JP2012025710A - Photobase generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound to generate a base having a higher catalytic activity than conventional photobase generators, a photobase generator containing the same, and a method for generating a base.SOLUTION: There are provided the compound represented by formula [1], the photobase generator containing the same, and the method for generating a base. In the formula, Ar denotes one selected from the group consisting of a coumalinyl group having a specific structure and an acenaphthenyl group having a specific structure; Ydenotes a quaternary ammonium group having a specific structure; Zdenotes a halogen anion, a borate anion, an N,N-dimethylcarbamate anion, an N,N-dimethyldithiocarbamate anion, a cyanate anion, a thiocyanate anion, a benzoate anion or a benzoylformate anion; Rand Reach independently denote a hydrogen atom, a 1-10C straight chain, branched chain or cyclic alkyl group, or a phenyl group which may have a substituent.

Description

  The present invention relates to a compound having a property of generating a base upon irradiation with light (active energy rays), a photobase generator comprising these, and a base generating method.

  Curing by a light (active energy ray) sensitive polymerization initiator (hereinafter sometimes simply referred to as a photopolymerization initiator) (hereinafter sometimes simply referred to as photocuring) is a heat sensitive polymerization initiation. Compared with curing by an agent (hereinafter sometimes simply abbreviated as thermal polymerization initiator) (hereinafter sometimes simply abbreviated as thermal curing), it can be cured at a low temperature and in a short time. Therefore, it is widely used in the field of surface processing of paints, printing inks, dental materials, resists and the like.

  Photopolymerization initiators used in the photocuring technique can be roughly classified into three groups, photoradical generators, photoacid generators, and photobase generators, depending on the active species generated. Photoradical generators are photopolymerization initiators that generate radical species by irradiation of light (active energy rays), typified by acetophenone and the like, and have been widely used in the past. Since it has the property of being deactivated by oxygen, there is a disadvantage that the polymerization reaction is inhibited and curing is suppressed in the presence of oxygen. For this reason, particularly when a thin film is to be cured using a photo radical generator, special measures such as blocking oxygen in the air are required. In addition, since a photoacid generator is a photopolymerization initiator that generates an acid upon irradiation with light (active energy rays), it has an advantage that it is not inhibited by oxygen. Although the generator is put to practical use, if the acid generated by irradiation with light (active energy rays) remains in the system even after curing, the problem of performance degradation due to the modification of the cured film, the semiconductor field, etc. Has pointed out the problem of corrosiveness to the substrate by acid. On the other hand, photobase generators generate bases by irradiation with light (active energy rays), so they are not affected by oxygen in the air, and also cause corrosive problems and degeneration of cured films. Because of its difficulty, it is a photopolymerization initiator that has been actively researched and developed in recent years.

  Examples of such a photobase generator include carbamate (urethane) photobase generators (for example, Patent Document 1), α-aminoketone-based photobase generators (for example, Patent Document 2), and quaternary ammonium. Various photobase generators are known, such as photobase generators (eg, Patent Documents 3 and 4) and O-acyloxime photobase generators (eg, Patent Document 5).

  However, for example, the photobase generators of Patent Document 1, Patent Document 2, Patent Document 5 and the like have a low basicity because the base generated by irradiation with light (active energy rays) is a primary or secondary amine, and the base is generated. There was a problem that the effect as an agent might not be shown enough. Further, although quaternary ammonium salt photobase generators such as Patent Document 3 and Patent Document 4 are known, these base generators are not sufficient in catalytic activity for curing an epoxy resin. Had problems.

  Under such circumstances, a photobase generator capable of generating a base exhibiting catalytic activity for sufficiently curing an epoxy resin, that is, light generating a base having a higher catalytic activity than a conventional photobase generator. Development of a base generator is desired.

Japanese Patent Laid-Open No. 10-77264 JP-A-11-71450 Japanese Patent Laid-Open No. 2003-212856 JP 2005-264156 A JP 2006-36895 A

  The problem to be solved by the present invention is to provide a novel compound that generates a base with higher catalytic activity than conventional photobase generators, a photobase generator comprising these compounds, and a base generation method. There is.

［式中、Ａｒは、一般式［I］

（式中、ｍ個のＲ^３は夫々独立して、ハロゲン原子、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基又は炭素数２〜１０の直鎖状、分枝状若しくは環状のアルキルカルボニル基を表し、ｍは、０〜５の整数を表す。）で示されるクマリニル基、及び一般式［II］

（式中、ｎ個のＲ^４は夫々独立して、ハロゲン原子、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基又は炭素数２〜１０の直鎖状、分枝状若しくは環状のアルキルカルボニル基を表し、ｎは、０〜７の整数を表す。）で示されるアセナフテニル基からなる群より選ばれる何れかの基を表し、Ｙ^＋は、一般式［III］

（式中、Ｒ^５〜Ｒ^７は夫々独立して、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基を表す。）で示される基、一般式［IV］

｛式中、Ａは、窒素原子又はメチン基（ＣＨ基）を表し、Ｒ^８は、水素原子又はヒドロキシル基を表す。｝で示される基、式［V］

で示される基、式［Vl］

で示される基及び一般式［VIl］

（式中、Ｒ^９及びＲ^１０は夫々独立して、水素原子又は炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基を表す。）で示される基からなる群より選ばれる何れかの基を表し、Ｚ⁻は、ハロゲンアニオン、ボレートアニオン、Ｎ，Ｎ-ジメチルカルバメートアニオン、Ｎ，Ｎ-ジメチルジチオカルバメートアニオン、シアネートアニオン、チオシアネートアニオン、安息香酸アニオン又はベンゾイルぎ酸アニオンを表し、Ｒ^１及びＲ^２は夫々独立して、水素原子、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基又は置換基を有していてもよいフェニル基を表す。］で示される化合物の発明である。 The present invention relates to a general formula [1]

[Wherein Ar represents the general formula [I]

(In the formula, m R ^{3 s} are each independently a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a linear or branched group having 2 to 10 carbon atoms. Or a cyclic alkylcarbonyl group, m represents an integer of 0 to 5), and a coumarinyl group represented by the general formula [II]

(Wherein n R ^{4 s} are each independently a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a linear or branched group having 2 to 10 carbon atoms. Or represents a cyclic alkylcarbonyl group, and n represents an integer of 0 to 7.) represents any group selected from the group consisting of acenaphthenyl groups, and Y ⁺ represents the general formula [III].

(Wherein R ^{5 to} R ⁷ each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms), a general formula [IV]

{In the formula, A represents a nitrogen atom or a methine group (CH group), and R ⁸ represents a hydrogen atom or a hydroxyl group. }, A group represented by the formula [V]

A group represented by the formula: [Vl]

And a group represented by the general formula [VIl]

(Wherein R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms). represents any group, Z ^- represents a halogen anion, a borate anion, N, N-dimethylcarbamate anion, N, N-dimethyldithiocarbamate anion, thiocyanate anion, thiocyanate anion, benzoic acid anion or benzoyl formic acid anion , R ¹ and R ² each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a phenyl group which may have a substituent. Is an invention of a compound represented by

  Moreover, this invention is invention of the photobase generator containing the compound shown by the said General formula [1].

  Furthermore, the present invention is an invention of a base generation method characterized by irradiating the compound represented by the general formula [1] with light.

