JPS606365B2 - Photosensitive polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel photosensitive polymer compositions and imaging thereof.

Conventionally, photosensitive polyimide is produced by adding about 1 to 5% dichromate to a polyamic acid intermediate, applying it to a substrate, irradiating it with light, developing it with Heji methylphoramide, and curing it at 250o0. [R.
E. Kerwin, etal, polymerEng&
Sci, 11(5) 426 (1971)].

However, the cured film obtained by this method has problems in terms of insulation reliability because dichromate remains in the cured film, and addition of dichromate makes the polymer unstable. Problems such as difficulty in handling have been addressed. In addition, the polyamic acid intermediate containing a photosensitive group is
A compound containing a photosensitive group, for example, [a mixture of two isomers shown in formula 11 and a mixture shown in formula '21] is synthesized by addition polycondensation (Hakamaseki Sho 49-115541)
.

During addition polycondensation, the compounds [1} and [2} must be purified as much as possible in order to increase the molecular weight of the polymer.

However, [1] is a low-viscosity mixture and is an acid chloride that dislikes water, making it difficult to purify and requiring many purification steps. Therefore, the material price for '1-' will increase. An object of the present invention is to provide a novel photosensitive polymer composition that solves the various problems mentioned above.

That is, the present invention relates to the general formula (wherein R is at least 2
R2 is a photosensitive group, X is H or Y-R2, Y is 10-, 1CH20-.

) 100 to 5% by weight of a diamine compound containing at least one photosensitive group represented by the formula 2N-R3-NH
2 (wherein R3 contains at least 2 carbon atoms)
It is a valent group, and the two amino groups are bonded to separate carbon atoms.

) A first compound consisting of 0 to 95% by weight of a diamine compound not containing at least one photosensitive group represented by the general formula (wherein R4 is a tetravalent group containing at least 4 carbon atoms); It is.

) and/or at least one tetracarboxylic dianhydride represented by the general formula (wherein R5 is a trivalent group containing at least 2 carbon atoms, and Z is a halogen atom).

) A photosensitive polyamic acid condensate (having an intrinsic viscosity of at least 0.1) with a compound consisting of at least one tricarboxylic acid anhydride monohalogen compound represented by ) and an organic polar solvent. It is a polymer composition. The production of the photosensitive polymer composition used in the present invention and the method of forming an image using the same are as follows.

The diamine component (first compound) and the acid anhydride component (second compound)
Either one of the compounds) is dissolved as well as possible in an organic polar solvent. The amount of organic polar solvent to be used is not particularly limited as long as it is sufficient to form a good polymerization system, but if it is used in an amount that contains 0.1% to 40% of the individual components, it will produce a high molecular weight polyamic acid intermediate. can be obtained. The reaction system is kept at a temperature of about 80° C. or lower, especially room temperature or lower, and the other components are added. The first compound used in the present invention contains 100 to 5% by weight of a diamine containing a photosensitive group, preferably 100 to 6% by weight, and 0 to 95% by weight of a diamine not containing a photosensitive group, preferably 0 to 4% by weight. 1st
It is preferable to use equivalent ratios of the compound and the second compound, but
It is also possible to use a slight excess of one of the two. When the amount of diamine containing a photosensitive group is 5% by weight or less, the sensitivity is poor, and when the amount of diamine not containing a photosensitive group is 95% or more, the solvent resistance of the exposed layer to a developer is poor. As the reaction continues, the viscosity of the reaction system gradually increases and photosensitive polyamic acid is produced.

It is essential that the photosensitive polyamic acid intermediate used in the composition of the invention has an intrinsic viscosity of at least 0.1, preferably from 0.3 to 5.0. Intrinsic viscosity is measured at 30 qo on a 0.5% by weight solution of polyamic acid in a suitable solvent. It is known that the intrinsic viscosity of a polymer has a direct relationship with its molecular weight. The photosensitive polymer used in the present invention has the general formula or, or, or, or (wherein, R is a trivalent or tetravalent group containing at least 2 carbon atoms, and R2 is Photosensitive group, Y is -○-
, one CH20- group, R3 is a divalent group containing at least 4 carbon atoms, R4 is a tetravalent group containing at least 4 carbon atoms, R5 is a group containing at least 2 carbon atoms trivalent, X is H or Y-R2, x is a positive integer of 0 to 95%, and n is a positive integer.

) is a novel photosensitive polyamic acid represented by: Next, a sensitizer is added to the photosensitive polyamic acid composition to prepare a coating solution.

The amount of sensitizer used is 0.5 to 2% by weight based on the polymer component.When adding colorants such as dyes and pigments, and stabilizers (e.g. hydroquinone, tertiary butylcatechol), The amount will be increased accordingly. The thus prepared polymer solution is applied onto a support and then dried.

Drying is carried out by applying heat, preferably at a temperature at which the photosensitive polyamic acid condensate is not cured by heat. Usually this temperature is below 100o0. Semiconductor wafers, ceramics, glass, etc. are used as the support base. The polymer film provided on the support is exposed to ultraviolet light through a mask, and processed in the following order: development, rinsing, and drying to form an image (pattern).

The light source for exposure is a suitable active light source, such as a 1 kilowatt high pressure mercury lamp. Exposure times and incident intensities are determined experimentally to obtain optimal results for a given mask and exposed film, but typically range from about 3 to 1 degrees of exposure time and from 3 to 50 milliwatts/c. The incident intensity of the fin gives satisfactory results. A polymerization solvent (for example, N-methyl-pyrrolidone, N,N-dimethylacetamide) is used as the developer, and acetone, ethanol, etc. can be added as appropriate. Examples of rinsing liquids include acetone and ethanol.
Solvents that are miscible with relatively low boiling point developers, such as toluene, give good results. There are 20 images created as above.
A final cured film is obtained by heat treatment at a temperature of 0 CO to 35,000.

When heating at 300°C or higher, create an inert gas atmosphere to prevent oxidation of the polymer.

An example of the above reaction is as shown in the following formula.

Examples of the diamine compound containing a photosensitive group used in the present invention include (where, Y represents -01, 1C ratio ○-, R2
etc.

). Examples of diamine compounds containing no photosensitive group include metaphenylene diamine, paraphenylene diamine, 4,4-diaminodiphenyl able,
4,4'-diaminodiphenyl pro/gun, 4,4-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzidine, 4,4-di(metaminophenoxy)diphene Nilsulfone, 4,4'-di(para-aminophenoxy)diphenylpropane, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diphenylamine, 3,3-dimethoxybenzidine, metaxylylene di amines, baraxylylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, etc.

Examples of carboxylic dianhydrides include pyromellitic acid;
2,2-bis(3,4-dicarboxyphenyl)propane; bis(3,4-dicarboxyphenyl) ether;
Bis(3,4-dicarboxyphenyl)sulfone; 3,
3',4,4-penzophenonetetracarboxylic acid; 3,
3,4,4-biphenyltetracarboxylic acid; 2,2',
3,3-biphenyltetracarboxylic acid; 1,2,5,6
-Naphthalenetetracarboxylic acid; 2,3,6,7-naphthalenetetracarboxylic acid; 3,4,9,10-berylenetetracarboxylic acid; 2,2,6,6-biphenyltetracarboxylic acid; 1,3- There are dianhydrides such as bis(3,4-dicarboxyphenyl)hexafluoropropane.

Examples of tricarboxylic anhydride monohalogen compounds include trimellitic anhydride; 2,3,6-naphthalenetricarboxylic anhydride; 2,3,5-naphthalenetricarboxylic anhydride: 2,2',3 -Biphenyltricarboxylic anhydride; 3,4,4-biphenyltricarboxylic anhydride; 2-(3,4-dicarboxyphenyl)-2-(3-carboxyphenylpropane anhydride; 1
, 2,4-naphthalenetricarboxylic anhydride; 1,4
, 5-naphthalenetricarboxylic anhydride: 2-(2,
3-dicarboxyphenyl)-2-(3-carboxyphenyl)propane anhydrous; 1-(2.3-dicarboxyphenyl)-1-(3-carpoxyphenyl)ethane anhydrous; 1- (3,4-dicarboxyphenyl)-1-(4-carboxyphenyl)ethane anhydride; (2
,5-dicarboxyphenyl)(2-carboxyphenyl)methane anhydride;1,2,5-benzenetricarboxylic anhydride;monocarboxylic acid halide of 3,3,4-tricarboxybenzophenone anhydride, etc. There is.
In the present invention, an inert solvent is used as the anhydrous organic polar solvent. This solvent is the first and second solvent.
It needs to be such that it dissolves all of the compound. Particularly preferred are those that have the effect of dissolving the polyamic acid intermediate produced. For example, N-
Methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone N,N-dimethylacetamide; N,N-
One or more of dimethylformamide; N,N-diethylformamide; dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, etc. may be used. In the present invention, dimethylsulfone; pyridine; tetramethylurea; and N-acetyl-2-pyrrolidone are also used as other anhydrous organic polar solvents.

These can be used alone or in combination, and benzene, toluene, nitrotoluene, chlorobenzene, cyclohexanone, etc. can also be added.

Examples of the sensitizer used in the present invention include anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, acetophenone, benzophenone, p, p '-Diaminobenzophenone, p,p'-dimethylaminobenzophenone,
pp-tetramethyldiaminobenzophenone (Michler's ketone) 2-nitrofluorene, 5-nitroacenaphane, 4-nitro-1-naphthylamine, N-acetyl-4-nitro-1-naphthylamine, p-nitroaniline, 2-chloro-4-nitroaniline , Picramid, 2
-tertiary butylanthraquinone, 1,2-benzanthraquinone, anthrone, 1,9-benzanthrone, 3
At least one of -methyl-1,3-diaza-1,9-penzoanthrone, dibenzalacetone, etc. is used.

Specific examples of the present invention will be described below.

Example 1 2.06 g (0.01 mol) of 3,5-diaminotryl methacrylate was placed in a four-necked flask equipped with a thermometer, a dosing machine, a calcium chloride tube, and a nitrogen inlet tube.
, 30 g of N-methyl-2-pyrrolidone was added, and the contents were thoroughly expanded and dissolved.

After the contents had dissolved, the flask was cooled on ice and 1.10 g (0.005 mol) of pyromellitic dianhydride, 3,3,4,4'-
Penzophenonetetracarboxylic dianhydride 1.61g (
0.005 mol) is gradually added. After addition, 15
Continue the reaction for 6 hours at qo. The intrinsic viscosity of this polymer was 1.23 (solvent N,N-dimethylacetamide 0.5%
The solution temperature was 3000, and the measurement conditions were the same below. next,
5% by weight of the sensitizer 2-methyl-anthraquinone was dissolved in the above polyamic acid composition prepared to have a viscosity of 60 p (25 x 0), spin coated onto a ceramic plate, dried at 80 oo for 3 minutes, and uniformly coated. A uniform coating film was obtained.

This coating film was fitted with a prescribed mask and irradiated with ultraviolet rays (illuminance: 2 plates W/c) for 5 minutes using a high-pressure mercury lamp. This ceramic plate was mixed with N-methyl-2-pyrrolidone and acetone in a 4:1 ratio.
Develop with a mixture of , rinse with acetone, 30 at 150oo
After drying for a few minutes, an image with sharp edges was obtained. Further, this image was heat-treated at 250° C. for 60 minutes to obtain a polyimide film. There was very little sag at the edge of the pattern during the heat treatment. Surface loss) Coating property: Uniform and non-uniform coating was rated as ○.

Image characteristics: Patterns with sharp green marks were marked as ○. Examples 2 to 8 Photosensitive polyamic acid solutions were prepared according to the method of Example 1 using the combinations of diamines and acid dianhydrides shown in Tables, and the intrinsic viscosity of each polymer was measured.
The samples were exposed to ultraviolet light using a predetermined mask, and then developed with the solvent used for each polymerization, and the degree of cutting of the film-formable image was determined, and the results shown in the table were obtained.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_1 is a tetravalent group containing at least two carbon atoms, R_2 is a photosensitive group, and X is H or Y- R_
2, Y is -O- or -CH_2O-. ) 100 to 5% by weight of a diamine compound containing at least one photosensitive group represented by the general formula H_2N-R_
3-NH_2 (wherein R_3 is a divalent group containing at least two carbon atoms, and the two amino groups are each bonded to separate carbon atoms.) A compound I consisting of 0 to 95% by weight of a diamine compound that does not contain at least one photosensitive group;
At least one type of tetracarboxylic dianhydride represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_4 is a tetravalent group containing at least 4 carbon atoms.) and/or General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_5 is a trivalent group containing at least 2 carbon atoms, and Z is a halogen atom.) 1. A photosensitive polymer composition comprising a photosensitive polyamic acid condensate (having an intrinsic viscosity of at least 0.1) with a II compound comprising a tricarboxylic anhydride monohalogen compound and an organic polar solvent.
2 A diamine compound containing a photosensitive group has ▲ a mathematical formula, a chemical formula, a table, etc. ▼ (However, R_1 in the formula is ▲ a ▲ has a mathematical formula, a chemical formula, a table, etc. ▼ and ▲ has a mathematical formula, a chemical formula, a table, etc. ▼ X_1 is -O-, X_2 is -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
-, Y represents a -CH_2O-, -O- group, R_2 represents a photosensitive group of ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
_6 represents alkylene or hydroxyalkylene, R_7 represents hydrogen or a methyl group, R_8 represents hydrogen or a cyano group, R_9 represents hydrogen, halogen, an alkyl group, or an alkoxy group, and X represents hydrogen or Y-R_2. ) The photosensitive polymer composition according to claim 1. 3 The diamine compound containing no photosensitive group is meta-phenylenediamine, para-phenylenediamine, benzidine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4
, 4'-di(para-phenoxy)diphenyl sulfone,
4,4'-di(meta-phenoxy)-diphenolsulfone, 2,2'-bis(para-diaminophenoxyphenyl)propane 4,4'-diaminodiphenyl ether-
The photosensitive polymer composition according to claim 1, which is a 3-carbonamide. 4 Tetracarboxylic dianhydride and/or tricarboxylic acid anhydride, monocarboxylic acid halide, pyromellitic dianhydride, 3,3',4,4-benzophenonetetracarboxylic dianhydride, 2,2 '-bis(3,4-
dicarboxyphenyl), propane dianhydride, 2,2'
-bis(3,4-dicarboxylphenyl), hexafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxylphenyl), ether dianhydride and/or trimellitic anhydride The photosensitive polymer composition according to claim 1, which is a monocarboxylic acid halide. 5 The organic polar solvent is N,N-dimethylacetamide, N
-Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylformamide, the photosensitive polymer composition according to claim 1.