JPS617357A - Bisazide compound - Google Patents

Abstract

NEW MATERIAL:A 2,6-bis(p-azide cinnamylidene)cyclohexanone derivative of formula (R is >=4C alkyl). EXAMPLE:2,6-Bis(p-azide cinnamylidene)-4-n-butyl cyclohexanone. USE:Photosensitizers for photoresist for use in making integrated circuits and large-scale integrated circuits; highly soluble to organic solvents. PREPARATION:A condensation is carried out at 10-50 deg.C in the presence of catalyst such as a caustic alkali, between 4-alkyl cyclohexanone and p-azide cinnamaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a bisazide compound, and more particularly to a sensitizing agent for photoresists used in the production of integrated circuits, large-scale integrated circuits, etc. in combination with cyclized rubber and the like. 2 with improved solubility in organic solvents, which is extremely useful as
, 6-bis-(p-azidocinnamylidene)cyclohexanone derivative.

BACKGROUND OF THE INVENTION Conventionally, rubber-based photoresists made of cyclized polyisoprene or polybutadiene and bisazide compounds have been widely used in the semiconductor industry as photoresists for microfabrication of integrated circuits and large-scale integrated circuits.

By the way, in recent years, with the rapid progress of the semiconductor industry, the required image accuracy has become increasingly strict, and at the same time, as printed images have become finer, photomasks have also become more expensive. There is a trend toward eliminating contact with the camera, that is, from a contact exposure method to a projection exposure method.

Therefore, a photoresist compatible with the projection exposure method is also required. In this projection exposure method, since exposure is performed using only the 436 nm g-line or 405 nm h-line of a mercury lamp, a bisazide compound that exhibits high sensitivity in this wavelength range is required.

As such a bisazide compound, for example, 2.6-
Bis(p-azidocinnamylidene)cyclohexanone, 2,6-bis(p-azidocinnamylidene)-4-methylcyclohexanone, and the like are known (US Pat. No. 3,695,886). However, these compounds have the disadvantage that they have extremely low solubility in organic solvents such as xylene and toluene that are commonly used in rubber-based photoresists, and cannot fully demonstrate their functions. Improvement in solubility is desired.

In view of these circumstances, the present inventors have conducted extensive research on 2,6-bis(p-azidocinnamylidene) cyclohexanone derivatives that have sufficient solubility in organic solvents, and have found that We have discovered that the objective can be achieved by introducing a linear or branched alkyl group having 4 or more carbon atoms into the 4-position of the cyclohexanone ring, and based on this knowledge, we have completed the present invention. It's arrived.

Means for solving all the problems, that is, the present invention provides a bisazide represented by the general formula % (1) (R in the formula is a linear or branched alkyl group having 4 or more carbon atoms) Furthermore, as a compound similar to the compound of the present invention, there is a compound described in US Pat. No. 3,695,886, but this compound is cyclohexanone), 2.6-bis(p-azidocinnamylidene)-4-methylcyclohexanone, etc. 1. The compounds of the present invention are those in which the substituent at the 4-position of the cyclohexanone ring is a lower alkyl group such as a methyl group. It differs in one respect.

The bisazide compound of the present invention is a 2,6-bis(p-azidocinnamylidene)cyclohexanone derivative represented by the general formula (1), and examples of such compounds include:
For example, R in general formula (1) is n-butyl group, te
rt-butyl group, n-amyl group, tart-amyl group,
Preferred examples include n-decyl groups and the like. These bisazide compounds have good solubility in organic solvents.

Moreover, the maximum absorption wavelength of each is 404 nm.

Table 1 shows the m general formula (1
An example of the relationship between the type of R and the solubility in organic solvents in ) is shown below.

As can be seen from this table, the bisazide compound of the present invention, in which R is a linear or branched alkyl group having 4 or more carbon atoms, has good solubility in organic solvents.

