JP7460288B2 - Carbamoyloxime compound, and polymerization initiator and polymerizable composition containing said compound - Google Patents

Description

The present invention relates to a compound useful as a polymerization initiator or the like for use in a polymerizable composition, a polymerizable composition comprising said compound in a polymerizable compound, and a cured product of said polymerizable composition.

In general, a polymerizable composition such as a photosensitive resin composition is made 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). Because of this, it is used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, etc.

Photopolymerization initiators are classified into photoradical generators, photoacid generators, and photobase generators depending on the active species generated by energy ray (light) irradiation. Photo-radical generators have advantages such as fast curing speed and no active species remaining after curing, but disadvantages include the need to provide a layer to block oxygen when curing thin films because oxygen inhibits curing. There is. While photoacid generators have the advantage of not being inhibited by oxygen, they have disadvantages such as residual active species of acid that corrode metal substrates and denature resins after curing. Photobase generators are attracting attention because they are less likely to cause the aforementioned problems of curing inhibition due to oxygen and corrosion due to residual active species, but they generally have a problem of lower sensitivity (lower curability) than photoacid generators. . Photobase generators are disclosed, for example, in Patent Documents 1 to 5.

US6551761(B1) US2011/233048(A1) International publication WO2010/064632 US2015/064623 (A1) JP2013-163670

However, conventional photobase generators are not sufficient in terms of sensitivity (base generating ability) and solubility in solvents.
Accordingly, an object of the present invention is to provide a compound which is highly soluble in a solvent and has satisfactory sensitivity (base generating ability), a polymerizable composition containing said compound as a polymerization initiator, and a cured product thereof.

The inventors conducted extensive research and discovered that compounds having a specific structure have high sensitivity (base generating ability) as polymerization initiators.

The present invention achieves the above-mentioned objective by providing a carbamoyl oxime compound represented by the following formula (I):

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a cyano group, a nitro group, -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a group containing a heterocycle having 2 to 20 carbon atoms, or the following: represents a group represented by formula (II),
R ¹¹ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
One or more hydrogen atoms in the groups represented ^by R ¹ , R ² , R ³ , R ⁴ , R 5 , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are halogen Atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group, or group containing a heterocycle having 2 to 20 carbon atoms may be replaced with
One or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the following formula (II).
In the formula, R ²¹ represents a hydrogen atom, a cyano group, a halogen atom, a nitro group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
X ¹ is -NR ²² R ²³ , a group represented by the following formula (a) or the following formula (b),
R ²² and R ²³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
R ²² and R ²³ are connected to each other and are a ring consisting of a nitrogen atom and a carbon atom, or a ring consisting of an oxygen atom, a nitrogen atom and a carbon atom,
One or more of the hydrogen atoms in the groups represented by R ²¹ , R ²² and R ²³ are a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group , may be substituted with a vinyl group, vinyl ether group, mercapto group, isocyanate group, or a group containing a heterocycle having 2 to 20 carbon atoms,
n represents 0 or 1, and * represents a bond.
In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are each independently a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms. Is it a hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ and R ³⁹ and R ⁴⁰ are connected to each other to form a ring consisting of a nitrogen atom and a carbon atom, or an oxygen atom, a nitrogen may form a ring consisting of atoms and carbon atoms,
One or more hydrogen atoms in the groups represented by R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are halogen atoms, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group, or a group containing a heterocycle having 2 to 20 carbon atoms. There may be cases where
* represents a bond.

The present invention also provides a latent basic compound containing at least one carbamoyloxime compound represented by the above formula (I).

The present invention also provides a polymerization initiator containing at least one carbamoyl oxime compound represented by the above formula (I).

The present invention also provides a polymerizable composition containing the above polymerization initiator (A) and polymerizable compound (B), and a cured product obtained from the polymerizable composition.

The present invention also provides a method for producing a cured product, which comprises a step of irradiating the above-mentioned polymerizable composition with energy rays.

When used as a polymerization initiator, the carbamoyl oxime compound of the present invention can generate a base more efficiently than conventional photobase generators, so it can cure polymerizable compounds even at low exposure doses. . Furthermore, the carbamoyloxime compound of the present invention has high solubility in solvents and is easy to handle.
Moreover, the polymerizable composition of the present invention exhibits high curability at low exposure doses.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The carbamoyloxime compound of the present invention is represented by the above formula (I). The carbamoyl oxime compound represented by formula (I) has geometric isomers due to the double bond of the oxime, but these are not distinguished.
That is, in this specification, the carbamoyl oxime compound represented by the above formula (I), and the compounds and exemplified compounds that are preferred forms of the compound described below represent a mixture of both or one of them, and are not an isomer. It is not limited to the structure shown. Hereinafter, the carbamoyloxime compound represented by formula (I) is also simply referred to as "the compound represented by formula (I)" or "the compound of the present invention."
In addition, when the groups represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ⁴⁰ in formula (I) are interrupted or substituted by a group containing carbon atoms, those carbon atoms The number including the number becomes the specified number of carbon atoms.

Examples of unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ¹¹ , R ²¹ to R ²³ , and R ³¹ to R ⁴⁰ in the above formula (I) include: Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, In addition to alkyl groups such as isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, and cyclohexylmethyl, one or more of the carbon-carbon single bonds of these alkyl groups can be replaced with a carbon-carbon double bond or carbon- Examples include unsaturated aliphatic hydrocarbon groups having a carbon triple bond. In these aliphatic hydrocarbon groups, one or more methylene groups in the group are -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO- , -SO ₂ -, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'-. However, these divalent groups are not adjacent to each other.
R and R' are hydrogen atoms or aliphatic hydrocarbon groups, and examples of the aliphatic hydrocarbon groups represented by R and R' include R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by ⁴⁰ include the same groups as those exemplified.

The aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ⁴⁰ in the above formula (I) are unsubstituted, for example, Examples include phenyl, naphthyl, phenanthryl, pyrenyl, and biphenyl (hereinafter collectively referred to as "phenyl, etc."), and phenyl substituted with an aliphatic hydrocarbon group. The bond between the aromatic ring and the aliphatic hydrocarbon group is -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -NR -, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'- may be interrupted. However, these intervening divalent groups are not adjacent to each other.
As the aliphatic hydrocarbon group substituting the above phenyl etc., the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ⁴⁰ mentioned above; Groups similar to those exemplified may be mentioned.

An aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ⁴⁰ and R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R When the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by ⁴⁰ has a substituent, the aliphatic hydrocarbon group and the aromatic hydrocarbon group having the substituent include , the unsubstituted hydrogen atom explained above is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, or Examples include those substituted with a group containing a heterocycle having 2 to 20 carbon atoms. The group containing a heterocycle having 2 to 20 carbon atoms is the same as the examples of groups containing an unsubstituted heterocycle having 2 to 20 carbon atoms represented by R ³ to R ¹⁰ described below. can be mentioned.

