WO2019188717A1 - Composé, initiateur de polymérisation radicalaire, composition, produit durci et procédé de production d'un produit durci - Google Patents

Composé, initiateur de polymérisation radicalaire, composition, produit durci et procédé de production d'un produit durci Download PDF

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WO2019188717A1
WO2019188717A1 PCT/JP2019/011881 JP2019011881W WO2019188717A1 WO 2019188717 A1 WO2019188717 A1 WO 2019188717A1 JP 2019011881 W JP2019011881 W JP 2019011881W WO 2019188717 A1 WO2019188717 A1 WO 2019188717A1
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carbon atoms
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groups
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直美 佐藤
大樹 三原
良智 竹内
和司 松川
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株式会社Adeka
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Priority to JP2020510811A priority Critical patent/JP7351830B2/ja
Priority to CN201980018353.5A priority patent/CN111836796A/zh
Priority to KR1020207023704A priority patent/KR20200135308A/ko
Publication of WO2019188717A1 publication Critical patent/WO2019188717A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/32—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to an acyclic carbon atom of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/38—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with the sulfur atom of the thio group bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/14—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

  • the present invention relates to a compound capable of forming a radical polymerization initiator excellent in heat resistance and solubility.
  • the radical curable composition is obtained by adding a radical polymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiating energy rays (light). Used in inks, photosensitive printing plates, various photoresists and the like.
  • the carbazole initiator described in the patent document may have insufficient heat resistance and solubility in an organic solvent.
  • the present invention has been made in view of the above problems, and has as its main object to provide a compound capable of forming a radical polymerization initiator excellent in heat resistance and solubility.
  • a methylene group in a group such as an aliphatic hydrocarbon group is substituted with an oxygen atom or a carbonyl group at the 9th position of the fluorene ring. It has been found that a compound having the above group becomes a radical polymerization initiator excellent in heat resistance and solubility, and the present invention has been completed.
  • the present invention is a compound represented by the following general formula (A).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, a hydroxyl group, NR 12 R 13 , CONR 12 R 13 , or a nitro group.
  • R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to Represents 20 heterocycle-containing groups
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , and R 12 and R 13 are each a hydrogen atom in the alkyl group, aryl group, arylalkyl group or heterocycle-containing group.
  • One or more of the above are ethylenically unsaturated groups, halogen atoms, acyl groups, acyloxy groups, substituted amino groups, sulfonamido groups, sulfonyl groups, carboxyl groups, cyano groups, sulfo groups, hydroxyl groups, nitro groups, mercapto groups ,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 and R 12 and R 13 are a methylene group in the alkyl group, aryl group, arylalkyl group or heterocyclic group-containing group.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a group represented by the general formula (B)
  • R 10 and R 11 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms.
  • At least one of R 10 and R 11 is a group represented by the general formula (C)
  • R 10 and R 11 may be connected to each other to form a ring.
  • R 21 and R 22 are each independently a hydrogen atom, hydroxyl group, NR 23 R 24 , CONR 23 R 24 , nitro group, cyano group, halogen atom, alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms;
  • R 23 and R 24 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms.
  • R 21 , R 22 , R 23 and R 24 are each an alkyl group, an aryl group, an arylalkyl group or a heterocyclic ring-containing group in which one or more hydrogen atoms are ethylenically unsaturated groups, halogen atoms, acyl Group, acyloxy group, substituted amino group, sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group or phosphoric acid group Or a group substituted with R 21 , R 22 , R 23 and R 24 each represents one or more of the methylene groups in the alkyl group, aryl group, arylalkyl group or heterocyclic group containing a carbon-carbon double bond, —O— , —S
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • b represents an integer of 0 or 1
  • L 1 is a direct bond or a c1 + 1 valent linking group
  • the c1 + 1 valent linking group is an aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same valence as c1 + 1, the number of carbon atoms Represents a hydrocarbon group containing 6 to 35 aromatic rings or a heterocyclic group containing 2 to 20 carbon atoms
  • X represents —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —S—CO—, —CO—S—, —O—.
  • R 31 and R 32 each independently represents an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms.
  • R 31 and R 32 may be a group in which a hydrogen atom in the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group or heterocyclic ring-containing group is substituted with an ethylenically unsaturated group or a halogen atom, R 31 and R 32 may each independently be linked to L 1 to form a ring, R 31 and R 32 may be connected to each other to form a ring, c1 represents an integer of 1 to 10, c2 represents an integer of 1 to 10, c3 represents an integer of 1 to 10, * Represents a bonding site with the fluorene ring. )
  • the compound represented by the above general formula (A) (hereinafter sometimes referred to as “compound A”) has the above-mentioned predetermined structure, so that the radical polymerization is excellent in heat resistance and solubility.
  • An initiator can be formed.
  • the group represented by the general formula (C) is a group satisfying the following condition (A), condition (B) or condition (C).
  • substituent C is a group satisfying the following condition (A), condition (B) or condition (C).
  • Condition (A) L 1 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms
  • R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms.
  • X is —O—, —S—, —CO—, —O—CO—, —CO—O—, —NR 32 — or —P ( ⁇ O) (OR 32 ) O—
  • the c1 is 1, the c2 is an integer of 1 to 4, and the c3 is 1.
  • Condition (B) L 1 is an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms, R 31 is an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms, and X is —O—, —S —, —CO—, —O—CO— or —CO—O—, wherein c1 is 1, c2 is an integer of 1 to 4, and c3 is 1.
  • L 1 is a direct bond
  • R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms
  • X is —O—, —S—, —CO—, —O—CO—, Or —CO—O—, wherein c1 is 1, c2 is an integer of 1 to 4, and c3 is 1.
  • the group represented by the general formula (C) is preferably a group satisfying the following condition (1) or condition (2). This is because the compound A can form a radical polymerization initiator excellent in heat resistance and solubility.
  • Condition (1) L 1 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms.
  • X is —O—, —S—, —CO—, —O—CO— or —CO—O—
  • c1 is 1
  • c2 is an integer of 1 to 2
  • c3 is 1.
  • L 1 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms
  • R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms.
  • X is —O—, —S—, —CO—, —O—CO—, —CO—O—, —NR 32 — or —P ( ⁇ O) (OR 32 ) O—
  • c2 is an integer of 1 to 4
  • c3 is 1, and at least one of c2 Xs is —NR 32 — or —P ( ⁇ O) (OR 32 ) O. -.
  • R 31 is an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, which does not form a ring with any of R 32 and L 1 , or A heterocyclic group having 2 to 20 carbon atoms is preferable. This is because R 31 does not form a ring with any of R 32 and L 1 , so that the structural change of Compound A due to the presence of the acid component is suppressed, and the storage stability is excellent.
  • R 2 and R 7 are a group represented by the above general formula (B) (hereinafter sometimes referred to as substituent B), and R 21 has 2 to 8 carbon atoms. It is preferably an alkyl group, R 22 is an alkyl group having 1 to 8 carbon atoms, and b is 1. It is because the compound A can form a radical polymerization initiator excellent in heat resistance and solubility because both R 2 and R 7 are the above-described groups.
  • the present invention provides a radical polymerization initiator characterized by containing the above-mentioned compound A.
  • the radical polymerization initiator becomes excellent in heat resistance and solubility.
  • the present invention provides a composition comprising the above-mentioned compound and a radically polymerizable compound.
  • the composition can form a cured product with less outgas and has excellent dispersion stability.
  • the present invention provides a cured product characterized by being a cured product of the above composition.
  • the cured product by being a cured product of the composition containing the compound A, the cured product has less outgas and less variation in the degree of curing.
  • This invention provides the manufacturing method of the hardened
  • the cured product can obtain a cured product with less outgas and less variation in the degree of curing.
  • the present invention relates to a compound, a radical polymerization initiator, a composition, a cured product, and a method for producing the cured product.
  • a compound, a radical polymerization initiator, a composition, a cured product, and a method for producing the cured product will be described in detail.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, a hydroxyl group, NR 12 R 13 , CONR 12 R 13 , or a nitro group.
  • R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to Represents 20 heterocycle-containing groups
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , and R 12 and R 13 are each a hydrogen atom in the alkyl group, aryl group, arylalkyl group or heterocycle-containing group.
  • One or more of the above are ethylenically unsaturated groups, halogen atoms, acyl groups, acyloxy groups, substituted amino groups, sulfonamido groups, sulfonyl groups, carboxyl groups, cyano groups, sulfo groups, hydroxyl groups, nitro groups, mercapto groups ,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 and R 12 and R 13 are a methylene group in the alkyl group, aryl group, arylalkyl group or heterocyclic group-containing group.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a group represented by the general formula (B)
  • R 10 and R 11 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms.
  • At least one of R 10 and R 11 is a group represented by the general formula (C)
  • R 10 and R 11 may be connected to each other to form a ring.
