JPS6081158A - Radiation-sensitive substance - Google Patents

Abstract

NEW MATERIAL:The compound of formula I -formula IV [X is halogen; Y is CH or N; when Y is CH, Z is H, lower alkyl, OR<1> (R' is H or lower alkyl) or COOR<1>, and when Y is N, Z is H, lower alkyl, or C(O)R<1>CO2R<1>; n and m are 0-1; the position of the N3 group on the benzene nucleus is para or meta]. EXAMPLE:2,3-Dibromo-1,3-(p-azidophenyl)propan-1-one. USE:Hardener for a radiation-sensitive resin. An aromatic bisazide-type radiation- sensitive substance having high sensitivity. PREPARATION:The compound of formula I or II can be produced by reacting the 4-substituted-2,6-bis(azidobezal)cyclohexanone, diazidochalcone or diazidobenzalacetone with N-methyl-2-pyrrolidone-halogen complex. The above compound can be converted to the compound of formula III or IV by the dehydrohalogenation reaction with pyridine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a halogen-containing aromatic at-based radiation-sensitive material used in radiation renost.

[Background of the invention]

Along with the rapid progress of the semiconductor industry in recent years, element micro IYa
The nolturn dimensions required in the field of processing technology are becoming increasingly finer, and in the future, ultra-fine and
It is hoped to get 9 turns.

In response to this demand, it has been theoretically difficult to obtain ultra-fine patterns of microns or less using photosensitive resins, which are conventional pattern-forming materials, due to light diffraction and interference. For this reason, lithography techniques using electron beams and X-rays, which have extremely low diffraction and interference, have attracted attention, and along with this, the demand for resin molds that are sensitive to these radiations has increased.

Aromatic azide compounds are currently widely used as photosensitizers for photosensitive resins because they have extremely high sensitivity to light, but they have low reactivity to radiation, so they are not effective as radiation-sensitive curing agents. could not be used for

[Purpose of the invention]

The purpose of the present invention is to use the following as a curing agent for radiation-sensitive 4m fat:
An object of the present invention is to provide an aromatic bisazide-based radiation-sensitive container having high radiation sensitivity.

[Summary of the invention]

The reason why bisazide compounds have high sensitivity when used in sensitive resins and low sensitivity when used in radiation-sensitive resins is because bisazide compounds have high light absorption efficiency, but radiation absorption efficiency is low. This is thought to be due to the low generation efficiency of active chemical species required for resin curing. Since the absorption efficiency of radiation depends on the electron density, we thought that in order to increase the absorption efficiency mentioned above, it would be sufficient to introduce a heavy atom, halodane, which has a high electron density, into the bisazide compound. As a result of extensive studies, the present inventors have reached the knowledge that the above object can be achieved with a halogen-containing aromatic bisazide compound represented by the following general formula.

However, X is halogen and Y is -CH- or -N-.

1.1 2 is hydrogen, lower alkyl group, 10R when Y is -CH-
I (R1 represents hydrogen or a lower alkyl group), is l
and the -N3 group is located at the para or meta position of the benzene nucleus.

The compound represented by general formula (1) or (2) is 4-
Substituted 2,6-bis(azidopendel)cyclohexanone, diazidochalcone or diazidopendelacetone was synthesized by reacting with N-methyl-2-pyrrolidone-halogen complex.

The compound represented by the general formula (3) or (4) is synthesized by treating the compound represented by the general formula (1) or (2) with pyridine in an aprotic polar solvent and causing a dehydrohalogenation reaction. did.

[Embodiments of the invention]

Hereinafter, the halogen-containing aromatic bisazide compound provided by the present invention and the method for synthesizing the same will be explained with reference to Examples.

In addition, all decomposition tests shown in the following examples were determined from exothermic peaks measured by a differential thermal analyzer. In addition, nuclear magnetic resonance CN
MR) Spectra are all dimethyl sulfoxide-d6
Chemical shifts are given in ppm using tetramethylsilane as an internal standard. Furthermore, the data in parentheses indicate the spectrum mi-turn, the cassilling constant, and the integral ratio in that order.

Example 9111 2,3-dibromo-1,3-(p-acidophenyl)cropan-1-one N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) against 150+m under cooling. Bromine was added dropwise to prepare an NMP solution of an NMP-bromine complex. To 40 IILe of this solution, 10't of 4,4'-diazide chalcone was added and reacted at room temperature for 2 days. Next, this solution was added to 500 d of water and left to stand at room temperature for 1 day, and the precipitated solid was filtered with suction to give 1% J, 10
0 x 3 washes, 50. After washing with methanol in step d, drying under reduced pressure is carried out at a decomposition temperature of 140 to 150'C.

A colorless solid 12f was obtained.

If the above reaction is expressed as a chemical formula, it can be written as follows.

0 This product was confirmed to be the title compound by spectral analysis. Infrared absorption spectrum and nuclear magnetic resonance spectrum data are shown below. Infrared absorption: 21
50 cIn-” (Ns) o Nuclear magnetic resonance: δ5.7 (2
Doublet, 1IHz, 11), 6.7 (Doublet, 11Hz.

IH), 7.2 (doublet, 9Hz, 2H), 7.3 (
Doublet, 9 Hz, 2 H), 7.9 (2
doublet, 9Hz, 2H).

8.4 (doublet, 9Hz, 2H).

Example 22.6-siglomu2.6-(α-diglomu-
p-azidobenzyl-4-methylcyclohexanone An NMP solution of the NMP-bromine complex prepared in Example 1 (1
)・a, 2,6-bis(p-azidopendel)-
7JO of 4-methylcyclohexay7F was added and allowed to react at room temperature for 2 days. Next, this solution was added to 500 mm of water and left at room temperature for 1 day, and the precipitated solids were collected by suction filtration, washed with 100 at. Decomposition temperature 110-120
A colorless solid 9f at °C was obtained.

