Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
  • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used

Definitions

• the present invention relates to a carbamoyloxime compound.
• a polymerizable composition such as a photosensitive resin composition is obtained by adding a photopolymerization initiator to a polymerizable compound such as a photosensitive resin, and can be polymerized and cured or developed by irradiation with energy rays (light). Therefore, it is used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, and the like.
• Photopolymerization initiators are classified into photoradical generators, photoacid generators, and photobase generators, depending on the active species generated by energy ray (light) irradiation.
• the photoradical generator has advantages such as a high curing rate and no active species remaining after curing, but has a disadvantage that a layer or the like that blocks oxygen must be provided in the curing of the thin film because the curing is inhibited by oxygen.
• the photoacid generator has an advantage that it is not inhibited by oxygen, but has a disadvantage that the residual active acid causes the metal substrate to corrode and the resin after curing is modified.
• Photobase generators are attracting attention because they are less likely to cause problems such as inhibition of curing by oxygen and corrosion by residual active species, but generally have a problem of low sensitivity (low curability) as compared with photoacid generators.
• Photobase generators are described, for example, in Patent Documents 1 and 2.
• Patent Document 1 describes a carbamoyloxime compound as a compound having a photobase generating ability.
• An object of the present invention is to provide a compound capable of generating a highly reactive active species (radical) at the same time as a base.
• the present invention has achieved the above object by providing the following [1] to [10] after diligent studies.
• R 1 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or the hydrocarbon group or the like.
• hydrocarbon groups, the heterocyclic groups or groups in which they have been replaced by groups selected from Group I have been replaced by divalent groups selected from Group II below.
• a group X 1 represents -NR 2 R 3 , or a group represented by the following general formula (a) or the following general formula (b).
• R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a monovalent group in which one or more hydrogen atoms in the hydrocarbon group are selected from the following group I.
• R 2 and R 3 are connected to each other and have a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom. It may form 10 rings, Group I is a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 4 , -COOR 4 , -CO-R 4 or -SR 4 .
• R 4 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group.
• R 4 represents a group, if R 4 is more present in the group, they may be the same or different and Group II is -O-, -CO-, -COO-, -OCO-, -NR 5- , -NR 5 CO- and -S-.
• R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 5s are present in the group, they may be the same or different.
• n represents 0 or 1 and represents * Represents a bond.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are independently hydrocarbonized with a hydrogen atom and 1 to 20 carbon atoms, respectively.
• Represents a hydrogen group, or a group in which one or more of the hydrogen atoms in the hydrocarbon group is replaced with a monovalent group selected from Group I above, or the hydrocarbon group or the hydrocarbon group Represents a group in which one or more of the methylene groups in the group replaced by a group selected from Group I has been replaced by a divalent group selected from Group II.
• R 11 and R 12 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 , and R 19 and R 20 are independently linked to each other from hydrogen, nitrogen and carbon atoms. It may form a ring having 2 to 10 carbon atoms or a ring having 2 to 10 carbon atoms composed of hydrogen atom, oxygen atom, nitrogen atom and carbon atom. * Represents a bond. )
• a 1 represents an aromatic ring structure having 6 to 20 carbon atoms.
• R 31 represents a group represented by the general formula (I).
• R 32 is a photoradical group having no carbamoyloxime group, a hydrocarbon group having 1 to 20 carbon atoms substituted with a photoradical generating group having no carbamoyloxime group, and a light having no carbamoyloxime group.
• a heterocyclic group having 2 to 20 carbon atoms substituted with a radical generating group, or one or more hydrogen atoms in the hydrocarbon group or the heterocyclic group is monovalent selected from the following group III.
• Represents a group Group III is a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 34 , -COOR 34 , -CO-R 34 or -SR 34 .
• R 34 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group.
• Group IV is, -O -, - CO -, - COO -, - OCO -, - NR 35 -, - NR 35 CO- or a -S-,
• R 35 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 35s are present in the group, they may be the same or different.
• a represents an integer of 1 to 19, when a is an integer of 2 or more, R 31 there are a plurality, may be the same or different and b represents an integer from 1 to 19, and when b is an integer of 2 or more, a plurality of R 32s existing may be the same or different.
• c represents an integer of 0 to 18, and when c is an integer of 2 or more, a plurality of R 33s existing may be the same or different.
• a + b + c is 20 or less.
• a 1 is carbamoyl oxime compound according to the structure represented by the following general formula (III) [2].
• Y 1 represents an oxygen atom, a sulfur atom, a selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 .
• Y 2 represents a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 .
• R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, the hydrocarbon group or the complex.
• Group V is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a heterocyclic group having 2 to 20 carbon atoms.
• the photoradical generating group having no carbamoyloxime group is represented by the following general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf) or (IVg).
• R 51 represents OR 81 , NR 82 R 83 or a heterocyclic group having 2 to 20 carbon atoms.
• R 52 and R 53 independently represent R 81 or OR 81 , respectively. R 52 and R 53 may be combined to form a ring.
• R 81 , R 82 and R 83 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64. , R 65 and R 71 represent an aryl group having 6 to 20 carbon atoms.
• R 54 , R 57 , R 60 , R 63 , R 66 and R 67 each independently represent an arylene group or a single bond having 6 to 20 carbon atoms.
• R 68 represents a hydrocarbon group having 1 to 20 carbon atoms.
• R 69 and R 70 independently represent R 81 or OR 81 , respectively. * Represents a bond. )
• the polymerizable composition according to any one of (1) to (5) below.
• a method for producing a cured product which comprises a step of irradiating the polymerizable composition according to the above [7] or [8] with energy rays.
• the carbamoyloxime compound of the present invention has a radical generation ability in addition to a high base generation efficiency, and when incorporated into a polymerizable composition as a polymerization initiator, a polymerizable composition containing a conventional photobase generator. It has higher adhesiveness and curability immediately after light irradiation. Therefore, the polymerizable composition containing the carbamoyloxime compound of the present invention is useful as an adhesive.
• the carbamoyloxime compound of the present invention is a carbamoyloxime compound having a group represented by the above general formula (I) and a photoradical generating group having no carbamoyloxime group in the same molecule.
• the carbamoyl oxime compound has geometric isomers due to double bonds of oxime, but these are not distinguished. That is, in the present specification, the carbamoyloxime compound of the present invention, and the compound and the exemplified compound which are preferable forms of the compound described later represent a mixture of isomers or one of them, and the isomer having the structure shown may be used. It is not limited.