  • R 21 and R 22 are each independently a hydrogen atom, hydroxyl group, NR 23 R 24 , CONR 23 R 24 , nitro group, cyano group, halogen atom, alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms;
  • R 23 and R 24 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms.
  • R 21 , R 22 , R 23 and R 24 are each an alkyl group, an aryl group, an arylalkyl group or a heterocyclic ring-containing group in which one or more hydrogen atoms are ethylenically unsaturated groups, halogen atoms, acyl Group, acyloxy group, substituted amino group, sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group or phosphoric acid group Or a group substituted with R 21 , R 22 , R 23 and R 24 each represents one or more of the methylene groups in the alkyl group, aryl group, arylalkyl group or heterocyclic group containing a carbon-carbon double bond, —O— , —S
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • b represents an integer of 0 or 1
  • L 1 is a direct bond or a c1 + 1 valent linking group
  • the c1 + 1 valent linking group is an aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same valence as c1 + 1, the number of carbon atoms Represents a hydrocarbon group containing 6 to 35 aromatic rings or a heterocyclic group containing 2 to 20 carbon atoms
  • X represents —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —S—CO—, —CO—S—, —O—.
  • R 31 and R 32 each independently represents an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms.
  • R 31 and R 32 may be a group in which a hydrogen atom in the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group or heterocyclic ring-containing group is substituted with an ethylenically unsaturated group or a halogen atom, R 31 and R 32 may each independently be linked to L 1 to form a ring, R 31 and R 32 may be connected to each other to form a ring, c1 represents an integer of 1 to 10, c2 represents an integer of 1 to 10, c3 represents an integer of 1 to 10, * Represents a bonding site with the fluorene ring. )
  • the compound represented by the above general formula (A) (hereinafter sometimes referred to as “compound A”) has the above-mentioned predetermined structure, so that the radical polymerization is excellent in heat resistance and solubility.
  • An initiator can be formed.
  • the reason why the above-described effect is achieved by having the predetermined structure is presumed as follows.
  • the compound A since the compound A has a fluorene ring, by introducing a substituent into the 9-position carbon, the planarity of the molecule is reduced and the compound is excellent in solubility in an organic solvent.
  • at least one of R 10 and R 11 is a substituent C having a structure in which a methylene group in a group such as an aliphatic hydrocarbon group is substituted with a predetermined atom or group,
  • the compounds A or the compound A and a resin or the like can be bonded by hydrogen bonding.
  • the compound A is excellent in heat resistance during heating. From the above, it is possible to form a radical polymerization initiator excellent in heat resistance and solubility in an organic solvent because the compound A has the above structure.
  • the composition excellent in dispersion stability can be obtained by using the compound A, and a cured product with less outgas can be formed.
  • the said compound has the above-mentioned structure, while being able to form the radical polymerization initiator excellent in the sensitivity, it becomes easy to obtain the hardened
  • the compound A has a ketoxime ester group that is a substituent B in at least one of R 1 to R 8 , so that when the compound A is used as a radical polymerization initiator, the substituent B is a fluorene ring. Cleavage occurs between carbonyl groups, resulting in shorter absorption wavelengths.
  • the said compound A shows deep part sclerosis
  • the compound A is excellent in sensitivity.
  • the composition can be cured with high sensitivity, the cured product can suppress the volatilization of Compound A and its decomposition product, the volatilization of the resin contained in the cured product, and the like with less outgas. Become.
  • the compound A has the above-described fluorene ring, the compound A has excellent visible light transmittance as compared with, for example, a compound having a carbazole ring. For this reason, by using the compound A, a cured product having excellent transparency can be easily obtained.
  • Substituent C The substituent C is a group represented by the following general formula (C).
  • L 1 is a direct bond or a c1 + 1 valent linking group
  • the c1 + 1 valent linking group is an aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same valence as c1 + 1, the number of carbon atoms Represents a hydrocarbon group containing 6 to 35 aromatic rings or a heterocyclic group containing 2 to 20 carbon atoms
  • X represents —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —S—CO—, —CO—S—, —O—.
  • R 31 and R 32 each independently represents an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms.
  • R 31 and R 32 may be a group in which a hydrogen atom in the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group or heterocyclic ring-containing group is substituted with an ethylenically unsaturated group or a halogen atom, R 31 and R 32 may each independently be linked to L 1 to form a ring, R 31 and R 32 may be connected to each other to form a ring, c1 represents an integer of 1 to 10, c2 represents an integer of 1 to 10, c3 represents an integer of 1 to 10, * Represents a bonding site with the fluorene ring. )
  • Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms represented by R 31 and R 32 include straight chain, branched chain, cyclic (alicyclic hydrocarbon) and those having a combination thereof. .
  • Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms those not containing the atom or group represented by X (hereinafter sometimes referred to as substituent X) can be used.
  • An alkyl group is mentioned.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, an isobutyl group, an amyl group, an isoamyl group, and a tertiary amyl group.
  • Cyclopentyl group hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, bicyclohexyl group, 1-methylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tertiary heptyl group N-octyl group, isooctyl group, tertiary octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group and the like.
  • aromatic hydrocarbon ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by R 31 and R 32 those containing no substituent X can be used.
  • An aromatic hydrocarbon ring group, an aromatic hydrocarbon ring A group in which one or more of the hydrogen atoms in the group are substituted with an aliphatic hydrocarbon group, and a group in which one or more of the hydrogen atoms in the aliphatic hydrocarbon group are substituted with an aromatic hydrocarbon ring group (Hereinafter, it may be referred to as an aromatic hydrocarbon ring-containing group).
  • aromatic hydrocarbon ring group include phenyl, naphthyl, and fluorene groups.
  • an aliphatic hydrocarbon group that substitutes one or more hydrogen atoms of an aromatic hydrocarbon ring group and an aliphatic carbon group in which one or more hydrogen atoms are substituted by an aromatic hydrocarbon ring group
  • the hydrogen group include those having a predetermined number of carbon atoms among the aliphatic hydrocarbon groups having 1 to 120 carbon atoms represented by R 31 and R 32 .
  • the aromatic hydrocarbon ring-containing group used as the aromatic ring-containing hydrocarbon group include one or more hydrogen atoms of an aliphatic hydrocarbon group such as benzyl, phenethyl, diphenylmethyl, and triphenylmethyl. Examples include a group substituted with an aromatic hydrocarbon ring group and a group in which one or more hydrogen atoms of an aromatic hydrocarbon ring group such as a tolyl group are substituted with an aliphatic hydrocarbon group.
  • Aromatic heterocyclic group hydrogen atom of aromatic heterocyclic group A group in which one or more of them are substituted with an aliphatic hydrocarbon group, a group in which one or more of the hydrogen atoms of an aromatic heterocyclic group are substituted with an aromatic ring-containing hydrocarbon group, aliphatic carbonization And a group in which one or two or more hydrogen atoms of the hydrogen group are substituted with an aromatic heterocyclic group (hereinafter may be referred to as an aromatic heterocyclic-containing substituent).
  • aromatic heterocyclic group examples include pyridyl, pyrimidyl, furyl, thienyl, benzoxazol-2-yl, imidazolyl, thiazolyl, isothiazolyl, isoxazolyl and the like.
  • one or two or more hydrogen atoms are substituted by an aliphatic hydrocarbon group and an aromatic ring-containing hydrocarbon group, or an aromatic heterocyclic group replacing one or two or more hydrogen atoms of an aromatic heterocyclic group.
  • Examples of the aliphatic hydrocarbon group and the aromatic ring-containing hydrocarbon group in which is substituted are the aliphatic hydrocarbon group having 1 to 120 carbon atoms and the aromatic group having 6 to 35 carbon atoms represented by R 31 and R 32 above.
  • the ring-containing hydrocarbon groups those having a predetermined number of carbon atoms can be mentioned.
  • the aliphatic hydrocarbon group having 1 to 120 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms represented by R 31 and R 32 are substituted.
  • the group may have a group, and unless otherwise specified, the group does not have a substituent and is unsubstituted or has a substituent. That is, R 31 and R 32 represent hydrogen in an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms.
  • the atom may be an ethylenically unsaturated group or a group substituted with a halogen atom.
  • substituents for substituting hydrogen atoms such as aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups include ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacryl; fluorine, chlorine , Halogen atoms such as bromine and iodine.
  • the number of carbon atoms of a group defines the number of carbon atoms of the group after the substitution when a hydrogen atom in the group is substituted with a substituent.
  • the 1 to 120 carbon atoms refers to the number of carbon atoms after the hydrogen atom is substituted, Does not refer to the number of carbon atoms before is replaced.
  • the definition of the number of carbon atoms for a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group shall define the number of carbon atoms of the group before the substitution. To do.
  • the number of carbon atoms of a group in which a methylene group in an aliphatic hydrocarbon group having 1 to 120 carbon atoms is replaced with a divalent group is 1 to 120.
  • R 31 and R 32 may be independently connected to L 1 to form a ring.
