JPH07267942A - Bis(3-(4-substituted coumaryl))ketone compound and photosensitizer - Google Patents

Abstract

PURPOSE:To provide a new bis[3-(4-substituted coumaryl)]ketone compound having high sensitivity to visible light and excellent storage stability and solubility in resin and useful as a photosensitizer for information recording field, etc. CONSTITUTION:This ketone compound is expressed by formula I [R1 and R2 each is H, an (alkoxy)alkyl, an alkenyl, a hydroxyalkyl, an aralkyl, etc.; R3 is H, an (alkoxy)alkyl, a hydroxyalkyl, a halogenoalkyl, OH, sulfonic acid group, a halogen, etc.; R4 is a (cyclo)alkoxy, OH, an aryloxy, an alkenyloxy, etc.], e.g. bis[3-(4-ethoxycarbonyl-7-diethylaminocoumaryl) ]ketone. The compound of formula I can be produced by reacting a compound of formula II with ethyl acetonedicarboxylate, cyanating the resultant compound of formula III to obtain a compound of formula IV, carboxylating the cyano group of the compound and reacting the product with alcohols, amino compounds, alkyl halides, various tosylates, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound, a bis [3- (4-substituted coumaryl)] ketone compound and a photosensitizer for use in a photocurable resin.

[0002]

2. Description of the Related Art In recent years,
In the field of information recording using photopolymerization reaction, a method of directly outputting a document directly electronically edited by a computer and recording it directly using a laser is examined instead of the conventional recording method using ultraviolet rays using a film document or the like. There is.
However, most of the commonly used high-power and stable laser light sources at present have an output wavelength in the visible region, such as an argon laser, and are not used in the conventionally used UV photosensitizers. , It could not be used because of its low sensitivity in the visible range. Further, although the sensitivity in the visible region can be improved by adding a pyrylium salt or a thiopyrylium salt, the storage stability of the photosensitive layer is low and it is difficult to use.

Conventionally, bis [3- (4-substituted coumaryl)]
When the 4-position is unsubstituted, the ketone derivative has a maximum wavelength near 450 nm, but generally used laser light source wavelengths are often longer than that.
For that reason, there are many cases where sufficient sensitivity cannot be obtained as a photosensitizer.

For example, bis [3- (7-diethylaminocoumaryl)] ketone has a maximum absorption wavelength of around 450 nm, so that it is more than 3 nm from 488 nm of an argon laser.
It has a short wavelength of 0 to 40 nm, leaving room for improvement in sensitivity. Further, within a certain range, a positive correlation is established between the rate of introduction of the photosensitizer into the resin and the sensitivity. Therefore, within that range, it is preferable that the photosensitizer is stably dissolved in the resin as much as possible. desirable. However, even in this case, since the above compound has poor solubility, the introduction rate of the photosensitizer into the resin is insufficient, and the target sensitivity is not obtained at present. Further, if the 4-position is cyanated, it is possible to shift the maximum absorption wavelength of the compound to a longer wavelength side (hereinafter, simply referred to as longer wavelength), but the solubility in the resin and the storage stability are impaired. There were many cases.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention found a compound represented by the general formula (1) and completed the present invention. That is,
The present invention is represented by the general formula (1)

[0006]

[Chemical 3]

[Wherein R ₁ and R ₂ are the same or independently of each other and represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which are bonded to each other. Or may be bonded to a benzene nucleus substituted with an amino group in the skeleton to form a ring, and R ₃ is a hydrogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, Represents an alkoxy group, an alkoxyalkoxy group, a sulfonic acid group, a halogen atom, R ₄ represents an alkoxy group, a cycloalkoxy group, a hydroxyl group, an aryloxy group, an alkenyloxy group,
An aralkyloxy group, an alkoxycarbonylalkoxy group, an alkylcarbonylalkoxy group, or the following substituent (Formula 4) is shown.

