JPS5988456A - Novel compound and photo-sensitive substance using said compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R<1> and R<2> are H or lower alkyl; n is 2 or 3; X and Y are H, -SO2N3 or -N3; provided that when X=H, Y is -SO2N3 or -N3, and when Y=H, X is -SO2N3 or -N3). EXAMPLE:p-Azido-alpha-cyanocinnamic acid 2-(N,N-dimethylamino)ethyl ester. USE:A photosensitive material. Since the compound has a sensitive range at a long wavelength region of >=300nm, an industrial inexpensive photo-mask transmitting the light of the above range and made of an emulsion-coated glass or soda glass can be used by the use of the agent as a photosensitive substance. PROCESS:The exemplified compound of formula I wherein R<1> and R<2> are CH3, n is 2, X is -N3 and Y is H can be prepared by (1) reacting the compound of formula II with cyanoacetic acid in the presence of a base, (2) reacting the resultant compound of formula III with thionyl chloride in the presence of a catalyst to obtain the compound of formula IV, and (3) reacting the compound with N,N-dimethylaminoethanol.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a novel compound containing an amine group and an aromatic azide group in the same molecule. The present invention also relates to a novel photosensitive substance selected from the compounds, which imparts photosensitivity to a carboxyl group-containing polymer to form a positive image.

[Prior art]

The amine group is introduced into the photosensitive polymer as described above, and the aromatic azide group has the effect of creating crosslinks between polymer molecules to form a positive image. , is used as such a photosensitive substance.

Conventionally, as a compound containing an aromatic azide group and an amine group in the same molecule, para-azidobenzoic acid 2-(N,
N-diethylamino)ethyl is known. (J,
V, BiocherrL by 5taros et al.
Biophys, Res Commun, 8(L
56B-572 (1978)). However, since the ultraviolet absorption range of this compound is below 300 nm, the sensitivity is too low to use an industrially inexpensive photomask made of soda glass or emulsion coating that blocks this wavelength range, and therefore it is not practical. The problem is that it is insufficient.

[Purpose of the invention]

In order to improve the drawbacks of the prior art described above, the present invention has the following features:
The purpose of the present invention is to provide a novel compound having a photosensitive region in a long wavelength range of 100 nm or longer.

Another purpose is to provide highly sensitive photosensitizers selected from such compounds.

[Summary of the invention]

As a result of intensive studies to achieve the above object, the present inventors found a general formula (in the CIJ formula, RI R7 is hydrogen or a lower alkyl group, n is 2 or self, and X and Y are hydrogen or -8o2Ns).

-N3 and when X is hydrogen, Y is -SO2N3 or -N
3° When Y is hydrogen, X is -802N or -N3.

) has been developed. It has also been found that this compound is a highly sensitive photosensitizer having a photosensitive region in a long wavelength region of 3DD nm or more.

The amine group contained in the above compound plays the role of introducing the photosensitizer into the polymer by ionic bonding with the carboxyl group of the carboxyl group-containing polymer. In addition, aromatic azide groups generate nitrene, which is an active species, when exposed to energy rays such as actinic radiation and radiation, and are capable of dimerization reactions between nitrenes, double bond reactions, hydrogen abstraction reactions, etc. This causes cross-linking between polymer molecules and enables positive image formation.

The photosensitive substance according to the present invention has an amine compound having an aromatic azide group as a photosensitive group, a carbon-carbon double bond at a position conjugated with the photosensitive group, and an electron-withdrawing cyano group added to the double bond. By doing so, the photosensitive area is reduced to 3o
onrn or more and is shifted to a longer wavelength range.

Industrially inexpensive soda glass or emulsion-coated photomasks have the ability to block wavelengths of 300 nm or less;
Since it transmits a wavelength range of 300 nm or more, the use of the photosensitive material of the present invention brings about the effect that even a photomask made of such an inexpensive material can be used with high sensitivity.

[Embodiments of the invention]

The present invention will be explained below using examples.

Example 1: Paraazido α-cyanocinnamic acid 2-(N,
Synthesis of N-dimethylamine)ethyl The target compound is represented by the following formula.

In the above formula [1], R', RF-C)J, , n
= 2X = -N3, Y=)l is an example of a compound.