Examples of the halogen atoms represented by R ³ to R ¹¹ and the halogen atoms with which hydrogen atoms in the groups represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ⁴⁰ may be substituted include fluorine, chlorine, bromine and iodine atoms.

In the present invention, "a ring consisting of a nitrogen atom and a carbon atom" means a ring in which the atoms forming the ring skeleton are only nitrogen atoms and carbon atoms. Moreover, "a ring consisting of an oxygen atom, a nitrogen atom, and a carbon atom" means a ring in which the atoms forming the ring skeleton are only an oxygen atom, a nitrogen atom, and a carbon atom.
A ring consisting of a nitrogen atom and a carbon atom formed by R ²² and R ²³ , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ connected to each other As a group including a bonded nitrogen atom, pyrrole ring, pyrrolidine ring, imidazole ring, imidazolidine ring, imidazoline ring, pyrazole ring, pyrazolidine ring, piperidine ring, piperazine ring, etc. (hereinafter collectively referred to as "pyrrole ring") etc.), as well as groups in which the pyrrole ring or the like is substituted with an aliphatic hydrocarbon group. Examples of this aliphatic hydrocarbon group include the same as those exemplified above as the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ^40. The following groups are mentioned.
One or more hydrogen atoms in the ring consisting of nitrogen atoms and carbon atoms are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups. , a mercapto group, an isocyanate group, or a group containing a heterocycle having 2 to 20 carbon atoms. The group containing a heterocycle having 2 to 20 carbon atoms is the same as the group containing an unsubstituted heterocycle having 2 to 20 carbon atoms represented by R ³ to R ¹⁰ described below. can be mentioned.

Oxygen atoms, nitrogen atoms, and carbon atoms formed by R ²² and R ²³ , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , and R ³⁹ and R ⁴⁰ connected to each other As a group containing a bonded nitrogen atom, examples include a morpholine ring, an oxazole ring, an oxazoline ring, an oxadiazole ring, etc. (hereinafter collectively referred to as "morpholine ring, etc."), as well as these morpholine rings. and the like are also substituted with an aliphatic hydrocarbon group. Examples of this aliphatic hydrocarbon group include the same as those exemplified above as the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ^40. The following groups are mentioned.
One or more of the hydrogen atoms in the rings etc. consisting of oxygen atoms, nitrogen atoms and carbon atoms are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl may be substituted by a group containing a group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocycle having 2 to 20 carbon atoms.
The above-mentioned group containing a heterocycle having 2 to 20 carbon atoms may be the same as the examples of groups containing an unsubstituted heterocycle having 2 to 20 carbon atoms represented by R ³ to R ¹⁰ described below. Things can be mentioned.

In the above formula (I), R ³ to R Examples of the group containing a heterocycle having 2 to 20 carbon atoms, represented by ¹⁰ , include unsubstituted tetrahydrofuran group, dioxolanyl group, tetrahydropyranyl group, morpholylfuran group, thiophene group, methylthiophene group, hexylthiophene group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperidine group and piperazine group, as well as tetrahydrofuran group, dioxolanyl group, tetrahydropyranyl group, morpholylfuran group, thiophene group, methylthiophene group, hexylthiophene group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, pyrazole group, pyrazolidine group, piperidine group and piperazine group substituted with an aliphatic hydrocarbon group (hereinafter collectively referred to as "tetrahydrofuran group, etc."), and groups in which these tetrahydrofuran groups, etc. are substituted with an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include the same groups as those exemplified as the aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ¹¹ , R ²¹ to R ²³ and R ³¹ to R ⁴⁰ above.
The alkyl group moiety in these heterocycle-containing groups and the bond between the heterocycle and the aliphatic hydrocarbon group may be interrupted by -O-, -COO-, -OCO-, -CO--CS-, -S-, -SO-, -SO ₂ -, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'-. However, these interrupting divalent groups should not be adjacent to each other. In this specification, "2 to 20" in "a group containing a heterocycle having 2 to 20 carbon atoms" specifies the number of carbon atoms of the "group containing a heterocycle", not the "heterocycle".

When the group containing a heterocycle having 2 to 20 carbon atoms represented by ^R to ^R has a substituent, examples of the heterocycle-containing group having the substituent include the above-described unsubstituted heterocycle-containing group in which a hydrogen atom is substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, or a group containing a heterocycle having 2 to 20 carbon atoms.

Among the compounds represented by the above formula (I), X ¹ in the formula (I) represents -NR ²² R ²³ ;
R ²² and R ²³ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
R ²² is a hydrogen atom, and R ²³ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
A compound in which R ²² and R ²³ are linked to each other to form a ring consisting of a nitrogen atom and a carbon atom, or a ring consisting of an oxygen atom, a nitrogen atom and a carbon atom is preferred because it has excellent sensitivity when used as a polymerization initiator.

In particular, X ¹ in the above formula (I) represents —NR ²² R ²³ ;
A compound in which R ²² and R ²³ are linked together to form a ring consisting of a nitrogen atom and a carbon atom is preferred because the reactivity of the generated base species is high and, when used as a polymerization initiator, the sensitivity is excellent. In particular, a compound in which the ring consisting of a nitrogen atom and a carbon atom is a 5- or 6-membered ring and the number of nitrogen atoms contained in the ring is 1 or 2 is preferred.
In addition, X ¹ in the above formula (I) represents -NR ²² R ²³ ,
Compounds in which R ²² and R ²³ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms are preferred due to their excellent solubility, and the hydrocarbon group is preferably an alkyl group having 1 to 10 carbon atoms.
In addition, X ¹ in the above formula (I) represents -NR ²² R ²³ ;
A compound in which R ²² is a hydrogen atom and R ²³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred due to its excellent stability, and the number of carbon atoms in the aromatic hydrocarbon group is preferably 1 to 10. The aromatic hydrocarbon group is preferably a phenyl group.

A compound in which two or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the above formula (I) is a group represented by the above formula (II) is When used as a polymerization initiator, it is preferable because it has excellent sensitivity and a high residual film rate of the obtained cured product, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ Particularly preferred are compounds in which two or three of them are groups represented by the above formula (II).

Among them, at least one of R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (I) is a group represented by the above formula (II), and at least one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the above formula (II). A compound in which one of the groups is a group represented by the above formula (II) is preferable because the stability of the compound is high. In particular, a compound in which R ⁴ or R ⁹ in the above formula (I) is a group represented by the above formula (II) is preferable because the compound has high stability and excellent productivity; ) in which R ⁴ and R ⁹ are groups represented by the above formula (II) are most preferred.

When two or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the above formula (I) are groups represented by the above formula (II), in the two or more groups represented by the above formula (II), two or more X ^1s may be the same or different. In the above case, two or more R ^21s may be the same or different. In addition, n in two or more groups represented by the above formula (II) may be the same or different. When two or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the above formula (I) are groups represented by the above formula (II), it is preferable in terms of productivity that X ^1s , R ^21s and n in the groups represented by the multiple formulas (II) are the same.

