JPH0610175B2 - 2,4-dibenzylidene-3-oxoglutarate derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel 2,4-dibenzylidene-3-oxoglutarate derivative having a high sensitizing effect on a photocrosslinkable resin.

[Conventional technology]

Hitherto, nitro compounds such as 5-nitroacenaphthene and tetranitrofluorene; ketone compounds such as 1,8-dimethoxyanthraquinone, anthrone and Michler's ketone have been used as sensitizers for photocrosslinkable resins. Photocrosslinkable resins using these sensitizers are used as image forming materials for printing and LSI devices, but the use of nitro compounds and Michler's ketone is not preferable from the viewpoints of danger and toxicity.

In recent years, a simplified plate making method has been proposed in which an image is printed directly on a photosensitive layer from an electric image signal using a laser beam, instead of printing an image through a halftone film.

However, most lasers currently available for plate making, such as an argon ion laser and a helium-cadmium laser, have a visible region of 440 nm or more in the emission energy, and a light-sensitive material using a conventional sensitizer has a visible region. Due to insufficient light sensitivity, use a large laser with high output,
The reality is that the emission energy in the ultraviolet region must be used. Therefore, it is desired that the photosensitive material has high sensitivity.

As a sensitizer used for such a purpose, 2-benzoylmethylene-1-methyl-β-naphthothiazoline, 2
Thiazoline derivatives such as-[bis (2-furoyl) methylene] -1-methylnaphtho [1,2-d] thiazoline (US Pat. No. 4,062,686); 3-benzoyl-7-methoxycoumarin, 3,3'-carbonylbis. 3-Ketocoumarin derivatives such as (7-dimethylaminocoumarin) (US Pat. No. 4,147,552); 2,4,6-tri (4-)
Methoxyphenyl) thiapyrylium perchlorate, 4
Thiapyrylium salts such as-(4-butoxyphenyl) -2,6-diphenylthiapyrylium perchlorate (JP-A-56-48626) have been reported. However, these sensitizers cannot be said to be sufficient in terms of economical efficiency such as difficulty in production, purification and acquisition of raw materials, or compatibility with a photosensitive resin.

[Problems to be solved by the invention]

An object of the present invention is to provide a sensitizer which exhibits a sensitizing effect in a wide wavelength range from the ultraviolet range to the visible range, is easy to manufacture and purify, and has no problems such as compatibility with resins, danger and toxicity. .

[Means for solving problems]

The present invention has the general formula (In the formula (I), two R _1's each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 5 carbon atoms, and two R _2's each independently have 2 to 2 carbon atoms. 8 represents a dialkylamino group of 8)
The above object was achieved by providing a dibenzylidene-3-oxoglutarate derivative.

2,4-dibenzylidene of the general formula (I) according to the present invention
Preferred specific examples of the 3-oxoglutarate derivative include, for example, dimethyl-2,4-bis (p-diethylaminobenzylidene) -3-oxoglutarate, dimethyl-2,4-bis (p-dimethylaminobenzylidene).
-3-oxoglutarate, diethyl-2,4-bis (p-diethylaminobenzylidene) -3-oxoglutarate, diethyl-2,4-bis (p-dimethylaminobenzylidene) -3-oxoglutarate and the like. To be

The 2,4-dibenzylidene-3-oxoglutarate derivative of the present invention has the general formula (In the above (II), R ₁ is a hydrogen atom and has 1 to 5 carbon atoms.
Represents an alkyl group or an aryl group. ) The 3-oxoglutarate represented by (In the above (III formulas, R ₂ can be easily prepared by a dehydration condensation reaction with benz Al Hideto compound represented by represents.) Dialkylamino group having 2 to 8 carbon atoms.

Examples of 3-oxoglutarates represented by the general formula (II) (hereinafter referred to as oxoglutarates) include acetonedicarboxylic acid, dimethylacetonedicarboxylate, diethylacetonedicarboxylate, isobutylacetonedicarboxylate, and acetonedicarboxylic acid. Acid di-tert-
Butyl, acetone dicarboxylic acid diphenyl, acetone dicarboxylic acid dibenzyl etc. are mentioned.

Examples of the benzaldehydes represented by the general formula (III) (hereinafter referred to as benzaldehydes) include, for example:
Examples thereof include p-diethylaminobenzaldehyde, m-diethylaminobenzaldehyde, p-dimethylaminobenzaldehyde, m-dimethylaminobenzaldehyde and the like.

In the reaction of oxoglutarates and benzaldehydes, it is desirable to select the compounding ratio at a ratio of 2 mol of benzaldehydes to 1 mol of oxoglutarates.

The dehydration condensation reaction between oxoglutarates and benzaldehydes can be carried out in the presence of a dehydration catalyst by dissolving predetermined amounts of 3-oxoglutarates and benzaldehydes in a suitable solvent. The preferred reaction temperature varies depending on the reactivity of the catalyst used, the type of solvent, etc., but is from room temperature to 1
The temperature is 10 ° C., and if necessary, the reaction is carried out under reflux with heating while removing water out of the reaction system. The reaction time is preferably 1 to 6 hours.

Examples of the catalyst used in the present invention include acetic acid, acetic acid-ammonium acetate, acetic acid-piperidine, benzoic acid-piperidine, piperidine, sodium hydroxide, sodium methoxide, sodium ethoxide, and the like. 0.1 to 1 mol of glutarates
0.5 mol is preferred.

Examples of the solvent used in the present invention include solvents which are inactive to the above-mentioned catalyst, and examples thereof include benzene, toluene, methanol, ethanol and the like.