  • R 31 and R 32 may be connected to each other to form a ring.
  • the ring formed by connecting R 31 and L 1, the ring formed by connecting R 32 and L 1 , and the ring formed by connecting R 31 and R 32 include a ring containing an oxygen atom.
  • Rings containing oxygen atoms include furan ring (5-membered ring), tetrahydrofuran ring (5-membered ring), tetrahydropyran ring (6-membered ring), hexamethylene oxide ring (7-membered ring), oxocan ring (8-membered ring) And an oxonane ring (nine-membered ring).
  • Examples of the ring containing a nitrogen atom include a pyrrole ring, a pyrrolidine ring, an imidazole ring, an imidazolidine ring, an imidazoline ring, a pyrazole ring, a pyrazolidine ring, a piperidine ring, and a piperazine ring.
  • Examples of the ring containing an oxygen atom and a nitrogen atom include a morpholine ring, an oxazole ring, an oxazoline ring, and an oxadiazole ring.
  • the compound represented by the formula (17) described below shows an example in which R 31 forms a ring with L 1 .
  • the compound represented by the formula (18) described below shows an example in which R 31 forms a ring with R 32 .
  • the rings formed in the compounds represented by formulas (17) and (18) are a tetrahydrofuran ring and a morpholine ring, respectively.
  • R 31 is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms.
  • an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms, and a heterocycle-containing group having 2 to 10 carbon atoms are particularly preferable.
  • an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms are preferable, and in particular, an aliphatic hydrocarbon group having 1 to 8 carbon atoms and carbon An aromatic ring-containing hydrocarbon group having 6 to 8 atoms is preferable, and an aliphatic hydrocarbon group having 1 to 8 carbon atoms is particularly preferable.
  • the aliphatic hydrocarbon group represented by R 31 is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • the aliphatic hydrocarbon group represented by R 31 is preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms, An aliphatic hydrocarbon group having 3 to 6 carbon atoms is preferable. This is because, when R 31 is the above-described substituent, the compound A has an excellent balance between heat resistance and solubility. In the present invention, it is preferable that R 31 does not have an ethylenically unsaturated group from the viewpoint of suppressing undesirable progress of the polymerization reaction and being excellent in storage stability.
  • R 31 does not form a ring with any of R 32 and L 1 , that is, It is preferable that the substituent C does not have a cyclic structure containing X as a ring component.
  • a preferable group for R 32 can be the same as R 31 described above. This is because the compound A has an excellent balance between heat resistance and solubility.
  • the structure of the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as c1 + 1 represented by L 1 can be appropriately set according to the use of the compound A and the like.
  • the aliphatic hydrocarbon group having 1 to 120 carbon atoms represented by L 1 those in which the methylene group is not replaced by the atom or group represented by X can be used.
  • the aliphatic hydrocarbon group any of linear, branched, cyclic (alicyclic hydrocarbon), and combinations thereof can be used.
  • Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms in which c1 + 1 is divalent or more include one hydrogen atom from the monovalent aliphatic hydrocarbon group having 1 to 120 carbon atoms represented by R 31 described above. It can be set as the structure from which the part removed.
  • the c1 + 1 is a divalent aliphatic hydrocarbon group having 1 to 120 carbon atoms.
  • alkylene such as methylene, ethylene, propylene, butylene, butyldiyl and the like, and these groups are substituted by a substituent described later. Groups and the like.
  • Specific examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms whose c1 + 1 is trivalent represented by L 1 include alkylidines such as propyridine and 1,1,3-butyridine, and groups thereof. Is a group substituted by a substituent described later.
  • the structure of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same number of valences as c1 + 1 represented by L 1 can be appropriately set depending on the use of compound A and the like.
  • Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms in which c1 + 1 is divalent or more and represented by L 1 include monovalent aromatic rings having 6 to 35 carbon atoms represented by R 31 described above. It can be set as the structure from which a part of hydrogen atom remove
  • hydrocarbon group containing 6 to 35 carbon atoms having a divalent carbon number of c1 + 1 represented by L 1 include arylene groups such as phenylene and naphthylene, and the substituents described later. And a group substituted by a group.
  • c1 + 1 represented by L 1 above trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, phenyl-1,3,5-trimethylene and these groups are substituted by a substituent described later. Groups.
  • the structure of the heterocyclic ring-containing group having 2 to 20 carbon atoms and having the same valence as c1 + 1 represented by L 1 can be appropriately set depending on the use of the compound.
  • Examples of the C2-C20 heterocycle-containing group in which c1 + 1 is divalent or more include, for example, a hydrogen atom from a monovalent C2-C35 heterocycle-containing group represented by R 31 described above. It can be set as the structure from which the part removed.
  • C1 + 1 divalent heterocyclic group containing 2 to 20 carbon atoms represented by L 1 include a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, Examples include groups having a thiophene ring, an indole ring, and the like, and groups in which these groups are substituted with a substituent described later.
  • Represented by L 1 as the c1 + 1 is 3-valent heterocyclic containing group having 2 to 20 carbon atoms, substituted with a substituent group, the groups and these groups having a triazine ring to be described later with isocyanuric ring Groups.
  • Each functional group represented by L 1 such as the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group may have a substituent, and there is a particular notice. Unless otherwise specified, the substituent is unsubstituted or has a substituent.
  • the substituent for substituting a hydrogen atom such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocyclic ring-containing group include the aliphatic hydrocarbon groups represented by the above R 31 and R 32 , aromatic The content can be the same as the substituent for substituting a hydrogen atom such as a ring-containing hydrocarbon group or a heterocycle-containing group.
  • L 1 can form a ring with other L 1 when c2 is 2 or more.
  • Compounds represented by the later-described equation (16) shows an example where L 1 is, form another L 1 and the ring.
  • the L 1, if c2 is 2 or more, each of L 1 may be the same, may be different, if L 1 is a group other than binding directly Preferably they are the same.
  • L 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 20 carbon atoms, a complex having 2 to 20 carbon atoms, and having the same valence as c1 + 1.
  • a ring-containing group is preferable, and in particular, an aliphatic hydrocarbon group having 1 to 8 carbon atoms having the same valence as c1 + 1, an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms, and 2 carbon atoms.
  • It is preferably a group containing 10 to 10 heterocycles, and in particular, an aliphatic hydrocarbon group having 1 to 8 carbon atoms having the same valence as c1 + 1, and an aromatic ring-containing hydrocarbon having 6 to 10 carbon atoms. And is particularly preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms having the same valence as c1 + 1, and in particular, a carbon having the same valence as c1 + 1.
  • L 1 is preferably a direct bond. This is because the compound A has an excellent balance between heat resistance and solubility.
  • the above c1 represents the number of X bonded to L1, that is, the bond group represented by L1 is a c1 + 1 valent bond group.
  • the above c1 is an integer of 1 to 10, but is preferably an integer of 1 to 6 from the viewpoint of easy synthesis, and more preferably an integer of 1 to 4, and in particular, 1 to 2 It is preferable that it is an integer, and it is especially preferable that it is one especially. This is because the compound A has an excellent balance between heat resistance and solubility.
  • C2 represents the number of repetitions of the structure represented by — [L 1- (X) c1 ] — in the substituent C. That is, c2 represents the number by which the methylene group is replaced by X.
  • c2 is an integer of 1 to 10, but is preferably an integer of 1 to 6 from the viewpoint of easy synthesis, and in particular, an integer of 1 to 4 is preferable. It is preferable that it is an integer, and it is especially preferable that it is one especially. This is because the compound A has an excellent balance between heat resistance and solubility.
  • c2 is 2 or more, the structure represented by — [L 1 — (X) c1 ] — contained in the substituent C may be the same or different.
  • two X contained in the substituent C may be the same or different.
  • two L1 contained in the substituent C may be the same or different.
  • the compound represented by the formula (4) described later has an example in which c2 is 2 or more and the structure represented by — [L 1- (X) c1 ] — contained in the substituent C is the same.
  • c2 is 2 or more, and the structure represented by — [L 1 — (X) c1 ] — contained in the substituent C is different. It is shown.
  • the c3 indicates the number of R 31 bonded to X.
  • C3 is an integer of 1 to 10, and is preferably an integer of 1 to 6, and preferably an integer of 1 to 4, particularly 1 to 2 from the viewpoint of easy synthesis. It is preferable that it is an integer, and it is especially preferable that it is one especially. This is because the compound A has an excellent balance between heat resistance and solubility.
  • X represents —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —S—CO—, —CO—S—, —O—.
  • —P ( ⁇ O) (OR 32 ) O— is preferable, and among them, —O—, —S—, —CO—O—, —NR 32 — or —P ( ⁇ O) (OR 32 ) O- is preferred. It is because the said compound A can form the radical polymerization initiator excellent in heat resistance and solubility because the said X is the above-mentioned atom or group.