If the above reaction is expressed as a chemical formula, it can be written as follows.

This product was confirmed to be the title compound by spectral analysis. Infrared absorption spectrum and nuclear magnetic resonance spectrum data are shown below. Infrared absorption: 21
5k t(-Ns). Nuclear magnetic resonance: δ1.05 (doublet, 5 Hz, 3H) 1.5-2.5 (multiplet,
5H).

6.05 (singlet, 2H), 7.1 (doublet, 8Hz,
4H).

7.6 (doublet, 8Hz, 4H).

Example 32.6-nopromu2.6-(α-bromo-p
-azidobennol)-4-cal? NMP 4 solution 2 of NMP-bromine complex prepared in oxycyclohexanone Example 1
5, 2,6-bis(p-azidobenzal)-4
-Cal yj? 3.5 tons of oxycyclohexanone was added and the reaction was carried out at room temperature for 2 days. Next, this solution was added to 300 ml of water and left at room temperature for 1 day, and the precipitated solids were collected by suction filtration, washed with 100 ml of water 3 times, and washed with water for 20 min.
After washing with mJ of methanol, drying under reduced pressure to a decomposition temperature of 1
10,... 3.7 tons of colorless solid of 1206C were obtained.

If the above reaction is expressed as a chemical formula, it can be written as follows.

This product was identified as the title compound by spectral analysis. Infrared absorption: 2150! :In'
C-Ns). Nuclear magnetic resonance: δ1.5-3 (multiplet, 5
H).

6.1 (singlet, 2H), 7.1 (doublet, 9H
z + 4 H) +7.65 (doublet, 9Hz,
4H).

Example 4 2,6-dipromu2,6-(α-zolomu p
-azidobenzyl)-4-hydroxycyclohexanone Example 1't' To 25 ml of the NMP solution of the prepared NMP-bromine complex, 2,6-bis(p-azidopendel)-4-hydroxycyclohexanone 3F was added. i. Reacted for 2 days at room temperature. Next, this solution was added to 300 ml of water and left at room temperature for one day, and the precipitated isomorphic material was collected by suction filtration, washed with 100 rnl x 3 times, and washed! d
After washing with methanol once, drying was carried out under reduced pressure to obtain colorless solid 3.2f with a decomposition temperature of 160-165°C.

If the above reaction is expressed as a chemical formula, it can be written as follows.

Of (This product was confirmed to be the title compound by spectral analysis.0 infrared absorption=2150crIL-1C
Ns). Nuclear magnetic resonance: δ1.5-3.0 (multiplet, 5H
).

6.0 (singlet, 2H), 7.1 (doublet, 9Hz, 4
H).

7.6 (Doublet, 9Hz, 4H).

Example 5 2-Brom-1,3-di(p-azidophenyl)-2-f Lopen-1-one 2,3-dibrom-1,3
-(P-azidophenyl)propan-1-one 7F
04 was dissolved in NMP, pyridine 102 was added thereto, and the mixture was allowed to react at room temperature for 2 days. Next, add this reaction@liquid to 500 pieces of 2
In addition to N-hydrochloric acid, the resulting reaction mixture was extracted with 200 rll×chloroborum twice. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 50 ml of methanol was added to the solution to crystallize the product, with a melting point of 123-124.
1.5t of crystalline product with 6C2 decomposition temperature of 140-150℃
I got it.

The above reaction can be expressed as a chemical formula as shown below.

This product was confirmed to be the title metal compound by spectral analysis. Infrared absorption: 2150/XrL'(
N3). Nuclear magnetic resonance: δ7.25 (doublet, 9Hz.

2H), 7.3 (doublet, 9Hz, 2H), 7.8 (1
Heavy items.

IH), 7.9 (doublet, 9Hz, 2H), 8.0 (2
Heavy items.

9Hz, 2H) Example 6 2,6-di(p-at-α-glomhensilide/)-4-carboxylcyclohexanone 2,6-dipromu2,6-(rχ-bromo-p-azidobenzyl)-4-caly1 ? Quincyclohexanone 5
t was dissolved in 30 ml of NMP', pyridi751 was added, and the mixture was allowed to react at room temperature for 2 days. Next, add 50% of this reaction solution to
001nl! of 2N hydrochloric acid. The precipitated product was collected by suction filtration, washed 3 times with 300 ml of water, further washed once with 20 ml of methanol, and dried under reduced pressure to obtain product 3.1f with a decomposition temperature of 110-120°C.

The above reaction can be expressed as a chemical formula as shown below.

OOH This product was confirmed to be the title compound by spectral analysis. Infrared absorption: 2150cm ”(-
N3). Nuclear magnetic resonance: δ1,5-3 (multiplet, 5H).

6, i (i multiplet, 2H), 7.15 (2M term, 9Hz
, 4H) + 7.65 (2i term, 9Hz, 4H).

〔Effect of the invention〕

As detailed above, the aromatic bisazide compound according to the present invention contains heavy atoms with high electron density, so it has high radiation absorption efficiency and can be used as a curing agent for radiation-sensitive resins. be able to.

Continuing from page 1 QInt, C1,' Identification code Internal reference number 0 Inventor Mitsuru Kojima Masaru Hitachi City Higashimachi 4 premises

Claims (1)

[Scope of Claims] A radiation-sensitive substance containing rhodan aromatic bisazide, characterized in that it is represented by any one of the following general formulas. However, X is Halodan and Y is 100- or -N-. 1 2 is hydrogen, lower alkyl group, hot-ol (al represents hydrogen or lower alkyl group) when Y is -CH-,
represents l, and the -N3 group is located at the planar or meta position of the benzene nucleus.