After completion of the dehydration condensation reaction, the solvent was distilled off, and a solvent having a lower polarity, for example, petroleum ether, ligroin, n-hexane, ether, etc. was added in a small amount to produce 2,
The 4-dibenzylidene-3-oxoglutarate derivative is crystallized, passed through, purified and collected, or after completion of the reaction, the solvent is distilled off and purified and collected by silica gel column chromatography and the like.

The 2,4-dibenzylidene-3-oxoglutarate derivative of the present invention can be confirmed by ordinary means for structural determination such as elemental analysis, infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum and mass spectrometry spectrum. . The 2,4-dibenzylidene-3-oxoglutarate derivative of the present invention is particularly superior to a photocrosslinkable resin containing a photosensitive double bond derived from cinnamic acid, phenylenediacrylic acid or the like. Shows a feeling effect.

The 2,4-dibenzylidene-3-oxoglutarate derivative of the present invention is a photocrosslinkable resin containing a photosensitive double bond.
It is preferable to add 1 part by weight or more to 0 part by weight, and more preferably 5 parts by weight or more.

The 2,4-dibenzylidene-3-oxoglutarate derivative of the present invention may be used in combination with other commonly used sensitizers or pigments.

Hereinafter, the present invention will be specifically described with reference to Examples, Reference Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

[Examples, Reference Examples and Comparative Examples]

Examples 1 to 4 300 m of each mixture having the composition shown in column A of Table 1
l of benzene and the catalyst listed in column B of Table 1,
A reactor equipped with a stirring device, a reflux device equipped with a water separation device (Dean Stark device) and a thermometer was charged,
The mixture was stirred at a reaction temperature of 75 to 82 ° C. under reflux for 6 hours while removing generated water, and then the solvent was distilled off under reduced pressure. After that, 300 ml of ether was added, and the separated crystals were taken, and subsequently the obtained crystals were recrystallized from benzene to obtain a 2,4-dibenzylidene-3-oxoglutarate derivative.

The structure of the obtained 2,4-dibenzylidene-3-oxoglutarate derivative was confirmed by ultraviolet absorption spectrum, infrared absorption spectrum, nuclear magnetic resonance spectrum, mass spectrometry,
It was carried out based on the data of elemental analysis.

Reference Examples 1 to 4 and Comparative Examples 1 to 5, 2,4-dibenzylidene-3-obtained in Examples 1 to 4 above
The sensitizing effect of the oxoglutarate derivative on the photocrosslinkable resin having a photosensitive double bond was measured.

Chain extension of a polyester precursor obtained by reacting 1.0 mol of diethyl p-phenylene diacrylate as a photocrosslinkable resin with 1.0 mol of an adduct of ethylene oxide (6.2 mol) of bisphenol A (1 mol) with diphenyl terephthalate The photosensitive resin (weight average molecular weight: 55,000) was used.

A solution of 3 g of the above resin dissolved in 97 g of monochlorobenzene (hereinafter referred to as a photosensitive solution) was prepared, and 0.05 g of a phthalocyanine pigment and a sensitizer were added to 30 g of the photosensitive solution.
A photosensitive composition was prepared in which 0.05 g of the 2,4-dibenzylidene-3-oxoglutarate derivative was added. After graining this composition, it was applied to an anodized aluminum plate with a whirler and dried to prepare a photosensitive image-forming material having a photosensitivity of 1 μm in thickness.

A metal halide lamp with an output of 1 KW ("Idlefin 1000" manufactured by Iwasaki Electric Co., Ltd.) provided at a position 1 m away from the image forming material by bringing a step wedge having a step of 0.15 into close contact with the obtained photosensitive image forming material, or an image A 500 W xenon lamp [manufactured by Ushio Electric Co., Ltd.] equipped with a filter [V-Y44 manufactured by Toshiba Glass Co., Ltd.] installed at a distance of 0.5 m from the forming material to cut light of 440 nm or less. UXL-500D "].

Then, this image-forming material was mixed with γ-butyrolactone-85.
% Phosphoric acid (98/2 volume ratio) developing solution to insolubilize the 5th step of step wedge (excluding 7.5 seconds exposure for metal halide lamp and 4 seconds exposure for xenon lamp) The value was converted from the number of steps) to obtain the photosensitivity.

For comparison, a photosensitive composition was prepared by adding 0.05 g of a phthalocyanine pigment and a known sensitizer shown in Table 2 to the above-mentioned photosensitive solution, and an image-forming material was prepared under the same conditions as in Reference Example. Exposed, developed, and measured photosensitivity.

The contents and results of each of the above examples are summarized in Tables 1 and 2.

In addition, * 1) and * 2) in the table are as shown below.

* 1) ε: Represents the molecular absorption coefficient.

* 2) Thiapyrylium salt: Represents 4- (4-n-amyloxyphenyl) -2,6-di (4-methoxyphenyl) thiapyrylium perchlorate.

[Effects of the Invention] The 2,4-dibenzylidene-3-oxoglutarate derivative of the present invention exhibits a sensitizing effect in a wide wavelength range from the ultraviolet region to the visible region of about 550 nm, and exhibits cinnamic acid and phenyldiacryl. The photosensitizing wavelength region of the photo-crosslinking resin containing a photosensitive double bond derived from an acid was spectrally sensitized to a long wavelength region of about 550 nm. Therefore, the invention of 2,4-
An image forming material using a photocrosslinkable resin containing a photosensitive double bond to which a dibenzylidene-3-oxoglutarate derivative is added is exposed to an image by exposing it to an argon ion laser having a main emission wavelength at 488 nm. It is possible to form

Claims (1)

[Claims] 1. A general formula (In the formula, two R _1's each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 5 carbon atoms, and two R _2's each independently represent a dialkyl group having 2 to 8 carbon atoms. 2,4-dibenzylidene-3-oxoglutarate derivative represented by: