), An aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms can be mentioned.
  • arylene group having 6 to 20 carbon atoms used in the above general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) examples thereof include a divalent group obtained by removing one hydrogen atom from an aryl group having 6 to 20 carbon atoms.
  • the ring may be a monocyclic ring or a condensed ring.
  • the monocycle include a monocyclic cycloalkane such as cyclopentane, cyclohexane and cyclopentene, a monocyclic aromatic ring such as benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring.
  • monocyclic heterocycles can be mentioned.
  • Examples of the fused ring include naphthalene and anthracene.
  • a aliphatic hydrocarbon group having 1 to 20 carbon atoms used in the above general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh).
  • heterocycle-containing group having a substituent an aryl group having a substituent, an arylene group having a substituent, and a hydrocarbon having a substituent, a heterocycle-containing group
  • substituent that substitutes one or more hydrogen atoms in the aryl group, the arylene group and the hydrocarbon group include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH and the like.
  • the compound A is preferably a compound represented by the following general formulas (A1) and (A2), and more preferably a compound represented by the following general formula (A1). This is because the radical polymerization initiator has more excellent sensitivity stability.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom, a group represented by R 31 in the general formula (A), and the above. It is a group represented by R 32 in the general formula (A) or a group represented by R 33 in the above general formula (A), and is R 11 and R 12 , R 12 and R 13 , R 14 and R 15. , R 15 and R 16 or R 16 and R 17 may be coupled to each other to form a ring. At least one of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is a group represented by R 31 in the above general formula (A). )
  • the ring formed by R 11 and R 12 , R 12 and R 13 , R 14 and R 15 , R 15 and R 16 or R 16 and R 17 may be monocyclic. , May be a fused ring.
  • the monocycle include a monocyclic cycloalkane such as cyclopentane, cyclohexane and cyclopentene, a monocyclic aromatic ring such as benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring.
  • Such as monocyclic heterocycles can be mentioned.
  • the fused ring include naphthalene and anthracene.
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are each independently represented by a hydrogen atom and R 31 in the above general formula (A).
  • a group, a group represented by R 32 in the general formula (A) or a group represented by R 33 in the general formula (A) R 21 and R 22 , R 22 and R 23 , R 23.
  • R 24 , R 25 and R 26 , R 26 and R 27 or R 27 and R 28 may be coupled to each other to form a ring.
  • X 1 is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 .
  • X 2 is an oxygen atom, a sulfur atom, a selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 .
  • R 41 , R 42 , R 43 and R 44 are each independently represented by a hydrogen atom, a group represented by R 31 in the general formula (A), and R 32 in the general formula (A).
  • R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 25 and R 26 , R 26 and R 27, or R 27 and R 28 are bonded to each other to form a ring. It can be the same as that exemplified as a ring formed by combining R 11 and R 12 and the like in the above general formula (A1).
  • R 11 in the general formula (A1) is R 31 in the general formula (A). That is, it is preferable that R 11 in the general formula (A1) is a group represented by the general formula (1). This is because the radical polymerization initiator has more excellent sensitivity stability.
  • R 13 and R 16 in the general formula (A1) is R 33 in the general formula (A). That is, one or more of R 13 and R 16 in the above general formula (A1) are halogen atom, nitro group, cyano group, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , -SR 34 , -SOR 34 , -SO 2 R 34 , -NR 35 R 36 , -NR 35 COR 36 , -CONR 35 R 36 , aliphatic hydrocarbon groups having substituents or substituents having 1 to 20 carbon atoms.
  • R 35 and R 36 are independently hydrogen atoms, aliphatic hydrocarbon groups having an unsubstituted or substituent having 1 to 20 carbon atoms, and an unsubstituted or substituent having 6 to 20 carbon atoms, respectively.
  • An aromatic hydrocarbon ring-containing group having a represents a group in which one or more of the hydrogen ring-containing group or the methylene group in the heterocycle-containing group is replaced with a divalent group selected from the following group I, and when a plurality of R 34 , R 35 or R 36 are present. , They may be the same or different, and have an aliphatic hydrocarbon group having the above substituent, an aromatic hydrocarbon ring-containing group having the above substituent, and the above substituent.
