JP2001240761A - Process for preparing pyrromethene dyestuff - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation process which can produce in high yields a pyrromethene dyestuff comprising an α,α-pyrromethene boron complex that contains a condensed aromatic ring. SOLUTION: There is provided a process for preparing a pyrromethene dyestuff, which comprises heating an α,α-pyrromethene boron complex containing a condensed bicyclo ring, represented by formula (I): wherein R1 is a hydrogen atom, alkyl group, aryl group or heterocyclic group; R2 and R3 are each independently a halogen atom, alkyl group, aryl group or heterocyclic group; the pyrrole rings may have substituting group(s); and the ring X is a condensed bicyclo ring formed by linking, with each other, two β-positioned substituting groups of at least one pyrrole ring to form an α,α-pyrromethene boron complex containing a condensed aromatic ring, represented by formula (II): wherein R1, R2 and R3 each has the same meaning as those in formula (I); the pyrrole rings may have substituting group(s); and the ring Y is a condensed aromatic ring formed at the two β-positions of at least one pyrrole ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a pyrromethene dye comprising a fused aromatic ring-containing α, α-pyrromethene boron complex, for example, a sensitizing dye for visible light and a dye for laser in a photosensitive material; And pyromethene dyes useful as fluorescent coloring dyes for electroluminescence, polymer colorants, and the like.

[0002]

2. Description of the Related Art A methine group has been conventionally used as a sensitizing dye for visible light and a dye for laser in a photosensitive material, and a fluorescent coloring dye for electroluminescence.
A pyrromethene dye in which α, α-pyrromethene in which two pyrrole rings are bonded at the α-position is known as a boron complex, and further a condensed aromatic ring in which two condensed aromatic rings are formed at two β-positions of the pyrrole ring Aromatic ring-containing α, α-pyrromethene boron complexes are also known as pyromethene dyes expected to improve sensitivity and the like.

However, the fused aromatic ring-containing α,
The method for producing the α-pyrromethene boron complex is not known in detail. .1, No.
5,389 (1990) and the like, a method of forming a boron complex by pyrromethene conversion was attempted, but the reactivity of the pyrromethene formation was extremely low and production was difficult.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and accordingly, the present invention provides a pyrromethene dye comprising a condensed aromatic ring-containing α, α-pyrromethene boron complex. It is an object of the present invention to provide a production method capable of producing a high yield.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by passing through a fused bicyclo ring-containing α, α-pyrromethene boron complex. That is, the present invention provides a compound represented by the following general formula (II) by heating a condensed bicyclo ring-containing α, α-pyrromethene boron complex represented by the following general formula (I). And a method for producing a pyrromethene-based dye to be a condensed aromatic ring-containing α, α-pyrromethene boron complex.

[0006]

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[In the formula (I), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a group which may have a substituent. A good heterocyclic group, wherein R ² and R ³ are each independently a halogen atom,
An alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; and a pyrrole ring has a substituent. Alternatively, ring X is a fused bicyclo ring formed by linking two β-substituents of at least one pyrrole ring to each other. ]

[0008]

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[In the formula (II), R ¹ , R ² and R ³ represent the formula (I)
And the pyrrole ring may have a substituent, and the ring Y is a condensed aromatic ring formed at two β-positions of at least one pyrrole ring. ]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing a pyrromethene dye of the present invention comprises heating a condensed bicyclo ring-containing α, α-pyrromethene boron complex into a condensed aromatic ring-containing α, α-pyrromethene boron complex. And its fused bicyclo ring-containing α, α
-The pyromethene boron complex is represented by the above general formula (I).

In the formula (I), when R ¹ , R ² and R ³ are an alkyl group, the number of carbon atoms is usually 1 to 15, preferably 1 to 10. The aryl group is, for example, phenyl. Group, naphthyl group, anthryl group and the like,
Examples of the heterocyclic group include a furyl group, a pyrrolyl group, and a pyridyl group. Examples of the halogen atom for R ² and R ³ include fluorine, chlorine, bromine, and iodine.
Among them, in the present invention, R ¹ is preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R ² and R ³ are each preferably a halogen atom, particularly a fluorine atom.