  • c2 is 2 or more, it is a condition that X contained in the substituent C is not adjacent. Therefore, c2 is equal to or greater than 2, if it contains a direct bond as L 1, L 1 as a direct bond, only when a terminal of the fluorene ring side of substituents C.
  • L 1 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms
  • R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or An aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms, wherein X is —O—, —S—, —CO—, —O—CO—, —CO—O—, —NR 32 — or —P.
  • a group satisfying ( O) (OR 32 ) O—, wherein c1 is 1, c2 is an integer of 1 to 4, and c3 is 1 (condition (A))
  • the group that satisfies the following condition (1) or condition (2) is preferable.
  • the said compound A can form the radical polymerization initiator excellent in the balance of heat resistance and solubility because the said substituent C is the above-mentioned group.
  • the substituent C is a group having a structure in which a methylene group in a group such as an aliphatic hydrocarbon group is substituted with a predetermined atom or group. For example, a predetermined atom or an alkoxy group is added to the fluorene ring. This is because, compared to the case where the group is directly bonded, the acid becomes stable, and as a result, the synthesis becomes easy and the heat resistance is excellent.
  • c2 is an integer of 1 to 2, and X is —O—, —S—, —CO—, —O—CO— or —CO—O—.
  • c2 is an integer of 1 to 4, and X is —O—, —S—, —CO—, —O—CO—, —CO—O—, —NR 32 — or —P ( ⁇ O) (OR 32 ) O—, and at least one of c2 Xs is —NR 32 — or —P ( ⁇ O) (OR 32 ) O—.
  • the group satisfying the condition (1) is preferably a group satisfying any of the following conditions (1-1) to (1-3). This is because the compound A has an excellent balance between heat resistance and solubility.
  • the group satisfying the condition (1-1) or the condition (1-3) among the groups satisfying the condition (1) is more preferable.
  • (1-1) c2 is 1, R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R 31 does not form a ring with L 1 .
  • (1-2) c2 is 1
  • R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R 31 forms a ring with L 1 .
  • (1-3) c2 is 1, and R 31 is an aromatic ring-containing hydrocarbon group having 6 to 10 carbon atoms.
  • the group satisfying the condition (2) is preferably a group satisfying the following condition (2-1) or condition (2-2). This is because the compound A has an excellent balance between heat resistance and solubility.
  • a group satisfying the condition (2-2) is preferable among the groups satisfying the condition (2).
  • the above c2 is 2, one of the two Xs is —O—, —S—, —CO—, —O—CO— or —CO—O—, and R 31 is , R 32 to form a ring.
  • c2 is 1, R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R 31 does not form a ring with R 32 .
  • the compound to be obtained is an example of a compound that satisfies the above condition (1-1).
  • the compound represented by the formula (14) described later is an example of a compound that satisfies the above condition (1-2).
  • the compounds represented by formulas (11) to (12) and formulas (23) to (24) described below are examples of compounds that satisfy the above condition (1-3).
  • the compound represented by the formula (18) described below is an example of a compound that satisfies the above condition (2-1).
  • the compound represented by the formula (37) to be described later is an example of a compound that satisfies the above condition (2-2).
  • condition (B) a group satisfying the following condition (B) or condition (C) can also be preferably used. It is because the said compound A can form the radical polymerization initiator excellent in the balance of heat resistance and solubility because the said substituent C is the above-mentioned group.
  • L 1 is a direct bond
  • R 31 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms
  • X is —O—, —S—, —CO—, —O. —CO— or —CO—O—, wherein c1 is 1, c2 is an integer of 1 to 4, and c3 is 1.
  • the substituent C is a group in which a methylene group in a group such as an aliphatic hydrocarbon group is substituted with a predetermined atom or group. This is because, compared with the case where the atoms or groups such as alkoxy groups are directly bonded, the acid is stable, the synthesis is easy, and the heat resistance is excellent. In addition, as a result of being stable against acid, it is excellent in storage stability and can exhibit desired curing such as heat resistance stably.
  • c2 is 1 and X is —CO—.
  • c2 is 1
  • R 31 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • X is —O— or —S—. More preferred.
  • the compound represented by Formula (70) mentioned later shows the example of the compound which satisfy
  • the compound represented by the formula (71) described later is an example of a compound that satisfies the above condition (C).
  • R 10 and R 11 are a group represented by the substituent C, but it is preferable that both R 10 and R 11 are the substituent C. It is because the compound A can form a radical polymerization initiator excellent in the balance between heat resistance and solubility because both R 10 and R 11 are the groups described above. In the present invention, when both R 10 and R 11 are substituents C, from the viewpoint of being able to form a radical polymerization initiator having an excellent balance between heat resistance and solubility, the substituents C are as defined above. A group satisfying any of (A), condition (B), and condition (C) can be preferably used.
  • a group satisfying condition (A) is preferable, and in particular, condition (1-1)
  • condition (1-1) a group satisfying the condition (1-2) is preferable, and among them, a group satisfying the condition (1-1) is particularly preferable from the viewpoint of excellent storage stability.
  • the substituent C when only one of R 10 and R 11 is the substituent C, the substituent C is formed from the viewpoint of forming a radical polymerization initiator having an excellent balance between heat resistance and solubility.
  • a group that satisfies any of the above conditions (A), (B), and (C) can be preferably used. Among them, a group that satisfies the conditions (A) or (B) is preferable.
  • a group satisfying the condition (A) is preferable, and a group satisfying the condition (1-1) is particularly preferable. This is because the compound A can form a radical polymerization initiator having an excellent balance between heat resistance and solubility and also having excellent storage stability.
  • R 10 and R 11 When both R 10 and R 11 are the substituent C, the substituents C represented by R 10 and R 11 can form a ring. That is, R 10 can be linked to R 11 to form a ring.
  • the substituent C used for R 10 is L 1 is an aliphatic hydrocarbon group
  • X is —O—
  • R 31 is an aliphatic hydrocarbon group
  • the substituent C used for R 11 is L 1.
  • X is —NR 32 —
  • R 31 is an aliphatic hydrocarbon group
  • R 10 and R 11 can form a ring containing an oxygen atom and a nitrogen atom, such as a morpholine ring.
  • Substituent B is a group represented by the following general formula (B).
  • R 21 and R 22 are each independently a hydrogen atom, hydroxyl group, NR 23 R 24 , CONR 23 R 24 , nitro group, cyano group, halogen atom, alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms; R 23 and R 24 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 21 , R 22 , R 23 and R 24 include straight chain, branched, cyclic (alicyclic hydrocarbon) and those having a combination thereof.
  • cyclic alicyclic hydrocarbon
  • Examples of the aryl group having 6 to 30 carbon atoms represented by R 21 , R 22 , R 23 and R 24 include phenyl, naphthyl, anthracenyl and the like.
  • Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R 21 , R 22 , R 23 and R 24 include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl and the like.
  • Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R 21 , R 22 , R 23 and R 24 include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl , Benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone- Examples thereof include 1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl
  • Each functional group such as a heterocyclic ring-containing group of formula 2 to 20 may have a substituent, and unless otherwise specified, is unsubstituted or has no substituent. It is what has.
  • substituents for substituting hydrogen atoms such as alkyl groups, aryl groups, arylalkyl groups, and heterocyclic-containing groups represented by R 21 , R 22 , R 23 and R 24 include vinyl, allyl, acrylic, methacryl and the like Ethylenically unsaturated groups; halogen atoms such as fluorine, chlorine, bromine, iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl , Acyloxy groups such as acetyloxy and benzoyloxy; amino, ethylamino, acetyloxy, benzoyloxy, and the like; Methylamino, diethylamino, butylamino, cyclopentyla
  • one or more of the hydrogen atoms in the alkyl group, aryl group, arylalkyl group and heterocyclic group represented by R 21 , R 22 , R 23 and R 24 are an ethylenically unsaturated group, Halogen atom, acyl group, acyloxy group, substituted amino group, sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group , R 21 , R 22 , R 23 and R 24 may be one of hydrogen atoms in the aforementioned alkyl group, aryl group, arylalkyl group and heterocyclic group-containing group.
  • two or more are ethylenically unsaturated groups, halogen atoms, acyl groups, acyloxy groups, substituted amino groups, sulfonamido groups, sulfonyl groups, Carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imido group, a carbamoyl group, a sulfonamido group, a phosphonic acid group may be a group which is substituted by phosphate groups.
  • the methylene group in the heterocyclic ring-containing group of 2 to 20 is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. That is, one or more of the methylene groups in the alkyl group, aryl group, arylalkyl group and heterocyclic group represented by R 21 , R 22 , R 23 and R 24 are a carbon-carbon double bond.
  • the group may be substituted with a group in which oxygen atoms are not adjacent to each other, and R 21 , R 22 , R 23, and R 24 include the above-described alkyl group, aryl group, arylalkyl group, and heterocyclic ring
  • R 21 , R 22 , R 23, and R 24 include the above-described alkyl group, aryl group, arylalkyl group, and heterocyclic ring
  • One or more of the methylene groups in the group are carbon-carbon double bonds, —O—, —S—, —CO—, O—CO—, —CO—O—, —O—CO—O—, —S—CO—, —CO—S—, —S—CO—O—, —O—CO—S—, —CO—.
  • R 21 can form a ring with a benzene ring contained in the fluorene ring.
  • R 21 is bonded to a position adjacent to the bonding position of the substituent B of the benzene ring, the benzene ring contained in the fluorene ring, and —C ( ⁇ O) —C ( ⁇ N) —R of the substituent B 21 can form a ring.
  • the compound A improves the light absorption efficiency in the long wavelength region and has excellent sensitivity.
  • the compounds represented by the formulas (43) to (45) described later are examples in which R 21 forms a ring with a benzene ring contained in the fluorene ring.
  • R 21 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms.
  • an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms is preferable.
  • an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable, and an alkyl group having 2 to 8 carbon atoms is particularly preferable.
  • an alkyl group having 4 to 8 carbon atoms is particularly preferable. It is because the compound A can form a radical polymerization initiator having an excellent balance between heat resistance and solubility when R 21 is the group described above.
  • R 21 when R 21 is an alkyl group, it may be any of a straight chain, a branched chain, a cyclic (alicyclic hydrocarbon) and a combination thereof, but is preferably a straight chain. This is because the compound A can form a radical polymerization initiator having an excellent balance between heat resistance and solubility.
  • R 22 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms.
  • an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms is preferable.
  • an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable, and an alkyl group having 1 to 8 carbon atoms is particularly preferable.
  • an alkyl group having 1 to 3 carbon atoms is particularly preferable. It is because the compound A can form a radical polymerization initiator excellent in the balance between heat resistance and solubility because R 22 is the group described above.
  • R 23 and R 24 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms.
  • a ring-containing group is preferred, and among them, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an aryl group having 2 to 20 carbon atoms. It is preferably a heterocycle-containing group, particularly preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and in particular, an alkyl group having 2 to 8 carbon atoms. It is preferable that It is because the compound A can form a radical polymerization initiator excellent in the balance between heat resistance and solubility because R 23 and R 24 are the groups described above.
  • B is an integer of 0 or 1, but is preferably 1. This is because the substituent B has a ketoxime ester structure, and the compound A has excellent deep permeability.
  • R 21 is an alkyl group having 2 to 8 carbon atoms and R 22 is 1 carbon atom from the viewpoint that the compound A has a good balance between heat resistance and solubility. It is preferable that the alkyl group is ⁇ 8 and b is 1.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is the substituent B.
  • the number of substituents B in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is 1 or more and 8 or less, preferably 2 or more and 4 or less. 2 or more and 3 or less are preferable, and 2 is preferable. This is because the compound A has an excellent balance of sensitivity and ease of synthesis.
  • R 2 and R 7 are preferably the substituent B.
  • Compound A An alkyl group having 1 to 20 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 and R 12 and R 13 ;
  • the aryl group, the arylalkyl group having 7 to 30 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms are represented by R 21 or the like described in the section “2.
  • One or more of the hydrogen atoms in the above are an ethylenically unsaturated group, halogen atom, acyl group, acyloxy group, substituted amino group, sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro A group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, a phosphoric acid group and the like, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 and R 12 and R 13 are alkyl groups mentioned above
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 and the methylene group in the alkyl group, aryl group, arylalkyl group and heterocycle-containing group used for R 12 and R 13 One or two or more of carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —S —CO—, —CO—S—, —S—CO—O—, —O—CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—.
  • —S—S— or —SO 2 — may be substituted with a group in which oxygen atoms are not adjacent to each other, and R 1 , R 2 , R 3 , R 4 , R 5, R 6, R 7 and R 8 and R 12 and R 13 are alkyl groups mentioned above, aryl group, arylalkyl group and heterocyclic ring-containing group
  • R 1 , R 2 , R 3 , R 4 , R 5, R 6, R 7 and R 8 and R 12 and R 13 are alkyl groups mentioned above, aryl group, arylalkyl group and heterocyclic ring-containing group
  • One or more of the methylene groups in the formula are a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms represented by R 10 and R 11 include: The group can be the same as the group represented by R 31 or the like described in the section “1. Substituent C”.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are groups other than the substituent B, each independently represents a hydrogen atom, a hydroxyl group, NR 12 R 13 , CONR 12 R 13 , nitro group, cyano group, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms Although it is a group containing 20 heterocycles, it is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 1 , R 3 , R 4 , R 5 , R 6 and R 8 are preferably hydrogen atoms. This is because the compound A has excellent synthesis ease.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are groups other than the substituent B, the light absorption efficiency of the compound A in the long wavelength region is improved. From the viewpoint of excellent sensitivity, those capable of forming a conjugated system with the fluorene ring are preferred, such as a nitro group and an aryl group having 6 to 30 carbon atoms.
  • R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to Although it is a group containing 20 heterocycles, it is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. This is because the compound A has an excellent balance between heat resistance and solubility.
  • R 10 and R 11 are groups other than the above substituent C, they are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 120 carbon atoms, or an aromatic ring-containing hydrocarbon having 6 to 35 carbon atoms.
  • a group containing 2 to 10 aromatic heterocycles is preferable, and a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms is particularly preferable. This is because the compound A has an excellent balance between heat resistance
  • R 10 and R 11 can form a ring.
  • both R 10 and R 11 are the above substituent C, and R 10 and R 11 do not form a ring, and only one of R 10 and R 11 is the above substituent C. Yes, and R 10 and R 11 do not form a ring, or only one of R 10 and R 11 is the substituent C, and R 10 and R 11 form a ring It is preferable. This is because when R 10 and R 11 are the groups described above, the compound A can form a radical polymerization initiator having an excellent balance between heat resistance and solubility.
  • R 10 and R 11 when only one of R 10 and R 11 is the substituent C, the ring formed by connecting R 10 and R 11 is a ring formed by combining R 31 and L 1.
  • R 10 is a substituent C
  • L 1 is an aliphatic hydrocarbon group
  • X is —O—
  • R 31 is an aliphatic hydrocarbon group
  • R 11 is an aliphatic hydrocarbon group.
  • R 10 and R 11 can form a ring containing an oxygen atom, such as a tetrahydropyran ring.
  • only one of R 10 or R 11 is the substituent group C can be preferably used those R 10 and R 11 form a ring.
  • the compound represented by the formula (69) described later shows an example of a compound in which only one of R 10 and R 11 is the substituent C, and R 10 and R 11 form a ring. is there. More specifically, in the compound represented by the formula (69), R 10 is the substituent C (L 1 is an aliphatic hydrocarbon group having 2 carbon atoms, X is —O—, R 31 is an aliphatic hydrocarbon group having 1 carbon atom.) And R 11 is an aliphatic hydrocarbon group having 1 carbon atom, and R 31 in R 10 is an aliphatic carbon group.
  • An example of a compound in which a hydrogen group and an aliphatic hydrocarbon group as R 11 are bonded by a covalent bond to form a ring (tetrahydropyran ring) is shown.
  • Specific examples of the compound A include compounds represented by the following formulas (1) to (71).
  • the decomposition point of the compound A is not limited as long as it can form a cured product with less outgas.
  • it can be 210 ° C. or higher, and preferably 220 ° C. or higher. It is preferable that it is 230 degreeC or more. This is because the compound A has excellent heat resistance.
  • the upper limit of the decomposition point is preferably as high as possible, and is not particularly limited.
  • the decomposition point was determined by using a differential thermothermal gravimetric simultaneous measurement apparatus at a temperature rising start temperature of 30 ° C., a temperature rising end temperature of 500 ° C., and a temperature rising rate of 10 ° C./min in an atmosphere of about 5 mg of nitrogen and 200 mL / min of nitrogen
  • the temperature at which the exothermic peak of the sample becomes maximum when the temperature is raised can be taken as the decomposition point (° C.).
  • Any differential thermal thermogravimetric simultaneous measurement device may be used as long as it can accurately measure the decomposition point. For example, Hitachi High-Tech, Model: STA7200 can be used.
  • the manufacturing method of the said compound A should just be a method which can obtain a desired structure, and can use a well-known method.
  • Examples of the production method include a method in which the reactions represented by the following reaction formulas 1 to 4 are carried out in this order when the substituent B has a ketoxime ester structure.
  • the implementation order of Reaction formula 1 and Reaction formula 2 is replaced, and the method of implementing in order of Reaction formula 2, 1, 3, and 4 can also be used.
  • a known method for introducing the substituent B having an oxime ester structure can be used except that the following reaction formulas 1 and 2 are carried out.
  • reaction Formula 1 A fluorene ring is prepared, and a halogenated alkyl agent having the structure of the substituent C is reacted.
  • reaction formula 2 A carboxylic acid halide is reacted.