  The compound of the present invention is a compound represented by the general formula [1] that generates a base having a higher catalytic activity than a base that generates a conventional photobase generator, and the compound is cured by a base (cross-linked). Even if it is an epoxy resin which is hard to occur), it has a property of generating a base capable of sufficiently curing the resin.

It is a figure showing the relationship between the irradiation time at the time of irradiating light (active energy ray) to the coating film using the compound of Example 1 in Example 6, and a remaining film rate. It is a figure showing the relationship between the irradiation time at the time of irradiating light (active energy ray) to the coating film using the compound of Example 2 in Example 6, and a remaining film rate. It is a figure showing the relationship between the irradiation time at the time of irradiating light (active energy ray) to the coating film using the compound of Example 2 in Example 6, and a remaining film rate.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² in the general formula [1] include, for example, a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl Group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl group, Chloheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group , Neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), adamantyl group, menthyl group (Menta-χ-yl group) and the like. Among them, a methyl group, an ethyl group, and an n-propyl group, which are linear alkyl groups having 1 to 3 carbon atoms, are preferable. A methyl group which is an alkyl group is more preferable.

Specific examples of the “substituent” in the “optionally substituted phenyl group” represented by R ¹ and R ² in the general formula [1] include, for example, a fluorine atom, a chlorine atom, and a bromine atom. And a halogen atom such as an iodine atom, for example, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

The ^{R 1} and ^{R 2} in the general formula [1], more preferably a hydrogen atom.

  Ar in the general formula [1] is more preferably a coumarinyl group represented by the above general formula [I].

  In the compound represented by the general formula [1] of the present invention, the coumalinyl group represented by the general formula [I] and the acenaphthenyl group represented by the general formula [II], which are groups represented by Ar, are absorbed light. (Active energy ray) can be efficiently converted into energy for generating a base. Therefore, by selecting any group selected from these, that is, a specific absorbance group, the compound of the present invention can be converted into the conventional one. The photobase generator can be a photobase generator capable of generating a base having a higher catalytic activity than the base from which the photobase generator is generated, particularly when the photophore is a coumarinyl group represented by the above general formula [I]. Can be a photobase generator capable of generating a base capable of sufficiently curing the resin, even if the epoxy resin is hard to be cured (crosslinked) by a base.

Specific examples of the halogen atom represented by R ³ and R ⁴ in the general formulas [I] and [II] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An atom and a bromine atom are preferable.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ in the general formulas [I] and [II] include, for example, methyl group, ethyl Group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group Group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neo Butyl group, cycloheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), adamantyl Group, menthyl group (menta-χ-yl group) and the like. Among them, a methyl group which is an alkyl group having 1 carbon atom is preferable.

Specific examples of the linear, branched or cyclic alkylcarbonyl group having 2 to 10 carbon atoms represented by R ³ and R ⁴ in the general formulas [I] and [II] include, for example, a methylcarbonyl group (Acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, tert-butylcarbonyl group, cyclobutylcarbonyl group, n-pentylcarbonyl Group, isopentylcarbonyl group, sec-pentylcarbonyl group, tert-pentylcarbonyl group, neopentylcarbonyl group, 2-methylbutylcarbonyl group, 1,2-dimethylpropylcarbonyl group, 1-ethylpropylcarbonyl group, cyclopentylcarbonyl group , N-hexylcarbonyl group, isohexylcarbonyl Group, sec-hexylcarbonyl group, tert-hexylcarbonyl group, neohexylcarbonyl group, 2-methylpentylcarbonyl group, 1,2-dimethylbutylcarbonyl group, 2,3-dimethylbutylcarbonyl group, 1-ethylbutylcarbonyl group Cyclohexylcarbonyl group, n-heptylcarbonyl group, isoheptylcarbonyl group, sec-heptylcarbonyl group, tert-heptylcarbonyl group, neoheptylcarbonyl group, cycloheptylcarbonyl group, n-octylcarbonyl group, isooctylcarbonyl group, sec -Octylcarbonyl group, tert-octylcarbonyl group, neooctylcarbonyl group, 2-ethylhexylcarbonyl group, cyclooctylcarbonyl group, n-nonylcarbonyl group, isononylcarbonyl group, sec-nonylcarbonyl group, tert-nonylcarbonyl Group, neononylcarbonyl group, cyclononylcarbonyl group, norbornylcarbonyl group and the like. Among them, a methylcarbonyl group (acetyl group) which is an alkylcarbonyl group having 2 carbon atoms is preferable.

  As m in the said general formula [I], the integer of 0-2 is more preferable, and 0 is especially preferable especially.

  As n in the general formula [II], an integer of 0 to 5 is more preferable, an integer of 0 to 3 is more preferable, and 0 is particularly preferable among them.

In the compound represented by the general formula [1], the substituent (—COCR ¹ R ² Y ⁺ ) containing a quaternary ammonium group is 3-4 of the coumarin ring in the coumarinyl group represented by the general formula [I]. In the acenaphthenyl group represented by the above general formula [II], it is bonded to any one of the 3 to 5 position carbon atoms of the acenaphthene ring. The coumarinyl group represented by I] is preferably bonded to the 3-position of the coumarin ring, and the acenaphthenyl group represented by the general formula [II] is preferably bonded to the 5-position of the acenaphthene ring.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ⁵ , R ⁶ and R ⁷ in the general formula [III] include, for example, a methyl group and an ethyl group. N-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neohep Butyl group, cycloheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), adamantyl Group, menthyl group (menta-χ-yl group) and the like, and among them, a methyl group, ethyl group, n-propyl group, n-butyl group, which is a linear alkyl group having 1 to 6 carbon atoms, An n-pentyl group and an n-hexyl group are preferred.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ⁹ and R ¹⁰ in the general formula [VII] include, for example, a methyl group, an ethyl group, n- Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, 2- Methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2 -Dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl Group, cycloheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert -Nonyl, neononyl, cyclononyl, n-decyl, isodecyl, sec-decyl, tert-decyl, neodecyl, cyclodecyl, norbornyl, bornyl (bornane-χ-yl), adamantyl And a menthyl group (menta-χ-yl group) and the like. Among them, a methyl group which is an alkyl group having 1 carbon atom is preferable.

Y ⁺ in the general formula [1] is a group represented by the above general formula [III], a group represented by the above general formula [IV], a group represented by the above formula [V], or a group represented by the above formula [VI]. And the group represented by the above general formula [IV] is particularly preferable.

In the compound represented by the general formula [1] of the present invention, a group represented by the above general formula [III], a group represented by the above general formula [IV], which is a group represented by Y ⁺ (quaternary ammonium group) The base (tertiary amine or amidine) generated from any one of the group represented by the above formula [V], the group represented by the above formula [VI], and the group represented by the above general formula [VII] is a conventional one. Therefore, a compound having any of these quaternary ammonium groups can be a photobase generator that generates a base with higher catalytic activity than a conventional photobase generator. It is. Furthermore, a compound having any one of the group represented by the general formula [III], the group represented by the general formula [IV], the group represented by the formula [V], and the group represented by the formula [VI] In addition, it can be a photobase generator that generates a base having higher catalytic activity than conventional photobase generators. In particular, a compound having a group represented by the above general formula [IV] is represented by the above general formula [IV]. Since the group shown is an aliphatic ammonium group, it does not inhibit the light (active energy ray) absorption of the photophore represented by Ar as described above, and the bulk of the ammonium group is not so large. The tertiary amine or amidine generated from the ammonium group not only has an appropriate nucleophilicity but also has a relatively high boiling point, so that the tertiary amine or amidine has a relatively high boiling point during the heating step during film formation with an epoxy resin or the like. Tertiary amine or Even if it is an epoxy resin that is less susceptible to curing (crosslinking) with a base compared to other compounds having a quaternary ammonium group, patterning can be performed more effectively with less evaporation of the midine. It is a useful compound because it can be a photobase generator that generates a curable base.

Specific examples of the halogen anion represented by Z ⁻ in the general formula [1] include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, and the like. Among them, a chloride ion, a bromide ion, and the like. Is preferred.

（式中、Ｒ^１１〜Ｒ^１４は夫々独立して、水素原子、ハロゲン原子、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基又は置換基を有していてもよいアリール基を表す。）で示されるボレートアニオンが挙げられる。 Specific examples of the borate anion represented by Z ⁻ in the general formula [1] include, for example, the general formula [VIII].

(Wherein R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl optionally having a substituent. A borate anion represented by a group).

Specific examples of the halogen atom represented by R ^{11 to} R ¹⁴ in the general formula [VIII] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferable.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ^{11 to} R ¹⁴ in the general formula [VIII] include, for example, a methyl group, an ethyl group, n- Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, 2- Methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2 -Dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl Group, cycloheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), adamantyl Group, menthyl group (menta-χ-yl group) and the like. Among them, n-butyl group which is a linear alkyl group having 4 carbon atoms is preferable.

Specific examples of the aryl group in the aryl group which may have a substituent represented by R ^{11 to} R ¹⁴ in the general formula [VIII] include, for example, a phenyl group, a naphthyl group, an azulenyl group, an anthryl group, and a phenanthryl group. Among them, a phenyl group is preferable.

Specific examples of the substituent in the aryl group which may have a substituent represented by R ^{11 to} R ¹⁴ in the general formula [VIII] include halogens such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Atoms, for example, a straight or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, such as a hydroxyl group, a mercapto group, a cyano group, and a nitro group It is done.

As R < ¹¹ > -R < ¹⁴ > in the said general formula [VIII], the aryl group which may have a substituent is more preferable.

  Specific examples of such borate anions include tetraphenyl borate anion, triphenyl-n-butyl borate anion, tetrakis (4-fluorophenyl) borate anion, tetrakis (3-chlorophenyl) borate anion, tetrakis (4-chlorophenyl). ) Borate anion, tetrakis (4-methylphenyl) borate anion, tetrakis (4-tert-butylphenyl) borate anion, tetrakis (4-methoxyphenyl) borate anion, tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate anions such as a borate anion. Among them, a tetraphenylborate anion and a triphenyl-n-butylborate anion are preferable, and a tetraphenylborate anion is more preferable. Good.

As Z ⁻ in the general formula [1], a borate anion is more preferable, and among them, a tetraphenyl borate anion is particularly preferable. That is, such a borate anion is preferable in that it can be a photobase generator that generates a base having high catalytic activity.

（式中、Ｒ^１、Ｒ^２、ｍ個のＲ^３、Ｒ^８、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ａ及びｍは上記に同じ。）で示されるもの、一般式［１］におけるＡｒが上記一般式［II］で示されるアセナフテニル基であり、Ｙ^＋が上記一般式［IV］で示される基であって、かつＺ⁻が上記一般式［VIII］で示されるボレートアニオンである、一般式［３］

（式中、Ｒ^１、Ｒ^２、ｎ個のＲ^４、Ｒ^８、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ａ及びｎは上記に同じ。）で示されるものが挙げられる。これらの化合物は、本発明の他の化合物と比較して、従来の光塩基発生剤が発生する塩基と比べてより触媒活性の高い塩基を発生する光塩基発生剤となり得るという点において、好ましい化合物である。 Among the compounds represented by the above general formula [1] of the present invention, more specific compounds include Ar in the general formula [1] is a coumarinyl group represented by the above general formula [I], and Y ⁺ represents the above. General formula [2], which is a group represented by general formula [IV], and Z ⁻ is a borate anion represented by general formula [VIII].

(Wherein, R ¹ , R ² , m R ³ , R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , A and m are the same as above), the general formula [1] In which Ar is an acenaphthenyl group represented by the above general formula [II], Y ⁺ is a group represented by the above general formula [IV], and Z ⁻ is a borate anion represented by the above general formula [VIII]. A general formula [3]

(Wherein R ¹ , R ² , n R ⁴ , R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , A and n are the same as above). These compounds are preferable compounds in that they can serve as photobase generators that generate bases with higher catalytic activity compared to bases that generate conventional photobase generators compared to other compounds of the present invention. It is.

（式中、Ｐｈは、フェニル基を表す。）で示される化合物、及び式［５］

（式中、Ｐｈは、フェニル基を表す。）で示される化合物が、より好ましいものとして挙げられる。 As a more preferred specific example of the compound represented by the general formula [2], R ¹ and R ² in the general formula [2] are both hydrogen atoms, R ⁸ is a hydrogen atom or a hydroxyl group, and R ^{11 to} R ¹⁴ are all phenyl groups, A is a nitrogen atom or a methine group (CH group), m is 0, and a substituent containing a quaternary ammonium group (—COCR ¹ R ² Y ⁺ ) Is bonded to the 3-position of the coumarin ring, more specifically, the formula [4]

(Wherein Ph represents a phenyl group) and the formula [5]

A compound represented by the formula (wherein Ph represents a phenyl group) is more preferred.

  The compounds represented by the above formulas [4] and [5] are epoxy resins that are not only easily and inexpensively produced as compared with other compounds of the present invention, but also difficult to cure (crosslink) with a base. Is a more preferable compound in that it can be a photobase generator that generates a base capable of sufficiently curing the resin.

In addition, as a precautionary note, in the compounds represented by the above formulas [4] to [5], R ¹ and R ² in the general formula [1] are both hydrogen atoms, and Ar is the above general formula [I]. Whether m in the coumarinyl group is 0, Y ⁺ is a group represented by the above general formula [IV], and A is a combination of a nitrogen atom and R ⁸ is a hydrogen atom. Or A is a combination of a methine group (CH group) and R ⁸ is a hydroxyl group, Z ⁻ is a tetraphenylborate anion, and a substituent containing a quaternary ammonium group (—COCR ¹ R ² Y ⁺ ) Corresponds to a bond to the 3-position of the coumarin ring.

（式中、Ｐｈは、フェニル基を表す。）で示される化合物が、より好ましいものとして挙げられる。 Furthermore, as a more preferable specific example of the compound represented by the general formula [3], R ¹ and R ² in the general formula [2] are both hydrogen atoms, R ⁸ is a hydroxyl group, R ¹¹ to R ¹⁴ is all a phenyl group, A is a methine group (CH group), n is 0, and the substituent containing a quaternary ammonium group (—COCR ¹ R ² Y ⁺ ) is 5 of the acenaphthene ring. And, more specifically, the formula [6]

A compound represented by the formula (wherein Ph represents a phenyl group) is more preferred.

As a precautionary note, in the compound represented by the above formula [6], R ¹ and R ² in the general formula [1] are both hydrogen atoms, and Ar is acenaphthenyl represented by the above general formula [I]. A group in which n in the acenaphthenyl group is 0, Y ⁺ is a group represented by the above general formula [IV], A is a combination of a methine group (CH group) and R ⁸ is a hydroxyl group, This corresponds to a case where Z ⁻ is a tetraphenylborate anion and a substituent (—COCR ¹ R ² Y ⁺ ) containing a quaternary ammonium group is bonded to the 5-position of the acenaphthene ring.

  The compound of the present invention generates a base upon irradiation with light (active energy ray) having a wavelength of 200 nm or more such as light (active energy ray) of 200 nm to 500 nm, and more specifically, for example, light having a wavelength of 365 nm ( Even when light (active energy ray) having a wavelength of 300 nm or more such as (active energy ray) is irradiated, a base is generated. A more preferable range of the light (active energy ray) is light having a wavelength of 300 nm to 500 nm (active energy ray). In these preferable ranges, the compound of the present invention exhibits good sensitivity, and more specifically. Since an absorption wavelength region having a molar extinction coefficient of 3000 or more exists in the above-mentioned wavelength region of 300 to 500 nm, a base can be generated efficiently.

（式中、Ａｒ、Ｒ^１及びＲ^２は上記に同じ。）で示される化合物にハロゲン原子を導入して、一般式［８］

（式中、Ｘは、塩素原子、臭素原子又はヨウ素原子を表し、Ａｒ、Ｒ^１及びＲ^２は上記に同じ。）で示される化合物を合成する。次いで、上記一般式［８］で示される化合物に対して、一般式［１］におけるＹ^＋で示される４級アンモニウム基に対応する３級アミン又はアミジンを反応させて、一般式［９］

（式中、Ｘ⁻は、塩化物イオン、臭化物イオン又はヨウ化物イオンを表し、Ａｒ、Ｙ^＋、Ｒ^１及びＲ^２は上記に同じ。）で示される化合物とし、更に、一般式［１］におけるＺ⁻で示される基に対応する、アニオンに変換して目的とする一般式［１］で示される化合物を合成すればよい。より具体的な製造方法としては、例えば上記一般式［７］で示される化合物に対して、通常０．８〜１０当量、好ましくは１〜３当量の塩素、臭素、ヨウ素等のハロゲン化剤を反応させて、上記一般式［８］で示される化合物を得る（第一工程）。次いで、第一工程で得られた一般式［８］で示される化合物に対して、通常０．８〜１０当量、好ましくは１〜３当量の３級アミン又はアミジンを反応させることにより、上記一般式［９］で示される化合物を得る（第二工程）。更に、第二工程で得られた一般式［９］で示される化合物に対して、通常０．８〜１０当量、好ましくは１〜３当量のＺ⁻に対応するアニオン成分を反応させることにより（第三工程）、本発明の一般式［１］で示される化合物を得ることができる。なお、一般式［１］で示される化合物におけるＺ⁻が塩素原子、臭素原子及びヨウ素原子の何れかである場合には、上記一般式［９］で示される化合物が一般式［１］で示される化合物に相当するので、上記第三工程は不要である。 Next, a method for producing the compound of the present invention will be described. Examples of the method for producing the compound represented by the general formula [1] of the present invention include the general formula [7].

(In the formula, Ar, R ¹ and R ² are the same as above) A halogen atom is introduced into the compound represented by the general formula [8]

(Wherein X represents a chlorine atom, a bromine atom or an iodine atom, and Ar, R ¹ and R ² are the same as above). Next, the compound represented by the general formula [8] is reacted with a tertiary amine or amidine corresponding to the quaternary ammonium group represented by Y ⁺ in the general formula [1], to thereby obtain the general formula [9].

(Wherein, X ⁻ represents a chloride ion, a bromide ion or an iodide ion, and Ar, Y ⁺ , R ¹ and R ² are the same as above), and further, the compound represented by the general formula [1] What is necessary is just to synthesize | combine the compound shown by the general formula [1] converted into the anion corresponding to the group shown by Z < ^- > in. As a more specific production method, for example, 0.8 to 10 equivalents, preferably 1 to 3 equivalents of a halogenating agent such as chlorine, bromine, iodine or the like is added to the compound represented by the general formula [7]. The reaction is performed to obtain the compound represented by the general formula [8] (first step). Next, the compound represented by the general formula [8] obtained in the first step is usually reacted with 0.8 to 10 equivalents, preferably 1 to 3 equivalents of a tertiary amine or amidine, to obtain the above general formula. A compound represented by the formula [9] is obtained (second step). Further, the compound represented by the general formula [9] obtained in the second step is usually reacted with an anion component corresponding to 0.8 to 10 equivalents, preferably 1 to 3 equivalents of Z ⁻ ( Third step), a compound represented by the general formula [1] of the present invention can be obtained. When Z ⁻ in the compound represented by the general formula [1] is any one of a chlorine atom, a bromine atom and an iodine atom, the compound represented by the general formula [9] is represented by the general formula [1]. Therefore, the third step is not necessary.

  As the compound represented by the general formula [7] used in the first step, a commercially available compound or a compound synthesized by a conventional method may be used as appropriate, and specifically, for example, 3-acetylcoumarin. 4-chloro-3-acetylcoumarin, 4-bromo-3-acetylcoumarin, 4-methyl-3-acetylcoumarin, 6-methyl-3-acetylcoumarin, 4-acetylcoumarin, 3-acetylacenaphthene, 4- Acetylacenaphthene, 5-acetylacenaphthene, 5-acetyl-6-chloroacenaphthene, 5-acetyl-6-bromoacenaphthene and the like, and depending on the structure of the compound represented by the general formula [1], Any one of the compounds as described above may be selected and used, but in particular, the compound represented by the general formula [1] can be produced inexpensively and easily. Cetyl coumarin, 5-acetyl acenaphthene are preferred. In addition, when synthesizing the compound represented by the general formula [7], usual alkylation, acylation, halogenation to an aromatic ring, nucleophilic substitution reaction by α-position carbon of a carbonyl group, etc. What is necessary is just to synthesize | combine by performing the chemical reaction performed in this field | area.

  In the first step, it is desirable to perform the reaction in an organic solvent. The organic solvent used in that case is not particularly limited as long as it is an organic solvent that does not react with the compound represented by the general formula [7] as a reaction raw material. Specifically, for example, pentane, hexane, octane, etc. Aliphatic hydrocarbon solvents such as aromatic hydrocarbon solvents such as benzene, toluene and xylene, halogen solvents such as dichloromethane, dichloroethane and chloroform, such as dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran (THF), dioxane And ether solvents such as ester solvents such as methyl acetate and ethyl acetate. These organic solvents may be used alone or in combination of two or more, and the amount of the organic solvent used is not particularly limited. For example, the amount is usually 0 with respect to 1 mmol of the compound represented by the general formula [7]. .1 mL to 20 mL, preferably 0.2 mL to 10 mL.