• the carbamoyloxime compound of the present invention is also simply referred to as "the compound of the present invention".
• the photoradical generating group having no carbamoyloxime group means a group other than the carbamoyloxime group that generates a radical by being irradiated with light (active energy) such as ultraviolet rays.
• the compound of the present invention has at least one photoradical generating group having no carbamoyloxime group in a portion of the molecule other than the group represented by the general formula (I).
• the carbamoyloxime compound of the present invention has high photobase generation efficiency due to high photodecomposition efficiency by a specific carbamoyloxime group and irreversibility in subsequent base species release.
• "general formula" may be simply described as "formula”.
• halogen atom described in the description of the above formula (I), the above formula (II) and the above formula (III) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the hydrocarbon groups having 1 to 20 carbon atoms include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and 6 to 20 carbon atoms. Of the above, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is particularly preferable from the viewpoint of sensitivity and solubility.
• Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an amyl group and an isoamyl.
• Examples thereof include an unsaturated aliphatic hydrocarbon group having a structure substituted with a heavy bond or a carbon-carbon triple bond, and a group having about 2 to 8 carbon atoms is particularly preferable from the viewpoint of solubility and sensitivity.
• a compound in which R 1 of the formula (I) is an aliphatic hydrocarbon group having 2 to 8 carbon atoms is preferable because it has excellent solubility and sensitivity.
• the aliphatic hydrocarbon group having 2 to 8 carbon atoms is particularly preferably an alkyl group having 2 to 8 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group.
• R 33 of the formula (II) is an aliphatic hydrocarbon group having 2 to 8 carbon atoms is particularly preferable from the viewpoint of solubility.
• R 33 of the formula (II) is R 43 of NR 43 when A 1 of the formula (II) is a carbazole ring, for example, from the viewpoint of solubility.
• the aliphatic hydrocarbon group having 2 to 8 carbon atoms is particularly preferably an alkyl group having 2 to 8 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group.
• the group represented by R 81 , R 82 and R 83 has one carbon atom.
• Compounds of 8 to 8, particularly 1 to 3 aliphatic hydrocarbon groups are particularly preferable from the viewpoint of sensitivity.
• R 68 in the formula (IVf) is an aliphatic group having 2 to 8 carbon atoms.
• Compounds that are hydrocarbon groups are particularly preferable from the viewpoint of solubility.
• Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, a mesityl group, a benzyl group, a naphthyl group, a phenanthryl group, a pyrenyl group and a biphenyl group.
• heterocyclic group having 2 to 20 carbon atoms examples include a tetrahydrofuranyl group, a dioxolanyl group, a tetrahydropyranyl group, a morpholic group, a thiazyl group, a furanyl group, a thiophenyl group and a methylthiophenyl group.
• heterocyclic groups such as hexylthiophenyl group, benzothiophenyl group, pyrrolyl group, pyrrolidinyl group, imidazolyl group, imidazolinyl group, imidazolidinyl group, pyrazolinyl group, pyrazolidinyl group, piperidinyl group and piperazinyl group, and heterocyclic groups thereof.
• the group and the like can be mentioned.
• the heterocyclic group is a heterocyclic group or a group in which a heterocyclic group and a hydrocarbon group are bonded.
• a monovalent heterocyclic group refers to a group obtained by removing one hydrogen atom from the heterocycle of a heterocyclic compound.
• a fused ring of a heterocycle and an aromatic ring (indole, etc.) is also included in the heterocycle.
• the heterocyclic group is a group in which a heterocyclic group and a hydrocarbon group are bonded
• the heterocyclic group is a group in which one or more hydrogen atoms in the heterocyclic group are substituted with the above aliphatic hydrocarbon group. It may be a group in which one or more hydrogen atoms in the aliphatic hydrocarbon group are substituted with the heterocyclic group.
• the number of carbon atoms of the heterocycle-containing group includes not only the number of carbon atoms of the heterocycle but also the number of carbon atoms derived from the structure other than the heterocycle.
• R 1, R 2, R 3 , R 11 of formula (a) and Formula (b), R 12, R 13, R 14, R 15, R 16, R 17 in the formula (I), R 18, R 19 and R 20 (hereinafter, also referred to as "R 1 etc.")
• One or two or more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are monovalently selected from the above group I.
• one or two or more hydrogen atoms in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms are a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 4 , or -COOR. 4. Examples include groups substituted with -CO-R 4 or -SR 4.
• the total number of carbon atoms of the group represented by R 1 or the like including the number of carbon atoms of the substituent is 1 to 25. It is preferably present, and particularly preferably 1 to 20. Further, in R 4 , one or more hydrogen atoms, a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group or a hydroxyl group.
• the above represents a group replaced with a divalent group selected from the above group II, and a group having a total number of carbon atoms of 1 to 20 can be mentioned.
• carbon atoms R 4 is 1-10, more preferably 1-5, particularly preferably 1-3.
• One or two or more hydrogen atoms in the heterocyclic group having 2 to 20 carbon atoms represented by R 1 etc. in the above formula (I) are replaced with a monovalent group selected from the above group I.
• one or two or more hydrogen atoms in the heterocycle-containing group having 2 to 20 carbon atoms are a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 4 , -COOR 4 , -. Examples include groups substituted with CO-R 4 or -SR 4.
• the total number of carbon atoms represented by R 1 or the like including the number of carbon atoms of the substituent is 2 to 25. Is preferable, and 2 to 20 is particularly preferable.
• One or two or more above group II of the methylene groups of the groups a hydrocarbon group or which is replaced by a group selected from the group I of the formula (I) having 1 to 20 carbon atoms represented by R 1 etc.
• the group substituted with the divalent group selected from is the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, or the group in which the hydrogen atom in the hydrocarbon group is substituted with the group selected from group I. Examples thereof include groups in which one or more methylene groups are substituted with -O-, -CO- , -COO-, -OCO-, -NR 5- , -NR 5 CO- or -S-.
• R 1 or the like When the hydrocarbon group represented by R 1 or the like or the methylene group of the group in which the group is replaced by the group selected from Group I is replaced by the divalent group selected from Group II, it is represented by R 1 or the like.
• the total number of carbon atoms in the group is preferably 1 to 25, particularly preferably 1 to 20, and even more preferably 1 to 18.
• R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 5s are present in the group, they may be the same or different.
• the number of carbon atoms of R 5 is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
• a group in which one or more of the methylene groups in the group are substituted with -O-, -CO- , -COO-, -OCO-, -NR 5- , -NR 5 CO- or -S-. Can be mentioned.
• R 1 or the like When the methylene group of the heterocyclic group represented by R 1 or the like or a group in which this is replaced by a group selected from Group I is replaced by a divalent group selected from Group II, the table is represented by R 1 or the like.
• the total number of carbon atoms of the group to be formed is preferably 2 to 25, particularly preferably 2 to 20, and even more preferably 2 to 18.
• R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 5s are present in the group, they may be the same or different.
• 18 , R 19 and R 20 may each be connected to each other to form each of the above-mentioned "rings having 2 to 10 carbon atoms consisting of hydrogen atoms, nitrogen atoms and carbon atoms". It is a ring composed of carbon atoms. Examples of a ring consisting of hydrogen atom, nitrogen atom and carbon atom having 2 to 10 carbon atoms include -NR 2 R 3 , -NR 11 R 12 , -NR 13 R 14 , -NR 15 R 16 , and -NR.
• Examples of the ring containing a nitrogen atom in each of 17 R 18 and -NR 19 R 20 include a pyrrol ring, a pyrrolidine ring, an imidazole ring, an imidazolidine ring, an imidazoline ring, a pyrazole ring, a pyrrolidine ring, a piperidine ring, and a piperazine ring.
• These rings may have a substituent, and examples of the substituent include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.
• the number of carbon atoms 2 to 10 in the "ring having 2 to 10 carbon atoms composed of the above hydrogen atom, nitrogen atom and carbon atom” means the number of carbon atoms constituting the ring.
• the number of carbon atoms in the above ring including the number of carbon atoms of the substituent is preferably 12 or less, and more preferably 10 or less.
• 18 , R 19 and R 20 may each be connected to each other to form each of the above-mentioned "rings having 2 to 10 carbon atoms consisting of hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms" having a ring skeleton. It is a ring composed of an oxygen atom, a nitrogen atom and a carbon atom.
• Examples of a ring having 2 to 10 carbon atoms consisting of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom include -NR 2 R 3 in the formula (I) and NR 11 R 12 and -NR in the formula (a).
• rings containing nitrogen atoms in 13 R 14 and -NR 15 R 16 , -NR 17 R 18 , and -NR 19 R 20 in formula (b) morpholin ring, oxazoline ring, oxazoline ring, and oxadiazole, respectively. Rings and the like can be mentioned. These rings may have a substituent, and examples of the substituent include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.
• the number of carbon atoms 2 to 10 in the "ring having 2 to 10 carbon atoms consisting of hydrogen atom, oxygen atom, nitrogen atom and carbon atom” means the number of carbon atoms constituting the ring.
• the number of carbon atoms in the above ring including the number of carbon atoms of the substituent is preferably 12 or less, and more preferably 10 or less.
• the aromatic ring structure containing an aromatic hydrocarbon ring means a structure containing an aromatic hydrocarbon ring without containing an aromatic heterocycle, for example, a cyclobutadiene ring, a benzene ring, a cyclooctatetraene ring, and a cyclo.
• Examples thereof include a tetradecaheptaene ring, a cyclooctadecanonaene ring, a naphthalene ring, an anthracene ring, a triphenylamine structure, a diphenylsulfide structure and a fluorene ring.
• the aromatic ring structure containing an aromatic heterocycle means a structure containing an aromatic heterocycle, for example, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, and a pyrimidine ring. , Pyrimidine ring, carbazole ring, indole ring and the like.
• a is an integer of 1 to 19, when a is an integer of 2 or more, R 31 there are a plurality or different and the same, b is an integer of 1 to 19
• a plurality of R 32s existing may be the same or different
• c represents an integer of 0 to 18, and when c is an integer of 2 or more, a plurality of R 32s exist.
• the existing R 33 may be the same or different, but a + b + c is 20 or less. However, a + b + c is limited to the number that can be bonded in the aromatic ring structure.
• the compound in which a in the formula (II) is 1 to 3 is preferable because it is excellent in sensitivity when used as a latent base generator or a polymerization initiator, and a is 1 Is more preferred.
• the compound in which b in the formula (II) is 1 to 3 is preferable because it has excellent sensitivity when used as a latent base generator or a polymerization initiator, and the compound in which b is 1 is more preferable.
• a compound in which both a and b are 1 is particularly preferable.
• the compound in which R 32 in the formula (II) is a photoradical generating group having no oxime ester group is preferable because it has excellent sensitivity.
• the compound in which c in the formula (II) is 0 to 3 is preferable because it is excellent in transparency and sensitivity when used as a latent base generator or a polymerization initiator, and the compound in which c is 0 or 1 is preferable. Especially preferable.
• the hydrocarbon group having 1 to 20 carbon atoms substituted with a photoradical generating group having no carbamoyloxime group represented by R 32 is a hydrocarbon group having 1 to 20 carbon atoms.
• One or more means a group substituted with a photoradical generating group that does not have a carbamoyloxime group.
• a hydrocarbon group having 1 to 20 carbon atoms in which R 32 is substituted with the photoradical generating group or a methylene group in the hydrocarbon group is substituted with a group selected from Group IV, and / or in the group.
• the total number of carbon atoms of R 32 including the number of carbon atoms of those substituents is preferably 1 to 25 carbon atoms. It is particularly preferably from 20 to 20, and most preferably from 1 to 18.
• a heterocyclic group having 2 to 20 carbon atoms in which R 32 is substituted with the photoradical generating group or a methylene group containing the heterocyclic atom is substituted with a group selected from Group IV, and / or in the group.
• the hydrogen atom of is a group substituted with a group selected from the group III
• the total number of carbon atoms of R 32 including the number of carbon atoms of those substituents is preferably 2 to 25, preferably 2 to 20. Is more preferable.
• a group in which one or more of the hydrogen atoms in the 20 hydrocarbon groups are replaced with a monovalent group selected from the above group III one or two of the hydrogen atoms in these hydrocarbon groups are used. Examples of the above include halogen atoms, cyano groups, nitro groups, hydroxyl groups, groups substituted with -OR 34 , -COOR 34 , -CO-R 34 or -SR 34.