  • reaction formula 3 A nitrite is reacted with a fluorene ring.
  • reaction formula 4 A carboxylic acid halide is reacted.
  • the compound A can be used as, for example, a radical polymerization initiator component that generates radicals. More specifically, the compound A can be used as a radical polymerization initiator component that generates radicals by heat, light irradiation, or the like. it can. Moreover, the said compound A can be used as a radical polymerization initiator component in a curable composition. Examples of the use of the photocurable composition include photocurable paints or varnishes, photocurable adhesives, printed circuit boards, and color display liquid crystal display elements such as color televisions, PC monitors, portable information terminals, and digital cameras.
  • the radical polymerization initiator of the present invention comprises the above-mentioned compound A.
  • the radical polymerization initiator becomes excellent in heat resistance and solubility.
  • the radical polymerization initiator of the present invention consists of the above compound A alone or a composition containing the above compound A.
  • each component of the radical polymerization initiator of the present invention will be described in detail.
  • Compound A is the compound A represented by the general formula (A).
  • the type of compound A may be only one type or two or more types in the radical polymerization initiator.
  • the radical polymerization initiator can contain, for example, 2 or more and 5 or less compounds A.
  • the content of the compound A is appropriately set according to the type of radical polymerization initiator.
  • 100 mass parts, ie, the said radical polymerization initiator shall be the said compound A.
  • the content may be less than 100 parts by mass in 100 parts by mass of the solid content of the radical polymerization initiator, that is, the composition in which the radical polymerization initiator includes the compound A and other components, for example, It can be more than 10 mass parts and 99 mass parts or less, and it is preferable that they are 50 mass parts or more and 95 mass parts or less. This is because the radical polymerization initiator can effectively cure the polymerizable compound.
  • the solid content includes all components other than the solvent.
  • the radical polymerization initiator may contain other components other than the compound A. Examples of such other components include “2. Radical polymerizable compound”, “3. Resin component”, “4. Solvent”, and “5. Other components” of “C. The contents described in the section can be listed.
  • the other components preferably include the non-photosensitive resin described in the section “3. Resin component” above.
  • the radical polymerization initiator preferably has a low solvent content, for example, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, in 100 parts by mass of the radical polymerization initiator. 1 part by mass or less is preferable.
  • the radical polymerization initiator may be in the form of a powder or a pellet composed of Compound A alone, or one containing Compound A and a resin component.
  • the radical polymerization initiator may be in the form of a solution such as a dispersion or solution containing Compound A and a solvent for dispersing or dissolving the compound A.
  • the said radical polymerization initiator As a use of the said radical polymerization initiator, it can be used as a radical polymerization initiator component in a photocurable composition.
  • the specific use of the photocurable composition can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.
  • composition of the present invention comprises the compound represented by the above general formula (A) and a radically polymerizable compound.
  • the composition when the compound A is included, the composition has less outgassing and excellent dispersion stability.
  • composition of this invention contains the compound A and a radically polymerizable compound.
  • each component of the composition of this invention is demonstrated in detail.
  • the content of the compound A is not particularly limited as long as desired curability can be imparted to the composition.
  • As said content for example in 100 mass parts of solid content of a composition, it can be set as 0.05 mass part or more and 10 mass parts or less, and it is preferable that it is 0.1 mass part or more and 5 mass parts or less. . It is because the composition is excellent in sensitivity when the content is in the above range.
  • the solid content includes all components other than the solvent.
  • the type of the compound A contained in the composition may be only one type or two or more types.
  • the above types can be, for example, 2 types or more and 5 types or less.
  • the content of the compound A can be 0.05 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the radical polymerizable compound. Is preferred. It is because the composition is excellent in sensitivity when the content is in the above range.
  • the radical polymerizable compound is a compound having a radical polymerizable group and capable of being polymerized by a radical.
  • a radical polymerizable group ethylenically unsaturated double bonds, such as a (meth) acryl group and a vinyl group, etc. can be mentioned, for example.
  • (meth) acryl is used in the meaning containing acryl and methacryl.
  • (meth) acrylate is used in the meaning containing acrylate and methacrylate.
  • the radical polymerizable compound may be a compound having an acid value or a compound having no acid value.
  • the compound having an acid value include a compound having a carboxyl group.
  • the solubility of the compound having an acid value to an alkaline developer at the light irradiation site is lowered.
  • the said composition can be used as a photosensitive composition from which the solubility to solvents, such as an alkali developing solution, changes before and after light irradiation, for example. More specifically, the said composition can be used as a negative composition by including the compound which has an acid value.
  • the alkali developer those generally used as an alkali developer such as an aqueous tetramethylammonium hydroxide (TMAH) solution or an aqueous potassium hydroxide solution can be used.
  • Examples of the compound having an acid value include (meth) acrylate compounds having a carboxyl group such as (meth) acrylic acid.
  • Examples of the compound having no acid value include an epoxy acrylate resin and a (meth) acrylate compound having no carboxyl group such as 2-hydroxyethyl (meth) acrylate.
  • the said radically polymerizable compound can be used individually or in mixture of 2 or more types.
  • the radical polymerizable compound is used in combination of a compound having an ethylenically unsaturated double bond group and having an acid value and a compound having an ethylenically unsaturated double bond group and having no acid value. Can do.
  • radical polymerizable compounds When two or more kinds of radically polymerizable compounds are mixed and used, they can be copolymerized in advance and used as a copolymer. More specific examples of such radical polymerizable compounds include the radical polymerizable compounds described in JP-A No. 2016-176209.
  • the content of the radical polymerizable compound is not particularly limited as long as a cured product having a desired strength can be obtained.
  • the composition can contain a resin component other than the radically polymerizable compound.
  • the resin component include a polymerizable compound having a polymerizable group such as a cationic polymerizable compound and an anion polymerizable compound, and a polymer having no polymerizable group.
  • the content of the resin component is appropriately selected depending on the purpose of use and is not particularly limited.
  • the total content of the resin component and the radical polymerizable compound is appropriately selected depending on the purpose of use and is not particularly limited. It can be below mass parts.
  • the cationic polymerizable compound may have one or more polymerizable groups capable of cationic polymerization, and may be a monofunctional compound having one of the polymerizable groups, or 2 of the polymerizable groups.
  • the polyfunctional compound having the above can be used.
  • the cationic polymerizable compound include compounds having a cyclic ether group such as an epoxy compound having an epoxy group and an oxetane compound having an oxetane group, and a vinyl ether compound having a vinyl ether group. More specific examples of such cationically polymerizable compounds include the cationically polymerizable compounds described in JP-A No. 2016-176209.
  • cationic polymerizable compounds When two or more cationic polymerizable compounds are used as a mixture, they can be copolymerized in advance and used as a copolymer.
  • the cationically polymerizable compound can be used together with a cationic initiator such as a photocationic initiator or a thermal cationic initiator.
  • the anionic polymerizable compound may have at least one polymerizable group capable of anionic polymerization, and may be a monofunctional compound having one polymerizable group, or 2 polymerizable groups.
  • the polyfunctional compound having the above can be used.
  • the anionic polymerizable compound include an epoxy compound having an epoxy group, a lactone compound having a lactone group, and a compound having a (meth) acryl group.
  • the lactone compound include ⁇ -propiolactone and ⁇ -caprolactone.
  • the epoxy compound illustrated as said cation polymeric compound can be used.
  • a compound which has a (meth) acryl group what was illustrated as said radically polymerizable compound can be used.
  • anionic polymerizable compounds When two or more kinds of anionic polymerizable compounds are mixed and used, they can be copolymerized in advance and used as a copolymer.
  • a compound having a photosensitive group capable of photodimerization (hereinafter sometimes referred to as a photosensitive group-containing compound) can also be used.
  • a photosensitive group and a photosensitive group-containing compound containing the photosensitive group can be the same as those described in JP-A-2016-193985.
  • the photosensitive group may be any group that can be bonded by a photodimerization reaction. Specific examples include a stilbazolium group and a cinnamoyl group.
  • polymer having no polymerizable group The polymer does not have a polymerizable group.
  • any polymer having a repeating structure may be used, and examples thereof include a photosensitive resin having photosensitivity and a non-photosensitive resin having no photosensitivity.
  • Photosensitive resin has photosensitivity, and is used together with an acid generator, for example, a developer that breaks a chemical bond such as an ester group or an acetal group by the action of an acid.
  • an acid generator for example, a developer that breaks a chemical bond such as an ester group or an acetal group by the action of an acid.
  • a positive type resin that changes in a direction in which the solubility in the resin increases.
  • a positive type resin for example, a resist base resin or a compound described in JP-A-2016-89085 can be used.
  • the non-photosensitive resin may be any non-photosensitive resin, such as polycarbonate (PC), polyethylene terephthalate (PET), polyethersulfone, polyvinyl butyral, polyphenylene.