The 4-alkylcyclohexanone used as a raw material for the bisazide compound of the present invention can be obtained by a conventional method, for example, by hydrogenating p-alkylphenol to form 4-alkylcyclohexanol and then dehydrogenating it. p-Azidocinnamaldehyde can be obtained, for example, by diazotizing p-aminobenzaldehyde, reacting it with thorium azide to obtain p-azidocinnamaldehyde, and then condensing this with acetaldehyde.

The bisazide compound of the present invention can be obtained by condensing the above-mentioned 4-alkylcyclohexanone and p-azidocinnamylidenedehyde in the presence of a catalyst. One example of a suitable condensation method is to dissolve 4-alkylcyclohexanone and p-azidocinnamaldehyde in a solvent such as methanol, add a catalyst, and condense the mixture at a temperature of 10 to 50°C to obtain the desired bisazide compound. . As the catalyst in this case, an alkali catalyst such as a caustic alkali, an alkali carbonate, or an alkali metal alcoholade is usually used.

Effects of the Invention The bisazide compound of the present invention has good solubility in organic solvents, and in combination with cyclized rubber, etc., is extremely useful as a photosensitizer for photoresists used in the production of integrated circuits and large-scale integrated circuits. .

Example Next, the present invention will be explained in more detail with reference to Examples.

Example 1 4-n-butylcyclohexanone 10? and p-azidocinnamaldehyde 22.6 t'ii 250m
7! of methanol and add 10% sodium hydroxide to this. Of'lz was added and stirred overnight at 30°C. The precipitate was filtered from the reaction solution, washed with methanol and acetone, and dried to give orange 2,6-bis(p-azidocinnamylidene)-4-n-butylcyclohexanone 15.4
I got f.

The solubility of this substance in m-xylene, toluene, benzene and chlorobenzene is 2.03% by weight, respectively.
They were 2.45% by weight, 3.01% by weight, and 5.07% by weight. Furthermore, the maximum absorption wavelength λrtax is 404 nm, and the molar absorption coefficient εmax at λmax is 7.0.
It was 2 x 10".

Example 2 2,6-bis(p-azidocinnamylidene)-4- was prepared in the same manner as in Example 1 except that 4-n-amylcyclohexanone 1or and p-azidocinnamaldehyde 20.6f'z were used. tert-amylcyclohexanone 1
I got 2.3t'i.

The solubility of this substance in m-xylene, toluene, benzene and chlorobenzene is 2.59 and 3.6, respectively.
1. 4.10 and 6.20% by weight.

λmax 404 nm, gmax 7.01X
It was 10.

Also, 4-n-amylcyclohexanone can be replaced with 4-n-amylcyclohexanone.
2,6-bis(p-azidocinnamylidene)-4-1 was prepared in the same manner using tert-amyl shift 5-hexanone.
So-amylcyclohexanone was obtained.

The solubility of Konomo in m-xylene, toluene, benzene and chlorobenzene is 1.75.2.0, respectively.
1.2.40 and 4.17% by weight.

λmax 404 nm, 'tmax 6.90
It was X10.

Example 3 4-n-decylcyclohexanone 10? 2,6-bis(p-azidocinnamylidene)-4-n-decylcyclohexanone 12.
Of'ii (obtained.

The solubility of this substance in m-xylene, toluene, benzene and hychlorobenzene is 3.68.4.6, respectively.
3.5, 30.7, 45% by weight, λmax'x 4
04 nm, gmax 6.96×10.

Comparative example cyclohexanone, 4-methylcyclohexanone, 4-
Isopropylcyclohexanone and 4-cyclohexylcyclohexanone were used, respectively.

These and p-azidocinnamaldehyde were condensed in the same manner as in Example 1 to obtain a bisazide compound.

Each solubility, λmax and ε of these bisazide compounds
max k is shown in Table 2 together with the data of the bisazide compounds obtained in Examples 1 to 3.

Claims (1)

[Claims] 1. A bisazide compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R in the formula is a linear or branched alkyl group having 4 or more carbon atoms).