• R 33 has a substituent selected from Group III in which a hydrogen atom in a hydrocarbon group is substituted
• the total number of carbon atoms of R 33 including the substituent is preferably 1 to 25, preferably 1 to 20. More preferably.
• one or more of the hydrogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the hydrogen atom in the hydrocarbon group is a halogen atom, a cyano group, a nitro group or a hydroxyl group.
• One or more represents a group replaced with a divalent group selected from the above group IV, and a group having a total number of carbon atoms of 1 to 20 can be mentioned.
• the number of carbon atoms of R 34 is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
• a group in which one or two or more hydrogen atoms in the heterocycle-containing radicals of ⁇ 20 are replaced with monovalent groups selected from the above group III the heterocycle-containing radicals having 2 to 20 carbon atoms are used.
• Examples include a group in which one or more of the hydrogen atoms of the above are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 34 , -COOR 34 , -CO-R 34 or -SR 34 .
• R 33 has a substituent selected from Group III in which a hydrogen atom in a heterocyclic group is substituted, the total number of carbon atoms of R 33 including the substituent is preferably 1 to 25, and 1 to 20 Is more preferable.
• R 34 one or two or more of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom in the hydrocarbon group is replaced with a halogen atom, a cyano group, a nitro group or a hydroxyl group.
• a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom in the hydrocarbon group is replaced with a halogen atom, a cyano group, a nitro group or a hydroxyl group.
• the above represents a group replaced with a divalent group selected from the above group IV, and a group having a total number of carbon atoms of 1 to 20 can be mentioned.
• the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or the methylene in the group in which the hydrogen atom of the hydrocarbon group is replaced by the group III. or one or two of groups, -O -, - CO -, - COO -, - OCO -, - NR 35 -, - NR 35 CO- or -S- include been substituted with.
• R 33 is a group in which the methylene group in the group of the hydrocarbon group substituted or unsubstituted in Group III is substituted with the group selected in Group IV
• the total number of carbon atoms of R 33 is 1 to 25. Is preferable, 1 to 20 is more preferable, and 1 to 18 is particularly preferable.
• R 35 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 35s are present in the group, they may be the same or different.
• the number of carbon atoms of R 35 is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
• the above carbon is used.
• one of methylene groups in the heterocyclic ring-containing group of 2-20 or two or more, -O -, - CO -, - COO -, - OCO -, - NR 35 -, - NR 35 CO- or Examples include groups substituted with —S—.
• R 33 is a group in which the methylene group in the group of the heterocyclic-containing group substituted or unsubstituted in Group III is substituted with the group selected in Group IV, the total number of carbon atoms of R 33 is 2 to 25. It is preferably 2 to 20, more preferably 2 to 18, and particularly preferably 2 to 18.
• R 35 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 35s are present in the group, they may be the same or different.
• a 1 in the formula (II) is the formula (III) structure
• a is compound represented by the case of using as a latent base generator or polymerization initiator, the sensitivity is high, the base and the radical generator It is preferable because of its high efficiency.
• it is a compound represented by the following formula (III-1).
• any one of R 90 , R 91 , R 92 and R 93 represents a group represented by the general formula (I), and the rest is synonymous with a hydrogen atom or R 33 of the formula (III).
• One of R 94 , R 95 , R 96 and R 97 represents a group synonymous with R 32 of formula (III), and the rest represents a hydrogen atom or a group synonymous with R 33 of formula (III).
• Y 1 and Y 2 are synonymous with equation (III).
• Preferred structures represented by the formulas (III) and (III-1) are a diphenylsulfide structure (Y 1 is a sulfur atom and Y 2 is unbonded) and a fluorene ring (Y 1 is CR 41) because of its high sensitivity.
• R 42 , Y 2 is a single bond) and a carbazole ring (Y 1 is NR 43 , Y 2 is a single bond), and a fluorene ring or a carbazole ring is particularly preferable.
• the compound in which Y 2 in the formulas (III) and (III-1) is a single bond is preferable because it has excellent sensitivity when used as a latent base generator or a polymerization initiator.
• the compound whose structure represented by the formula (III) is a carbazole ring
• it has high sensitivity even in a long wavelength light source of 365 nm or more, and is used in combination with a pigment or the like. Is also preferable because of its high sensitivity.
• a compound having a diphenylsulfide structure in the structure represented by the formula (III) is preferable because it has high sensitivity and excellent transparency when used as a latent base generator or a polymerization initiator.
• a compound having a fluorene ring structure represented by the formula (III) is preferable because it has high sensitivity and excellent transparency when used as a latent base generator or a polymerization initiator.
• the photoradical generating group having no carbamoyloxime group in the compound of the present invention is not particularly limited, but is represented by any of the above formulas (IVa) to (IVg) because it has a high radical generating ability with respect to ultraviolet rays.
• the radical to be used is preferred.
• (IVa) to (IVg) are preferable because of their high sensitivity
• a compound having a photoradical generating group of formula (IVa) having no carbamoyloxime group is preferable because of its excellent sensitivity, and R 51 in formula (IVa) is OR 81 , NR 82 R 83, or 2 carbon atoms.
• R 51 in formula (IVa) is OR 81 , NR 82 R 83, or 2 carbon atoms.
• Compounds having a heterocycle-containing group of about 20 to 20 are more preferable, and compounds in which R 51 in the formula (IVa) is NR 82 R 83 or a heterocycle-containing group having 2 to 20 carbon atoms are particularly preferable.
• the heterocyclic group having 2 to 20 carbon atoms represented by R 51 in the formula (IVa) is preferably a heterocycle in which one hydrogen atom is removed from the heterocycle containing a nitrogen atom in the ring skeleton.
• Examples thereof include a group or a group in which the heterocyclic group and a hydrocarbon group are bonded.
• the heterocycle containing a nitrogen atom in the ring skeleton include an aziridine ring, an azetidine ring, an aziridine ring, an azole ring, an azinan ring, an azepan ring, a morpholine ring, a thiazine ring, and the like.
• the morpholine ring and the thiazine ring are particularly preferable, and the morpholine ring is particularly preferable.
• the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R 51 in formula (IVa) a heterocyclic group obtained by removing one hydrogen atom from a heterocyclic ring containing the nitrogen atom in the ring skeleton It is preferable that the nitrogen atom in the ring skeleton is a heterocyclic group bonded to the carbon atom to which R 52 and R 53 in the formula (IVa) are bonded.
• the heterocyclic group having 2 to 20 carbon atoms represented by R 51 preferably has 2 to 10 carbon atoms.
• the ring formed by R 52 and R 53 in the above formula (IVa) is not particularly limited, and for example, a saturated alicyclic ring such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane ring, and the above aromatics. Examples thereof include a hydrocarbon ring and the above-mentioned aromatic heterocycle.
• a saturated alicyclic ring is preferable because of its high transparency and high solubility in a solvent, and a cyclohexane ring is particularly preferable because of its high stability of the compound.
• aryl group having 6 to 20 carbon atoms represented by R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 and R 71 in the above formulas (IVa) to (IVg).
• examples include, for example, a phenyl group, a tolyl group, a xsilyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, a phenyl group substituted with one or more of the above alkyl groups, a biphenylyl group, a naphthyl group, an anthryl group and the like. Be done.
• the aryl group preferably has 6 to 10 carbon atoms.
• the arylene group having 6 to 20 carbon atoms used in R 54 , R 57 , R 60 , R 63 , R 66 and R 67 in the above formulas (IVa) to (IVg) is an aryl having 6 to 20 carbon atoms. Examples thereof include a group obtained by removing one hydrogen atom from the group.
• the arylene group preferably has 6 to 10 carbon atoms.
• the number of carbon atoms of the hydrocarbon groups represented by R 81 , R 82 and R 83 in the above formulas (IVa) to (IVg) is preferably 1 to 8, preferably 1 to 3. Is particularly preferable.
• Preferred photoradical generating groups include the following formulas (IVa1) to (IVa5), (IVb1), (IVc1), (IVd1), (IVe1), (IVf1), (IVg1) and (IVh1).
• the photoradical generating group represented by any of (IVa1) to (IVa5) and (IVf1) is preferable because the sensitivity is high when combined with the group represented by the formula (I).
• any one of (IVb1), (IVc1), (IVd1), (IVe1), (IVf1) and (IVh1) is used because of its high sensitivity.
• the photoradical generating group represented by is preferable.
• carbamoyl oxime compound that binds to the benzene ring in the aromatic ring of 6 to 20 carbon atoms represented by A 1 it is used as a polymerization initiator, low exposure It is preferable because it cures in an amount. Also has an aromatic ring is more benzene rings of 6 to 20 carbon atoms represented by A 1, a group and a photo-radical generating group of the formula (I) are each bonded to another benzene ring The compound is preferable in terms of the stability of the compound and the ease of production.
• it is a compound represented by the formula (III-1), in which any one of R 91 and R 92 represents a group represented by the formula (I), and any one of R 95 and R 96.
• a compound having the same meaning as R 32 of the formula (III) is preferable from the viewpoint of ease of production.
• the compound in which X 1 in the formula (I) is ⁇ NR 2 R 3 is preferable because the compound has high stability, and R 2 and R 3 are linked to each other to form a hydrogen atom, a nitrogen atom and a carbon atom. It is more preferable to form a ring having 2 to 10 carbon atoms or a ring having 2 to 10 carbon atoms consisting of hydrogen atom, oxygen atom, nitrogen atom and carbon atom because the reactivity of the generated base is high. ..
• R 2 and R 3 are connected to each other to form a ring having 2 to 10 carbon atoms composed of a hydrogen atom, a nitrogen atom and a carbon atom, and form a piperidine ring or a pyrrolidine ring. It is more preferable to have.
• a compound in which X 1 in the formula (I) is ⁇ NR 2 R 3 and R 2 and R 3 are aliphatic hydrocarbon groups having 2 to 8 carbon atoms are preferable because they have high solubility.
• the compound in which R 32 is a photoradical generating group having no carbamoyloxime group is preferable because of its high sensitivity.
• n in the above formula (I) is 0 is preferable because it has high heat stability.
• the compound in which n in the above formula (I) is 1 is preferable because it cures at a low exposure amount.
• carbamoyloxime compound of the present invention examples include the following No. 1 to No. Examples include the compound represented by 181. However, the present invention is not limited by the following compounds.
• the method for producing the compound of the present invention is not particularly limited, but for example, a known ketone compound and hydroxylamine hydrochloride are reacted in the presence of a base such as pyridine to obtain an oxime compound. Subsequently, the oxime compound is reacted with 4-nitrophenyl chloroformate and then with an amine to obtain the carbamoyl oxime compound of the present invention.
• a compound in which X 1 is -NR 2 R 3 and is a group represented by the above formula (a) or the above formula (b) can also be produced.
• a ketone compound in which a ketone group is introduced at an arbitrary position as a raw material a compound in which a group represented by the formula (I) is introduced at an arbitrary position can also be obtained.
• the oxime compound can also be produced by the method described in Japanese Patent No. 4223071.
• the carbamoyloxime compound of the present invention is useful as a latent base generator and a polymerization initiator because it efficiently generates bases and radicals by irradiation with light such as ultraviolet rays or heating, and is particularly useful as a latent base generator. Is.
• the latent base generator of the present invention means a composition containing a compound having a function of efficiently generating a base by irradiating with light such as ultraviolet rays, and its use is as a pH adjuster.
• Examples include a catalyst using a base.
• the carbamoyloxime compound of the present invention is useful as a photobase generator and a photoradical polymerization initiator because of its high efficiency of generating bases and radicals by light irradiation among the above-mentioned polymerization initiators, and has a high base generation efficiency. Since it is very expensive, it is particularly useful as a photobase generator.
• the polymerization initiator of the present invention contains at least one compound of the present invention.
• the polymerization initiator that can be used in combination with the carbamoyloxime compound represented by the above formula (I) is not particularly limited, and examples thereof include conventionally known photobase generators and photoradical polymerization initiators.
• the content of the compound represented by the above formula (I) in the above-mentioned polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass because the generation efficiency of bases and radicals is high. More preferably, it is 70 to 100% by mass.
• the polymerizable composition of the present invention contains a polymerization initiator (A) containing at least one compound of the present invention and a polymerizable compound (B).
• the content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound (B).
• the content of the polymerization initiator (A) is 1 part by mass or more, it is easy to prevent curing failure due to insufficient curing sensitivity. Therefore, when it is 20 parts by mass or less, it volatilizes during light irradiation or heating. It is preferable because it can suppress objects.