  • non-photosensitive resin such as polycarbonate (PC), polyethylene terephthalate (PET), polyethersulfone, polyvinyl butyral, polyphenylene.
  • examples include thermoplastic resins such as ether, polyamide, polyamideimide, polyetherimide, norbornene resin, acrylic resin, methacrylic resin, isobutylene maleic anhydride copolymer resin, cyclic olefin resin, polyvinyl alcohol, polyethylene glycol, and polynibil pyrrolidone. be able to.
  • a polymer of the polymerizable compound can also be used as the non-photosensitive resin. That is, the composition may be a cured product of a composition containing a polymerizable compound.
  • the weight average molecular weight (Mw) of the said polymer is suitably set according to the use etc. of a composition, it can be 1500 or more, for example, can be 1500 or more and 300000 or less.
  • the weight average molecular weight Mw is, for example, HLC-8120GPC manufactured by Tosoh Corporation, and the elution solvent is N-methylpyrrolidone to which 0.01 mol / liter lithium bromide is added, and polystyrene standard for calibration curve.
  • the measurement temperature can be 40 ° C.
  • the flow rate can be 1.0 mL / min.
  • the composition of this invention can contain a solvent other than the said compound A, a radically polymerizable compound, and a resin component.
  • the solvent is liquid at 25 ° C. and atmospheric pressure, and can disperse or dissolve each component of the composition.
  • the solvent does not react with the compound A, radically polymerizable compound, resin component and the like. Therefore, for example, compounds classified as compound A and radical polymerizable compounds are not solvents in the composition of the present invention even if they are liquid at 25 ° C. and atmospheric pressure.
  • the solvent is not particularly limited as long as it can disperse or dissolve each component of the composition, and examples thereof include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone.
  • Ketones ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, Ester solvents such as n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; cellosolv solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-a
  • ketones, ether ester solvents and the like particularly organic solvents such as propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as “PGMEA” or “propylene glycol monomethyl ether acetate”), cyclohexanone, From the viewpoint of good compatibility with the compound A and the like.
  • the said solvent can be used as 1 type, or 2 or more types of mixed solvents.
  • the content of the solvent is appropriately set according to the use of the composition, for example, in 100 parts by mass of the composition, can be 1 part by mass or more and 99 parts by mass or less, It is preferable that it is 10 to 80 mass parts. This is because it is easy to form a coating film having a desired thickness.
  • the said composition can contain another component as needed other than the compound A, a radically polymerizable compound, a resin component, and a solvent.
  • a polymerization initiator such as a cationic polymerization initiator that can be added together with the cationic polymerizable compound or an acid generator together with the photosensitive compound, and an anionic polymerization initiator that can be added together with the anionic polymerizable compound.
  • Etc. The polymerization initiator can also contain a radical polymerization initiator other than the compound A. More specific examples of the radical polymerization initiator and the cationic polymerization initiator other than the compound A include the radical polymerization initiator and the cationic initiator described in JP-A No. 2016-176209.
  • the anionic polymerization initiator include a photoanionic polymerization initiator and a thermal anionic polymerization initiator described in JP-A-2017-073389.
  • the other components include a colorant, an inorganic compound, a dispersant for dispersing the colorant and the inorganic compound, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine And the like.
  • a well-known material can be used, For example, the thing of international publication 2014/021023 can be used.
  • latent additives that exhibit ultraviolet absorption ability, antioxidant ability, etc.
  • a latent additive for example, those described in International Publication No. 2014/021023 can be used.
  • content of the said other component is suitably selected according to the use purpose, and it does not restrict
  • the production method of the composition may be any method that can mix the above components so as to have a desired content, and a known mixing method can be used.
  • a use of the said composition it can use as a photocurable composition hardened
  • the specific use can be the same as that described in the above section “A. Compound”.
  • the cured product of the present invention is a cured product of the above-described composition.
  • the cured product is a composition containing the compound A
  • the cured product has little variation in the degree of curing.
  • the cured product has less outgas.
  • the cured product of the present invention uses the above-described composition.
  • the cured product of the present invention will be described in detail.
  • it can be made to be the same as that of the content as described in the term of the said "C. composition”.
  • the cured product usually contains at least a polymer of a radical polymerizable compound.
  • the content of the polymer of the radical polymerizable compound can be the same as the content of the radical polymerizable compound described in the section “C. Composition”.
  • the cured product may be substantially free of solvent.
  • cured material it can be 1 mass part or less in 100 mass parts of hardened
  • plan view shape, thickness, and the like of the cured product can be appropriately set according to the use of the cured product.
  • the method for producing the cured product is not particularly limited as long as the cured product of the composition can be formed into a desired shape.
  • a manufacturing method for example, since it can be the same as the content described in the section of “E. Method for manufacturing a cured product” described later, description here is omitted.
  • the use of the cured product can be the same as the content described in the section “A. Compound”.
  • cured material of this invention has the process of light-irradiating the above-mentioned composition, It is characterized by the above-mentioned.
  • the cured product is a composition containing the compound A
  • the cured product has little variation in the degree of curing.
  • the cured product has less outgas.
  • the production method of the present invention includes a light irradiation step.
  • a light irradiation step is demonstrated in detail.
  • Step of Light Irradiation This step is a step of irradiating the above composition with light.
  • the irradiation amount of the irradiated light is appropriately adjusted according to the thickness of the coating film of the composition and the like as long as it can form a cured product having a desired hardness.
  • the light source for light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, and xenon arc. Laser light can be used as the irradiated light.
  • the laser light one containing light having a wavelength of 340 nm to 430 nm can be used.
  • the light source of the laser light those emitting light in the visible to infrared region such as an argon ion laser, helium neon laser, YAG laser, and semiconductor laser can be used.
  • the said composition can contain the sensitizing dye which absorbs the said area
  • the light irradiation method may be a method of irradiating the entire surface of the coating film of the composition in a plan view or a method of irradiating a part of the coating film with light.
  • the method of light irradiation can be, for example, a method of irradiating light through a mask or the like, a method of irradiating only the portion where the composition is cured, or the like. .
  • composition contains a polymeric compound normally for formation of hardened
  • the above manufacturing method includes a step of irradiating light, but may include other steps as necessary.
  • the process of forming the coating film of the said composition implemented before the said process of light irradiation, the process of developing implemented after the said process of light irradiation, and forming the said coating film examples include a step of removing a solvent, a step of heating (post-baking step) performed after the step of irradiating the light, and the like.
  • the composition contains a thermal polymerization initiator such as a thermal radical polymerization initiator, a thermal cationic polymerization initiator, or a thermal anion polymerization initiator
  • a thermal polymerization initiator such as a thermal radical polymerization initiator, a thermal cationic polymerization initiator, or a thermal anion polymerization initiator
  • the composition is heated and cured before and after the light irradiation step.
  • a process may be included.
  • the step of forming the coating film is not limited as long as it is a method capable of obtaining a coating film having a desired thickness.
  • a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types A known method such as printing or dipping can be used.
  • the substrate on which the coating film of the composition is formed can be appropriately set according to the use of the cured product, and includes, for example, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. Can be mentioned.
  • cured material on a base material even if it peels and uses from a base material, it can also transfer and use it from a base material to another base material.
  • the developing method in the developing step is not particularly limited as long as it can remove the uncured composition, and for example, a known developing method such as a method of removing using an alkaline developer can be used.
  • the method for removing the solvent in the step of removing the solvent is not limited as long as the content of the solvent contained in the cured product can be set to a desired amount.
  • the method of heating that is, the step of removing.
  • the method etc. which implement a prebaking process can be mentioned.
  • the heating temperature in the heating step (post-baking step), which is performed after the light irradiation step, is not limited as long as it is a temperature that can improve the mechanical strength of the cured product. It can be set accordingly.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
  • Example 1 A reaction vessel was charged with aluminum chloride (9.56 g, 71.7 mmol) and dichloroethane 30.0 g, and under ice cooling, fluorene (3.97 g, 23.9 mmol), octanoyl chloride (7.97 g, 49.0 mmol). In the order of. After reacting at room temperature for 1 hour, the reaction solution was poured into ice water and the precipitate was filtered off. Washing with ion-exchanged water and methanol gave pale yellow solid intermediate A-1.
  • intermediate A-1 (7.43 g, 17.8 mmol), tetrabutylammonium bromide (0.57 g, 1.78 mmol), THF 20.0 g, sodium hydroxide (8.88 g, 106.6 mmol), Bromoethyl ethyl ether (8.16 g, 53.3 mmol) was charged and reacted at 40 ° C. for 12 hours.
  • the reaction vessel was charged with ion exchange water, extracted with ethyl acetate, and the organic layer was washed with ion exchange water. After removing the solvent, recrystallization was performed with ethyl acetate / hexane to obtain a light yellow solid intermediate A-2.