Furthermore, a compound in which one of R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (I) is a group represented by the above formula (II) and the other three are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, is preferred in terms of having high sensitivity and being easy to produce, and a compound in which one of R ⁴ and R ⁶ is a group represented by the above formula (II) and the others, R ³ and R ⁵ are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, is particularly preferred.
Similarly, a compound in which one of R ⁷ to R ¹⁰ in formula (I) is a group represented by formula (II) above and the others are a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 12 carbon atoms is preferred in that it has high sensitivity and is easy to produce.

A compound in which one of R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (I) is a group represented by the above formula (II) and at least one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a hydrogen atom, a nitro group or an aromatic hydrocarbon group having 6 to 12 carbon atoms, preferably a nitro group or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and particularly a compound in which one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a nitro group or an aromatic hydrocarbon group having 6 to 12 carbon atoms, is preferred in terms of high sensitivity and ease of production. The aromatic hydrocarbon group may be unsubstituted or may have a substituent, but the aromatic hydrocarbon group is preferably a benzoyl group.

Compounds in which R ⁴ or R ⁹ in the above formula (I) is a nitro group, a trifluoromethyl group or a benzoyl group are preferred because they have excellent sensitivity.

The groups represented by R ¹ and R ² may be the same or different, but it is preferable that they are the same in terms of ease of production.

Compounds in which R ¹ and R ² in the above formula (I) are aliphatic hydrocarbon groups having 2 or more carbon atoms are preferred because they have excellent solubility in solvents, and aliphatic hydrocarbon groups having 2 to 10 carbon atoms are particularly preferred.
As R ¹ and R ² in the above formula (I), among aliphatic hydrocarbon groups, alkyl groups are preferred because they have excellent solubility in solvents, sensitivity and transparency.

Compounds in which R ¹ and R ² in the above formula (I) are aliphatic hydrocarbon groups having 1 to 4 carbon atoms are also preferred because they have excellent solubility in solvents. As the aliphatic hydrocarbon group, an alkyl group is preferable because it has excellent solubility in a solvent, sensitivity, and transparency.

Compounds in which R ^{21 is an aliphatic hydrocarbon group having 2 or more carbon atoms are preferred because they have excellent solubility in solvents, and compounds in which R 21} is an aliphatic hydrocarbon group having 2 to 10 carbon atoms are preferred because they have excellent solubility in solvents. Particularly preferred.
Among aliphatic hydrocarbon groups, R ²¹ is preferably an alkyl group because it has excellent solubility in solvents, sensitivity, and transparency.

A compound in which n in formula (II) is 0 is preferred because it has high stability against heat when used as a polymerization initiator.

A compound in which n in formula (II) is 1 is preferable because it cures at a low exposure dose when used as a polymerization initiator.

Specific examples of the compound represented by the above formula (I) include the following compounds No. 1 to No. 54. However, the present invention is not limited in any way by the following compounds.

The carbamoyl oxime compound of the present invention represented by the above formula (I) is not particularly limited, but when n=0, the following method may be used to produce it according to Reaction Formula 1 below.
That is, ketone compound A is obtained by reacting a known and commercially available fluorene compound with an acid chloride in the presence of a Lewis acid such as aluminum chloride, and ketone compound A and hydroxylamine hydrochloride are reacted with a base such as pyridine. Oxime compound A is obtained by reacting in the presence of. Subsequently, the oxime compound A is reacted with 4-nitrophenyl chloroformate, and then the corresponding amine is reacted to obtain the carbamoyl oxime compound A of the present invention, which is represented by the above formula (I) and where n=0. .

Reaction formula 1
(In the formula, R ¹ to R ¹² and R ²¹ to R ²³ are the same as in formula (I) above.)

When n=1, ketone compound B is obtained by reacting a known and commercially available fluorene compound with an acid chloride in the presence of a Lewis acid such as aluminum chloride according to Reaction Formula 2 below, and the ketone compound B is obtained under acidic conditions. Oxime compound B is obtained by reacting ketone body B with isobutyl nitrite below. Subsequently, the oxime compound B is reacted with 4-nitrophenyl chloroformate, and then the corresponding amine is reacted to obtain the carbamoyloxime compound B of the present invention, which is represented by the above formula (I) and where n=1. .

Reaction Scheme 2
(In the formula, R ¹ to R ¹² and R ²¹ to R ²³ are the same as those in formula (I) above.)

The ketone bodies used may be publicly known.
Although both of the above reaction formulas 1 and 2 show the case where X ¹ is —NR ²² R ²³ , by changing the amine to be used, it is also possible to produce a compound in which X ¹ is a group represented by formula (a) or formula (b).
The above reaction formula 1 and reaction formula 2 each show the case where ^R4 is a group represented by formula (II). However, when a group represented by formula (II) is introduced into another position in fluorene, it can be obtained by a method of introducing a ketone group during the formation of the fluorene ring.
Furthermore, for example, a compound in which two or more of ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , and ^R10 are groups represented by formula (II) can be produced by ^a method similar to that of the above reaction schemes 1 and 2, by using a diketone body in which a carbonyl group is bonded to two or more of ^R3 , ^R4 , R5, ^R6 , ^R7 , ^R8 , ^R9 , and ^R10 as a ketone body.
Oxime compound A can also be produced by the method described in Japanese Patent No. 4223071.

The compound of the present invention has excellent curing properties for photosensitive resins and high sensitivity to energy rays, so it can be suitably used as a polymerization initiator, which is a photobase generator explained below, and can also be used as a chemically amplified polymerization initiator. It can be used for resists, etc.

A compound having a solubility in propylene glycol-1-monomethylether-2-acetate at 25°C of 15% or more can be selected from many polymerizable compounds when preparing the polymerizable composition of the present invention. preferable. In addition, solubility can be measured by the method described in Examples described later.

Next, the latent base compound, polymerization initiator, and polymerizable composition of the present invention will be described. Note that, for points that are not specifically described, the explanation for the compound of the present invention will be applied as appropriate.

<Latent base compounds>
The carbamoyl oxime compound represented by the above formula (I) is a latent base compound. The latent base compound is a compound that generates a base by irradiation with light such as ultraviolet light or heating, and can be used as a polymerization initiator, a base catalyst, or a pH adjuster. A photolatent base compound that generates a base by irradiation with light is more preferred because of its excellent operability.

<Polymerization initiator (A)>
In the polymerization initiator of the present invention and the polymerizable composition of the present invention, the polymerization initiator (A) contains at least one carbamoyloxime compound represented by the above formula (I). Since the carbamoyl compound of the present invention efficiently generates bases and radicals by irradiation with light or heating, it is useful as a base generator and a radical polymerization initiator, and is particularly useful as a base generator.

Among the above-mentioned base generators and radical polymerization initiators, it is useful as a photobase generator and a photoradical polymerization initiator because of its excellent operability, and is particularly useful as a photobase generator.

