JPS62145241A - Positive type photosensitive heat resistant material - Google Patents

Abstract

PURPOSE:To obtain a positive type photosensitive heat resistant material which permits patterning with direct light and electron rays, obviates the disturbance of the pattern and has high heat resistance and high resolution by incorporating specific polymers therein. CONSTITUTION:This positive type photosensitive heat resistant material contains the polymers having the structures expressed by the formula (I) and the formula (II). In the formula (I), R1 is a bivalent org. group, R2 is tetravalent org. group, n is an optional positive integer, and R3 is a residual group of oxime deriv. In the formula (II), R4 denotes a monovalent org. group, and R5 denotes hydrogen or monovalent org. group. This positive type potosensitive heat resistant material is preferably used in the form of a soln. of the polymer expressed by the formula (I) in an org. solvent at 10-50wt% concn. The concn. thereof is selectable as desired according to the conditions for work. Any org. solvent which is inert to the polymer expressed by the formula (I) and is a good solvent is usable. N-methyl-2-pyrolidone and N, N-dimethyl formamide are more preferable solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a positive photosensitive heat-resistant material having novel positive photosensitive characteristics.

[Conventional technology]

Conventionally, as a heat-resistant resin with photosensitivity, (1) a mixture of polyamic acid and dichromium or salt (Japanese Patent Publication No. 49-1'73
74 '), photosensitive polyamide 1'' synthesized from +21 pyromellit e derivative (JP-A-49-115
54U Publication), a mixture of t3I polyamic acid and unsaturated amine (JP-A-54-145794 Ji+ Publication)
, +41 Reaction product of polyamic acid and unsaturated epoxy (JP-A-55-45'746 Ji+ publication)
Various proposals have been made, such as Japanese Patent No. 6'7'724).

[Problem that the invention seeks to solve]

However, all of the above-mentioned materials have negative photosensitive characteristics. Negative photosensitive resins are those in which a soluble resin is photo-crosslinked to become insolubilized, and developed and patterned using the difference in solubility between the resin and the unexposed area. If the photo-crosslinking reaction could occur completely, it would be possible to create a good solubility difference between the exposed area and the unexposed area, but it is usually difficult to cause this reaction to occur completely. Therefore, in the development step for washing out the trailing portion, the insufficiently crosslinked portions of the exposed portions are partially washed out, which causes film roughening on the surface.

Furthermore, negative photosensitive resins form images by causing a photocrosslinking reaction to insolubilize the resin that dissolves in the developer, and in this development process, the crosslinked portion (
Swelling f4 caused by the developer in the exposed area (exposed area) cannot be avoided. As a result, pattern disturbances, peeling, etc. occur, which not only impairs the reliability of image color warmth, but also becomes extremely disadvantageous in performing high-resolution image shape sharpening.

This invention was made to improve these above-mentioned drawbacks, and obtains a positive photosensitive heat-resistant material that can be patterned with direct light and electron beams, has no pattern disturbance, has high thermal stability, and has high resolution. The purpose is to

[Means for solving the gap] The positive photosensitive heat-resistant material of the present invention has a general formula in which R1
is a divalent organic group, RzH is a tetravalent organic group, n is an arbitrary positive integer, and R3rI′i is an oxime derivative residue, and is represented by the following general formula (21% formula% (wherein, R4 is a monovalent organic group is represented by R[+ represents hydrogen or a monovalent organic group.

It contains a polymer represented by:

〔Example〕

The polymer represented by the general formula txt related to this invention can be synthesized by various methods, but a typical method is as follows: OCN -R1-NCO...(31 (in the formula, R1, Rli, R3 is a general formula (same as 11)
Diisocyanate represented by general formula (31) and general formula (4
1, or H2N -R1-NH,... (61 R300CC00R3 (wherein, R1, R2, R1 are general formulas (same as 1+) general formula (5) Examples include a method of polycondensation of a diamine represented by the formula (6) and a dicarboxylic acid chloride r represented by the general formula (6).

Examples of the diisocyanate represented by the above general formula (31) include diphenylmethane diisocyanate, toluene diisocyanate, diphenyl ether diisocyanate, benzophenone diisocyanate, and diphenylsulfone diisocyanate.

Aromatic diisocyanates such as biphenyl diisocyanate and phenylene diisocyanate are preferred.

Examples of diamines represented by the general formula (51) include evaphenylene diamine, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl meta7.4.
4'-diaminodiphenylsulfide, 4.4'-diaminodiphenylsulfone, p, p-benzidine, 3.
s'-diaminobenzophenone, 0-tolidine, 1,5
-di(P-aminophenyl)tetramethyldisiloxane,
Bis(r-aminopropyl)tetramethyldisiloxane and diaminophenyl indene can be mentioned.

The dicarboxylic acid diesters and acid halides thereof involved in the above reaction can be synthesized by the following method. That is, by reacting an acid dianhydride represented by general formula (7) with an oxime represented by general formula (8) (wherein R2 is the same as general formula (11)).

HON -C-R4...(8) "(In the formula, R4 and R5 are the same as general formula (2)) General formula (4)
The carboxylic acid diester of No. 1 can be synthesized. Further, this compound can be easily converted into the compound of general formula (6) by using a halogenating reagent such as thionyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, acetic acid chloride, or the like.

Examples of acid dianhydrides such as these necessary compounds include pyromellitic anhydride.

3.3',4,4/-benzophenonetetracarboxylic acid: no 1 + 3.3',4.4'-biphenyltetracarboxylic dianhydride, 1,2,5.6-naphthalenetetracarboxylic acid difJM 2.2-bis(dicarboxyphenyl)hexafluoropropane anhydride,
Examples include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2°3,4-cyclopenkunetetracarboxylic acid anhydride.