  The reaction temperature in the first step may be set to a temperature at which the compound represented by the general formula [7] reacts with a halogenating agent such as chlorine, bromine or iodine. In the general formula [7], It is preferable to set the temperature so that the compound shown and the halogenating agent react efficiently, and the compound represented by the general formula [8] can be synthesized with good yield. Specifically, for example, it is usually −40 ° C. to 100 ° C., preferably −20 ° C. to 60 ° C.

  The reaction time in the first step may vary depending on the amount of the halogenating agent used for the compound represented by the general formula [7], the type and amount of the organic solvent, the reaction temperature, etc. Usually, it is set in the range of 0.1 to 24 hours, preferably 0.2 to 12 hours.

  In the first step, the method for isolating and purifying the compound represented by the general formula [8], which is the product of the first step, from the solution after completion of the reaction may be a general post-treatment or purification operation. . Specifically, for example, the reaction solution after completion of the reaction is filtered and the crystals are collected by filtration and then washed with an appropriate organic solvent. For example, water is added to the reaction solution after completion of the reaction, followed by extraction and washing treatment. Then, the organic layer after washing is concentrated, and a method of drying the crystals generated therein can be used for efficient purification. In addition, you may perform the refinement | purification operation by normal column chromatography, not the above refinement | purification operation.

（式中、Ｒ^５〜Ｒ^７は上記に同じ。）で示される３級アミン、一般式［IV'］

（式中、Ａ及びＲ^８は上記に同じ。）で示される３級アミン、式［V'］

で示されるアミジン、式［VI'］

で示されるアミジン及び一般式［VII'］

（式中、Ｒ^９及びＲ^１０は上記に同じ。）で示されるアミジンが挙げられ、目的とする一般式［１］で示される化合物の構造により、上記３級アミン又はアミジンの何れかを適宜選択して用いればよいが、なかでも、上記一般式［III'］〜［VI'］で示される３級アミン又はアミジンが好ましく、そのなかでも、上記一般式［IV'］で示される３級アミンがより好ましい。なお、これらの３級アミン又はアミジンは、市販のものを用いれば足りる。 The tertiary amine or amidine used in the second step is a tertiary amine or amidine corresponding to the quaternary ammonium group represented by Y ⁺ in the general formula [1], and more specifically, for example, the general formula [III ']

(Wherein R ^{5 to} R ⁷ are the same as above), a tertiary amine represented by the general formula [IV ′]

(Wherein A and R ⁸ are the same as above), a tertiary amine represented by the formula [V ′]

Amidine represented by the formula [VI ']

And an amidine represented by the general formula [VII ′]

(Wherein R ⁹ and R ¹⁰ are the same as above), and depending on the structure of the target compound represented by the general formula [1], either the tertiary amine or amidine is appropriately selected. Among them, a tertiary amine or amidine represented by the above general formulas [III ′] to [VI ′] is preferable, and among them, a tertiary class represented by the general formula [IV ′] is preferable. Amines are more preferred. In addition, it is sufficient if these tertiary amines or amidines are commercially available.

  In the second step, it is desirable to perform the reaction in an organic solvent. The organic solvent used in that case is not particularly limited as long as it is an organic solvent that does not react with the compound represented by the general formula [8], a tertiary amine, or amidine as a reaction raw material. Aliphatic hydrocarbon solvents such as hexane and octane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, halogen solvents such as dichloromethane, dichloroethane and chloroform, such as dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, Ether solvents such as tetrahydrofuran (THF), dioxane, etc., ketone solvents such as dimethyl ketone (acetone), ethyl methyl ketone, diethyl ketone, amide solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), etc. Sulfoxide solvents such as dimethyl sulfoxide (DMSO). These organic solvents may be used alone or in combination of two or more, and the amount of the organic solvent to be used is not particularly limited. For example, 1 mL is usually used per 1 mmol of the compound represented by the general formula [8]. ~ 100mL, preferably 2mL ~ 50mL.

  The reaction temperature in the second step may be set to a temperature at which the compound represented by the general formula [8] reacts with the tertiary amine or amidine, but the compound represented by the general formula [8] It is preferable to set the temperature so that the tertiary amine or amidine efficiently reacts and the compound represented by the general formula [9] can be synthesized with high yield. Specifically, for example, it is usually −20 ° C. to 120 ° C., preferably 0 ° C. to 100 ° C.

  Since the reaction time in the second step may vary depending on the amount of tertiary amine or amidine used relative to the compound represented by the general formula [8], the type and amount of organic solvent used, the reaction temperature, etc., it can be said generally. However, it is usually set in the range of 0.1 to 24 hours, preferably 0.2 to 12 hours.

  In the second step, as a method for isolating and purifying the compound represented by the general formula [9], which is the product of the second step, from the solution after completion of the reaction, general post-treatment and purification operations may be used. . Specifically, for example, the reaction solution after completion of the reaction is filtered, and the crystals are collected by filtration and then washed with an appropriate organic solvent for efficient purification. In addition, you may perform the refinement | purification operation by normal column chromatography, not the above refinement | purification operation.

（式中、Ｍはアルカリ金属原子又はアンモニウム基（ＮＨ_４）を表し、Ｒ^１１〜Ｒ^１４は上記に同じ。）で示されるホウ酸塩、例えばＮ，Ｎ-ジメチルカルバミン酸ナトリウム、Ｎ，Ｎ-ジメチルカルバミン酸カリウム、Ｎ，Ｎ-ジメチルカルバミン酸リチウム等のＮ，Ｎ-ジメチルカルバミン酸塩、例えばＮ，Ｎ-ジメチルジチオカルバミン酸ナトリウム、Ｎ，Ｎ-ジメチルジチオカルバミン酸カリウム、Ｎ，Ｎ-ジメチルジチオカルバミン酸リチウム等のＮ，Ｎ-ジメチルジチオカルバミン酸塩、例えばシアン酸ナトリウム、シアン酸カリウム、シアン酸リチウム等のシアン酸塩、例えばチオシアン酸ナトリウム、チオシアン酸カリウム、チオシアン酸リチウム等のチオシアン酸塩、例えば安息香酸ナトリウム、安息香酸カリウム、安息香酸リチウム等の安息香酸塩、例えばベンゾイルぎ酸ナトリウム、ベンゾイルぎ酸カリウム、ベンゾイルぎ酸リチウム等のベンゾイルぎ酸塩等が挙げられるが、これらの例に何ら限定されるものではない。 The anion component used in the third step is an anion component corresponding to the group represented by Z ⁻ in the general formula [1]. More specifically, for example, the general formula [VIII ′]

(Wherein M represents an alkali metal atom or an ammonium group (NH ₄ ), and R ^{11 to} R ¹⁴ are the same as above), for example, sodium N, N-dimethylcarbamate, N, N N, N-dimethylcarbamate such as potassium dimethylcarbamate, lithium N, N-dimethylcarbamate, such as sodium N, N-dimethyldithiocarbamate, potassium N, N-dimethyldithiocarbamate, N, N-dimethyldithiocarbamine N, N-dimethyldithiocarbamate such as lithium oxide, for example, cyanate such as sodium cyanate, potassium cyanate, lithium cyanate, thiocyanate such as sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, for example Sodium benzoate, potassium benzoate, lithium benzoate Benzoic acid salts such as benzoic acid such as sodium benzoylformate, potassium benzoylformate, lithium benzoylformate and the like, but are not limited to these examples.