The content of the compound represented by formula (I) in the polymerization initiator is preferably 1 to 100% by mass, and more preferably 50 to 100% by mass.
In the polymerizable composition of the present invention, the content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the polymerizable compound (B). The content of the polymerization initiator (A) is preferably 1 part by mass or more, since it is easy to prevent curing defects due to insufficient sensitivity, and is preferably 20 parts by mass or less, since it is possible to suppress volatile matters during light irradiation or heating.

<Polymerizable compound (B)>
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 adds, and a radically polymerizable compound. It is preferable to use a photosensitive resin that is polymerized and cured by irradiation with energy rays such as ultraviolet rays or a cured resin that has a low curing temperature. The above-mentioned anionically polymerizable functional group refers to a functional group that can be polymerized by a base generated from a photobase generator by energy rays such as ultraviolet rays, and includes, for example, an epoxy group, an episulfide group, a cyclic monomer (σ-valerolactone, ε - caprolactam), malonic acid esters, etc. Reactions in which a base acts as a catalyst or addition reactions in which a base acts include a urethane bond forming 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, etc.

Examples of compounds having anionic polymerizable functional groups include epoxy resins, oxetane resins, episulfide resins, cyclic amides (lactam compounds), cyclic esters (lactone compounds), cyclic carbonate compounds, malonic acid esters, 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 acts as an addition include polyamide resins (polyimidization reaction by cyclodehydration), epoxy/hydroxyl group systems (ring-opening addition reaction), and epoxy/carboxylic acid systems. (ring-opening addition reaction), epoxy/thiol system (ring-opening addition reaction), epoxy/acid anhydride system (ring-opening polycondensation), cyanate ester (cyclization reaction), cyanate ester/epoxy system (cyclization reaction), Cyanate ester (cyclization reaction), cyanate ester/maleimide system (crosslinking copolymerization), oxetane/hydroxyl system (ring-opening addition reaction), oxetane/carboxylic acid system (ring-opening addition reaction), oxetane/thiol system (ring-opening addition reaction) reaction), oxetane/acid anhydride system (ring-opening polycondensation), episulfide/hydroxyl system (ring-opening addition reaction), episulfide/carboxylic acid system (ring-opening addition reaction), episulfide/thiol system (ring-opening addition reaction), Episulfide/acid anhydride system (ring-opening polycondensation), acrylic/thiol system (Michael addition reaction), methacryl/thiol system (Michael addition reaction), acrylic/amine system (Michael addition reaction), methacryl/amine system (Michael addition reaction) ), carboxylic acid/hydroxyl group type (polyesterification reaction), carboxylic acid/amine type (polyamidation reaction), isocyanate/hydroxyl group type (polyurethanization reaction), alkoxysilane type (hydrolysis/polycondensation reaction), etc. Examples of compounds that are polymerized by radicals include ethylenically unsaturated compounds. It is preferable to use a compound that undergoes radical polymerization because of its high reactivity. These resins may be used alone or in combination of two or more. Preferred combinations are the combination of epoxy resin and phenol resin, because the reaction progresses quickly and good adhesion, and the combination of epoxy resin and thiol compound, which has high reactivity because of its excellent low-temperature curing properties. Therefore, a combination of an ethylenically unsaturated compound and a thiol compound can be mentioned.

Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), and methylene bis (orthocresol). , ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidene bis (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)ethane, thiobisphenol, sulfobisphenol, oxy Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as bisphenol, phenol novolac, orthocresol novolak, ethylphenol novolak, butylphenol novolac, octylphenol novolac, resorcinol novolac, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, poly Polyglycidyl ethers of polyhydric alcohols such as glycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberin Acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as acids, and homopolymers or copolymers of glycidyl methacrylate; N,N-diglycidylaniline, bis(4-(N-methyl-N -Epoxy compounds having a glycidylamino group such as -glycidylamino)phenyl)methane, diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate , 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate and other epoxidized products of cyclic olefin compounds; epoxidized polybutadiene, epoxidized Examples include epoxidized conjugated diene polymers such as acrylonitrile-butadiene copolymer and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate. Furthermore, these epoxy resins may be internally crosslinked with a terminal isocyanate prepolymer or may have a high molecular weight with a polyhydric active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphoric acid ester, etc.). .
Among the above-mentioned epoxy resins, those having a glycidyl group are preferred, and those having a difunctional or higher glycidyl group are more preferred from the viewpoint of excellent curability.

As the phenolic resin, a phenolic resin having two or more hydroxyl groups in one molecule is preferable, and generally known phenolic resins can be used. Examples of the phenolic resin include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac type phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, polymerizable unsaturated hydrocarbon group-containing phenolic resin, and hydroxyl group-containing silicone resins, but are not particularly limited. These phenolic resins can be used alone or in combination of two or more.

The thiol compound is not particularly limited and includes all thiol compounds, but is preferably one having two or more thiol groups in one molecule.
Specific preferred examples of the thiol compound include bis(2-mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythrithiol, 1,1,3,3-tetrakis(mercaptomethyl) Examples of the mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane include 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, and trimethylolpropane trismercaptopropionate, and more preferably, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol thiol, bis(2-mercaptoethyl)sulfide, 2,5-bis(2-mercaptomethyl)-1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,3-bis(mercaptomethyl)benzene, pentaerythritol tetrakismercaptopropionate, and pentaerythritol tetrakisthioglycolate.
Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythrithiol, bis(2-mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
The thiol compounds can be used alone or in combination of two or more.

Examples of the acid dianhydride for the polyamide resin include ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and 1,2,3,4-cyclohexanetetracarboxylic dianhydride. 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , as the diamine, (o-, m- or p-) phenylene diamine, (3,3'- or 4,4'-) diaminodiphenyl ether, diaminobenzophenononone, (3,3'- or 4,4'-) ) Examples include resins made from diaminodiphenylmethane and the like.

The above-mentioned polyurethane resin uses polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate as diisocyanates, and polyols (polyfunctional alcohols) such as polyether polyols, polyester polyols, and polycarbonate polyols as raw materials. Examples include resins that can be used.
Further, examples of the nylon resin include resins made from cyclic monomers such as ε-caprolactam and lauryllactam.
Examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone.