Examples of the oxime include acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, -Tcetophenone oxime, benzophenone oxime, and diethyl ketoxime.

The positive photosensitive heat-resistant material of one embodiment of the present invention is preferably used as a solution of the polymer of the general formula (11) in an organic solvent of 10 to 5 degrees by weight; Any organic solvent can be selected according to the above conditions.Any organic solvent can be used as long as it is inert to the polymer of general formula (1+) and is a good solvent. , N-methyl-2-pyrrolidone, N,N-dimethylacetamide.

Preferred solvents include N,N-dimethylsulfoxide and N,N-dimethylformamide.

The positive photosensitive heat-generating material of this invention is spin-coated onto a glass plate or a silicon wafer, and then breccured at 50 to 90°C to form a film. On this occasion,
By using a substrate treated with a camping agent such as α-aminopropyltrimethoxysilane and 4-aminophenyltrimethoxysilane, truly excellent adhesion can be provided.

A mask having a predetermined pattern is mounted on the above-mentioned film,
By irradiating it with light or an electron beam and developing it with an alkaline aqueous solution, the exposed areas are washed out and a sharp relief pattern on the end face is obtained. At this time, the developer used may be any alkaline aqueous solution, and examples include aqueous solutions of caustic potassium, tetramethylammonium hydroxyl F, ethanolamine, and N,N-dimethylethanolamine. can.

20 pieces of substrate with a sloped relief pattern obtained by smelting
By performing heat treatment at 0 to 400°C, heatability,
! It can be converted into Boliimi V with excellent chemical resistance and electrical properties, and a cured product with a good relief pattern can be obtained.

EXAMPLES Hereinafter, this invention will be explained in more detail with reference to examples, but the invention is not limited thereby.

Persimmon example 1 27.72 g (0.22 mol) of cyclohexanone oxime and 800 g of cyclohexanone oxime were placed in a 10100O four-bottle flask equipped with a slow stirrer, a thermometer, a nitrogen introduction tube, and a calcium chloride tube.
Dry toluene was added and dissolved. 21. Pyromellitic dianhydride purified by sublimation. After adding Bg (o, 1 mol), reflux was performed for 5 hours, and the precipitated crystals were collected and expressed by general formula (4). This was done using absorption spectra.

20 g of the obtained pyromellitic acid derivative was added to 150 g of thionyl chloride 1'' and reacted at 40°C for 3 hours.
Acid halogenation was performed.

4.4'-diaminodiphenyl ether Ig (0,0
0.05 mol) and 0.63 g (0.00
6 mol), 100 mt of distilled water, 200 mt of acetone, and a total of 1 no. On the other hand, top 2
2.545 g of pyromellitic acid chloride I' obtained in
(0,005 mol) and 100 g of dried chloroform were uniformly dissolved. These two liquids were added while cooling and stirred at high speed. After stirring for 15 minutes, the mixture was reprecipitated into methanol, thoroughly washed, and collected once.

2 g of this polymer was dissolved in 15 g of N-methyl-2-pyrrolidone, and a positive-working photosensitive #
The thermal material was obtained.

The material was applied to a glass plate, dried at 80° C. for 30 minutes, and then irradiated with ultraviolet M (Hg-Xe lamp) for 30 seconds through a prescribed mask.

After exposure, 3 of tetramethylammonium hydroxide
It was immersed in an aqueous solution for 3 minutes, washed with water, and forced air-dried in a nitrogen stream. At this time, a good pattern was obtained.

Next, heat treatment was performed to 300° C. at a temperature increase rate of 5° C./min to form an imitation V, but no pattern disturbance occurred.

Example 2 4.72 g (0,01
mol) and 45 g of dried N-methyl-2-pyrrolidone were uniformly dissolved. Then, 2.5 g (0.01 mol) of diphenylmethane diisocyanate was added and 10
The reaction was continued at 0-110°C for 8 hours. After the reaction, a positive-working photosensitive heat-resistant material of another practical example of the present invention of a viscous polymer solution was obtained. It was processed in the same manner as in Example 1 to obtain a good-looking pattern. Furthermore, the same heat treatment as in Practical Example 1 was carried out to form an imitation F, but no pattern disturbance occurred here as well.

Practical Examples 3 to 6 Using the compounds in Table 1, in the same manner as in Example 1,
A positive photosensitive thermal material according to another example of the present invention was obtained. Furthermore, by performing exposure and development in the same manner as in Example 1, it was possible to perform good patterning. In addition, when thermal analysis was conducted on the cured product heated in nitrogen at 350°C for 30 minutes, it was found that
11-, thermal decomposition occurred from a temperature of 420°403, 405'C. This also indicates that the obtained cured product exhibits high thermal stability.

〔Effect of the invention〕

As explained above, the present invention provides Rzld in the general formula
a divalent organic group, RQd a tetravalent organic group, n is any positive integer, R5ff is an oxime derivative residue, and is represented by the following general formula (
It is represented by 21% formula % (21 (wherein, R4 represents a monovalent organic group, and ReI represents hydrogen or a monovalent organic group).

By using a polymer containing the following,
1. Patterning is possible with directed light and electron beams, and a positive photosensitive heat-resistant material with high heat resistance and high resolution can be obtained without pattern disturbance.

Claims (1)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) In the formula, R_1 is a divalent organic group, R_2 is a tetravalent organic group,
n is any positive integer, R_3 is an oxime derivative residue, and the following general formula (2) ▲ Numerical formula, chemical formula, table, etc. are available ▼... (2) (In the formula, R_4 is a monovalent organic group , R_5 represents hydrogen or a monovalent organic group). A positive photosensitive heat-resistant material containing a polymer represented by: