JPS58160320A - Photopolymer composition - Google Patents

Abstract

PURPOSE:A photopolymer composition capable of forming films with good heat stability at a high sensitivity, prepared by mixing a specified polyamic acid with an amine compound. CONSTITUTION:100pts.wt. polymer consisting mainly of repeating units of formulaI(wherein R<1> is a trivalent or tetravalent organic group, R<2> is a vibalent organic group, M is H or an ammonium ion and n is 1 or 2), e.g., a polyamic acid prepared by reacting pyromellitic dianhydride with 4,4'-diaminodiphenyl ether, is blended with about 10-400pts.wt. amine compound of formula II (wherein R<3> and R<4> are each a lower alkyl, Z is a group of formula III, a group of formula IV, -CH2O- or -CH2NH-, p is 1-3 and q is 2-6), e.g., a compound of formula V. If necessary, a sensitizer (e.g., anthraquinone) may also be used.

Description

[Detailed description of the invention] The present invention is a novel photosensitive heat-resistant polymer.

TECHNICAL FIELD The present invention relates to polymer compositions.

Traditionally, photosensitive polymer compositions are heat-resistant polymers.

As a product, the following formula [110] shows a polymer whose main component is polyamide acid, which is a precursor of polyimide.

A carbon-1 carbon double bond and an amine group or a quaternized salt thereof that can be bilayered or polymerized by actinic radiation.

A mixture of compounds containing

(However, R5 is hydrogen or a thunyl group, R6 is hydrogen or a lower alkyl group, R7 is a substituted or unsubstituted hydrocarbon group, R
8 represents a substituted or unsubstituted alkyl group. )It has been known.

In order to form a coating film from the material of B1 in a varnish state, it is coated onto a substrate such as metal, glass, or semiconductor by means such as spinner rotation coating, dipping, or spray printing. It is necessary to remove the solvent present.

At that time, use.

The solvent that can be used is the solubility of polyamic acid.

N-methyl-2-pyrrolidone, dime.

tylacetamide, dimethyl sulfoxide, etc.

Aprotic polar solvents with high boiling points are mainly used, and it is difficult to remove these solvents and obtain a uniform coating film.

Therefore, it is necessary to heat it to at least 80"C or higher.

The photosensitizer also needs to be a material with excellent thermal stability. .

Moreover, as a matter of course, the photosensitizer has high sensitivity.

That's good.

However, among the conventionally known photosensitizers represented by the formula [nT], when R is 7 = nyl group and R6 is hydrogen, the thermal stability is excellent, but the sensitivity is several thousand m J/c, The sensitivity was extremely low and it was not suitable for practical use.

In addition, when /<' and R6 are both hydrogen, or when R5 is hydrogen and R is a methyl group, the thermal stability is poor in both cases.
When the film was dried by heating at a temperature of 80°C, the film hardened. After irradiation with ultraviolet rays, the unexposed areas were washed away with a developer, making it impossible to obtain a relief pattern.

The purpose of the present invention is to overcome the drawbacks of the prior art described above.

It has good thermal stability when made into a paint film.

An object of the present invention is to provide a highly sensitive photosensitive polymer composition.

This is the result of careful consideration to achieve the above objectives.

(α1 general formula [1) (However, in formula 1, R is a trivalent or tetravalent organic group, R2 is a divalent organic group, 1M represents hydrogen or ammonium ion, and n is 1 or 2.) A polymer whose main component is the repeating unit shown.

Ibl general formula CI+) group, P represents an integer from 1 to 3, and q represents an integer from 2 to 6. ) and an amine compound represented by

・　4　・ A sensitizer consisting of lCl and a sensitizer added as necessary.

The coating film of the polymer composition is better than that of the conventional method described above.

Thermal stability when closed is extremely good and high.

I found that sensitivity.

That is, we have discovered an effective method for imparting photosensitivity to polyamic acid by using an amine compound (formula ■) that is difficult to polymerize by heat and contains a double bond that is active against light as a photosensitizer. There are major features of the present invention.

The present invention has improved workability, particularly in forming a coating film, and has made it possible to form a positive image in a short time.

The materials used in the present invention will be explained below.

The polyamic acid represented by the general formula [I] can be converted into polyimide by heat treatment.

These polyimides have heat resistance. A polymer whose main component is a repeating unit represented by the general formula [I] may be one consisting only of a polyamic acid represented by the general formula [■],
It may also be a copolymer of this and other repeating units.

Examples of these include polyesteramic acid, polyhydrazideamic acid, and the like. The type and amount of repeating units used in the copolymerization are desirably selected within a range that does not significantly impair the heat resistance of the polyimide obtained by the final heat treatment. As for the heat resistance of the polyimide, it is desirable that the formed relief pattern is maintained even when heated at 300 to 400 V for 1 hour in a nitrogen atmosphere.

R1 and R2 in the general formula II) are preferably aromatic-containing organic groups or complex-containing organic groups from the viewpoint of heat resistance when formed into a polyimide. Examples of these are U, S, P, 3.

179, 614, U, S, P, 3.740,
505, as shown in Japanese Patent Publication No. 4B-2956. However, the material is not limited to these as long as it imparts heat resistance to polyimide.

Specifically, R1 is -0-, -■-〇-00-.　　.

−〇−co−■− (In the formula, the bond is with the carbonyl group of the polymer main chain.

represents a bond, and the carboxyl group pairs with the bond.

Examples include.

In addition, these have a negative effect on the heat resistance of polyimide.

Amino group, amide group, carbo group within the range that does not give.

It has a substituent such as a xyl group or a sulfonic acid group.

It's okay to be there. 1. ) In addition, polyamic acid represented by the general formula [■].

The preferred one is pyromellitic dianhydride.

and 4,4'-diaminodiphenyl ether, bimellitic dianhydride, and 5,5',4,4'-benzo.

Phenonetetracarboxylic dianhydride and 4,4-di.

Aminodiphenyl ether, pyromellitic dianhydride and 5,3,4,4-benzophenonetetracarboxylic acid and 4,4'-diaminodiphenyl ether and 4.
4-diaminodiphenyl ether-3-carbonamide, pyromellitic dianhydride and 5.5,4,4-benzophenonetetracarboxylic dianhydride, 4,4-diaminosyphenyl ether and bis(3-aminopropyl) Examples include polyamic acid derived from tetramethyldisiloxane.

As mentioned above, the polyamic acid represented by the general formula [I] is usually obtained by reacting a diamine compound with an acid dianhydride in an approximately equimolar amount. An aprotic polar solvent is preferably used from the viewpoint of solubility of the polyamic acid.

reactor. N-methyl-2-pyrrolidone, N,N-di,methane.

Chylformamide, N,N-dimethylacetamide,
Typical examples include dimethyl sulfoxide, 7v-acetyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolidinone.

It will be done.

Examples of the amine compound represented by the general formula [■] include the following.

The blending ratio of the amine compound is represented by general formula (1).

10 parts by weight or less and 400 parts by weight or less per 100 parts by weight of the polymer whose main component is a repeating unit.

However, it is used in an amount of 20 parts by weight or more and 200 parts by weight or less.

It is desirable to If it deviates from the above range, sensitivity may be insufficient or the film quality after development may be adversely affected.

A sensitizer may be appropriately added to the above composition for the purpose of improving sensitivity, but the amount added is at least 10 parts by weight based on the total weight of the polymer (1,) and the amine compound (II,). It is preferable to use them in the following proportions; deviations from this range will have an adverse effect on the developability and heat resistance of the polyimide final product.Sensitizers include anthraquinone, 2-methylanthraquinone, benzoquinone, and 1,2-naphthoquinone.

1.4-naphthoquinone, 1.2-benzoanthraquinone, benzophenone, p, p-dimethylbenzophenone, Mihiraketone, 2-nitrofluore 715-di) loacetinthene. 4-Nitro-1-naphthylamine, anthrone, 1,9-benzanthrone, sibenzalacetone, henzine ether, 4,4'-bis(diethylamino)pene.

Examples include siphenon, which can be used alone.

Alternatively, two or more types may be used in combination.

The photosensitive polymer composition according to the present invention has the above structure.

Used in the form of a bath solution with the ingredients dissolved in an appropriate organic bath agent.

However, the solvent used in this case is preferably an aprotic polar solvent from the viewpoint of solubility, such as A'-methyl-2-pyrrolidone, 7v-acetyl-2-pyrrolidone, and Iv-benzyl-2-pyrrolidone.

Examples include IV, N-dimethylformamide, IV, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, 7v-acetyl-ε-caprolactam, dimethylimidazolidinone, and the like. These may be used alone or in combination. The amount of solvent is determined by the polymer whose main component is a repeating unit represented by the general formula CD. When the total of the amine compound represented by the general formula (n) and the sensitizer is 100 parts by weight, it is preferable to use 100 parts by weight or more and less than 1,000 parts by weight, more preferably 200 parts by weight or less. Parts by weight or more 5. rloo It is preferable to use parts by weight or less, and if it deviates from this range, film formability will deteriorate.

have a negative impact on

In order to improve the adhesion between the coating film of the photosensitive polymer composition according to the present invention or the polyimide coating after heat curing and the supporting substrate, the supporting substrate may be appropriately treated with an adhesion promoter.

Support substrates include metal, glass, and semiconductors.

Metal oxide insulators (e.g. TiO2, Ta20g,
5in2), silicon nitride, etc.

The photosensitive polymer composition according to the present invention can be patterned using conventional microfabrication techniques. The present polymer composition can be applied to the support by means such as spin coating using a spinner, dipping, and spray printing, which can be selected as appropriate. The thickness of the coating film can be adjusted by adjusting the solid content concentration, viscosity, etc. of the varnish of the polymer composition using one coating means.

A relief 12 pattern is obtained by irradiating the photosensitive polymer composition of the present invention, which has become a coating film on a display substrate, with ultraviolet rays, and then dissolving and removing the unexposed portions with a developer. The light source is not limited to ultraviolet rays, but may also be visible light or radiation.

A-methyl-2-pyrrolidone is used as a developer.

A-acetyl-2-pyrrolidone, IV, IV-dimethylformamide, #, A'-dimethylacetamide.

Aprotic polar solvents such as dimethyl sulfoxide, hexamethylbosphortriamide, dimethylimidazolidinone, N-benzyl-2-pyrrolidone, 7V-acetyl-ε-caprolactam alone or methanol, ethanol, isopropyl alcohol, benzene, toluene It can be used as a mixture with a polyamic acid non-solvent such as xylene, methyl cellosolve, etc.

The relief pattern formed by development is then washed with a rinse solution to remove the developing solvent.

leave For the rinsing solution, a polyamic acid non-solvent with good miscibility with the developer is used, including methanol.

Suitable examples include ethanol, isopropyl alcohol, benzene, toluene, xylene, and methyl cellosolve.

The relief pattern polymer obtained by the above treatment is a precursor of polyimide,
By processing at a heating temperature selected from a range up to t, a relief pattern of a heat-resistant polymer having imide rings or other cyclic groups is obtained.

The present invention will be explained below by way of examples.

Example 1 Under nitrogen flow, 4.4'diaminosifenyl ether 1
aOy (0.5 mol) was dissolved in AI-methyl-2-pyrrolidone 1791 f to prepare an amine solution. Next, while keeping this solution at a temperature of about 15'C by water cooling, pyromellitic dianhydride + o9y (0,
5 mol) was added. After the addition was completed, the reaction was further carried out at 15υ for 3 hours to obtain a polyamic acid solution G4+ with a viscosity of 60 poise (30°C).

1.9 y (o, o+mol) of 2-(N,N-dimethylamine)propyl sorbate was dissolved in solution group 2Of, and then filtered under pressure using a filter with 1 μm pores.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 80 υ for 30 minutes to obtain a coating film with a thickness of 15 μm. This coating film was closely covered with a striped soda glass photomask and irradiated with ultraviolet light using a 500 F high pressure mercury lamp.

The intensity of ultraviolet rays on the exposed surface is 565 nm wavelength.
Met. Exposure ff1. A relief pattern was obtained by developing with a mixture of 4 volumes of A'-methyl-2-pyrrolidone and 1 volume of ethanol, and then washing with a rinse solution (ethanol). The change over time in the film thickness after development was measured, and when the sensitivity was defined as the amount by which the film thickness after development became 1/2 of the coating film thickness, the sensitivity was 120 mJ/crl. A relief pattern with sharp edges was obtained with a dose three times the sensitivity. No blurring of the pattern was observed even when this pattern was heated at 400° C. for 60 minutes.

Example 2 Polyamic acid solution obtained in Example 1 (,41201
Then, sorbic acid 2(N,A'-dimethylamine)propyl t9r (o, old mole) and Michler's ketone 051 were dissolved in a bath and then filtered under pressure using a filter with 1 μm pores.