Examples of the ethylenically unsaturated compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloride, and other unsaturated aliphatic hydrocarbons; Acrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hemic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyl] mono(meth)acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as mono(meth)acryloyloxyethyl], mono[2-(meth)acryloyloxyethyl] phthalate, and ω-carboxypolycaprolactone mono(meth)acrylate; hydroxy Polyfunctional (meth)acrylates such as ethyl (meth)acrylate malate, hydroxypropyl (meth)acrylate malate, dicyclopentadiene malate, or polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups. Saturated polybasic acids: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following acrylic compound No. 1~No. 4. Methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, ( Isooctyl meth)acrylate, Isononyl (meth)acrylate, Stearyl (meth)acrylate, Lauryl (meth)acrylate, Methoxyethyl (meth)acrylate, Dimethylaminomethyl (meth)acrylate, Dimethyl (meth)acrylate Aminoethyl, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, (meth)acrylate ) Ethylhexyl acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, Unsaturated monobasic acids and polyhydric alcohols or polyhydric alcohols such as pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester(meth)acrylate oligomers Ester of phenol; Metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydro Phthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Acid adducts, acid anhydrides of unsaturated polybasic acids such as dodecenyl succinic anhydride and methylhimic anhydride; (meth)acrylamide, methylene bis-(meth)acrylamide, diethylenetriamine tris(meth)acrylamide, xylylene bis(meth)acrylamide Amides of unsaturated monobasic acids and polyvalent amines such as , α-chloroacrylamide and N-2-hydroxyethyl (meth)acrylamide; Unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide , unsaturated nitriles such as allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, Unsaturated aromatic compounds such as vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzylglycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine, etc. Unsaturated amine compounds; Vinyl alcohols such as allyl alcohol and crotyl alcohol; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; Maleimide, N-phenylmaleimide, N-cyclohexylmaleimide unsaturated imides such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth) ) Macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as acrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallylisocyanine Examples include vinyl urethane compounds such as lato, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds.
Ethylenically unsaturated compounds can be used alone or in combination of two or more.

As the above ethylenically unsaturated compound, commercially available products can be used, such as Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (all manufactured by Nippon Kayaku Co., Ltd.); Aronix M-215, M-350 (all manufactured by Toagosei Co., Ltd.); NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (all manufactured by Showa Denko Co., Ltd.); and the like.

The content of the polymerizable composition (B) may be an appropriate amount depending on the purpose of use, but in order to prevent curing failure, the content of the polymerizable composition (B) should be within the solid content (all components other than the solvent). , is preferably contained in an amount of 50 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more.

<Additives>
The polymerizable composition of the present invention may contain, as optional components, additives such as inorganic compounds, coloring materials, latent epoxy curing agents, chain transfer agents, sensitizers, and solvents.

Examples of the inorganic compounds 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, calcium carbonate, Magnesium carbonate, cobalt type, manganese type, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenide, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Examples include gold, silver, copper, etc. These inorganic compounds are used, for example, as a filler, an antireflection agent, a conductive material, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, an ink forming agent, and the like.

Examples of the coloring materials 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 pigments include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthranthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid, metal complex compounds of azo dyes and cyanine dyes, and lake pigments. carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black; the above carbon black adjusted or coated with an epoxy resin; the above carbon black previously dispersed in a solvent with a resin to adsorb 20 to 200 mg/g of resin; the above carbon black subjected to an acidic or alkaline surface treatment; carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less; Carbon black having a total oxygen content of 9 mg or more per ¹⁰⁰ m2 of surface area calculated from the above formula ₂ ; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, synthetic iron black, amber, and other organic or inorganic pigments can be used. These pigments can be used alone or in combination.

As the pigment, commercially available pigments can also be used, such as Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, Pigment green 7, 10, 36; Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

Examples of the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and these may be used in combination.

Examples of the latent epoxy curing agent include dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenylsulfone, boron trifluoride amine complex salts, imidazoles, guanamines, imidazoles, ureas, and melamine. Can be mentioned.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-( 2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis Mercapto compounds such as (3-mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid Iodinated alkyl compounds such as trimethylolpropane tris(3-mercaptoisobutyrate), butanediolbis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediolbisthio Propionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate , pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, and Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko.

The above-mentioned solvent is usually a solvent capable of dissolving or dispersing each of the above-mentioned components (polymerization initiator (A) and polymerizable compound (B), etc.), for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc.; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, Texanol, etc.; cellosolve-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, etc.; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl Ether ester solvents such as ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; paraffin solvents such as mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.). agents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc.; halogenated aromatic hydrocarbon solvents such as chlorobenzene, etc.; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; water, etc. can be used, and these solvents can be used alone or as a mixed solvent of two or more kinds.
Among these, from the viewpoints of alkaline developability, patterning ability, film-forming ability, and solubility, ketones or ether ester solvents, in particular, propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as "PGMEA") or cyclohexanone are preferably used.
In the polymerizable composition of the present invention, the content of the solvent is not particularly limited as long as each component is uniformly dispersed or dissolved and the polymerizable composition of the present invention exhibits a liquid or paste state suitable for each application. However, it is usually preferable to contain the solvent in such a range that the amount of solids in the polymerizable composition of the present invention (all components other than the solvent) is 10 to 90 mass %.

Moreover, the properties of the cured product can also be improved by using an organic polymer in the polymerizable composition of the present invention. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, and (meth)acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Examples include polyester, phenol resin, phenoxy resin, and the like.
When using the above organic polymer, the amount used is preferably 10 to 500 parts by weight per 100 parts by weight of the polymerizable compound (B).

The polymerizable composition of the present invention may further contain a surfactant, a silane coupling agent, a melamine compound, etc.

The above-mentioned surfactants include fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; Cationic surfactants such as amine halogenates and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; silicone interfaces Surfactants such as active agents can be used, and these may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, KBE-9007, KBM-502, KBE-403, etc., having an isocyanate group, a methacryloyl group, or an epoxy group can be used. A silane coupling agent is preferably used.

The above-mentioned melamine compounds include all or part of the active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly)methylolmelamine, (poly)methylolglycoluril, (poly)methylolbenzoguanamine, and (poly)methylolurea. Examples include compounds in which (at least two of them) are alkyl etherified.
Here, 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. Furthermore, the methylol groups that have not been alkyl etherified may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred from the viewpoint of solubility in solvents and resistance to crystallization from the polymerizable composition.

In the polymerizable composition of the present invention, the amount of optional components other than the polymerization initiator (A) and the polymerizable compound (B) (excluding inorganic compounds, colorants, and solvents) used is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total per 100 parts by mass of the polymerizable compound (B).

The polymerizable composition of the present invention can be cured by irradiation with energy rays. The cured product is formed into an appropriate shape depending on the intended use. For example, when forming a cured product in the form of a film, the polymerizable composition of the present invention can be coated with soda using known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and dipping. It can be applied on supporting substrates such as glass, quartz glass, semiconductor substrates, metal, paper, plastic, etc. In addition, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and there are no restrictions on the method of application.

Energy ray light sources used for curing the polymerizable composition of the present invention include ultra-high pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, and carbon arc lamps. Electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., and high energy rays such as electron beams, Preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc. that emit light with a wavelength of 300 to 450 nm is used.

Furthermore, by using laser light as the exposure light source, the laser direct writing method, which directly forms images from digital information from computers etc. without using a mask, improves not only productivity but also resolution and positional accuracy. It is useful because it can also be used as a laser beam, and light with a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser , various semiconductor lasers, YAG lasers, and other lasers that emit light in the visible to infrared region can also be used. When using these laser beams, preferably a sensitizing dye that absorbs in the visible to infrared region is added.

In addition, in order to harden the polymerizable composition of the present invention, heating is usually required after irradiation with the above-mentioned energy rays, and heating to about 40 to 150°C is preferred in terms of the hardening rate.

The polymerizable composition of the present invention is useful in the manufacture of photocurable paints or varnishes; photocurable adhesives; coatings for metals; printed circuit boards; color filters in liquid crystal display elements for color displays such as color televisions, PC monitors, personal digital assistants, and digital cameras; color filters in CCD image sensors; electrode materials for plasma display panels; powder coatings; printing inks; printing plates; adhesives; dental compositions; gel coats; photoresists for electronics; electroplating resists; etching resists; dry films; solder resists; resists for producing color filters for various display applications or for forming the structures thereof in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; and resists for encapsulating electrical and electronic components. the like, and there is no particular limitation on the uses thereof.

The polymerizable composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for the purpose of forming protrusions for vertical alignment type liquid crystal display elements. It is particularly useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for vertical alignment type liquid crystal display elements.

The above-mentioned spacer for liquid crystal display panels is preferably formed by the steps of (I) forming a coating film of the polymerizable composition of the present invention on a substrate, (2) irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape, (3) baking after exposure, (4) developing the coating film after exposure, and (5) heating the coating film after development.

The polymerizable composition of the present invention to which a coloring material has been added is suitably used as a resist that constitutes each pixel of RGB, etc. in a color filter, and a resist for a black matrix that forms partition walls of each pixel. Furthermore, in the case of a black matrix resist to which an ink repellent is added, it is preferably used for partition walls for inkjet color filters having a profile angle of 50° or more. As the ink repellent, a fluorosurfactant and a composition containing the fluorosurfactant are preferably used.

When used in the partition wall for the above-mentioned inkjet color filter, the partition wall formed from the polymerizable composition of the present invention partitions the transfer target, and droplets are applied to the divided recesses on the transfer target by the inkjet method. An optical element is manufactured by the method of forming an image area. In this case, it is preferable that the droplet contains a colorant and the image area is colored. In this case, the optical element manufactured by the above manufacturing method is formed from a plurality of colored areas on the substrate. The pixel group has at least a partition wall that separates each colored region of the pixel group.

The polymerizable composition of the present invention can also be used as a composition for a protective film or an insulating film. In this case, it may contain an ultraviolet absorber, an alkylated modified melamine and/or an acrylic modified melamine, a mono- or difunctional (meth)acrylate monomer containing an alcoholic hydroxyl group in the molecule, and/or a silica sol.

The insulating film is used in an insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable supporting substrate, the laminate can be developed with an alkaline aqueous solution, and it is preferable that the insulating resin layer has a thickness of 10 to 100 μm.

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 fired product patterns such as barrier rib patterns, dielectric patterns, electrode patterns, and black matrix patterns of plasma display panels.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the properties of the compound obtained below are those at 25° C. under atmospheric pressure.

[Production Example 1] Synthesis of Oxime Compound 1 2.40 g of aluminum chloride and 34.56 g of dichloroethane (EDC) were placed in a 100 mL four-neck flask and stirred at -5°C on an ice bath. A solution of 5.02 g of 9,9'-dihexylfluorene and 2.44 g of octanoyl chloride dissolved in 20 g of dichloroethane was added dropwise thereto. After raising the temperature to room temperature, the mixture was stirred for 3 hours, cooled again in an ice bath, and 20 g of a 5% by mass aqueous sodium hydroxide solution was added dropwise. Oil-water separation was performed, and the organic layer was washed three times with water. The organic layer was concentrated under reduced pressure using an evaporator, and the following ketone compound 1 was obtained in a yield of 6.91 g.

3.00 g of Ketone Compound 1, 0.50 g of hydroxylamine hydrochloride, 9.30 g of dimethylformamide (DMF), and 0.62 g of pyridine were added in this order to a 100 mL four-necked flask, and the mixture was heated and stirred at 80° C. for 5 hours on an oil bath. After cooling to room temperature, it was poured into 50 g of ionized water. Ethyl acetate was added to perform oil/water separation, and the organic layer was washed three times with water. The organic layer was concentrated under reduced pressure using an evaporator to obtain the following oxime compound 1 in a yield of 3.10 g.

[Production Example 2] Synthesis of Oxime Compound 2 2.00 g of Ketone Compound 1, 6.39 g of DMF, and 0.45 g of 35% by mass hydrochloric acid were added in this order to a 100 mL four-necked flask, and the mixture was stirred at 5°C on an ice bath. . 0.50 g of isobutyl nitrite was added dropwise thereto. After raising the temperature to room temperature, the mixture was stirred for 6 hours. After that, it was poured into 50 g of ionized water. Ethyl acetate was added to perform oil/water separation, and the organic layer was washed three times with water. The organic layer was concentrated under reduced pressure using an evaporator to obtain the following oxime compound 2 in a yield of 2.13 g.

[Production Example 3] Synthesis of oxime compound 3 3.63 g of ketone compound 2 below, 1.67 g of hydroxylamine hydrochloride, 11.78 g of DMF, and 1.90 g of pyridine were added to a 100 mL four-neck flask in this order, and the mixture was heated and stirred at 80° C. on an oil bath for 5 hours. After cooling to room temperature, the mixture was poured into 50 g of ionized water. Ethyl acetate was added to separate the oil and water, and the organic layer was washed three times with water. The organic layer was concentrated under reduced pressure using an evaporator. Methanol was added to the residue to perform crystallization, and the following oxime compound 3 was obtained in a yield of 3.13 g.

[Production Example 4] Synthesis of oxime compound 4 1.0 eq. of 1-(9,9-dimethyl-7-(2-methylbenzoyl)-9H-fluoren-2-yl)octan-1-one was added to a 100 ml four-neck flask and dissolved in dimethylformamide (400% by weight of theoretical yield). 1.2 eq. of hydroxyammonium chloride and 1.2 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 55°C for 9 hours, ion-exchanged water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with 5% by mass hydrochloric acid, ion-exchanged water, a saturated aqueous sodium bicarbonate solution twice, and ion-exchanged water three times, in that order, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:6) to obtain oxime compound 4 in a yield of 70%.

[Production Example 4] Synthesis of oxime compound 5 1.0 eq. of 3-cyclopentyl-1-(9,9-dimethyl-7-nitro-9H-fluoren-2-yl)propan-1-one was added to a 100 ml four-neck flask and dissolved in dimethylformamide (400% by weight of theoretical yield). 1.2 eq. of hydroxyammonium chloride and 1.2 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 55°C for 7 hours, ion-exchanged water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed three times with ion-exchanged water, dried over magnesium sulfate, and concentrated. Methanol (1700% by weight of theoretical yield) was added to the mixture to perform crystallization, and oxime compound 5 was obtained as a light brown powdery compound in a yield of 65%.