  Specific examples of the alkali metal atom represented by M in the general formula [VIII ′] include a lithium atom, a sodium atom, a potassium atom, a rubidium atom, and a cesium atom. Among these, a sodium atom, potassium An atom is preferable, and a sodium atom is more preferable among them.

  As M in the general formula [VIII ′], an alkali metal atom is more preferable.

  Specific examples of the borate represented by the general formula [VIII ′] include, for example, sodium tetraphenylborate, potassium tetraphenylborate, lithium tetraphenylborate, ammonium tetraphenylborate, triphenyl-n-butylborohydride. Lithium oxide, sodium tetrakis (4-fluorophenyl) borate, ammonium tetrakis (3-chlorophenyl) borate, potassium tetrakis (4-chlorophenyl) borate, ammonium tetrakis (4-chlorophenyl) borate, tetrakis (4-methylphenyl) Boric acid such as sodium borate, potassium tetrakis (4-tert-butylphenyl) borate, ammonium tetrakis (4-methoxyphenyl) borate, sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate Salt Among them, sodium tetraphenylborate, potassium tetraphenylborate, lithium preferably triphenyl -n- butylboron acid, Among them, sodium tetraphenyl borate are more preferred.

  Among specific examples of such anionic components, sodium tetraphenylborate, potassium tetraphenylborate, sodium N, N-dimethylcarbamate, potassium N, N-dimethylcarbamate, sodium N, N-dimethyldithiocarbamate N, N-dimethyldithiocarbamate, sodium cyanate, potassium cyanate, sodium thiocyanate, potassium thiocyanate, sodium benzoate, potassium benzoate, sodium benzoylformate, potassium benzoylformate Depending on the structure of the compound represented by the formula [1], any one of the above anionic components may be appropriately selected and used, among which sodium tetraphenylborate and potassium tetraphenylborate are more preferable. But Tet Sodium raphenylborate is particularly preferred. In addition, it is sufficient to use a commercially available anion component as described above.

  In the third step, it is desirable to perform the reaction in an organic solvent. The organic solvent used in that case is not particularly limited as long as it is an organic solvent that does not react with the compound represented by the general formula [9], which is a reaction raw material, or an anion component. Specifically, for example, pentane, hexane, Aliphatic hydrocarbon solvents such as octane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, halogen solvents such as dichloromethane, dichloroethane and chloroform, alcohol solvents such as methanol, ethanol, propanol and butanol Ether solvents such as dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran (THF), dioxane, etc., ketone solvents such as dimethyl ketone (acetone), ethyl methyl ketone, diethyl ketone, etc., such as dimethylformamide DMF), amide solvents such as dimethylacetamide (DMAc), such as dimethyl sulfoxide sulfoxide solvents such (DMSO). These organic solvents may be used alone or in combination of two or more, and the amount of the organic solvent to be used is not particularly limited. For example, 1 mL is usually used per 1 mmol of the compound represented by the general formula [9]. ~ 100mL, preferably 2mL ~ 50mL.

  The reaction temperature in the third step may be set to a temperature at which the compound represented by the general formula [9] reacts with the anion component, but the compound represented by the general formula [9] and the anion component Is preferably set at a temperature at which the compound represented by the general formula [1] can be synthesized with good yield. Specifically, for example, it is usually −20 ° C. to 120 ° C., preferably 0 ° C. to 100 ° C.

  Although the reaction time in the third step may vary depending on the amount of the anion component used for the compound represented by the general formula [9], the type and amount of the organic solvent, the reaction temperature, etc. Usually, it is set in the range of 0.1 to 24 hours, preferably 0.2 to 12 hours.

In the third step, the method for isolating and purifying the target compound represented by the general formula [1] from the solution after completion of the reaction may be a general post-treatment and purification operation. Specifically, for example, if the reaction solution after completion of the reaction is concentrated, and the resulting crystals are collected by filtration and then washed with an appropriate organic solvent, it can be purified efficiently. In addition, you may perform the refinement | purification operation by normal column chromatography, not the above refinement | purification operation. As described above, when Z ⁻ in the compound represented by the general formula [1] is any one of a chlorine atom, a bromine atom and an iodine atom, the compound represented by the general formula [9] Since it corresponds to the compound represented by the general formula [1], the third step is unnecessary.

  The compound represented by the general formula [1] of the present invention thus obtained is, for example, a resist material in the manufacturing process of a semiconductor element, a surface protective film or an interlayer insulating film of a semiconductor element, an electron as described above. It is useful as a photobase generator for curing a photocurable resin useful as an insulating material for parts. In particular, the compound of the present invention is used as a conventional photobase generator for curing a photocurable resin such as an epoxy resin that has been pointed out to be insensitive to a photobase generator, that is, as a base supply source for resin curing. It is very useful in that it can.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by these examples.

Synthesis Example 1 Synthesis of 3- (2-bromoacetyl) -2H-1-benzopyran (first step)
To a solution of 10.0 g (53.1 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of 3-acetylcoumarin in 50 mL of dichloromethane, 9.3 g (58.2 mmol) of bromine was added dropwise under ice cooling, and the same temperature. For 1 hour with stirring. After completion of the reaction, crystals produced by the reaction were collected by filtration, and the obtained crystals were dried to give 14.1 g (yield: 99) of pale yellow crystals of 3- (2-bromoacetyl) -2H-1-benzopyran. 4%). The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 4.90 (2H, s, CH ₂ Br), 7.43-7.53 (2H, m, ArH), 7.80 (1H, t, ArH), 8.00 (1H, d, ArH), 8.84 (1H, s, ArH)

Synthesis Example 2 Synthesis of 1- [2- (2-oxo-2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-4-azabicyclo [2.2.2] octane bromide (second Process)
To a solution of 6.0 g (22.5 mmol) of 14.1 g (52.8 mmol) of 3- (2-bromoacetyl) -2H-1-benzopyran obtained in Synthesis Example 1 in 600 mL of acetone, 3.0 g (26.7 mmol) of 1,4-diazabicyclo [2.2.2] octane (DABCO) dissolved in 50 mL of acetone was added dropwise, and the reaction was allowed to stir at room temperature for 2 hours. After completion of the reaction, the crystals produced by the reaction were collected by filtration, and the obtained crystals were dried to give 1- [2- (2-oxo-2H-1-benzopyran-3-yl) -2- 8.50 g (yield: 99.6%) of oxoethyl] -1-azonia-4-azabicyclo [2.2.2] octane bromide was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 3.05-3.13 (6H, m, DABCO), 3.57-3.61 (6H, m, DABCO), 5.00 (2H, s, CH ₂ ), 7.47-7.55 (2H, m, ArH), 7.82 (1H, t, ArH), 8.07 (1H, d, ArH), 8.92 (1H, s) , ArH)