• Examples of the polymerizable compound (B) used in the present invention include a compound having an anionic polymerizable functional group, a compound that is cured by a reaction in which a base acts as a catalyst or a reaction in which a base is added, and a radically polymerizable compound. It is preferably a photosensitive resin that polymerizes and cures by irradiating with energy rays such as ultraviolet rays, or a cured resin that lowers the curing temperature.
• the anion-polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator by an active energy ray such as ultraviolet rays, and for example, an epoxy group, an episulfide group, or a cyclic monomer ( ⁇ -valerolactone, ⁇ -Caprolactam), malonic acid ester and the like.
• Reactions in which a base acts as a catalyst or a base is added include a urethane bond formation reaction between isocyanate and alcohol, an addition reaction between an epoxy resin and a compound containing a hydroxyl group, and an addition reaction between an epoxy resin and a compound containing a carboxylic acid group.
• Addition reaction of epoxy resin and thiol compound Michael addition reaction of (meth) acrylic group, dehydration condensation reaction of polyamic acid, hydrolysis / polycondensation reaction of alkoxysilane and the like.
• Examples of the compound having an anionic polymerizable functional group include epoxy resin, oxetane resin, episulfide resin, cyclic amide (lactam compound), cyclic ester (lactone compound), cyclic carbonate compound, malonic acid ester and the like.
• Examples of compounds that are cured by a reaction in which a base acts as a catalyst or a reaction in which a base is added include polyamide resin (polynitation reaction by dehydration cyclization), epoxy / hydroxyl group (ring-opening addition reaction), and epoxy / carboxylic acid type.
• Examples of the compound polymerized by radicals include ethylenically unsaturated compounds. Since it has high reactivity, it is preferable to use a compound that undergoes radical polymerization. These resins may be used alone or in combination of two or more. As a preferable combination, a combination of an epoxy resin and a phenol resin is excellent in that the reaction proceeds quickly and the adhesiveness is good, and a combination of an epoxy resin and a thiol compound and a high reactivity because of excellent low-temperature curability. Therefore, a combination of an ethylenically unsaturated compound and a thiol compound can be mentioned.
• the epoxy resin may be a compound having an epoxy group and is not particularly limited, but for example, a polyglycidyl ether compound of a mononuclear polyvalent phenol compound such as hydroquinone, resorcin, pyrocatechol, fluoroglucosinol; dihydroxynaphthalene, Biphenol, Methylenebisphenol (Bisphenol F), Methylenebis (Orthocresol), Echilidenbisphenol, Isopropyridenebisphenol (Bisphenol A), 4,4'-Dihydroxybenzophenone, Isopropyridenebis (Orthocresol), Tetrabromobisphenol A, 1,3 -Bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra ( 4-Hydroxyphenyl) Polyglycidyl ether compound of polynuclear polyvalent phenolic compounds such
• these epoxy resins may be those internally crosslinked by a prepolymer of terminal isocyanate or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphoric acid ester, etc.). ..
• a polyvalent active hydrogen compound polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphoric acid ester, etc.
• those having a glycidyl group are preferable, and those having a bifunctional or higher functional glycidyl group are more preferable, from the viewpoint of excellent curability.
• the phenol resin is a compound that has a phenolic hydroxyl group and is not classified as the epoxy resin.
• a phenol resin having two or more hydroxy groups in one molecule is preferable because of its excellent curability, and generally known ones can be used.
• the phenol resin include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, and aralkyl novolac.
• the thiol compound has a thiol group and is not classified into the epoxy resin and the phenol resin.
• the thiol compound is preferably one having two or more thiol groups in one molecule because of its excellent curability.
• Preferred specific examples of the thiol compound include bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithian, 1,3-bis (mercaptomethyl) benzene, and 1,4-bis (mercapto).
• Methyl) benzene 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di Mercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecan, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecan, 1,2,6,7 -Tetramercapto-4-thiaheptan, pentaerythrithiol, 1,1,3,3-tetrakis (mercaptomethylthio) propane, pentaerythritol tetrakis mercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate , And trimethylolpropanthris mercapto
• Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptan, pentaerythrithiol, bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and 4 -Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
• the thiol compound may be used alone or in combination of two or more.
• the above-mentioned polyamide resin is a compound having an amide group, and is not classified into the above-mentioned epoxy resin, the above-mentioned phenol resin, and the above-mentioned thiol compound.
• the polyamide resin includes ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride as acid dianhydride.
• the polyurethane resin is a compound having a urethane group, and is not classified into the epoxy resin, the phenol resin, the thiol compound, the polyamide resin, and the ethylenically unsaturated compound.
• the polyurethane resin include resins made from polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate, and polyols (polyfunctional alcohols) such as polyether polyols, polyester polyols and polycarbonate polyols. Can be mentioned.
• nylon resin examples include resins made from cyclic monomers such as ⁇ -caprolactam and lauryl lactam.
• polyester resin examples include resins made from cyclic monomers such as ⁇ -valerolactone and ⁇ -propiolactone.
• the ethylenically unsaturated compound is a compound having an ethylenically unsaturated group, and is not classified into the epoxy resin, the phenol resin, the thiol compound, and the polyamide resin.
• Examples of the ethylenically unsaturated compound include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth) acrylic acid and ⁇ -chloro.
• Acrylic acid itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allylacetic acid, cinnamon acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloy Roxyethyl], mono (2- (meth) acrylicyloxyethyl] phthalate, ⁇ -carboxypolycaprolactone mono (meth) acrylate, etc.
• hydroxy Non-functional (meth) acrylates such as ethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acrylicoyl groups.
• vinyl urethane compounds as compounds, vinyl monomer containing hydroxyl groups, and vinyl epoxy compounds as polyepoxy compounds.
• the ethylenically unsaturated compound can be used alone or in combination of two or more.
• Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 all manufactured by Nippon Kayaku.
• Aronix M-215, M-350 above, manufactured by Toagosei
• NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N aboveve, Shin-Nakamura Chemical Industry Co., Ltd.
• SPC-1000, SPC-3000 all manufactured by Showa Denko); etc.
• the polymerizable composition which is any of the combinations (1) to (5) below is preferable because it starts with a radical or a base and the reaction proceeds rapidly and is excellent in curability, and has high initial curability. Therefore, the combination of (2) is preferable, the combination of (4) is preferable because the curing temperature is lowered, and since both characteristics can be obtained, the compound contains all of the epoxy resin, the ethylenically unsaturated compound and the thiol compound. Is particularly preferable.