[Example 1-1] Compound No. Synthesis of 1 1.00 g of oxime compound 1 and 6.00 g of acetonitrile were placed in a 100 mL four-necked flask and stirred at room temperature. A solution of 0.41 g of 1,1'-carbonyldiimidazole dispersed in 5 g of acetonitrile was added thereto over 10 minutes. After stirring for 3 hours, the precipitated crystals were removed and the filtrate was concentrated. Drying under reduced pressure was further performed for 3 hours to obtain a white powdery compound with a yield of 59%. The obtained solid was analyzed by TG-DTA (melting point/°C) and ¹ H-NMR, and the target compound, Compound No. It was confirmed that it was 1. The analysis results are shown in [Table 1] and [Table 2].

[Example 1-2] Compound No. Synthesis of 2 2.13 g of oxime compound 2 and 29.00 g of acetonitrile were placed in a 100 mL four-necked flask and stirred at room temperature. A solution of 0.86 g of 1,1'-carbonyldiimidazole dispersed in 5 g of acetonitrile was added thereto over 10 minutes. After stirring for 1 hour, the precipitated crystals were removed and the filtrate was concentrated. Drying under reduced pressure was further performed for 4 hours to obtain a white powdery compound with a yield of 51%. The obtained solid was analyzed by TG-DTA (melting point/°C) and ¹ H-NMR, and the target compound, Compound No. It was confirmed that it was 2. The analysis results are shown in [Table 1] and [Table 2].

[Example 1-3] Compound No. Synthesis of No. 3 1.18 g of oxime compound 3, 1.17 g of 1,1'-carbonyldiimidazole and 1.04 g of tetrahydrofuran (THF) were placed in a 100 mL four-necked flask and stirred at room temperature for 2 hours. 0.61 g of piperidine was added dropwise thereto, and the mixture was stirred on an oil bath at 60° C. for 6 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure using an evaporator, chloroform was added to the residue, and the mixture was washed five times with ion-exchanged water. The organic layer was concentrated under reduced pressure, and methanol was added to perform crystallization to obtain a pale yellow powder in a yield of 74%. The obtained solid was analyzed by TG-DTA (melting point/°C) and ¹ H-NMR, and the target compound, Compound No. It was confirmed that it was 3. The analysis results are shown in [Table 1] and [Table 2].

[Example 1-4] Compound No. Synthesis of 50 In a 100 ml four-necked flask, 1.0 eq. of oxime compound 4 was added. , dichloroethane (600% by weight of theoretical yield), triethylamine 2.0 eq. was added and stirred at 5°C on an ice bath. There was added 1.5 eq. of 4-nitrophenyl chloroformate. was added dropwise in dichloroethane. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. After cooling again to 5°C on an ice bath, 1.5 eq. of aniline was added. was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate and ion-exchanged water were added thereto to separate oil and water. Furthermore, the organic layer was washed twice with a 1% by mass aqueous sodium hydroxide solution and twice with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent=ethyl acetate:toluene=1:30) to obtain compound No. 50 was obtained as a pale yellow transparent solid in a yield of 56%. The obtained compound was analyzed by TG-DTA (melting point) and ¹ H-NMR. The results are shown in [Table 2A] and [Table 2B]. Compound no. The reaction formula for the synthesis of 50 is as follows.

[Example 1-5] Compound No. Synthesis of 51 In a 100 ml four-necked flask, 1.0 eq. of oxime compound 4 was added. , dichloroethane (600% by weight of theoretical yield), triethylamine 2.0 eq. was added and stirred at 5°C on an ice bath. There was added 1.5 eq. of 4-nitrophenyl chloroformate. was added dropwise in dichloroethane. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. After cooling again to 5°C on an ice bath, 1.5 eq. of piperidine was added. was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate and ion-exchanged water were added thereto to separate oil and water. Furthermore, the organic layer was washed twice with a 1% by mass aqueous sodium hydroxide solution and three times with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent=ethyl acetate:toluene=1:10) to obtain compound No. 51 was obtained as a pale yellow transparent liquid in a yield of 67%. The obtained compound was analyzed by TG-DTA (melting point) and ¹ H-NMR. The results are shown in [Table 2B]. Compound no. The reaction formula for synthesis of 51 is as follows.

[Example 1-6] Synthesis of Compound No. 52 1.0 eq. of oxime compound 5, dichloroethane (600% by weight of theoretical yield), and 2.0 eq. of triethylamine were added to a 100 ml four-neck flask, and the mixture was stirred at 5°C on an ice bath. 1.5 eq. of 4-nitrophenyl chloroformate dissolved in dichloroethane was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling to 5°C on an ice bath again, 1.5 eq. of dibutylamine was added dropwise thereto. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate and ion-exchanged water were added thereto, and oil-water separation was performed. The organic layer was further washed twice with a 1% by weight aqueous sodium hydroxide solution and three times with ion-exchanged water, dried over magnesium sulfate, and concentrated. Methanol (600% by weight of theoretical yield) was added thereto, and crystallization was performed, and Compound No. 52 was obtained as a light brown solid with a yield of 78%. The compound obtained was analyzed by TG-DTA (melting point) and ¹ H-NMR. The results are shown in Table 2A and Table 2B. The reaction formula for the synthesis of compound No. 52 is as follows.

[Example 1-7] Compound No. Synthesis of 53 In a 100 ml four-necked flask, 1.0 eq. of oxime compound 5 was added. , dichloroethane (600% by weight of theoretical yield), triethylamine 2.0 eq. was added and stirred at 5°C on an ice bath. There was added 1.5 eq. of 4-nitrophenyl chloroformate. was added dropwise in dichloroethane. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. After cooling again to 5°C on an ice bath, 1.5 eq. of 3,5-dimethylpiperidine was added. was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate and ion-exchanged water were added thereto to separate oil and water. The organic layer was further washed three times with ion-exchanged water, dried over magnesium sulfate, and concentrated. Ethanol (7000% by weight of the theoretical yield) was added to this to perform crystallization, and compound No. 53 was obtained as a pale yellow solid in a yield of 79%. The obtained compound was analyzed by TG-DTA (melting point) and ¹ H-NMR. The results are shown in [Table 2A] and [Table 2B]. Compound no. The reaction formula for the synthesis of 53 is as follows.

[Example 1-8] Compound No. Synthesis of 54 In a 100 ml four-necked flask, 1.0 eq. of oxime compound 4 was added. , acetonitrile (200% by weight of the theoretical yield) was added and stirred at room temperature. 1.1 eq. of 1,1'-carbonyldiimidazole was added thereto. The mixture was stirred at room temperature for 30 minutes, and the solvent was distilled off under reduced pressure. Purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 60:40) to obtain compound No. 54 was obtained as a pale yellow solid in a yield of 44%. The obtained compound was analyzed by TG-DTA (melting point) and ¹ H-NMR. The results are shown in [Table 2A] and [Table 2B]. Compound no. The reaction formula for the synthesis of 54 is as follows.

Comparative Example 1-1
As comparative compound No. 1, the following compound was used.