Example 1 1- [2- (2-Oxo-2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-4-azabicyclo [2.2.2] octane of tetraphenylborate Synthesis (third process)
1- [2- (2-Oxo-2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-4-azabicyclo [2.2.2] octane bromide 8 obtained in Synthesis Example 2 6.9 g (20.2 mmol) of sodium tetraphenylborate dissolved in 60 mL of methanol at 40 ° C. in a solution of 7.0 g (18.5 mmol) of .50 g (22.4 mmol) in 600 mL of methanol ) Was added dropwise, and the reaction was allowed to stir at room temperature for 2 hours. After completion of the reaction, the reaction mixture is concentrated, and the resulting crystals are collected by filtration. The obtained crystals are dried to give 1- [2- (2-oxo of the yellow crystals represented by the formula [4]. -2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-4-azabicyclo [2.2.2] octane tetraphenylborate (9.49 g, yield: 82.7%). Obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 3.09-3.13 (6H, m, DABCO), 3.57-3.60 (6H, m, DABCO), 5.00 (2H, _{s, CH 2), 6.79 (} 4H, t, BPh 4), 6.92 (8H, t, BPh 4), 7.16-7.20 (8H, m, BPh 4), 7.47- 7.56 (2H, m, ArH), 7.82 (1H, dt, ArH), 8.06 (1H, dd, ArH), 8.92 (1H, s, ArH)

Synthesis Example 3 Synthesis of 3-hydroxy-1- [2- (2-oxo-2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-bicyclo [2.2.2] octane bromide ( Second step)
To a solution of 6.0 g (22.5 mmol) of 14.1 g (52.8 mmol) of 3- (2-bromoacetyl) -2H-1-benzopyran obtained in Synthesis Example 1 in 600 mL of acetone, 3.42 g (26.9 mmol) of 3-quinuclidinol dissolved in 300 mL of acetone was added dropwise, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, the crystals produced by the reaction were collected by filtration, and the obtained crystals were dried to give 3-hydroxy-1- [2- (2-oxo-2H-1-benzopyran-3-yl] as white crystals. ) -2-Oxoethyl] -1-azonia-bicyclo [2.2.2] octane bromide (8.02 g, yield: 90.2%) was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 1.75-2.24 (5H, m, quinuclidine), 3.44-3.78 (5H, m, quinuclidine), 3.87-3. 92 (1H, m, quinuclidine) , 4.12-4.14 (1H, m, quinuclidine), 4.98 (2H, s, CH 2), 5.61 (1H, s, OH), 7.47 -7.56 (2H, m, ArH), 7.84 (1H, t, ArH), 8.07 (1H, d, ArH), 8.92 (1H, s, ArH)

Example 2 3-Hydroxy-1- [2- (2-oxo-2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-bicyclo [2.2.2] octane tetraphenylboric acid Salt synthesis (third step)
3-Hydroxy-1- [2- (2-oxo-2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-bicyclo [2.2.2] octane obtained in Synthesis Example 3 In a solution of 7.0 g (17.8 mmol) of 8.02 g (20.3 mmol) of bromide in 600 mL of methanol, 6.7 g (19 of sodium tetraphenylborate) dissolved in 60 mL of methanol at 40 ° C. .6 mmol) was added dropwise and the reaction was allowed to stir at room temperature for 2 hours. After completion of the reaction, the reaction solution is concentrated, and the resulting crystals are collected by filtration. The obtained crystals are dried to give yellow crystals of 3-hydroxy-1- [2-] represented by the formula [5]. 7.5 g of (2-oxo-2H-1-benzopyran-3-yl) -2-oxoethyl] -1-azonia-bicyclo [2.2.2] octane tetraphenylborate (yield: 66.3% ) The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 1.75-2.25 (5H, m, quinuclidine), 3.42-3.78 (5H, m, quinuclidine), 3.86-3. 92 (1H, m, quinuclidine) , 4.10-4.17 (1H, m, quinuclidine), 4.96 (2H, s, CH 2), 5.61 (1H, d, OH), 6.79 (4H, t, BPh ₄ ), 6.92 (8H, t, BPh ₄ ), 7.16-7.20 (8H, m, BPh ₄ ), 7.46-7.55 (2H, m, ArH ), 7.83 (1H, dt, ArH), 8.06 (1H, dd, ArH), 8.91 (1H, s, ArH)

Synthesis Example 4 Synthesis of 1-acenaphthen-5-yl-2-bromo-ethanone (first step)
To a solution of 1-4.0 g (71.3 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of 5-acetyl-1,2-dihydroacenaphthene dissolved in 300 mL of ethyl acetate, 12.0 g (75. 1 mmol) was added dropwise, and the reaction was allowed to stir at the same temperature for 1 hour. After completion of the reaction, the reaction solution is extracted by adding 200 mL of water, and the organic layer after extraction is washed with water, and the resulting organic layer is dried to dry the crystals, thereby producing 1-acenaphthene of yellow crystals. 19.6 g (yield: 99.9%) of -5-yl-2-bromo-ethanone was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 3.36 (4H, s, CH ₂ ), 4.96 (2H, s, CH ₂ Br), 7.41 (2H, dd, ArH), 7.62 (1H, dd, ArH), 8.29 (1H, d, ArH), 8.48 (1H, d, ArH)

Synthesis Example 5 Synthesis of 1- (2-acenaphthen-5-yl-2-oxo-ethyl) -3-hydroxy-1-azonia-bicyclo [2.2.2] octane bromide (second step)
A solution of 13.0 g (47.2 mmol) of 1-acenaphthen-5-yl-2-bromo-ethanone 19.6 g (71.2 mmol) obtained in Synthesis Example 4 in 100 mL of acetone was added to acetone. 7.20 g (56.6 mmol) of 3-quinuclidinol dissolved in 800 mL was added dropwise, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, the crystals produced by the reaction are collected by filtration, and the obtained crystals are dried to give 1- (2-acenaphthen-5-yl-2-oxo-ethyl) -3-hydroxy-1 as yellow crystals. 15.7 g (yield: 82.6%) of -azonia-bicyclo [2.2.2] octane bromide was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 1.80-2.23 (5H, m, quinuclidine), 3.40 (4H, s, CH ₂ ), 3.52-3.82 (5H , m, quinuclidine), 3.95-4.00 ( 1H, m, quinuclidine), 4.15-4.22 (1H, m, quinuclidine), 5.22 (2H, s, CH 2), 5. 64 (1H, d, OH), 7.49-7.51 (2H, dd, ArH), 7.69 (1H, dd, ArH), 8.27 (1H, d, ArH), 8.55 ( 1H, d, ArH)

Example 3 Synthesis of 1- (2-acenaphthen-5-yl-2-oxo-ethyl) -3-hydroxy-1-azonia-bicyclo [2.2.2] octane tetraphenylborate (third step)
15.7 g (39.0 mmol) of 1- (2-acenaphthen-5-yl-2-oxo-ethyl) -3-hydroxy-1-azonia-bicyclo [2.2.2] octane bromide obtained in Synthesis Example 5 Of sodium tetraphenylborate dissolved in 50 mL of methanol at 40 ° C. was added dropwise to a solution of 7.0 g (17.4 mmol) of For 2 hours with stirring. After completion of the reaction, the crystals produced in the reaction are collected by filtration, and the obtained crystals are dried to give 1- (2-acenaphthen-5-yl-2-oxo- represented by the formula [6] as yellow crystals. Ethyl) -3-hydroxy-1-azonia-bicyclo [2.2.2] octane tetraphenylborate 9.24 g (yield: 82.8%) was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO) δ (ppm): 1.81-2.24 (5H, m, quinuclidine), 3.41 (4H, s, CH ₂ ), 3.51-3.81 (5H , m, quinuclidine), 3.92-3.98 ( 1H, m, quinuclidine), 4.12-4.20 (1H, m, quinuclidine), 5.16 (2H, s, CH 2), 5. _{65 (1H, br, OH)} , 6.79 (4H, t, BPh 4), 6.92 (8H, t, BPh 4), 7.17-7.20 (8H, m, BPh 4), 7 .48 (1H, dd, ArH), 7.68 (1H, dd, ArH), 8.24 (1H, d, ArH), 8.56 (1H, d, ArH)