  • Example 2 Compound A (hereinafter referred to as compound) represented by the following formula (2) was prepared in the same manner except that bromoethyl ethyl ether (halogenated alkyl) used for intermediate A-1 was changed to bromoethyl methyl ether. 2). It was confirmed by 1 H-NMR and IR that the obtained solid was the target product. The results of 1 H-NMR measurement of the obtained compound are shown in Table 1 below.
  • Example 3 The same method except that octanoyl chloride used for fluorene was changed to hexanoyl chloride and bromoethyl ethyl ether (halogenated alkyl) used for intermediate A-1 was changed to bromoethyl methyl ether.
  • compound A represented by the following formula (3) (hereinafter sometimes referred to as compound 3) was obtained. It was confirmed by 1 H-NMR and IR that the obtained solid was the target product. The results of 1 H-NMR measurement of the obtained compound are shown in Table 1 below.
  • Example 4 Compound A represented by the following formula (14) (hereinafter referred to as Formula A) (hereinafter referred to as Formula A) except that bromoethyl ethyl ether (halogenated alkyl) used for Intermediate A-1 was changed to 2- (bromomethyl) tetrahydrofuran. , Sometimes referred to as Compound 14). It was confirmed by 1 H-NMR and IR that the obtained solid was the target product.
  • Example 5 Compound A represented by the following formula (18) was prepared in the same manner except that bromoethyl ethyl ether (halogenated alkyl) used for intermediate A-1 was changed to 4- (2-chloroethyl) morpholine. (Hereinafter may be referred to as Compound 18). It was confirmed by 1 H-NMR and IR that the obtained solid was the target product.
  • Example 6 Compound A represented by the following formula (20) (hereinafter referred to as the following formula (20)) was changed in the same manner except that bromoethyl ethyl ether (alkyl halide) used for intermediate A-1 was changed to methyl 4-bromobutyrate. May be referred to as Compound 20.). It was confirmed by 1 H-NMR and IR that the obtained solid was the target product.
  • Example 7 Compound A represented by the following formula (21) (hereinafter referred to as Formula A) (hereinafter referred to as Formula A) was changed in the same manner except that bromoethyl ethyl ether (alkyl halide) used for Intermediate A-1 was changed to methyl 2-bromopropionate , Sometimes referred to as Compound 21). It was confirmed by 1 H-NMR and IR that the obtained solid was the target product.
  • Example 8 Compound A represented by the following formula (37) was prepared in the same manner except that bromoethyl ethyl ether (alkyl halide) used for intermediate A-1 was changed to diethyl 2-bromoethylphosphonate. Hereinafter, this may be referred to as Compound 37). It was confirmed by 1 H-NMR and IR that the obtained solid was the target product.
  • Examples 9 to 10 It is represented by the following formulas (66) and (67) in the same manner except that the bromoethyl ethyl ether (halogenated alkyl) used for the intermediate A-1 is changed to ethyl 2-bromopropionate.
  • Compound A (hereinafter sometimes referred to as compounds 66 and 67) was obtained. It was confirmed by 1 H-NMR that the obtained solid was the target product.
  • Example 11 The same method except that octanoyl chloride used for fluorene was changed to butyryl chloride and bromoethyl ethyl ether (halogenated alkyl) used for intermediate A-1 was changed to bromoethyl methyl ether
  • compound A represented by the following formula (68) (hereinafter sometimes referred to as compound 68) was obtained. It was confirmed by 1 H-NMR that the obtained solid was the target product.
  • Example 12 Compound A represented by the following formula (69) was prepared in the same manner except that bromoethyl ethyl ether (alkyl halide) used for intermediate A-1 was changed to bis (2-bromoethyl) ether. Hereinafter, it may be referred to as Compound 69). It was confirmed by 1 H-NMR that the obtained solid was the target product.
  • Example 13 The same method except that octanoyl chloride used for fluorene was changed to hexanoyl chloride and bromoethyl ethyl ether (halogenated alkyl) used for intermediate A-1 was changed to 4-fluorobenzophenone.
  • compound A represented by the following formula (70) (hereinafter sometimes referred to as compound 70) was obtained. It was confirmed by 1 H-NMR that the obtained solid was the target product.
  • Example 14 A reaction vessel was charged with 9-hydroxyfluorene (9.29 g, 50.9 mmol), methyl iodide (7.23 g, 50.9 mmol), potassium carbonate (3.87 g, 28.0 mmol), and 20.0 g of acetone. Stir at room temperature for 1 hour. Thereafter, ion exchange water was charged into the reaction vessel, extraction was performed with ethyl acetate, and the organic layer was washed with ion exchange water. After removing the solvent, intermediate 71-A1 (9-methoxyfluorene) was obtained.
  • Compound A represented by the following formula (71) (hereinafter referred to as Compound 71) was produced in the same manner as in Example 1 except that octanoyl chloride was changed to hexanoyl chloride for the obtained intermediate 71-A1. There is a case.) It was confirmed by 1 H-NMR that the obtained solid was the target product.
  • solubility of 15 wt% or more Solubility of 10 wt% or more and less than 15 wt%
  • Solubility of 5 wt% or more and less than 10 wt% ⁇ Solubility of less than 5 wt%
  • the solubility is a temperature of 25 ° C, relative humidity (RH) )
  • RH relative humidity
  • the compounds obtained in Examples and Comparative Examples were gradually dissolved every 0.1 g, and became insoluble (floating or precipitated, By measuring the amount of addition at the time when precipitation and white turbidity were observed, the solubility in an organic solvent (compound addition amount (g) / organic solvent 100 g ⁇ 100 (%)) was obtained.
  • Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-5 Each component was stirred at room temperature for 1 hour according to the composition of Table 4 below to obtain a composition. In addition, a number represents a mass part.
  • D-1 Blue pigment dispersion (solid content concentration 22.4% by mass, pigment concentration in the solid content 62.5% by mass, solvent PGMEA)
  • E-1 KBE-403 (coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • F-1 Propylene glycol-1-monomethyl ether-2-acetate (solvent)
  • Sensitivity evaluation (line width sensitivity)
  • a line width of 35 ⁇ m or more was designated A, B less than 35 ⁇ m and 30 ⁇ m or more B, and C less than 30 ⁇ m.
  • Table 4 The results are shown in Table 4 below. It can be determined that the sensitivity is better as the line width is larger.
  • the sample was pre-baked at 90 ° C. for 120 seconds and then cooled at 23 ° C. for 60 seconds. Then, it exposed through the photomask (mask opening 30 micrometers) using the ultra high pressure mercury lamp (exposure gap 300 micrometers, exposure amount 40mJ / cm ⁇ 2 >). After developing using 0.04 mass% KOH aqueous solution as a developing solution, it was washed thoroughly with water and post-baked at 230 ° C.
  • Luminance Spin coating the composition of the example and the comparative example on the glass substrate (so that the chromaticity coordinates (x, y) (0.135, 0.098) after post-baking), and using a hot plate Then, after pre-baking at 90 ° C. for 120 seconds, it was cooled at 23 ° C. for 60 seconds. Thereafter, after exposure at 150 mJ / cm 2 using an ultrahigh pressure mercury lamp, post-baking was performed at 230 ° C. for 20 minutes using a clean oven to prepare an evaluation sample. From the transmittance of the obtained sample at 380 to 780 nm, the Y value was determined according to JIS Z8701. The results are shown in Table 3 below.
  • a Y value of 11.0 or more was designated as A, 11.0 or less and 10.8 or more as B, and less than 10.8 as C.
  • the results are shown in Table 4 below. It can be determined that the higher the Y value, the higher the luminance and the higher the transmittance in the visible light region, which is useful.
  • the compound A of the examples can be used as a radical polymerization initiator that is excellent in heat resistance and solubility and excellent in sensitivity and the like. Moreover, it has confirmed that the said compound A obtained the hardened
  • the present invention has an effect of providing a compound capable of forming a radical polymerization initiator excellent in heat resistance and solubility.

Abstract

Le problème à résoudre par la présente invention concerne la fourniture d'un composé capable de former un initiateur de polymérisation radicalaire qui présente une excellente résistance à la chaleur et une excellente solubilité. La présente invention concerne un composé représenté par la formule générale (A). (Dans la formule, chacun de R1, R2, R3, R4, R5, R6, R7 et R8 représentent indépendamment un atome d'hydrogène, un groupe représenté par la formule générale (B) ou similaire ; au moins l'un parmi les fragments R1, R2, R3, R4, R5, R6, R7 et R8 représente un groupe représenté par la formule générale (B) ; chacun de R10 et R11 représente indépendamment un groupe hydrocarboné aliphatique ayant de 1 à 120 atomes de carbone, un groupe représenté par la formule générale (C) ou similaire ; et au moins l'un parmi les fragments R10 et R11 est un groupe représenté par la formule générale (C), voir la description pour d'autres détails.)
PCT/JP2019/011881 2018-03-27 2019-03-20 Composé, initiateur de polymérisation radicalaire, composition, produit durci et procédé de production d'un produit durci WO2019188717A1 (fr)

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