JPS62275129A - Heat-resistant photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant photosensitive material excellent in storage stability and heat resistance, simple in a production process and useful as, e.g., a coating material for various semiconductors, containing a polyimide precursor obtained by reacting a tetracarboxylic dianhydride with a silylated diamine. CONSTITUTION:This heat-resistant photosensitive material contains a polyimide precursor obtained by reacting a tetracarboxylic acid dianhydride (a) of formula I (wherein R<1> is a tetravelent organic group) with a silylated diamine (b) of formula II (wherein R<2> is a bivalent organic group and R<3>, R<4>, R<5>, R<6>, R<7> and R<8> are each a monovalent aliphatic or aromatic group, at least one of them is a group having a double bond which can be dimerized or polymerized with light or radiation and the rest may be the same or different).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel heat-resistant photosensitive material.

[Conventional technology and its problems]

Conventionally, it has been known that when about 7-s% of dichromic acid groups are added to polyamic acid, which is a heat-resistant polyimide precursor, and irradiated with ultraviolet rays, it cures at 2JO℃ (%Ko Akihiro Turf 237≠ Publication). .

However, with this combination, dichromic acid remains in the protective coating, which causes problems with the reliability of the insulating film, and addition of dichromic acid makes the polymer unstable, making it difficult to handle. there were.

It is also known that a polyamic acid having a photosensitive group can be synthesized by addition polycondensation or polymerization of a polyfunctional cyclic compound having a photosensitive group and a polyfunctional cyclic compound. (Unexamined Japanese Patent Publication Akihiroter//j!Hiroshi/issue). However, the synthesis of the above-mentioned polyfunctional cyclic compound having a photosensitive group and the synthesis of polyamic acid are complicated and extremely expensive.

And even more polyamic acid! A photosensitive polyamic acid has been proposed by reacting with unsaturated epoxy (Japanese Patent Application Laid-Open No. 1986-≠57).
(Hiroi issue). However, this reaction requires a reaction promoter, and the storage stability after the reaction is also extremely poor.

[Means for solving problems]

The present invention was made in order to overcome the above-mentioned drawbacks of the conventional products, and the present invention has been made to combine a tetracarboxylic dianhydride represented by the general formula % (in the formula 11 Jd represents an organic group) and the general formula (formula %). In the middle, R2 represents a covalent organic group, and BS, R4, R5, R6, R' and Up" ha/
oJ]'fr indicates an aliphatic group or an aromatic 'S group, at least one of which has a double bond that can be dimerized or polymerized by light or radiation, and the rest may be the same or different. You can leave it there. ) It is an object of the present invention to obtain an innovative heat-resistant photosensitive material that has excellent storage stability and a simple manufacturing process, which contains a polyimide precursor obtained by reacting a heptalylated diamine represented by the following formula.

The present invention will be explained in detail below.

The polyimide precursor of the present invention can be obtained by preparing a tetracarboxylic dianhydride represented by the general formula CD and a silylated diamyl y represented by the general formula (If) in approximately equimolar amounts and reacting them in an organic polar solvent at a low temperature. Specific examples of the tetracarboxylic dianhydride represented by the general formula (1) in the present invention include pyromellitic dianhydride (PMDA), j,≠.

3', Hiro'-benzophenone tetracarboxylic dianhydride (BTDA), /, II, j, ? -su7talentetracarboxylic dianhydride, J, J, t, ? -su7talentetracarboxylic dianhydride, /, 2. j, 6-su7talentetate dicarboxylic dianhydride, 3.3', Hiro, Hiro'-diphenyltetracarboxylic dianhydride, 2. J,! , 31-
Diphenyltetracarboxylic dianhydride, λ, 3°Jl,
4L/-diphenyltetracarboxylic dianhydride, 2
-bis(j,tA-dicarboxyphenyl)propylene(ilk product, -2,2-bis[hiro-(3,≠-dicarboxyphenoxy)phenyl]propanihydride, co, 2
-bis[≠-[co,3-dicarboxyphenoxy]phenyl]propanihydride, bis(3,≠-dicarboxyphenyl)sulfone dianhydride, bis(3,≠-dicarboxyphenyl)ether dianhydride, bis (3,≠-dicarboxyphenyl)methane dianhydride and perylene-3,
Examples of the dianhydride include dianhydride, /θ-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, and mixtures thereof can also be used.

- The silylated diamine represented by the formula (It) can be obtained by a known condensation reaction.