  • the substituent substituting one or more of the hydrogen atoms in the heterocycle-containing group is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group or -COOH. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • R 13 is preferably a R 33 in the general formula (A), among others, R 33 for use in R 13 is unsubstituted or substituted having 6 to 20 carbon atoms It is a group in which one or more of the aromatic hydrocarbon ring-containing group or the methylene group in the aromatic hydrocarbon ring-containing group is replaced with a divalent group selected from the above group I. preferable. This is because the radical polymerization initiator has more excellent sensitivity stability because R 13 has the above structure.
  • aromatic hydrocarbon ring-containing group in the aromatic hydrocarbon ring-containing groups having an unsubstituted or substituted group of 6 to 20 carbon atoms for use in R 13 may be a single ring structure or an aromatic hydrocarbon
  • An aryl group having 6 to 20 carbon atoms in a structure in which rings are linked is preferable, and an aryl group having 12 to 18 carbon atoms in a structure in which an aromatic hydrocarbon ring is linked is more preferable, and particularly aromatic.
  • An aryl group having 12 to 15 carbon atoms in a structure in which a group hydrocarbon ring is linked is preferable, and an aryl group having a carbon atom number in 12 to 15 in a structure in which an aromatic hydrocarbon ring is linked by a carbonyl group is particularly preferable. This is because the radical polymerization initiator has more excellent sensitivity stability because R 13 has the above structure.
  • R 16 may be either a hydrogen atom or R 33 in the above general formula (A), but is an aliphatic hydrocarbon having a hydrogen atom or an unsubstituted or substituent having 1 to 20 carbon atoms. It is preferably a group, and more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms. It is preferable that it is a hydrogen atom. This is because the radical polymerization initiator has more excellent sensitivity stability because R16 has the above structure.
  • R 12 , R 14 , R 15 and R 17 may be either a hydrogen atom or R 33 in the above general formula (A).
  • R 11 in the general formula (A1) is a group represented by the general formula (1)
  • R 13 is R 33 .
  • R 33 used for R 13 is one or more of an aromatic hydrocarbon ring-containing group having an unsubstituted or substituent having 6 to 20 carbon atoms or a methylene group in the above aromatic hydrocarbon ring-containing group. Is a group replaced with a divalent group selected from the above group I, and it is more preferable that R 12 , R 14 , R 15 , R 16 and R 17 are hydrogen atoms. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the preferable compounds include, for example, the compounds represented by the following general formulas (A21), (A22) and (A23).
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 41 , R 42 and R 43 are the same as the above general formula (A2).
  • the compound represented by the general formula (A) can be produced by a known method described in International Publication No. 2015/152153, International Publication No. 2008/077868, Japanese Patent Application Laid-Open No. 2011-132215, and the like. ..
  • the compound in which n in the general formula (1) is 0 is subjected to the following method according to the reaction formula shown in ⁇ Example 1> below.
  • the compound A1 can be produced by reacting the oxime compound 3 with an acid anhydride 4, an acid chloride 4'or a carboxylate 4'.
  • the compound A1 in which n is 1 in the general formula (1) can also be produced according to the reaction formula shown in ⁇ Example 2> below according to the compound A1 in which n is 0.
  • the content of the compound A is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and particularly 90 parts by mass or more in 100 parts by mass of the radical polymerization initiator. preferable. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the content of the compound A is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and particularly 90 parts by mass or more in 100 parts by mass of the solid content of the radical polymerization initiator. It is preferable to have. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the solid content is the total of all components other than the solvent (water and organic solvent).
  • Acid component The acid component is contained as a component other than the compound A and can donate a proton (H +). Therefore, the compound A having an acidic group such as a carboxyl group is not included in the acid component.
  • an acid component either an organic acid having a carbon atom or an inorganic acid having no carbon atom can be used.