The substituents for the alkyl group, aryl group, heterocyclic group and pyrrole ring in R ¹ , R ² and R ³ include, for example, an alkyl group, an alkoxy group, an acyl group, Examples include an acyloxy group, an aryl group, an arylalkyl group, an alkylthio group, a hydroxyl group, and a halogen atom. Among them, in the present invention, an alkyl group having 1 to 5 carbon atoms or a phenyl group is preferable.

As the fused bicyclo ring of the ring X formed at the two β-positions of the pyrrole ring, the two fused carbon atoms forming the fused bicyclo ring at the two β-position carbon atoms constituting the pyrrole ring may be used. The bridgehead carbon atoms are bonded, one of the three bridges shares the two carbon atoms that make up the pyrrole ring, and the other two bridges are, for example, ethylene, vinylene, 1,2-phenylene, , 3-naphthylene group, 1,8-naphthylene group and the like, and these condensed bicyclo rings further include an alkoxy group, an acyl group, an acyloxy group, a phenylthio group, a hydroxyl group, and a halogen. It may have a substituent such as an atom.

In the present invention, as these fused bicyclo rings, specifically, for example, bicyclo [2.2.
2] octane, bicyclo [2.2.2] octene wherein the other two divalent groups are an ethylene group and a vinylene group, and other two divalent groups are an ethylene group and a 1,2-phenylene group 1,4-o-benzeno-cyclohexane, 2,3 in which both of the other two divalent groups are 1,2-phenylene groups
-Benzo-1,4-o-benzeno-cyclohexane, 1,4-β, β-naphtheno-cyclohexane in which the other two divalent groups are an ethylene group and a 2,3-naphthylene group, and the other two divalent groups 2,3-naphth-1,4-β, β-naphtheno-cyclohexane in which all groups are 2,3-naphthylene groups, and 1 in which the other two divalent groups are an ethylene group and a 1,8-naphthylene group , 4-α, α-naphtheno-cyclohexane, and 2,3-α, α-naphth-1,4-α, α-naphtheno-cyclo, each of which has two other divalent groups as 1,8-naphthylene groups Heptane and the like. In the present invention, bicyclo [2.2.2] octene, 1,4
-O-benzeno-cyclohexane, 1,4-α, α-naphtheno-cyclohexane and the like are preferable, and bicyclo [2.
2.2] octene is particularly preferred.

The fused bicyclo ring-containing α, α-pyrromethene boron complex is described, for example, in S. Ito, T. Murashima, N. Ono, J. Ch.
em.Soc., Perkin Trans.1, 3161 (1997), etc., bicyclopyrrole synthesized by the method described, for example,
U.S. Pat. No. 4,774,339 and JHBoger
et al, Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990).

Specifically, for example, an α, α-pyrromethene boron complex in which a bicyclo [2.2.2] octene ring is formed at two β-positions of a pyrrole ring will be described. As shown in (2), α-methylpyrrole having a bicyclo [2.2.2] octene ring formed at two β-positions of a pyrrole ring is added to an acid such as acetyl chloride in a solvent such as methylene chloride. By reacting chloride, bicyclo [2.2.
2] Synthesis of α, α-pyrromethene hydrochloride having an octene ring formed thereon, and then combining the α, α-pyrromethene hydrochloride with a borate such as trifluoroboron diethyl ether complex in a solvent such as toluene in triethylamine Or a method of synthesizing a boron complex by reacting in the presence of a catalyst such as, or as shown in the following formulas (1 ′) to (2 ′),
Α-methylpyrrole having a bicyclo [2.2.2] octene ring formed at the β-position and acetylaniline or the like are subjected to a Vilsmeier reaction in the presence of a catalyst such as phosphonyl chloride to give α-methyl-α-acetyl. Synthesize pyrrole,
α-methyl-β-ethyl-β-methylpyrrole is subjected to a condensation reaction in an aqueous hydrochloric acid solution to thereby form α, in which a bicyclo [2.2.2] octene ring is formed on one pyrrole ring.
α-pyrromethene hydrochloride is synthesized and then its α, α-
It is produced by a method of reacting pyromethene hydrochloride with a borate such as trifluoroboron diethyl ether complex in a solvent such as toluene in the presence of a catalyst such as triethylamine to synthesize a boron complex.

Thereafter, as shown in the following formula (3), the obtained α, α-pyrromethene boron complex in which a condensed bicyclo ring is formed at two β-positions of two pyrrole rings,
Alternatively, as shown in the following equation (3 ′),
An α, α-pyrromethene boron complex in which a condensed bicyclo ring is formed at two β-positions of one pyrrole ring is usually used in an amount of 50 to 40.
By performing a heat treatment at a temperature of 0 ° C., preferably 100 to 300 ° C., and if necessary under reduced pressure, usually for a period of 0.1 to 100 hours, preferably 0.5 to 50 hours, a condensed aromatic ring is obtained. To produce a contained α, α-pyrromethene boron complex.

[0018]

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[0019]

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In the method for producing a pyrromethene dye of the present invention, preferred specific examples include the following formulas.

[0021]

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The pyrromethene dye produced by the production method of the present invention can be obtained by coating a photosensitive composition such as an ethylenically unsaturated compound, a photopolymerization initiator, Used as a sensitizing dye contained in a photosensitive material in which a layer of a photopolymerizable composition comprising a molecular binder and the like is formed, and the composition layer is exposed to a light source. The resist image is formed by exposure and development.

The ethylenically unsaturated compound used in the photopolymerizable composition is preferably a compound having two or more double bonds in the molecule, and the double bond is preferably (meth) acryloyloxy. Acrylate compounds derived from groups are preferred. As those acrylate compounds, typically, ester (meth) acrylates of (meth) acrylic acid and polyhydroxy compound, (meth) acrylate
Epoxy (meth) acrylates of acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound, urethane (meth) acrylates of hydroxy (meth) acrylate compound and polyisocyanate compound, and containing (meth) acryloyloxy group Phosphates and the like. Here, “(meth) acryl” means acryl and methacryl.

As the photopolymerization initiator, typically,
Examples include titanocene compounds, halogenated hydrocarbon derivatives, hexaarylbiimidazole compounds, organic boron complexes, carbonyl compounds, and organic peroxides.

As the polymer binder, typically,
Examples thereof include alkali-soluble resins such as a carboxyl group-containing vinyl resin and a phenolic hydroxyl group-containing resin.

The formation of the above-mentioned composition layer on the support is carried out by
Usually, the composition is applied by applying the composition on a support surface as a coating solution in which the composition is dissolved or dispersed in an appropriate solvent, followed by heating and drying.

In this case, as the α, α-pyrromethene dye used in the composition, the above condensed aromatic ring-containing α, α-pyrromethene boron complex produced by the method of the present invention may be used. The group-containing α, α-pyrromethene boron complex generally has poor solubility in a coating solvent at the time of coating on the support surface, has poor dispersion in the composition, and is expected to exhibit sensitization sensitivity. Since the α, α-pyrromethene dye used in the composition, the condensed bicyclo ring-containing α, α-pyrromethene boron complex having excellent solubility in a coating solvent is used as the α, α-pyrromethene dye used in the composition. The condensed bicyclo ring-containing α, α-pyrromethene boron complex may be converted to a condensed aromatic ring-containing α, α-pyrromethene boron complex by heating at the time of drying after being applied to the coating. invention Is included as an embodiment of the manufacturing method of the present invention.

[0028]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

Example 1 In a reaction vessel, bicyclo [2.
2.2] 0.398 g of α-methylpyrrole having an octene ring was added, 0.40 ml of acetyl chloride dissolved in 50 ml of methylene chloride was added, and the mixture was heated for 3 hours while refluxing with a reflux condenser attached. After the reaction, the reaction solution is allowed to cool to room temperature, and the reaction solution is diluted with hexane 5
Then, the mixture was poured overnight, stirred overnight to precipitate crystals, and filtered to obtain bicyclo [2.2.
2] 0.398 g of α, α-pyrromethene hydrochloride as an orange crystal having an octene ring was synthesized. At this time, the yield was 80%.

Subsequently, 0.522 g of the obtained condensed bicyclo ring-containing α, α-pyrromethene hydrochloride was placed in a reaction vessel, dissolved in 200 ml of toluene, 1.31 ml of triethylamine was added, and the mixture was stirred at room temperature for 15 minutes. Then, 1.74 ml of trifluoroboron diethyl ether complex was added, and the mixture was stirred and reacted at 80 ° C. for 15 minutes. Then, the mixture was allowed to cool to room temperature, washed with water and saturated saline, dried over sodium sulfate, and concentrated. Then, the residue was purified by silica gel chromatography to obtain an α, α-crystal of an orange crystal having a bicyclo [2.2.2] octene ring formed on two pyrrole rings.
0.391 g of α-pyrromethene boron complex was obtained. At this time, the yield was 73%.