[Evaluation 1] Solvent solubility test 1.0 g of each of the above compounds No. 1 to No. 3 and comparative compound No. 1 was weighed out, and each solvent shown in the following [Table 3] was added thereto at room temperature (25° C.), the amount of the solvent added when the compound was completely dissolved was measured, and the solubility of the compound was calculated according to the following formula. The results are shown in [Table 3].

Solubility of compound in each solvent (%)=1.0 g/(1.0 g+amount of solvent added (g))×100

From Table 3, it is clear that the compounds of the present invention have higher solubility in each solvent than the comparative compounds.

[Examples 2-1 to 2-3 and Comparative Example 2-1] Preparation of polymerizable compositions Polymerizable compositions of Examples 2-1 to 2-3 and Comparative Example 2-1 were obtained by carrying out the blending described in [Table 4]. The symbols of each component in [Table 4] represent the following components.
A-1 Compound No. 1
A-2 Compound No. 2
A-3 Compound No. 3
A'-1 Comparative Compound No. 1
B-1 EPPN-201
(Phenol novolac type epoxy resin, epoxy equivalent 193 g/eq., manufactured by Nippon Kayaku Co., Ltd.)
B-2 TRR-5010G
(Cresol novolac type phenolic resin, hydroxyl equivalent 120 g/eq., Mw=8,000, manufactured by Asahi Yukizai Kogyo Co., Ltd.)
C-1 FZ-2122
(Polyether modified polysiloxane, manufactured by Dow Corning Toray Co., Ltd.)
D-1 Cyclopentanone (solvent)

[Evaluation 2] Evaluation of polymerizable compositions and cured products The polymerizable compositions of Examples 2-1 to 2-3 and Comparative Example 2-1 obtained above were evaluated for line width sensitivity and residual film rate of the cured products by the following procedures. The results are shown in [Table 5].

[Evaluation sample creation method and evaluation method]
The polymerizable compositions of Examples 2-1 to 2-3 and Comparative Example 2-1 (approximately 2.0 cc of each composition) were applied to a glass substrate using a spin coater (500 rpm x 2 seconds → 1800 rpm x 15 seconds). A film was applied (seconds → slope x 5 seconds) and prebaked on a hot plate (90°C x 120 seconds).
Thereafter, UV light was exposed in sections using a Topcon exposure machine (60,120 mJ/cm ² , gap: 20 μm, illuminance: 20.0 mW/cm ² ).
After exposure, post-bake was performed on a hot plate (120°C x 5 minutes), and then developed with PGMEA (temperature: 23°C): 200 rpm x 10 seconds → IPA (isopropyl alcohol) cleaning (200 rpm x 10 seconds → drying: 500 rpm x 5 seconds).
Regarding the obtained samples, the line width and residual film rate of a pattern with a mask opening of 20 μm at each exposure dose were measured.

As shown in Table 5, the polymerizable composition of the present invention exhibited a larger line width (high sensitivity) and a higher film remaining rate (high curability) than the comparative polymerizable composition. This clearly shows that the compound of the present invention is an excellent polymerization initiator.

[Evaluation 3] Photodegradability test (Examples 3-1 to 3-3, Comparative Example 3-1)
The above compound No. 1~No. 3 and comparative compound no. 1 was prepared into an acetonitrile solution with a concentration of 1.0×10 ⁻⁴ mol and placed in a quartz cell with a lid. Each of these samples was irradiated with light from an ultra-high pressure mercury lamp at conditions of 100 mJ/cm ² , 500 mJ/cm ² and 1000 mJ/cm ² (integrated light intensity at 365 nm) to examine decomposition. For evaluation of decomposition, the peak area of the compound before and after irradiation with light was measured using HPLC, and the decomposition rate was calculated using the following formula. The obtained decomposition rates are listed in Table 6 below.

Decomposition rate (%) = [(HPLC area before light irradiation) - (HPLC area after light irradiation)] /
(HPLC area when not irradiated with light) x 100

From the results in Table 6, it is clear that the compounds of the present invention have a higher decomposition rate and superior sensitivity compared to the comparative compounds.

Claims (14)

A carbamoyl oxime compound represented by the following formula (I):

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a cyano group, a nitro group, -OR ¹¹ , -COOR ¹¹ , -CO-R ¹¹ , -SR ¹¹ , a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a group containing a heterocycle having 2 to 20 carbon atoms, or a group represented by the following formula (II):
R ¹¹ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
one or more of the hydrogen atoms in the groups represented ^by R ¹ , R ² , R ³ , R ⁴ , R 5 , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a group containing a heterocycle having 2 to 20 carbon atoms;
At least one of R ³ , R ⁴ , R ⁵ and R ⁶ is a group represented by the following formula (II), and at least one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the following formula (II).

In the formula, R ²¹ represents a hydrogen atom, a cyano group, a halogen atom, a nitro group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
X ¹ is a group represented by -NR ²² R ²³ ,
R ²² and R ²³ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
R ²² and R ²³ are linked to each other to form a ring consisting of a nitrogen atom and a carbon atom, or a ring consisting of an oxygen atom, a nitrogen atom and a carbon atom;
one or more of the hydrogen atoms in the groups represented by R ²¹ , R ²² and R ²³ may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a group containing a heterocycle having 2 to 20 carbon atoms;
n represents 0 or 1, and * represents a bond. The carbamoyl oxime compound according to claim 1, wherein R ²² and R ²³ are linked to each other to form a ring consisting of a nitrogen atom and a carbon atom. 2. The carbamoyl oxime compound according to claim 1, wherein R ²² and R ²³ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Claim 1, wherein at least one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the above formula (I) is a hydrogen atom, a nitro group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. The carbamoyl oxime compounds described. The carbamoyl according to claim 1, wherein at least one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the above formula (I) is a nitro group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Oxime compounds. The carbamoyl oxime compound according to claim 5, wherein one of R ³ , R ⁴ , R ⁵ and R ⁶ in formula (I) is a group represented by formula (II), and one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a nitro group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. 7. The carbamoyl oxime compound according to claim 5 , wherein R ⁹ in the formula (I) is a nitro group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. The carbamoyl oxime compound according to any one of claims 3 to 7 , wherein R ⁴ in formula (I) is a group represented by formula (II). A latent base compound comprising the carbamoyl oxime compound according to any one of claims 1 to 8 . A polymerization initiator containing at least one carbamoyloxime compound according to any one of claims 1 to 8 . A polymerizable composition comprising the polymerization initiator (A) according to claim 10 and a polymerizable compound (B). The polymerizable composition according to claim 11, wherein the polymerizable compound (B) is an epoxy resin or an ethylenically unsaturated compound, or a mixture containing an epoxy resin and a phenolic resin, a mixture containing an epoxy resin and a thiol compound, or a mixture containing an ethylenically unsaturated compound and a thiol compound. A cured product of the polymerizable composition according to claim 11 or 12 . A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to claim 11 or 12 with energy rays.