  • the acid component is an organic acid. This is because the radical polymerization initiator has more excellent sensitivity stability when the type of the acid component is the above type.
  • the degree of regulation of the acid component may be 1 or more, such as acetic acid, or 2 or more, such as oxalic acid.
  • the normality of the acid component is preferably 1 or more and 3 or less, preferably 1 or more and 2 or less, and preferably 1. This is because when the normality is within the above range, the radical polymerization initiator becomes more excellent in sensitivity stability.
  • the molecular weight of the acid component is preferably 250 or less, more preferably 200 or less, and particularly preferably 50 or more and 100 or less. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • a carboxy group As the acid group of the above acid component, a carboxy group, a sulfonic acid group, a phosphoric acid group, a nitric acid group and a boric acid group are preferable, and a carboxy group is particularly preferable. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc.
  • An aliphatic dicarboxylic acid having 1 to 12 carbon atoms aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane.
  • Examples thereof include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids.
  • inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfite, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, boric acid, perchloric acid and the like.
  • the organic acid is more preferably an aliphatic monocarboxylic acid having 1 to 18 carbon atoms and an aliphatic dicarboxylic acid having 1 to 12 carbon atoms, and among them, 1 to 18 carbon atoms.
  • the aliphatic monocarboxylic acid of the above is more preferable, and the aliphatic monocarboxylic acid having 1 to 10 carbon atoms is more preferable, and the aliphatic monocarboxylic acid having 1 to 5 carbon atoms is particularly preferable.
  • an aliphatic monocarboxylic acid having 2 to 4 carbon atoms is more preferable, and acetic acid is particularly preferable. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the organic acid and the inorganic acid may be used alone or in combination of two or more.
  • the content of the acid component in the total of the compound A and the acid component is 1 ppm or more and 400 ppm or less, more preferably 3 ppm or more and 200 ppm or less, and particularly preferably 5 ppm or more and 30 ppm or less. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the content of the acid component is based on mass. Moreover, the content of the acid component can be obtained by an ion chromatography method.
  • the content of the acid component in the radical polymerization initiator is preferably 1 ppm or more and 400 ppm or less, more preferably 3 ppm or more and 200 ppm or less, and particularly preferably 5 ppm or more and 30 ppm or less. This is because the radical polymerization initiator has more excellent sensitivity stability.
  • the content of the acid component is based on mass.
  • the radical polymerization initiator contains compound A and an acid component, but may contain a solvent if necessary.
  • the solvent is liquid at room temperature (25 ° C.) at atmospheric pressure, and can disperse or dissolve compound A, an acid component, and other components described later. Therefore, the compound A and the acid component are not contained in the solvent even if they are liquid at room temperature (25 ° C.) at atmospheric pressure.
  • the solvent include water and organic solvents described in "3. Solvent" of "B. Composition” described later.
  • the content of the solvent may be one that can obtain the desired stability of sensitivity, but may be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the radical polymerization initiator.
  • the radical polymerization initiator may contain water, if necessary, as long as it can obtain the desired stability of sensitivity.
  • the content of the water is preferably 5% by mass or less, particularly preferably 1% by mass or less, and particularly 0.5% by mass or less in the total of the compound A, the acid component and the water. It is preferable that it is 0.1% by mass or less. This is because when the water content is within the above range, the radical polymerization initiator becomes more excellent in sensitivity stability.
  • the lower limit of the water content is not particularly limited as long as the desired stability of sensitivity can be obtained, but from the viewpoint of ease of preparation, ease of storage, etc. of the radical polymerization initiator. It can be 0.01% by mass or more.
  • the water content can be measured using the Karl Fischer method.
  • the radical polymerization initiator contains compound A and an acid component and can contain a solvent, but may also contain other components if necessary. Examples of such other components include the components described in the section “4. Other components” of “B. Composition” described later. As other components, as a compound that generates radicals, a compound having a structure other than compound A can be included.
  • the above radical polymerization initiator generates radicals.
  • the method of generating radicals from the radical polymerization initiator may be any method generally used for radical generators, and specifically, a method of irradiating energy rays, a method of heat treatment, and these methods. Can be mentioned as a method of performing the above simultaneously or in sequence. That is, the radical polymerization initiator may be a photoradical polymerization initiator that generates radicals by irradiation with energy rays, or may be a thermal radical polymerization initiator that generates radicals by heat treatment.
  • the energy rays include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), visible rays, ultraviolet rays, far-ultraviolet rays, X-rays and charged particle rays.
  • the energy ray used for radical generation preferably has a maximum spectrum in a wavelength range of 200 nm or more and 450 nm and a wavelength range of 300 nm or more and 400 nm or less, and a maximum spectrum in a wavelength range of 340 nm or more and 380 nm or less. It is more preferable to have. This is because radicals can be effectively generated from the radical polymerization initiator.
  • the light sources of the energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halogen lamps, electron beam irradiators, X-ray irradiators, lasers (argon lasers, dye lasers, nitrogen lasers, etc.).
  • a light emitting diode (LED), a helium cadmium laser, etc.) can be mentioned.
  • the exposure amount of the energy rays is not particularly limited as long as it can generate a desired amount of radicals, and can be appropriately determined according to the use of the compound A and the like.
  • the exposure amount 5 mJ / cm 2 or more 2000 mJ / cm 2 or less. This is because radicals can be effectively generated from the radical polymerization initiator.
  • the heating temperature in the above heat treatment is, for example, preferably 70 ° C. or higher and 450 ° C. or lower, and more preferably 150 ° C. or higher and 300 ° C. or lower.
  • the heating time in the heat treatment is preferably, for example, 1 minute or more and 100 minutes or less. This is because radicals can be effectively generated from the radical polymerization initiator.
  • the shape of the radical polymerization initiator may be powder or pellet.
  • a method for producing the same for example, a method of mixing the above-mentioned compound A, an acid component and other components using an extruder or the like and then molding into a pellet form can be mentioned.
  • the shape of the radical polymerization initiator may be in the form of a solution in which the compound A and the acid component are dispersed or dissolved in a solvent.
  • radical polymerization initiator examples include a curable composition containing a radically polymerizable compound.
  • the curable composition is used, for example, in a photocurable paint or varnish, a photoresist adhesive, a printed substrate, or a color display liquid crystal display element such as a color television, a PC monitor, a mobile information terminal, or a digital camera.
  • compositions For manufacturing three-dimensional objects by compositions, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencil, stereolithography.
  • Materials holographic recording materials, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and It can be used for various purposes such as a photoresist material for a visible laser direct image system, a photoresist material used for forming a dielectric layer in sequential lamination of printed circuit substrates, a protective film, and the like, and there is no particular limitation on the application. ..
  • the curable composition is used for optics such as color filters, partition materials, and insulating films used in organic electroluminescence (organic EL) displays, quantum dot (QD) displays, and micro light emitting diode ( ⁇ LED) displays.
  • a composition for forming a member is also mentioned.
  • examples of the use of the curable composition include various curable ink compositions such as a polymerizable liquid crystal coating composition, a conductive paste, and a UV curable ink.
  • examples of the use of the curable composition include compositions for forming an insulating member in an electronic substrate circuit for various purposes such as a solder resist used for a semiconductor package, a circuit-forming resist, and a bump resist.
  • composition of the present invention is characterized by containing the above-mentioned radical polymerization initiator and a radically polymerizable compound.
  • the composition of the present invention has excellent sensitivity stability.
  • the content of the radical polymerization initiator 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 radical polymerization initiator in the composition of the present invention can be, for example, 0.001 part by mass or more and less than 30 parts by mass in 100 parts by mass of the solid content of the composition, and 0.005 parts by mass or more. It is preferably 10 parts by mass or less. This is because the above composition has more excellent sensitivity stability.
  • the solid content includes all components other than the solvent.
  • the content of the radical polymerization initiator is preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, and particularly 5 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. 20 parts by mass or more is preferable. This is because the above composition has more excellent sensitivity stability.