This compound can be obtained by the process shown in the following reaction formula 1-)
O The manufacturing method is as follows. Para-azidobenz, 58.8 g (0.4 mol) of aldehyde was dissolved in 600 g of methanol, and 323 g (0.38 mol) of cyanacetic acid was added to this solution.
2.5 g of sodium hydroxide dissolved in water (C5m) was added, and the mixture was heated under reflux for 5 hours. After refluxing, the reaction solution was poured into two volumes of water, and the precipitated crystals (para-azide α
-cyanocinnamic acid) was collected by suction filtration and purified by recrystallization using acetonitrile. (Yield: 25 g, Yield: 30 g) Next, 22 g of para-azido α-cyanocinnamic acid (
0.1 mol) in dry toluene 90m! suspended in
0.5 mn of N,N-dimethylformamide was added as a catalyst, and 20 mn (0.27 mol) of thionyl chloride was added, followed by refluxing at 60°C. Reflux is stopped when the generation of sulfur dioxide gas stops, and excess thionyl chloride and toluene are removed under reduced pressure, leaving varazide α as a distillation residue.
-20g of cyanocinnamic acid chloride was obtained.

Next, this para-azido α-cyanocinnamic acid chloride 1
0 g (0.04 mol) in 50 cc of anhydrous methylene chloride
Dissolve in 1N and keep the reaction temperature at 20°C.
3.4 g (0.04 mol) of N-dimethylaminoethanol was gradually added dropwise, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. The precipitated crystals were dissolved in water, and while cooling, an aqueous sodium hydroxide solution was added until the system became alkaline. The separated crystals decomposed with exothermic foaming at 130-140°C.

It was confirmed by the following analytical results (1) (11+) that the obtained compound was a compound according to the present invention.

(1) Infrared absorption; 1725''-' (,:C=O), 2140'n-
'(-N, ).

2220 鑵-1 (-CN).

(11) Elemental analysis; Cl4H1s02 Calculated value with N stop: C, 58, 9
i)I.

5.5; N, 24.6 Experimental value: C, 59.0; H, 5.1; N, 24
．． 5. The compound according to the present invention has a maximum ultraviolet absorption region at 345 nm, and has two absorption edges extending beyond 400 nm, and is sensitive to ultraviolet light in the target long wavelength region.

Example 2: Bala-azido α-cyanocinnamic acid 3-(N,
The target compound for synthesis of N-dimethylamine)propyl is represented by the following formula.

This means that in the above formula (1), R1, R2=CH,, n=3,
X=N3. This is an example of a compound where Y=H. This compound can be obtained by the process shown in the reaction formula below.

That is, 10 g (0.04 mol) of para-azido α-cyanocinnamic acid chloride obtained in Example 1 was dissolved in 50 cc of anhydrous methylene chloride, and while keeping the reaction temperature at 10 to 20°C, N,N-dimethyl Amituburobanol 4.1g
(0.04 mol) was gradually added dropwise, and after the completion of the dropping, 1
Stir for hours. The precipitated crystals were dissolved in water, and while cooling, an aqueous sodium hydroxide solution was added until the system became alkaline. The separated tar-like substance was extracted with methylene chloride, and the extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain an oily residue. This oil decomposed with exothermic foaming at 5 to 140°C. It was confirmed by the following analytical results (1) (11+) that this oily substance was a compound according to the present invention.

(1) Infrared absorption: 1730 side-1 (2C=0), 2140 country-'
(N3).

2220(1)-1(-CN).

(11) Elemental analysis: 015H1ri0. Calculated value as N: C,60,2
iH.

to 5.7+, 234 Experimental value: C, 60,9; It feels like ultraviolet light in the target long wavelength range.

〔Effect of the invention〕

According to the novel compound of the present invention, its photosensitive range is 300nr.
Since it is in the long wavelength range of n or more, it is recommended to use it as a photosensitive material, and it is also possible to use an industrially inexpensive photomask made of emulsion coating or soda glass that transmits light in the 7'Bi long range. This method is possible and extremely advantageous in practice.

Continuation of page 1 ■Applicant: Hitachi Chemical Co., Ltd. 2-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 1

Claims (1)

[Claims] 1. General formula % formula % (However, in the CI3 formula, R7 and R2 are hydrogen or a lower alkyl group, n is 2 or 6, X and Y are hydrogen or -8QNs, Ns
? : When X is hydrogen, Y is -SO2N3 or 2, general formula (however, CI), where R1 and R2 are hydrogen or lower alkyl groups, n is 2 or 6, X and Y are hydrogen or -80° to 81
Representing N11, when X is hydrogen, Y is -802N, or -N3; when Y is hydrogen, X is -8O2N, or -N. ) A photosensitive substance selected from the compounds represented by