For example, it can be obtained by reaction of the corresponding diamine H2N-R2-NH2 with 7-rehydrogenhydrogenide (HX) (for example, J
, Polym, Sci, , part B, 10
79 (/ri6≠)) Specific examples of corresponding diamines include m- and p-phenylenediamine, ≠, ≠l- and 3,3'-diaminobiphenyl, ≠, Hiro'- and 3,3'. -Diaminodiphenyl ale, ≠, 4c'- and 3,3'-diaminodiphenylmethane, Sushi Hiroshi'- and 3,3'-diaminodiphenylsulfone, ≠,! I
'- and 3,3'-thiodianiline, bis-(4t-
aminophenyl)bis(trifluoromethyl)methane,
Hiro, ≠′-diaminobenzophenone, /, j-diaminonaphthalene, bis-(Hiro-aminophenyl)-dimethylsilane, bis-(4=-aminophenyl)-diethylsilane, bis-(4L-aminophenyl)-diphenylsilane , bis-(4L-aminophenyloxy)-dimethylsilane, bis-(hiro-aminophenyl)-ethylphosphine oxide, N-[bis-(≠-aminophenyl)
)-N-methylamine, N-(bis-(p-7minophenyl))-N-phenylamine, Hiroshi, 3'-methylenebis-(o-chloroaniline), ≠, ≠'-methylenebis-(j-methyl aniline), Sapphiro'-methylenebis-(
coethylaniline), ≠, 4”-methylenebis-(2
-methoxyaniline),! , Jr'-methylenebis-(
2-7 minophenol), +, p'-methylenebis-(
2-methylaniline), ≠, Hiro'-oxybis-(-1methoxyaniline), "+≠'-oxybis-(2-chloroaniline)%'l"-oxybis-(2-aminephenol), ≠, μ' -Thiobis-(2-methylaniline), ≠, φ′-thiobis-(2-methoxyaniline)
,<c,e'-thiobis-(2-roloaniline), Hiro, Hiro'-sulfonylbis-(x-methylaniline),"
+ Hiro'-sulfonyl bis(2-ethoxyaniline),
≠, ≠'-sulfonylbis-<2-1'loroaniline)
, s, j'-sulfonylbis-(2-aminophenol), 3,3'-dimethyl-Hiroshi, ≠'-diaminobenzophenone, ! , 3'-Dimethoxy-Fadzin'-Diaminobenzophenone, J,! '-dichloro-tag ψ'-diaminobentzphenone, Hiroshi, 4"-oxydianiline, ≠, 4L
'-Isopropylidene dianiline, 3,3'-dichlorobenzidine, J,! '−, G. Lupentidine, 3°3
'-Dimethoxybenzidine, ! , 3'-dicarboxypentidine, diaminotoluene, IA, Hiro'-methylenebis-(3-carboxyaniline) and various esters thereof,! -amino/-(≠-aminophenyl) -/, 3. j -trimethylindane and 6-
Amino-/-(≠'-aminophenyl)-/, 3.3
- Trimethylindane is mentioned.

At least one of R8 and R8 is a group having a double bond that can be converted or polymerized by light or radiation, and the remaining group is at least one group selected from an aromatic group or an aliphatic group. It is what is shown.

A specific example of a group having a double bond that can be converted or polymerized by light or radiation is CH3 CH, =CC0NRCH2CH2-1C)! ! =CHC
0NHCH,CH,-101(2=CH000CH,(
R2-1CE2=CHCOOC1'12CH, CH2-
Examples include 1OU.

In addition, aliphatic groups include alkyl groups such as methyl, ethyl, ]'robyl, and cycloalkyl groups such as cyclohexyl//l groups, and aromatic groups include aryl groups such as phenyl and tolyl, and arylalkyl groups such as benzyl. Examples include groups. These R3~Ha may be different, but usually R
3. R4, R5 and R6, R1, R8 have the same corresponding groups.

Specific examples of organic polar solvents used include N, N-
Dimethylacetamide, N,N-diethylacetamide, N,N-di-n-propylacetamide, N,N
-diethylpropionamide, N.

Carvone such as N-diethylpropionamide, N,N-di-n-propylpropionamide, N,N-dimethylbutanamide, N,N-diethylbutanamide, N,N-di-n-propylbutanamide, etc. N-substituted amides of acids,
Amides of carboxylic acids and cyclic amines such as N-acetylpyrrolidine, N-propionylpyrrolidine, N-butyrylpyrrolidine, N-methyl-pyrrolidone,
N-ethyl-2-pyrrolidone, N-methylco2
J)", N-substituted cyclic amides such as N-ethyl-2-piperitone, N-methyl-e-caprolactam, N-ethyl-g-caprolactam, N, N, N',
Examples include N-[1-substituted urea compounds such as N'-tetramethylurea, N,N'-dimethylethyleneurea, and N,N'-dimethylpropyleneurea.