, 15.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried for 80 minutes to obtain a coating film with a thickness of 1.5 μm. This coating film was closely covered with a striped soda glass photomask and irradiated with ultraviolet light using a 500 F high pressure mercury lamp. After exposure, it was developed with a mixture of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of ethanol, and then washed with ethanol to obtain a relief pattern. Sensitivity is IOD*//
i, and the resulting pattern is 400 kl! , 6
No blurring of the pattern was observed even after heating for 0 minutes.

Example 3 Polymer and amine were prepared in the same manner as in Example 1.2.

Experiments were carried out by changing the types of sensitizer and solvent. The mixing ratios of the materials are shown in Tables 1 and 2, N(L 3 to l@16), and the obtained results are shown in floors 3 to Nα16 of Table 6.

A photosensitive polymer composition formulated as shown in Table 1 and Table 2 (S) was applied to various substrates using a spinner, and then heated and dried at 80 tons for 30 minutes to form a coating film. The film was irradiated with ultraviolet rays using a 5-W high-pressure mercury lamp through a striped photomask, developed, rinsed, and heated at 350E for 1 hour.See Table 6.

Sensitivity is a value that normalizes the film thickness after development by the coating film thickness.

2 n with a dose (measured at 365n1n) that gives TE05
omJ44 or less is considered good, and 1 or more is bad.

did. Heat resistance: 350 E for 1 hour, 300-
A case where the weight loss was 1% or less after heating for C1 hour and the formed pattern did not become blurred was considered good, and a case where the formed pattern was not blurred was judged as poor.

(Cao・1-now chest 2 Table 6 In Table 3, those with poor sensitivity are listed in [I] above.

of an amine compound for a polymer of formula.

Due to the blending ratio, the range stated in the detailed invention section.

This was especially noticeable in those that deviated from the above. Also high.

3 to 1B all have thermal stability when made into coatings.

It was excellent.

Comparative Example 1 The experimental results obtained by the method according to Shige 1 above are shown below as a comparative example.

Polymer bath solution obtained in Example 1 (4120f, dimethylamine ethyl methacrylate) 1.6 t (o,
o + mol) was dissolved and filtered under pressure using a 5 μm pore filter.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 80 υ for 30 minutes to obtain a coating film with a thickness of 18 μm. This coating film was closely covered with a striped soda glass photomask and irradiated with ultraviolet light using a 500 F high pressure mercury lamp. After exposure, it was developed with a mixture of 4 volumes of N,IV-dimethylacetamide and 1 volume of ethanol, but the entire coating film became insoluble in the developing solvent, making it impossible to obtain a relief pattern.

There wasn't.

Comparative example 2゜ The same composition as Comparative Example 1 was dried at 70V for 30 minutes.

After that, ultraviolet rays were irradiated using the same procedure. After exposure, it was developed and then washed with ethanol to obtain a relief pattern. Sensitivity is 2.000 mJ/a1. Yes.

The sensitivity was lower than in any case of Example 1S18 of the present invention.

Comparative Example 3゜To the polymer solution obtained in Example 1 (, (12Of), 2.2 f of dimethylamine ethyl cinnamate (0,0+
ml) was dissolved and filtered under pressure using a 5 μm pore filter.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried for 80 t+ 50 minutes to obtain a coating film with a thickness of 21 μm. This coating film was tightly covered with a striped soda glass photomask and irradiated with ultraviolet rays using a 5 oor high pressure mercury lamp. After exposure, it was developed with a mixture of 4 volumes of 7v-methyl-2-pyrrolidone and 1 volume of ethanol, and then washed with ethanol to obtain a relief pattern. Sensitivity is 5.200" chrysanthemum.

1 The sensitivity was lower than in any of Examples 1 to 18 of the present invention.

0 Continuation of page 1 ■Applicant: Hitachi Chemical Co., Ltd. 2-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 1 156-

Claims (1)

[Claims] +a+General formula [1] (However, in formula 1, Noi1 is a trivalent or tetravalent organic group, R2゜ is a divalent organic group 1M is hydrogen or ammonium. n represents an ion. 1 or 2) as a main component. An amine compound represented by the general formula (n) 4 (P represents an integer from 1 to 3, and q represents an integer from 2 to 6). +7?1 A photosensitive polymer composition comprising a sensitizer added as necessary.