  • radical polymerization initiator is the same as that described in the section "A. Radical polymerization initiator".
  • the radical-polymerizable compound may be any radically polymerizable compound, and examples thereof include compounds having an ethylenically unsaturated double bond such as an acrylic group, a methacryl group, and a vinyl group.
  • the radically polymerizable compound has one or more radically polymerizable groups, and may be either a monofunctional compound having one radically polymerizable group or a polyfunctional compound having two or more radically polymerizable groups.
  • the radically polymerizable compound may be either a compound having an acid value or a compound having no acid value.
  • the compound having an acid value include an acrylate compound having a carboxy group such as methacrylic acid and acrylic acid, and a methacrylate compound.
  • the compound having an acid value include a polymer containing a structural unit having a carboxy group and a structural unit having an ethylenically unsaturated group.
  • Examples of the compound having no acid value include acrylates having no carboxy group such as urethane acrylate resin, urethane methacrylate resin, epoxy acrylate resin, epoxy methacrylate resin, 2-hydroxyethyl acrylate, and -2-hydroxyethyl methacrylate. Examples thereof include compounds and methacrylate compounds.
  • the radically polymerizable compound can be used alone or in combination of two or more.
  • a compound having an ethylenically unsaturated group and having an acid value and a compound having an ethylenically unsaturated group and having no acid value can be used in combination.
  • two or more radically polymerizable compounds are mixed and used, they can be copolymerized in advance and used as a copolymer.
  • such radically polymerizable compounds include the radically polymerizable compound described in JP-A-2016-17609 and the polymerizable group having a radically polymerizable group described in International Publication No. 2019/088055. Examples include compounds.
  • the polymer containing a structural unit having a carboxyl group and a structural unit having an ethylenically unsaturated group is, for example, a polymer containing a structural unit having a carboxyl group [A] described in JP-A-2016-151744.
  • a polymer containing the structural unit having a (meth) acryloyl group as the structural unit (A2) having a crosslinkable group and the polymer having a hydrophilic group (2) described in International Publication No. 2019/088055.
  • a polymer or the like containing a structural unit having a methacryloyl group or an acryloyl group as a structural unit (U2) can also be used.
  • the content of the radically polymerizable compound is not particularly limited as long as a desired cured product can be obtained, but for example, 1 part by mass or more and 50 parts by mass in 100 parts by mass of the solid content of the composition. It can be as follows, preferably 5 parts by mass or more and 40 parts by mass or less, more preferably 8 parts by mass or more and 30 parts by mass or less, and particularly preferably 10 parts by mass or more and 20 parts by mass or less. .. This is because the above composition has excellent curability.
  • the composition may contain a solvent in addition to the radical polymerization initiator and the radically polymerizable compound.
  • the solvent is liquid at room temperature (25 ° C.) and atmospheric pressure, and can disperse or dissolve a radical polymerization initiator, a radically polymerizable compound, and other components described below. Therefore, the radical polymerization initiator and the radically polymerizable compound are not contained in the solvent even if they are liquid at room temperature (25 ° C.) at atmospheric pressure.
  • the solvent either water or an organic solvent can be used.
  • the solvent is an organic solvent. This is because the radical polymerization initiator and the radically polymerizable compound can be easily dissolved or dispersed.
  • organic solvent examples include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol-1-monomethyl ether-2-acetate.
  • Ether esters such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; polyhydric alcohols such as ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol; Cyclic ethers; esters such as ethyl formate, 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; lactones such as ⁇ -caprolactone and ⁇ -caprolactone.
  • the organic solvent contains ether esters. This is because it is easy to obtain a composition having excellent dispersion stability.
  • the content of the solvent can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition.
  • composition may contain other components, if necessary, in addition to the radical polymerization initiator, the radically polymerizable compound and the solvent.