• (1) A polymerizable composition containing the polymerization initiator of the present invention and an epoxy resin.
• a polymerizable composition containing the polymerization initiator of the present invention an epoxy resin and a phenol resin.
• a polymerizable composition containing the polymerization initiator, epoxy resin and thiol compound of the present invention A polymerizable composition containing the polymerization initiator of the present invention, an ethylenically unsaturated compound and a thiol compound.
• the content of the polymerizable compound may be an amount suitable for the purpose of use, but in order to prevent curing failure, 50 parts by mass of the solid content (all components other than the solvent) in the polymerizable composition. It is preferable that the content is as described above, 60 parts by mass or more is more preferable, and 70 parts by mass or more is particularly preferable.
• the polymerizable composition of the present invention contains an epoxy resin
• the preferable amount thereof is 10% by mass or more and 90% by mass or less of the components other than the solvent in the composition for curability and adhesive strength. It is preferable in terms of expression, and more preferably 30% by mass or more and 70% by mass or less.
• the preferred amount thereof is 10% by mass or more and 90% by mass or less of the components other than the solvent in the composition. It is preferable from the viewpoint of initial curability, and more preferably 10% by mass or more and 50% by mass or less.
• the preferable amount thereof is 10% by mass or more and 60% by mass or less of the components other than the solvent in the composition for curability and reactivity. It is preferable in terms of points, and more preferably 20% by mass or more and 50% by mass or less.
• additives such as an inorganic compound, a coloring material, a latent epoxy curing agent, a chain transfer agent, a sensitizer, and a solvent can be used as optional components.
• the inorganic compound examples include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; layered clay minerals, miloli blue and calcium carbonate.
• metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; layered clay minerals, miloli blue and calcium carbonate.
• These inorganic compounds are used as, for example, fillers, antireflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink generators and the like.
• coloring material examples include pigments, dyes, natural pigments and the like. These coloring materials can be used alone or in combination of two or more.
• Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolin compounds; quinacridone compounds; antanthurone compounds; perinone.
• pigment a commercially available pigment can also be used.
• Examples of the above dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acrydin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes.
• Dyes such as cyanine dyes, and the like, and a plurality of these may be mixed and used.
• latent epoxy curing agent examples include dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenylsulfone, boron trifluoride amine complex salts, imidazoles, guanamines, imidazoles, ureas and melamines. Can be mentioned.
• a sulfur atom-containing compound is generally used.
• Alkyliodated compounds such as, trimethylolpropanetris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthio.
• Propionate Butanediol Bisthioglycolate, Ethethylene Glycol Bisthioglycolate, Trimethylol Propanetristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanetristhiopropionate, Trimethylol Propanetristhioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. Examples thereof include aliphatic polyfunctional thiol compounds such as C1, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, and Karenz MT BD1, PE1, NR1 manufactured by Showa Denko.
• the solvent is a liquid at 25 ° C. and 1 atm, which is not classified into the compound of the present invention and the polymerizable compound, and usually dissolves each of the above components (polymerization initiator (A), polymerizable compound (B), etc.). Or it means a compound that can be dispersed.
• the solvent examples include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2- Ether solvents such as dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate , Texanol and other ester solvents; ⁇ butyrolactone and other lactone solvents; ethylene glycol monomethyl ether, ethylene glycol monoeth
• Ether ester solvent such as benzene, toluene, xylene; aliphatic hydrocarbon solvent such as hexane, heptane, octane, cyclohexane; terpene hydrocarbon oil such as terepine oil, D-lymonen, pinen; mineral Paraffinic solvents such as Spirit, Swazole # 310 (Cosmo Matsuyama Petroleum Co., Ltd.), Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenization of carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc.
• BTX solvent such as benzene, toluene, xylene
• aliphatic hydrocarbon solvent such as hexane, heptane, octane, cyclohexane
• terpene hydrocarbon oil such as terepine oil, D
• Aliphatic hydrocarbon solvent such as chlorobenzene; carbitol solvent; basic solvent such as aniline, triethylamine, pyridine, N, N-dimethylformamide, N-methylpyrrolidone; acetic acid; acetonitrile Carbon disulfide; dimethylsulfoxide; water and the like can be used, and these solvents can be used alone or as a mixed solvent of two or more kinds.
• ketones, lactone solvents, ether ester solvents or basic solvents are preferable, and propylene glycol-1-monomethyl is particularly preferable, from the viewpoints of alkali developability, patterning property, film forming property, solubility and handleability.
• Ether-2-acetate hereinafter, also referred to as "PGMEA"
• cyclopentanone cyclohexanone
• ⁇ butyrolactone dimethylformamide
• the content of the solvent is not particularly limited, each component is uniformly dispersed or dissolved, and the polymerizable composition of the present invention exhibits a liquid or paste suitable for each application.
• it may be an amount it is usually preferable to contain the solvent in a range in which the amount of the solid content (all components other than the solvent) in the polymerizable composition of the present invention is 10 to 98% by mass.
• the polymerizable composition of the present invention can also improve the characteristics of the cured product by using an organic polymer.
• organic polymer include polystyrene, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methylmethacrylate.
• Copolymer ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Examples thereof include polyester, phenol resin, and phenoxy resin.
• its content is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound (B).
• a surfactant a silane coupling agent, a melamine compound and the like can be used in combination with the polymerizable composition of the present invention.
• the surfactant examples include fluorine-based surfactants such as perfluoroalkyl phosphate and perfluoroalkyl carboxylate; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher grades. Cationic surfactants such as amine halides and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; amphoteric surfactants; silicone-based surfactants Surfactants such as activators can be used, and these may be used in combination.
• fluorine-based surfactants such as perfluoroalkyl phosphate and perfluoroalkyl carboxylate
• anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher
• silane coupling agent for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, it has an isocyanate group, a methacryloyl group, or an epoxy group such as KBE-9007, KBM-502, and KBE-403. Silane coupling agents are preferably used.
• Examples of the melamine compound include all or a part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycol uryl, (poly) methylolbenzoguanamine, and (poly) methylol urea.
• nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycol uryl, (poly) methylolbenzoguanamine, and (poly) methylol urea.
• examples thereof include compounds in which (at least two) are alkyl etherified.
• examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, which may be the same or different from each other.
• the methylol group which has not been alkyl etherized may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
• hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluryl, tetrabutoxymethylglycoluryl and the like can be used.
• alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable from the viewpoint of solubility in a solvent and difficulty in crystal precipitation from the polymerizable composition.
• the content of optional components (excluding inorganic compounds, coloring materials, and solvents) other than the polymerization initiator (A) and the polymerizable compound (B) depends on the purpose of use thereof. It is appropriately selected and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the polymerizable compound (B).
• the polymerizable composition of the present invention can be made into a cured product by irradiating it with energy rays.
• the cured product is formed into an appropriate shape according to the application.
• the polymerizable composition of the present invention is a soda by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and immersion. It can be applied on supporting substrates such as glass, quartz glass, semiconductor substrates, metals, paper, and plastics. Further, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.
• an ultra-high pressure mercury lamp such as electromagnetic energy, electron beam, X-ray, radiation, etc. having a wavelength of 2000 angstrom to 7000 angstrom obtained from lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, sterilization lamps, light emitting diodes, CRT light sources, etc.
• an ultra-high pressure mercury lamp, a mercury steam arc lamp, a carbon arc lamp, a xenon arc lamp, or the like that emits light having a wavelength of 300 to 450 nm is preferably used.
• the laser direct drawing method which forms an image directly from digital information of a computer or the like without using a mask, improves not only productivity but also resolution and position accuracy.
• the laser light light having a wavelength of 340 to 430 nm is preferably used, but an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, and a krypton ion laser are used.
• Various semiconductor lasers, YAG lasers and the like that emit light in the visible to infrared region can also be used.
• a sensitizing dye that absorbs the visible to infrared region is preferably added because of its excellent curability.
• the polymerizable composition of the present invention it is usually necessary to heat after irradiation with the above energy rays, and heating at about 40 to 150 ° C. is preferable from the viewpoint of curability.
• the polymerizable composition of the present invention is a photocurable paint or varnish; a photocurable adhesive; a coating agent for metals; a printed substrate; a color display liquid crystal display element such as a color television, a PC monitor, a mobile information terminal, or a digital camera.
• the polymerizable composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a protrusion for a vertically oriented liquid crystal display element.
• it is useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for a vertically oriented liquid crystal display element.
• the above spacers for liquid crystal display panels include (1) a step of forming a coating film of the polymerizable composition of the present invention on a substrate, and (2) energy rays (2) through a mask having a predetermined pattern shape on the coating film. It is preferably formed by a step of irradiating (light), (3) a baking step after exposure, (4) a step of developing a film after exposure, and (5) a step of heating the film after development.
• the polymerizable composition of the present invention to which a coloring material is added is suitably used as a resist that constitutes each pixel such as RGB in a color filter and a resist for a black matrix that forms a partition wall of each pixel. Further, in the case of a black matrix resist to which an ink repellent is added, it is preferably used for an inkjet color filter partition wall having a profile angle of 50 ° or more.
• a composition containing a fluorine-based surfactant and a fluorine-based surfactant is preferably used as the ink repellent.
• the partition wall formed from the polymerizable composition of the present invention partitions on the transferred body, and droplets are applied to the recesses on the partitioned partition by the inkjet method.
• the optical element is manufactured by the method of forming an image region. At this time, it is preferable that the droplets contain a colorant and the image region is colored. In that case, the optical element manufactured by the above manufacturing method is formed from a plurality of colored regions on the substrate. It has at least a partition wall that separates the pixel group and each colored region of the pixel group.
• the polymerizable composition of the present invention can also be used as a protective film or insulating film composition.
• an ultraviolet absorber an alkylation-modified melamine and / or an acrylic-modified melamine, a mono- or bifunctional (meth) acrylate monomer and / or a silica sol containing an alcoholic hydroxyl group in the molecule can be contained.
• the insulating film is used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable supporting base material.
• the laminate can be developed with an alkaline aqueous solution, and the thickness of the insulating resin layer is preferably 10 to 100 ⁇ m because it has an excellent balance between insulating properties and curability.
• the polymerizable composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound.
• the photosensitive paste composition can be used to form a fired product pattern such as a partition wall pattern, a dielectric pattern, an electrode pattern and a black matrix pattern of a plasma display panel.
• Example 1 Synthesis of compound 1 In a 100 ml four-necked flask, 1.0 eq of oxime compound 1 was added. , Dichloromethane (500% by weight of theoretical yield), triethylamine 2.0eq. Was added, and the mixture was stirred on an ice bath at 5 ° C. There, 4-nitrophenyl chloroformate 1.1 eq. Was dissolved in dichloromethane and added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes. After cooling to 5 ° C. on an ice bath again, piperidine 1.1 eq. Was added dropwise. The mixture was stirred at 45 ° C. for 7 hours, and the solvent was distilled off under reduced pressure.
• Example 3 Synthesis of compound 3 In a 100 ml four-necked flask, 1.0 eq of oxime compound 3 was added. , Chloroform (500% by weight of theoretical yield), triethylamine 2.0eq. was added, and the mixture was stirred on an ice bath at 5 ° C. There, 4-nitrophenyl chloroformate 1.1 eq. Was dissolved in chloroform (500% by weight of the theoretical yield) and added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 1 hour. After cooling to 5 ° C. on an ice bath again, dibutylamine 1.1eq. Was added dropwise.
• A-1 Compound 1 A'-2: 1- (4-((4-nitrophenyl) thio) phenyl) -2-(((piperidin-1-carbonyl) oxy) imino) dodecane-1-one (carbamoyl photobase generator)
• A'-3 Omnirad819 (manufactured by IGM Resins)
• B Dipentaerythritol hexaacrylate (Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.)
• C EP-4100E (manufactured by ADEKA)
• D Pentaerythritol-Tetrakis (3-mercaptobutyrate) (PE-1, manufactured by Showa Denko KK)
• E N, N-dimethylformamide
• the compounds of the present invention are excellent as polymerization initiators capable of curing various compositions, as a single initiator component can cause a curing reaction between an anion curable component and a radically polymerizable component. Is obvious.

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• 2020
  • 2020-12-14 JP JP2021565569A patent/JPWO2021125132A1/ja active Pending
  • 2020-12-14 WO PCT/JP2020/046548 patent/WO2021125132A1/ja not_active Ceased
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