Example 4 Measurement Test of UV-Vis Absorption Spectrum Acetonitrile solutions (about 5 × 10 ⁻⁵ mol / L) of the compounds obtained in Examples 1 to 3 were respectively prepared, and quartz cell TOS-UV-10 (1 cm × 1) was prepared. After injection into 1 cm × 4 cm (manufactured by Toshin Riko Co., Ltd.), an ultraviolet-visible absorption spectrum was measured using a spectrophotometer UV-2550 (manufactured by Shimadzu Corporation). Table 1 shows the molar extinction coefficient (ε) at 365 nm (i-line) for each compound.

Example 5 Test for measuring reactivity to light (active energy ray) 100 mg of the compound obtained in each of Examples 1 to 3 was put in a quartz test tube and dissolved in 1 mL of acetonitrile. Next, this solution was irradiated with light (active energy rays) for 10 minutes with a high-pressure mercury lamp (Handicure 100 W; manufactured by Sen Special Light Source). The pH of the solution before and after irradiation with light (active energy rays) is measured with a pH meter, and the pH is inclined to be alkaline, that is, whether the base (tertiary amine) is liberated by irradiation with light (active energy rays). I confirmed. The measurement results are shown in Table 2.

Example 6 Curing test with poly (glycidyl methacrylate) N containing 0.2 g of poly (glycidyl methacrylate) and 20% by weight of the compound obtained in Example 1 or 2 with respect to 0.2 g of poly (glycidyl methacrylate) A solution of 1 mL of methylpyrrolidone (NMP) was spin-coated on a silicon wafer and heated at 100 ° C. for 1 minute to produce a coating film having a thickness of about 1.5 μm. For this coating film, two kinds of ultraviolet irradiation light source devices having a specific exposure intensity, that is, a coating film using the compound of Example 1, was subjected to a predetermined time using SP-9 (USHIO INC.). The coating film using the compound of Example 2 was irradiated with ultraviolet rays and irradiated with ultraviolet rays for a predetermined time using SP-9 (made by USHIO INC.) And REX-250 (made by Asahi Spectroscopy). A base was generated from each of the compounds of Examples 1 and 2 and heated at 120 ° C. for 2 hours to cure the coating film. Furthermore, the thickness of the coating film was measured by immersing this coating film in acetone for 30 seconds and developed, and the film thickness of the coating film before and after development was determined as the remaining film ratio. Table 3 shows the exposure intensity of each light source device at a specific wavelength, and FIGS.

  From the results of Examples 4 to 5, it can be seen that the compound of the present invention has a photosensitive region at a wavelength of 200 nm or more and high sensitivity to light (active energy rays) of 300 nm or more. From this, it was found that the compound of the present invention generates a base even when irradiated with light (active energy ray) having a wavelength of 300 nm or more. In addition, as is clear from the results of FIGS. 1 to 3 obtained in Example 6, the compound of the present invention is compared to a photocurable resin such as an epoxy resin that has been pointed out to be insensitive to a photobase generator. Was found to have good curing properties. That is, for example, in the imidazolium salt of Patent Document 3, the remaining film ratio is obtained with a coating film having a film thickness of 1 μm, but in Example 6 of the present application, the remaining film ratio is obtained with a coating film having a film thickness of 1.5 μm. The results show that the remaining film ratio is equivalent to that of the conventional film even if the film is thicker than the conventional film. This suggests that the compound of the present invention can cure the epoxy resin more effectively than the conventional photobase generator. As described above, the compound of the present invention can generate a base having higher catalytic activity than the conventional photobase generator. The compound of the present invention has a specific structure of a photophore and a specific quaternary ammonium salt. It is suggested that this is due to the combination. From these results, it was found that the compound of the present invention is useful as, for example, a photobase generator for curing an epoxy resin.

  Since the compound of the present invention is capable of generating a base having higher catalytic activity than conventional photobase generators, photocuring properties such as epoxy resins that have been pointed out to be particularly insensitive to photobase generators. Also for a resin, it is useful as a photobase generator capable of sufficiently curing the resin, and as a photocurable resin material using the photobase generator.

Claims (12)

General formula [1]

[Wherein Ar represents the general formula [I]

(In the formula, m R ^{3 s} are each independently a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a linear or branched group having 2 to 10 carbon atoms. Or a cyclic alkylcarbonyl group, m represents an integer of 0 to 5), and a coumarinyl group represented by the general formula [II]

(Wherein n R ^{4 s} are each independently a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a linear or branched group having 2 to 10 carbon atoms. Or represents a cyclic alkylcarbonyl group, and n represents an integer of 0 to 7.) represents any group selected from the group consisting of acenaphthenyl groups, and Y ⁺ represents the general formula [III].

(Wherein R ^{5 to} R ⁷ each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms), a general formula [IV]

{In the formula, A represents a nitrogen atom or a methine group (CH group), and R ⁸ represents a hydrogen atom or a hydroxyl group. }, A group represented by the formula [V]

A group represented by the formula: [Vl]

And a group represented by the general formula [VIl]

(Wherein R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms). represents any group, Z ^- represents a halogen anion, a borate anion, N, N-dimethylcarbamate anion, N, N-dimethyldithiocarbamate anion, thiocyanate anion, thiocyanate anion, benzoic acid anion or benzoyl formic acid anion , R ¹ and R ² each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a phenyl group which may have a substituent. ] The compound shown. The compound according to claim 1, wherein Ar in the general formula [1] is a coumarinyl group represented by the general formula [1]. Y ⁺ in the general formula [1] is any group selected from the group consisting of the general formula [III], the general formula [IV], the formula [V], and the group represented by the formula [VI]. The compound of claim 1, wherein The compound according to claim 1, wherein Y ⁺ in the general formula [1] is a group represented by the general formula [IV]. The compound according to claim 1, wherein Z ⁻ in the general formula [1] is a borate anion. The compound according to claim 1, wherein Z ⁻ in the general formula [1] is a tetraphenylborate anion. The compound according to claim 1, wherein R ¹ and R ² in the general formula [1] are both hydrogen atoms. The compound represented by the general formula [1] is represented by the formula [4].

(Wherein Ph represents a phenyl group), a formula [5]

(Wherein Ph represents a phenyl group) or the formula [6]

The compound according to claim 1, wherein Ph represents a phenyl group. The compound represented by the general formula [1] is represented by the formula [4].

(Wherein Ph represents a phenyl group) or the formula [5]

The compound according to claim 1, wherein Ph represents a phenyl group. A photobase generator comprising the compound according to claim 1. The photobase generator according to claim 10, which generates a base upon irradiation with light having a wavelength of 200 nm to 500 nm. A method for generating a base, which comprises irradiating the compound according to claim 1 with light.

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