[0008]

[Chemical 4]

(Wherein R _{5 to} R ₈ represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, and a cycloalkyl group, and n and m are integers of 1 to 5, respectively. The present invention provides a bis [3- (4-substituted coumaryl)] ketone compound represented by the formula) and a photosensitizer.

The compound of the present invention is a novel bis (3-coumaryl) ketone compound useful as a photosensitizer.
That is, by introducing a substituted carbonyl group into the 4-position of the bis (3-coumaryl) ketone skeleton, the wavelength of the maximum absorption wavelength and the high solubility in the resin were realized at the same time. For example, a photopolymerizable or photocrosslinkable compound having at least one ethylenic unsaturated bond in the molecule, and a compound extremely useful as a photoincrease applicable to photocuring using a photopolymerization initiator.

Further, the sensitivity of conventional photosensitizers fluctuates largely depending on the coating method, but the photosensitizer of the present invention shows stable sensitivity in any of the methods, and the demand of the market is high. It is a very satisfying one. Hereinafter, the present invention will be described in detail. The compound of the present invention has the general formula (1)

[0012]

[Chemical 5]

As is clear from the structural formula represented by
A bis (3-coumaryl) ketone compound having a substituted carbonyl group at the position. In the general formula (1), R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group,
It represents an aralkyl group, an aryl group, or an alkoxycarbonylalkyl group, which may be the same or different.

Specifically, a hydrogen atom; methyl, ethyl,
n-propyl, iso-propyl, n-butyl, iso
-Butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl and other alkyl groups; methoxymethyl,
Methoxyethyl, ethoxymethyl, ethoxyethyl, γ
-Alkoxyalkyl groups such as ethoxypropyl group; alkenyl groups such as allyl, 2-butenyl and 2-pentenyl groups; hydroxyalkyl such as hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and 2-hydroxybutyl groups. Groups; aralkyl groups such as benzyl and phenethyl groups; phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, 2,
An aryl group such as 4-dimethylphenyl group; an alkoxycarbonylalkyl group such as methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl group and the like. Further, R ₁ and R ₂ may be bonded to each other or to a benzene nucleus substituted by an amino group in the skeleton to form the following ring.

[0015]

[Chemical 6]

[In these rings, R ₂ and R ₃ have the same meanings as described above. Further, in the general formula (1), R ₃ represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, a sulfonic acid group or a halogen atom, Specifically, a hydrogen atom; an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, and n-butyl group; an alkoxyalkyl group such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl group; hydroxymethyl, Hydroxyalkyl groups such as hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl groups; halogenoalkyl groups such as chloromethyl and trifluoromethyl groups; hydroxyl groups; methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-
An alkoxy group such as butoxy, sec-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy; an alkoxyalkoxy group such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, n-propoxyethoxy; a sulfonic acid group; Fluorine, chlorine,
Examples thereof include halogen atoms such as bromine. Similarly, in the general formula (1), R ₄ is an alkoxy group, a cycloalkoxy group, a hydroxyl group, an aryloxy group, an alkenyloxy group, an aralkyloxy group, an alkoxycarbonylalkoxy group, an alkylcarbonylalkoxy group, or the following substituent 7).

[0017]

[Chemical 7]

(Here, R _{5 to} R ₈ and n and m have the same meanings as described above.)

Examples of R ₄ are methoxy, ethoxy,
n-propoxy, iso-propoxy, n-butoxy,
iso-butoxy, sec-butoxy, t-butoxy,
Alkoxy group such as n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy group; cycloalkoxy group such as cyclopentyloxy, cyclohexyloxy group; hydroxyl group; phenoxy, p-methylphenoxy, m-methylphenoxy , O-methylphenoxy, 2,4-dimethylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-phenylphenoxy and other aryloxy groups; propenoxy, 2-butenoxy and other alkenyloxy groups Groups; aralkyloxy groups such as benzyloxy, methylbenzyloxy and phenethyloxy groups; alkoxy groups such as methoxycarbonylmethoxy, ethoxycarbonylmethoxy, n-propoxycarbonylmethoxy and iso-propoxycarbonylmethoxy groups Boniruarukokishi group; methylcarbonyl methoxy, ethylcarbonyl alkylcarbonyl alkoxycarbonyl groups such as a methoxy group; hydroxymethyl butoxy, hydroxyethoxy, 2-hydroxypropoxy,
Hydroxyalkoxy group such as 3-hydroxypropoxy group; alkoxyalkoxy group such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, γ-ethoxypropoxy group; hydroxyethoxy, hydroxyethoxyethoxy hydroxypropoxypropoxy, hydroxyethoxyethoxyethoxy group, etc. Polyether group; amino group; methylamino, ethylamino,
Monoalkylamino groups such as n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-octylamino groups; dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, Dialkylamino groups such as dioctylamino groups; mono (hydroxyalkyl) amino groups such as hydroxyethylamino, 2-hydroxypropylamino, 3-hydroxypropylamino groups; di (hydroxyethyl) amino, di (2-hydroxypropyl)
Di (hydroxyalkyl) amino groups such as amino and di (3-hydroxypropyl) amino groups; mono (hydroxyalkoxyalkyl) amino groups such as hydroxyethoxyethylamino, hydroxypropoxyethylamino, hydroxypropoxypropylamino groups; di (hydroxy Di (hydroxyalkoxy) amino groups such as ethoxyethyl) amino, di (hydroxypropoxyethyl) amino, di (hydroxypropoxypropyl) amino groups; methoxymethylamino, methoxyethylamino, ethoxymethylamino, ethoxyethylamino, propoxyethyl Mono (alkoxyalkyl) amino groups such as amino groups; di (methoxymethyl) amino, di (methoxyethyl) amino, di (ethoxymethyl) amino, di (ethoxyethyl) amino, (Propoxyethyl) amino group, di (alkoxyalkyl) amino group; cyclopentylamino, cycloalkylamino group such as cyclohexylamino group. Compound of the present invention (photosensitizer)
Can be produced, for example, by the reaction route shown below.

[0020]

[Chemical 8]

The 4-substituted aminosalicylaldehyde (2) and ethyl acetone dicarboxylate, which are the starting materials, are
Methanol, ethanol, N, N-dimethylformamide (hereinafter abbreviated as DMF), dimethyl sulfoxide,
1,3-Dimethyl-2-imidazolidinone (hereinafter DMI
(Abbreviated as)) and a 1: 1 mixture in a polar solvent, a catalytic amount of about 1/10 of a weak base is added. As the weak base, amines such as piperidine, pyrrolidine, pyridine and aniline are preferable. The mixture is reacted at 0 to 80 ° C for 1 to 12 hours to obtain compound (3).

Cyanation was carried out by subjecting the resulting compound (3) to "D
With reference to the method for cyanating a coumarin compound described in “yes and Pigments, Vol. 1, pages 3 to 15 (1980)”, the cyano compound (4) is obtained by reacting with NaCN in DMF and then oxidizing with bromine.

The novel compound (1) is obtained from the cyano compound (4) by heating to 70 to 100 ° C. with 50 to 98% by weight of sulfuric acid to hydrolyze the cyano group to obtain a carboxylic acid (5). Later, with alcohols, aminos, alkyl halides, various tosylates, or phenols, a chlorinating agent is used to first convert the acid chloride into an acid chloride and then react, or in the presence of an acid catalyst, a dehydrating agent, or no catalyst. However, concentrated sulfuric acid is added dropwise to a mixture of alcohols or the like containing approximately equimolar water with the cyano compound (4), and
The compound (1) can be directly obtained by heating to 100 ° C.

[0024]

The present invention will be described in more detail with reference to the following examples. Parts in the examples are parts by weight and% is% by weight.