A specific method for producing the polyimide precursor that is the object of the present invention by reacting tetracarboxylic dianhydride and silylated diamine in such a solvent is the usual reaction of tetracarboxylic dianhydride and diamine. There is no particular difference. Namely, first.

After the aromatic diamine is fully dissolved in a solvent at room temperature or at room temperature, depending on the case, cooling, then heating at room temperature or below, and at room temperature or above, the solution is heated to a temperature of 60°C or lower, and in some cases, 0°C or lower. After cooling, the tetracarboxylic dianhydride is added while stirring the solution to carry out the reaction. The reaction occurs immediately and exotherm is observed, and the viscosity of the reactant also increases. The reaction usually completes in 7 to 244 hours. The contribution of polyimide precursor in the resulting solution is usually 5 to 20% by weight. After the reaction is completed, the reaction solution is treated with water, acetone, alcohol, etc., and taken out from the polymer 1j reactant system. Furthermore, a polyimide precursor can be obtained by thoroughly washing with water, acetone, alcohol, etc., and vacuum drying at a temperature of 100° C. or lower.

The intrinsic viscosity of the obtained polyimide precursor was 0. /~s, O
dl/? It is desirable that If it is smaller than 0.7 dllf, film forming properties will be poor, and if it is larger than j, Odt/f, there will be problems with solubility.

The obtained polyimide precursor is used as a heat-resistant photosensitive material by dissolving it in the same organic polar solvent as used in the reaction described above, usually at a concentration of about 5 to -0% by weight. Depending on the purpose, the reaction solution may be used as it is.

If necessary, the photosensitive polyimide precursor solution may be sensitized with other copolymer monomers such as monomaleimide to the extent that heat resistance is not impaired, and further with sensitizing agents such as Michler's ketone and 44,4L'-bis(diethylamino)benzophenol. Agents etc.
0, / ~ / θ weight% (to polymer) is added, coated on a glass, ceramic, or silicon substrate, and after drying, radiation such as ultraviolet rays #i! By irradiating the polymer, it is possible to make the polymer insoluble in the solvent. If a suitable mask is used during ultraviolet irradiation, a polyimide precursor coating with an arbitrary pattern can be obtained. The sensitizer has no effect unless it is 0.7 weight or more based on the polymer, and if it is added in an amount of 10 weight or more, the heat resistance of the resulting film decreases.

Another feature of the present invention is that by heating the polyimide precursor, the photo-crosslinked portion is volatilized and scattered, and the polyimide structure is entirely formed by intramolecular ring closure. It is preferable to heat to 20θ°C or higher in order to volatilize the imidization and photocrosslinking parts.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples unless the gist thereof is exceeded.

Example/ Under nitrogen gas atmosphere! ,≦♂9y (10mzO1) N + N'-bis(methacryloxydimethylsilyl)
-p, p'-diaminodiphenyl ether at 70-〇N
-Methyl-copyrrolidone (hereinafter abbreviated as NMP)
Dissolve. After dissolving, pyromellitic dianhydride, //
/P(/θmmol) was added at once. The reaction was carried out under stirring at room temperature for 5 hours to obtain a highly viscous polyimide precursor solution. The lt of the polyimide precursor in solution was 70% by weight. This polyimide precursor has a temperature of 0.0% at 30°C. ! t/
The intrinsic viscosity measured in NMP solution of dt is /, Odt/f
Met.

After adding 2 parts by weight of Michler's ketone (relative to the polyimide precursor) as a sensitizer to the polyiide precursor solution, it was spin-coded onto a glass plate, and then ? After drying at θ℃ for 7 hours, it was exposed for 7 minutes through a contact mask using a high-pressure mercury lamp from J″OOOW, and then developed in dimethylacetamide for 7 minutes to obtain a clear relief structure. Heat treatment was performed for 3θ minutes to obtain a relief pattern of heat-resistant polyimide.

〔Effect of the invention〕

The heat-resistant photosensitive material according to the present invention has excellent storage stability and heat resistance, is easy to manufacture, and is useful as a variety of semiconductor coating materials.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (7 others)

Claims (1)

[Claims] 1) Tetracarboxylic dianhydride represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1 represents a tetravalent organic group) and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [II] (In the formula, R^2 represents a divalent organic group, R^3, R^4, R^5, R^6, R^7 and R^8 represent a monovalent aliphatic group or an aromatic group, at least one is a group having a double bond that can be dimerized or polymerized by light or radiation, and the rest are the same and ) A heat-resistant photosensitive material containing a polyimide precursor obtained by reacting a silylated diamine represented by the following.