Subsequently, 0.117 g of the obtained condensed bicyclo ring-containing α, α-pyrromethene boron complex was placed in a reaction vessel.
And heated at 220 to 230 ° C. for 3 hours under vacuum conditions to obtain 0.100 g of an α, α-pyrromethene boron complex having a benzene ring formed on two pyrrole rings.
At this time, the yield was 100%.

Application Example 1 An aluminum plate (0.24 mm thick) subjected to graining treatment and anodizing treatment was used as a support, and trimethylolpropane triethylate as an ethylenically unsaturated compound was applied to the surface of the aluminum plate support. 100 parts by weight of acrylate,
1 part by weight of the condensed benzene ring-containing α, α-pyrromethene boron complex obtained in Example 1 as a sensitizing dye, and dicyclopentadienyltitanium bis [2,6-
Difluoro-3- (1-pyrrolyl) phenyl] 10 parts by weight, and a methyl methacrylate / methacrylic acid copolymer (molar ratio 85/15, weight average molecular weight 4) as a polymer binder
5,000) 100 parts by weight, and p-
10 parts by weight of ethyl dimethylaminobenzoate and 1600 parts by weight of methyl ethyl ketone and 1600 parts by weight of N-methylpyrrolidone were stirred at room temperature for 10 minutes to prepare a coating solution, which was applied using a wire bar. After drying for 2 minutes, a photopolymerizable composition layer having a thickness of 2 μm was formed, and an aqueous solution of polyvinyl alcohol was further applied thereon.
By drying at 0 ° C. for 2 minutes to form a protective layer having a thickness of 3 μm, a photopolymerizable lithographic printing plate as a photosensitive material was produced.

Using a spectral sensitivity measuring device (manufactured by Narumi), the obtained photopolymerizable lithographic printing plate was subjected to spectroscopy using a xenon lamp (“US-501C” manufactured by Ushio Inc.) as a light source, and the horizontal axis of the spectrum was used for the light. Exposure is performed by irradiating for 10 seconds with the exposure wavelength set linearly in the direction and the exposure intensity logarithmically changed in the vertical direction, and then 1% by weight of sodium silicate containing 1% by weight of butyl cellosolve. 3 at 25 ° C in aqueous solution
A resist image corresponding to the sensitivity at each exposure wavelength was obtained as a spectral sensitivity curve by immersion for 0 second and developed, and the minimum exposure required for image formation at a wavelength of 532 nm in the spectral sensitivity curve was determined to be 1.5 mJ. / Cm ² .

[0034]

According to the present invention, the fused aromatic ring-containing α,
It is possible to provide a production method capable of producing a pyrromethene dye comprising an α-pyrromethene boron complex in a high yield.

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Claims (4)

[Claims] 1. A fused aromatic bicyclic ring-containing α, α-pyrromethene boron complex represented by the following general formula (I) is heated to obtain a fused aromatic ring-containing α represented by the following general formula (II): And a .alpha.-pyrromethene boron complex. Embedded image [In the formula (I), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic ring which may have a substituent. A group represented by R
² and R ³ are each independently a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent Wherein the pyrrole ring may have a substituent, and ring X is a condensed bicyclo ring formed by linking two β-substituents of at least one pyrrole ring to each other. [Chemical formula 2] [In the formula (II), R ¹ , R ² and R ³ are the same as those in the formula (I), the pyrrole ring may have a substituent, and the ring Y is at least two of the pyrrole rings. Is a fused aromatic ring formed at the β-position. ] 2. A ring X is formed on two pyrrole rings in the general formula (I), and a ring X in the general formula (II)
The method for producing a pyrromethene dye according to claim 1, wherein a ring Y is formed in one pyrrole ring. 3. The ring according to claim 1, wherein the ring X in the general formula (I) has a bicyclo [2.2.2] octene structure, and the ring Y in the general formula (II) is a benzene ring. A method for producing a pyrromethene dye. 4. The method for producing a pyrromethene dye according to claim 1, wherein the heating temperature is 100 to 300 ° C.