Example 1 57 parts of 4-diethylaminosalicylaldehyde and 25 parts of ethyl acetonedicarboxylate were added with 2 parts of piperidine, and the mixture was reacted in an ethanol solvent at 80 ° C. for 4 hours and cooled to obtain crystals. After filtration, washing with ethanol, and drying, bis [3- (7-diethylaminocoumaryl)]
55 parts of ketone was obtained. 40 parts of this compound to D of 200 parts
After suspending in MF, 57 parts of 30% NaCN aqueous solution was added dropwise thereto at room temperature, and the reaction was continued for 1 hour as it was.
1 part was added dropwise at 0 to 10 ° C., stirred for 2 hours, filtered, washed well with water, and dried to obtain 42 parts of bis [3- (4-cyano-7-diethylaminocoumaryl)] ketone. Further, 9 parts of the above cyano compound was reacted with 21.6 parts of 98% sulfuric acid in 100 parts of ethanol at 80 ° C. for 3 hours, and after standing to cool to 300
It was neutralized by discharging into some water. The precipitated crystals were filtered, washed well with water, and dried to obtain 9 parts of bis [3- (4-ethoxycarbonyl-7-diethylaminocoumaryl)] ketone. The electron beam spectrum and elemental analysis results of this compound are as follows. Electronic spectrum; absorption maximum [λmax] 495 nm
(In acetone) Elemental analysis value C H N calculated value (%) 65.55 6.00 4.63 Measured value (%) 65.51 6.10 4.59 Also, 5 parts of the above ketocoumarin compound and polyvinylpyrrolidone were used as binders. As a polymer, 100 parts of pentaerythritol triacrylate 100 parts, polymerization initiator 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 4 parts, methylcellosolve 10
A photosensitive solution was prepared by using 00 parts and was applied onto a laminated copper plate using a spinner. Next, when the photosensitive layer was irradiated with light using an argon laser, it was confirmed that the resin was rapidly cured. Similar results were obtained with the xenon lamp irradiation.

Example 2 54 parts of 4-diethylaminosalicylaldehyde and 25 parts of ethyl acetonedicarboxylate were added with 2 parts of piperidine, and the mixture was reacted in DMF solvent at 70 ° C. for 6 hours, and after cooling, the obtained crystals were obtained. After filtering, washing with ethanol and drying, 56 parts of bis [3- (7-diethylaminocoumaryl)] ketone was obtained. This compound was cyanated by the same method as in Example 1, and 9 parts of this cyano compound was treated with 10% sulfuric acid in 70% sulfuric acid.
When hydrolyzed at 0 ° C. for 8 hours, bis [3- (4-carboxy-7-diethylaminocoumaryl)] ketone was converted to 8.7.
I got a copy. This was reacted with 8 parts of dicyclohexylcarboximide in 100 parts of dehydrated tetrahydrofuran solvent at room temperature for 1 hour, and then 9.6 parts of isopropyl alcohol was added dropwise at 10 ° C. for 30 minutes and reacted at the same temperature for 3 hours.
9 parts of bis [3- (4-isopropoxycarbonyl-7-diethylaminocoumaryl)] ketone was obtained. The electron beam spectrum and elemental analysis results of this compound are as follows. Electronic spectrum; absorption maximum [λmax] 494
nm (in acetone) Elemental analysis value C H N calculated value (%) 66.44 6.37 4.43 Measured value (%) 66.29 6.15 4.58 Further, using the above ketocoumarin compound, Example 1 When a photosensitive solution having the same composition as that shown in 1 was prepared to form a photosensitive layer and the above photosensitive layer was irradiated with light by an argon laser, it was confirmed that the resin was rapidly cured. Similar results were obtained with the xenon lamp irradiation.

Example 3 In the same manner as in Example 1, diethylene glycol was used instead of 100 parts of ethanol in the ester synthesis,
10 parts of bis [3- (4-hydroxyethoxyethoxycarbonyl-7-diethylaminocoumaryl)] ketone was obtained. The electron beam spectrum and elemental analysis results of this compound are as follows. Electronic spectrum; absorption maximum [λ
max] 498 nm (in acetone) Elemental analysis value CHN calculated value (%) 61.32 6.12 3.87 Measured value (%) 61.51 6.05 3.82 Also carried out using the above ketocoumarin compound. When a photosensitive solution having the same composition as that shown in Example 1 was prepared to form a photosensitive layer and the above photosensitive layer was irradiated with light by an argon laser, it was confirmed that the resin was rapidly cured. Similar results were obtained with the xenon lamp irradiation.