  • the other components include polymerizable compounds, polymers having a hydrophilic group, colorants, inorganic compounds, organic polymers other than polymers having a hydrophilic group, chain transfer agents, sensitizers, and surface activity. Examples thereof include agents, silane coupling agents, melamines, colorants, dispersants for dispersing inorganic compounds and the like.
  • other components include those described as other components in International Publication No. 2019/088055.
  • Examples of the polymer having a hydrophilic group include (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) epoxy group-containing unsaturated compound and (a2) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride described in JP-A-2005-234362. a3) [A] copolymer which is a polymer of another unsaturated compound, [A] a polymer containing a structural unit having a carboxyl group described in JP-A-2016-151744, International Publication No.
  • a polymer containing no structural unit having a radically polymerizable group such as a methacryloyl group or an acryloyl group can also be used.
  • the content of the additive is appropriately selected according to the purpose of use and is not particularly limited.
  • the content of the additive can be 50 parts by mass or less in total with respect to 100 parts by mass of the solid content of the composition, and is 30 parts by mass. The following is preferable.
  • composition As a method for producing the above composition, any known mixing method can be used as long as each of the above components can be mixed so as to have a desired content.
  • the composition can be used, for example, as a photocurable composition that is cured by light irradiation. Specific uses are the same as those described in the above section "A. Radical Polymerization Initiator".
  • 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 above-mentioned composition, the durability and the like can be easily adjusted.
  • the above-mentioned composition is the same as that described in the above-mentioned "B. Composition” section.
  • 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. Examples of such a manufacturing method include the manufacturing method described in the section “D. Manufacturing method of cured product” described later.
  • the method for producing a cured product of the present invention is characterized by having a polymerization step of polymerizing radically polymerizable compounds in the above-mentioned composition.
  • the polymerization step in the present invention is a step of curing the above-mentioned composition.
  • the method for curing the composition may be any method as long as it can polymerize and cure radically polymerizable compounds, and examples thereof include a method for generating radicals from the radical polymerization initiator.
  • the method for generating radicals from the radical polymerization initiator may be any method capable of generating a desired amount of radicals from the radical polymerization initiator, for example, a method of irradiating energy rays, a method of heat treatment, and a method of simultaneously performing these. Alternatively, a method of performing in order can be mentioned. Examples of the method of irradiating such energy rays, the method of heat treatment, and the like include the same methods as those described in the above section "A. Radical polymerization initiator".
  • the method for generating the radical includes a method for irradiating energy rays. This is because radicals can be effectively generated from the radical polymerization initiator, and the radically polymerizable compound can be effectively cured.
  • the composition is the same as that described in the section "B. Composition”.
  • the method for producing a cured product of the present invention may include other steps, if necessary, in addition to the above polymerization step.
  • Other steps include a development step of removing an unpolymerized portion in the coating film of the composition to obtain a patterned cured product after the polymerization step, a post-baking step of heat-treating the cured product after the polymerization step. Examples thereof include a prebaking step of heat-treating the composition to remove the solvent in the composition before the polymerization step, a step of forming a coating film of the composition before the polymerization step, and the like.
  • the other steps preferably include a post-baking step. This is because the radicals generated from the radical polymerization initiator can be effectively diffused, and as a result, the formation of a cured product in which the polymerization of the radically polymerizable compound has sufficiently proceeded becomes easy.
  • Examples of the method for removing the unpolymerized portion in the development step include a method of applying a developing solution such as an alkaline developer to the unpolymerized portion.
  • a developing solution such as an alkaline developer
  • those generally used as an alkaline developer such as an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of potassium hydroxide, and an aqueous solution of potassium carbonate can be used.
  • TMAH tetramethylammonium hydroxide
  • potassium hydroxide an aqueous solution of potassium carbonate
  • the developing solution those generally used as solvent developing solutions such as propylene glycol monomethyl ether acetate (PEGMEA) and cyclohexanone can be used.
  • the developing method using the developing solution may be any method as long as it can bring the developing solution into contact with the part to be developed, and known methods such as a shower method, a spraying method, and a dipping method can be used.
  • the execution timing of the development step may be after the curing step.
