JPS62184055A - Polyamic acid composition - Google Patents

Abstract

PURPOSE:To provide a polyamic acid compsn. which readily gives a polyimide membrane having good adhesion to substrates, a light-screening membrane having a high light-screening property, etc., containing a polyamic acid and a light absorber. CONSTITUTION:A polyamic acid of the formula (wherein R1 is a bivalent org. group and R2 is a tetravalent org. group) is blended with a light absorber to obtain the desired polyamic acid compsn. As the light absorber, a black dye (e.g., Direct Deep Black XA) and an infrared absorber [e.g., PA1006, (a product of Mitsui Toatsu Kagaku K.K.)] are used. 1-200pts.wt. black dye and 0.1-50 pts.wt. infrared absorber are used per 100pts.wt. polyamic acid. The resulting polyamic acid compsn. is dissolved in an org. solvent (e.g., N,N'- dimethylformamide). The soln. is applied to a substrate and heat-treated to obtain a polyimide membrane.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to polyamic acid compositions.

[Conventional technology]

Polyimide, which has not only electrical insulation properties but also excellent heat resistance, has been used as a material for insulating films and pasteboard films for solid-state devices, and as an interlayer insulating material for semiconductor integrated circuits. in general.

The polyimide film is a precursor polyamide fI2.1-f
It is formed by converting polyamic acid into polyimide by applying fi cloth and heat treatment.

On the other hand, when providing a light shielding film on a part of a device that needs to be shielded from incident light, especially transparent, a method is known in which it is formed by turning an evaporated film of aluminum, chromium, or the like. This method will be explained in detail below.

Some of the semiconductor elements incorporated in devices where transparency is important, such as liquid crystal display elements, have a function that deteriorates due to incident light from the outside; In order to achieve this, when a deposited film is used to shield incident light, it is necessary to insulate the semiconductor portion and the aluminum deposited film, and for this purpose an insulating film must be provided between them.

In order to form a light shielding film, a film of aluminum must be formed on the insulating film by vapor deposition, and then photo-etching must be performed. in this way.

This has the disadvantage that the manufacturing process tends to be complicated, which increases costs.

An invention described in Japanese Unexamined Patent Application Publication No. 17422/1983 has been made to solve the above-mentioned problems. In this invention, a dyed resin layer is provided as a light shielding film, but the resin layer is first formed on the element, and a mask formed by photoetching is provided at a predetermined location before dyeing. The dyeing density is low and it is impossible to absorb and block incident light sufficiently. Furthermore, since the resin used is soluble in water, a water-resistant insolubilizing agent such as highly toxic ammonium dichromate must be used.

It has drawbacks such as poor heat resistance of resins such as polyvinyl alcohol.

[Problem that the invention seeks to solve]

As mentioned above, polyimide is used as an insulating film for solid-state devices, but the adhesion between the polyimide film and solid-state devices is poor, so 7-minosilane is added to polyamic acid, which is the precursor of the polyimide film.

By adding a silane coupling agent such as epoxy silane or vinyl silane and a titanate coupling agent, the adhesion to the substrate is improved. However, since such a coupling agent is expensive, it is one of the factors that increases the cost when using a polyimide film as an insulating film.

On the other hand, when a dyed resin layer is used as the light shielding film as in the invention described in JP-A-60-17422, there is a drawback that the light shielding property is low.

The present invention has been made in view of the above-mentioned problems, and a first object thereof is to provide a polyamic acid composition that serves as a precursor for a polyimide film that has good adhesion to a substrate.

A second object of the present invention is to provide a polyamic acid composition that can be formed by a simple method and serves as a precursor for a light-shielding film having high light-shielding properties.

[Means and effects for solving problem 1] The present invention is a polyamic acid composition characterized by containing a polyamic acid and a light absorber.

The polyamic acid in the present invention is a polymer consisting of repeating structural sites of the following formula (wherein R1 represents a divalent organic group and R2 represents a tetravalent organic group). This polymer is usually produced by polycondensation of a diamino compound and a tetracarboxylic dianhydride.

Specific examples of diamino compounds include 1m-phenylenediamine, aji-phenylenediamine, 2,4-tolylenediamine% 3,3'-diaminodiphenyl ether, 4
, 4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone,
3.4'-') aminodiphenyl sulfone, 3.3
'-9 aminodiphenylmethane.

s, C-J aminodiphenylmethane, 4.4'-diaminodiphenylmethane, 4.4'-diaminodiphenyl sulfide, 3.3'diaminodiphenyl ketone, 3.4
'-Diamino diphenyl ketone, 4.4'-diaminodiphenyl ketone, 2.2'-''su(m-aminophenyl)propane, l, 3-his(m-aminophenoxy)benzene, 1,3-bis(? φ-aminophenoxy)benzene, 1,4-bis! (◆-aminophenoxy)benzene, 4-methyl? -2,4-bis(-aminophenyl)-1-pentene, 4-methyl-2,4- Bis(-monoaminophenyl)-
2-Pentene, J, 4-bis(2°2-dimethyl-lyaminopenzyl)benzene.

imino- or -fuynylene diamine, 1,5-diaminonaphthalene, 2,6-diamitunaphthalene.

4-Methyl-2,4-bis(calyx-aminophenyl)pentane, 5(or 6)-amino-1-(!-aminophenyl)-1,3,3-trimethylenedan, bis(4-7minophenyl) ) phosphine oxyto,
4.4'-diaminoazobenzene, 4.4'-diaminodiphenylurea, 4.4'-bis(4-7?2.2-bisCtk-(m-7minophenoxy)phenyl]furopane, 4.4'- Bis(≠-7minophenoxy)benzophenone, 4.4'-t'su(φ-aminophenoxy)diphenylsulfones4*4'-bis(?←aminophenoxy)diphenylsulfone, 4°?f'4'-bis[ φ-(2,2-dimethyl-C-7 minopenzyl)phenoxifbenzophenone 14,4'?-bisC4-(2,2-dimethyl-f-7 minopenzyl)phenoxyfudiphenyl sulfone, bis(4-aminophenyl) Dimethylsilane, bis(4-aminophenyl)tetramethyldisiloxane.

Bis(r-7minoprovir)tetramethylurea xane, 1,4-bis(r-7minoprovirdimethylsilyl)
Examples of these aromatic diamines include benzene, bis(4-7-minobutyl)tetramethyldisiloxane, bis(r-aminopropyl)tetraphenyldisiloxane, and bis(aminophenyl)tetramethyldisiloxane. Even if it is a compound in which the hydrogen atom of the aromatic nucleus is substituted with at least one substituent selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, a phenyl group, etc. good. Also, dimethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 1,2-bis(3'-
7minopropoxy)ethane, H2N-(CH2)3-
0-(CH,)2-0-(CH2)3-NH4I,
4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane s 1,4-bisaminomethylcyclohexane, 1,3-diaminocyclohexane, 4,4'-
Diaminodicyclohexylisopropane, 1,4-xylylenediamine% 2,6-diamitupyridine, 2,4
-diamino-8-) riazine, and the like.

In the present invention, a selected one from the group consisting of these
A species or two or more species may be used.

Specific examples of tetracarboxylic dianhydride include:

Pyromellitic dianhydride 3.3', 4.4'-benzophenonetetracarboxylic dianhydride, 2,3.3'.

4'-benzophenonetetracarboxylic dianhydride.

3.3',4.4'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methanidianhydride, 2,2-bis(3',4'-dicarboxyphenyl)propane dianhydride m-hydrate, bis(3,4-dicarboxyphenyl) ether m-hydrate, bis(3,4-dicarboxyphenyl)sulfone dianhydride.

Bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)tetramethyldisiloxane dianhydride, 1,4,5.8-naphthalenetetracarboxylic dianhydride, 2,3 , 6,7-naphthalenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, etc. Furthermore, the hydrogen atoms of these compounds are chlorine atom, 7, tsuso atom, bromine atom, methyl group, methoxy group. The compound may be substituted with at least one substituent selected from the group consisting of , cyano group, phenyl group, etc.5 In the present invention, one type selected from the group consisting of these Alternatively, two or more types are used.

Polyamic acid is usually produced in the presence of an organic solvent. Specific examples of organic solvents used at this time include N,N-dimethylformamide%N, N-dimethylacetamide, N-
Methyl-2-pyrrolidone, dimethyl sulfoxide, N-
Methyl-ε-caprolactam, sulfolane %N, N, N
', N'-tetramethylurea, and hexamethylphosphoramide.

The polyamic acid used in the present invention is prepared by combining a diamino compound and a tetracarboxylic dianhydride in the presence of an organic solvent in an excess or insufficient amount within the range of equimolar or 5 molar or less of the former relative to 1 reactant. It is produced by reacting under conditions of 20 to 70°C and reaction time of 10 minutes to 20 hours, and the resulting polyamic acid solution is mixed with water, methanol, ethanol, acetone,
It can also be used in the obtained state by injecting it into a poor solvent such as methyl ethyl ketone to precipitate the polymer, followed by washing and drying. The molecular weight of the polyamic acid is not particularly limited and may be as large as it can form a film that maintains sufficient physical strength when applied to a substrate.

The light absorber used in the polyamic acid composition of the present invention may be any of the following, such as a black dye, an infrared absorber, an ultraviolet absorber, etc. The black dye absorbs light in the wavelength range of 400 to 7001 m. Any kind of material is acceptable, as a specific example is Sumitomo Chemical's part name, Amyl Black F-
8BL, Sumilite Black GcC1nt, Direct Deep Black XA, Sumifix Black B, Aluminum Black F'-GL, Sumikalon Black 8-B
P.

Spirit Black No-920, Japanol Fast Black Dconc, Sumika Color Black PRk3
P365. Scar color black PR-gT364,
Sumika Color Black PR-sT-363, Oil Black Nα1. Made by Mitsui Toatsu Chemical Product name Mitsui PS Black B, Mitsui PS Black BG, Mitsui Black EX
-58, Mitsui Black EX-174, Taoka Kagaku ■ trade name Ooleosol Fast Black BLN, and the like. The present invention is not limited to these black dyes, but includes all known black dyes, and further uses two or more colored dyes to produce optical butylene dyes in the visible light range of 400 to 7QQnm. It also includes a method of forming a black or cross-shield.

In the present invention, the amount of black dye used is 100% of polyamic acid.
In the range of 1 to 200 parts by weight.

A range of 5 to 70 parts by weight is optimally preferred. If the amount of black dye used is less than 1 part by weight, the light shielding effect is small, and if it exceeds 200 parts by weight, the coating properties tend to be poor and the electrical performance tends to be poor.

The infrared absorber is not particularly limited as long as it absorbs light in a wavelength range of 700 to 1500 mm.

Specific examples include the FA series manufactured by Mitsui Toatsu Chemical Co., Ltd. In the present invention, the amount of infrared absorber used is 0.1 to 100 parts by weight of polyamic acid.
A range of 50 parts by weight, most preferably a range of 0.5 to 40 parts by weight. If the amount of infrared absorber used is less than 0.1 parts by weight, the light shielding effect will be small, and if it exceeds 50 parts by weight, the coating properties will be poor. electrical performance tends to be poor.

The ultraviolet absorber is not particularly limited as long as it absorbs light in the wavelength range of 4 to 4001 m. Hydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)penztriazole, 2-ethylhexyl-2-cyano-3
, 3'-diphenylacrylate and the like. In the present invention, the amount of ultraviolet absorber used is preferably in the range of 0.1 to 50 parts by weight, most preferably in the range of 0.5 to 40 parts by weight, based on 100 parts by weight of polyamic acid. If it is less than .1 part by weight, the light shielding effect is small.

If it exceeds 50 parts by weight, coating properties tend to be poor and Ml vapor performance tends to be poor.

In the present invention, the light absorber may be a black dye, an infrared absorber, or an ultraviolet absorber such as those described above, and may be used in combination of two or more types.

In the present invention, the polyamic acid composition is used in the form of a solution. The organic solvent used at this time is N,N-dimethylformamide, N,N-dimethylacetamide, N
-Methyl-2-pyrrolidone, dimethyl sulfoxide, N
-Methyl ε-caglolactam, sulfolane, N, N,
N'1. N'-tetramethylurea and hexamethylphosphoramide can be mentioned. Furthermore, methanol, ethanol, propatool, methyl ethyl ketone, acetone, toluene, xylene, methyl acetate, ethyl acetate, methyl cellosolve, cellosolve, butyl cellosolve can be used in these organic solvents as long as the polyamic acid does not precipitate.

It is also possible to add cellosolve acetate, butyl cellosolve acetate, and the like. The concentration of polyamic acid in the polyamic acid solution is 0.1 to 301J, 1ij
- H, preferably in the range of 0.5 to 20 f#-.

In the present invention, light shielding properties can be enhanced by further adding carbon powder, ultrafine silicon dioxide, ultrafine aluminum oxide, ultrafine titanium oxide, and the like.

Furthermore, in order to further improve the adhesion to the substrate, a silane coupling agent such as aminosilane, epoxysilane, vinylsilane or a titanate coupling agent may be added.

Example 1゜500rrL with stirring bar, thermometer, and dropping funnel set
Pyromellitic dianhydride 13.08 to the reaction flask at
7F.

3,3',4,4'-benzophenonetetracarboxylic dianhydride 19332F and N,N-dimethylacetate 7'mide 130 fvi - Stir thoroughly and reduce to 0.
Cooled to ℃. This suspension was then maintained at 0°C and 4.
4'-diaminodiphenyl ether IZO12? and 1,4-bis(rim-aminophenoxy)benzene17.
540v N, N'-dimethylacetamide 170
A solution dissolved in f was gradually added dropwise from the dropping funnel. After completion of the dropwise addition, stirring was continued for 3.5 hours at θ to 10°C to obtain a polyamic acid solution. This solution was applied uniformly onto a glass substrate using a spinner at 12000 RPM, dried at 130°C for 30 minutes to remove the solvent, and peeled off from the substrate for 25 minutes.
A polyimide film having a thickness of 1.1 μm was obtained by heat treatment at 0° C. for 1 hour. The spectral transmittance of this polyimide film is as shown by curve a in the F1 diagram. on the other hand.

To 10 l of the polyamic acid solution obtained above, add 4.7 liters of black dye Spirit Black NQ920 (product name manufactured by Sumitomo Chemical ■)
A black polyimide film with a thickness of 1.2 μm was prepared in the same way from a solution of 2. ! ! I got it. The spectral transmittance of this black polyimide film is shown in Figure 1, song #i! This is indicated by b.

Example 2 Pyromellitic dianhydride 15.268F, 3, 3'
, 4,4'-benzophenonetetracarboxylic dianhydride 9.667 Bird? A polyamic acid solution was obtained in the same manner as in Example 1 using 20.525 f of 4.4'-bis(1-aminophenoxy)biphenylphenyl]propane and 362 f of N,N-dimethylacetamide. Next, a polyimide film having a film thickness of 0.97 μm was obtained from this polyamic acid solution in the same manner as in Example, and its spectral transmittance was shown by curve a in FIG. On the other hand, black dye Mitsui PS Black B (trade name manufactured by Mitsui Toatsu Chemical ■) s, o was added to 100 f of the polyamic acid solution obtained above.
r and infrared absorber PA1006 (Mitsui Toatsu Chemical ■trade name) 1.3 ft-A film thickness of 1 was prepared in the same manner from the dissolved solution.
．． A 1 μm black polyimide film was obtained. The spectral transmittance of this black polyimide film is shown in curve Ilb in Figure 2.

Further, the above black polyamide solution was applied to a ceramic substrate on which a switching element (thin film transistor) array was formed in accordance with Example 1 and dried.

After heat treatment (imidization), only the switching element portion was coated with black polyimide using a known patterning method using photoresist, a liquid crystal display device using this substrate was constructed, and the driving characteristics of the switching element were evaluated. Even when irradiated with white light of 10,000 lux, a slight increase in current was observed when the gate voltage was below 0 volts, but this poses no problem in practice.

Example 3゜The polyamic acid solution obtained in Example 1 without blending the black dye was applied uniformly onto a glass substrate at 3000 RPM using a spinner, and then dried at 130°C for 30 minutes, at 200°C for 30 minutes, and at 250°C. After heat treatment for 1 hour, the film thickness was 0.
A 78 μm polyimide coating was obtained. Cut this film into the substrate with an NT cutter knife to a size of 2111 squares9. Transparent adhesive tape on its surface (Sumitomo 3M's product name: Uvia)
When the adhesion to the p-substrate was examined by gluing them together and peeling off the tape, all 100 substrates were peeled off from the substrate. On the other hand, an O polyimide film having a thickness of 0.82 μm was formed on a glass substrate using the same method as above from the polyamic acid solution containing the black dye obtained in Example 1, and the adhesion to the substrate was examined in the same manner as above.

Only 37 out of 100 pieces of the board were peeled off.

〔Effect of the invention〕

According to the present invention, it is possible to provide a polyamic acid composition that serves as a precursor for a polyimide film that has good adhesion to a substrate, can be formed by a simple method, and has a high light-shielding property. A polyamic acid composition that is a precursor of a shielding film can be provided.

[Brief explanation of drawings]

FIGS. 1 and 2 are diagrams for explaining the spectral transmission characteristics of a light-shielding polyimide composition obtained by heat-treating a light-shielding polyamic acid composition obtained according to the present invention. Agent Patent Attorney Noriyuki Ken Yudo Takehana Kikuo Kanaga (υShun No. 1)

Claims (4)

[Claims] (1) A polyamic acid composition containing a polyamic acid and a light absorber. (2) The polyamic acid composition according to claim 1, wherein the light absorbing agent is 1 to 200 parts by weight of a black dye based on 100 parts by weight of the polyamic acid. (3) The polyamic acid composition according to claim 1, wherein the light absorber is an infrared absorber in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyamic acid. (4) The light absorbing agent is 1 to 200 parts by weight of a black dye and 0.1 to 50 parts by weight of an infrared absorber, based on 100 parts by weight of polyamic acid. The polyamic acid composition according to item 2 or 3.