Example 4 57 parts of 9-formyl-8-hydroxyeurolidine,
Piperidine (2 parts) was added to ethyl acetate dicarboxylate (25 parts), and the mixture was reacted in an ethanol solvent at 80 ° C for 5 hours. After cooling, the obtained crystals were filtered, washed with ethanol and dried to give bis ( 57 parts of 10-eurolysyl coumaryl) ketone were obtained. 44 parts of this compound
and Pigments, Vol. 1, pages 3 to 15 (1980) ”, 200 parts of DMF.
Suspended in it, and 57 parts of 30% NaCN aqueous solution was added dropwise thereto at room temperature, and the reaction was continued for 1 hour. Then, 31 parts of bromine was added dropwise at 0 to 10 ° C., stirred for 2 hours, washed well with water after filtration. After drying, 45 parts of bis [10- (11-cyanoeurolidylcoumaryl)] ketone was obtained. Further, 10 parts of the above cyano compound was reacted with 21.6 parts of 98% sulfuric acid in 100 parts of diethylene glycol monomethyl ether at 80 ° C. for 3 hours, allowed to cool, and then discharged into 300 parts of water for neutralization.
The precipitated crystals were filtered, washed well with water, dried and then washed with bis [1
11.5 parts of 0- (11-methoxyethoxyethoxycarbonyl eurolysylcoumaryl)] ketone was obtained. The electron beam spectrum and elemental analysis results of this compound are as follows. Electronic spectrum; absorption maximum [λmax] 5
13 nm (in acetone) Elemental analysis value CHN calculated value (%) 64.49 6.04 3.50 Measured value (%) 64.38 6.21 3.59 Further, using the above ketocoumarin compound, Example 1 When a photosensitive solution having the same composition as that shown in 1 was prepared to form a photosensitive layer and the above photosensitive layer was irradiated with light by an argon laser, it was confirmed that the resin was rapidly cured. Similar results were obtained with the xenon lamp irradiation.

Examples 5 to 30 Table 1 shows the bis [3- (4-substituted coumaryl)] ketone compounds synthesized in the same manner as in Example 1. All the compounds showed the same photosensitivity as the compound of Example 1.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

INDUSTRIAL APPLICABILITY In the field of information recording using photopolymerization reaction,
The method of directly outputting an original document electronically edited by a computer by using a laser for recording has a problem in that the sensitivity, solubility, and storage stability of the photosensitive layer are low.
However, the photosensitive layer obtained by applying the photocurable resin containing the photosensitizer of the present invention is excellent in sensitivity, solubility and storage stability, and the present invention is extremely useful in practice.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/031

Claims (2)

[Claims] 1. General formula (1) (Chemical formula 1) [In the formula, R ₁ and R ₂ each independently or independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which may be bonded to each other; It may combine with a benzene nucleus substituted with an amino group in the skeleton to form a ring, and R ₃ is a hydrogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, An alkoxyalkoxy group, a sulfonic acid group, a halogen atom, R ₄ represents an alkoxy group, a cycloalkoxy group, a hydroxyl group, an aryloxy group, an alkenyloxy group, an aralkyloxy group, an alkoxycarbonylalkoxy group, an alkylcarbonylalkoxy group, or The substituent (Chemical Formula 2) is shown. [Chemical 2] (Here, R _{5 to} R ₈ represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group or a cycloalkyl group, and n, m
Represents an integer of 1 to 5, respectively. )] Is a bis [3- (4-substituted coumaryl)] ketone compound. 2. A photosensitizer represented by the general formula (1) according to claim 1.