  • the heating conditions in the post-baking step may be any one that can improve the strength of the cured product obtained in the curing step, and can be, for example, 20 to 90 minutes at 200 ° C. or higher and 250 ° C. or lower.
  • the heating conditions in the prebaking step may be any one that can remove the solvent in the composition, and can be, for example, 70 ° C. or higher and 150 ° C. or lower for 30 seconds to 300 seconds.
  • the composition in the step of forming the coating film As a method of applying the composition in the step of forming the coating film, known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, and immersion can be used.
  • the coating film can be formed on a substrate.
  • the base material can be appropriately set according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like. Further, the cured product may be formed on a base material and then peeled off from the base material, or may be transferred from the base material to another adherend and used.
  • the present invention is not limited to the above embodiment.
  • the above embodiment is an example, and any one having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. It is included in the technical scope of the invention.
  • Examples 1 to 67, Comparative Examples 1 to 8 The acid components of the compounds A produced in Production Examples 1 to 62 were adjusted so as to have the formulations shown in Tables 4 to 6, and a radical polymerization initiator was prepared. The content of the acid component was quantified by ion chromatography.
  • A-1 Radical polymerization initiator prepared in Examples 1 to 67 and Comparative Examples 1 to 8
  • B-1 SPC-3000 (polymer having a hydrophilic group; manufactured by Showa Denko KK, solid content 42.7%, PGMEA solution)
  • C-1 Kayarad DPHA (polymerizable compound (polyfunctional acrylate); manufactured by Nippon Kayaku Co., Ltd.)
  • D-1 Blue pigment dispersion liquid (blue pigment dispersion liquid produced in Production Example 9)
  • E-1 KBE-403 (Coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • F-1 Propylene glycol-1-monomethyl ether-2-acetate (solvent)
  • Each composition was spin-coated on a glass substrate, prebaked at 90 ° C. for 120 seconds using a hot plate, and then cooled at 23 ° C. for 60 seconds. Then, it was exposed through a photomask (mask opening 30 ⁇ m) using an ultra-high pressure mercury lamp (exposure gap 100 ⁇ m, exposure amount 40 mJ / cm 2 ). After developing with a 0.04 mass% KOH aqueous solution as a developing solution, it was washed well with water and post-baked at 230 ° C. for 20 minutes using a clean oven to fix the pattern. The obtained pattern was observed with an electron microscope, and the line width of the portion corresponding to the mask opening was measured.
  • Sensitivity evaluation is based on the following criteria for the case where the radical polymerization initiator immediately after preparation is used and the case where the radical polymerization initiator is used after being sealed with air in a screw tube and stored at 60 ° C. for 1 week. went.
  • the results are shown in Tables 2-4. +: No difference before and after storage (line width change rate is ⁇ 10% or less)
  • the radical polymerization initiator of the example can be easily uniformly dissolved or uniformly dispersed when mixed with each component of the composition used for the evaluation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'objectif de la présente invention est de fournir un initiateur de polymérisation radicalaire qui présente une sensibilité parfaitement stable.　La présente invention concerne un initiateur de polymérisation radicalaire comprenant un composé représenté par la formule générale suivante (A), et un composant acide, la teneur en composant acide étant égale à 1 à 400 ppm par rapport au total du composé représenté par la formule générale (A) et du composant acide. (A représente un groupe cyclique aromatique en C6-20, R31 représente un groupe ester d'oxime, R32 représente un groupe générateur de radicaux autre qu'un groupe ester d'oxime, R33 représente un groupe hydrocarboné aliphatique substitué ou non substitué en C1-20 ou un groupe comprenant un cycle hydrocarboné aromatique substitué ou non substitué en C6-20, a représente un nombre entier de 1 à 20, b représente un nombre entier de 0 à 20 et c représente un nombre entier de 0 à 20.)
PCT/JP2021/013268 2020-03-30 2021-03-29 Initiateur de polymérisation radicalaire, composition, produit durci et procédé de fabrication de produit durci WO2021200815A1 (fr)

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