JPS60135935A - Polymer composition sensitive to chemical ray - Google Patents

Abstract

PURPOSE:To obtain a polymer composition having superior sensitivity to chemical rays by blending a polymer having specified principal structural units with a compound dimerizable or polymerizable under chemical rays and contg. an unsatd. bond and an amino group or a quaternized salt thereof, an aromatic secondary or tertiary amino compound nonsensitive to chemical rays, and an o-quinonediazido compound. CONSTITUTION:This polymer composition is obtd. by blending a polymer having principal structural units represented by formula I (where R<1> is a ter- or quatervalent org. group having two or more carbon atoms, R2 is a bivalent org. group having two or more carbon atoms, R<3> is H or an ammonium ion, and n is 1 or 2) with a compound dimerizable or polymerizable under chemical rays and contg. an unsatd. bond and an amino group or a quaternized salt thereof, an aromatic secondary or tertiary amino compound nonsensitive to chemical rays, and an o- quinonediazido compound. In order to improve the heat resistance of the polyimide polymer, the polymer is preferably provided with a structure in which the bonding of R<1> to a carbonyl group in the principal chain of the polymer and the bonding of R<2> to an amido group in the principal chain of the polymer are carried out directly from an aromatic ring or an aromatic heterocyclic ring.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymer composition that is a precursor of a heat-resistant polymer and has excellent sensitivity to actinic radiation.

[Prior art]

As polyimide precursor compositions imparted with actinic radiation, particularly photosensitivity, the following ones developed for use in semiconductor insulating layers and/or oxidation layers are known.

(a) A composition comprising a polyamic acid and a 1 to 5 wt chromate (e.g. USP 562387D) (b
) A polyimide precursor composition into which a photosensitive group is introduced with an ester group having a structure as exemplified by the following formula (for example, USP 3.957
,512. usp4,040,8ro1).

(c) A composition in which a compound containing a carbon-carbon double bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation is added to polyamic acid (for example, JP-A-54-1999
145'794).

All of these are dissolved in a suitable organic solvent and applied to the substrate in the form of a varnish, and then dried to form a coating film.

After irradiating with ultraviolet rays through a suitable photomask, the film is developed and rinsed to obtain the desired relief pattern.

The patterned polyimide precursor film is further subjected to an appropriate heat treatment to form a heat-resistant polyimide film.

However, although such conventional compositions can be directly patterned with light, they have the following drawbacks. Namely.

In (a), the stability of the composition is extremely poor and it is necessary to use it immediately after mixing the polyamic acid and dichromic acid, which is a drawback in that it is a major restriction on industrial use. Furthermore, since inorganic ions exist in the patterned film, it is unsuitable for semiconductor applications where the presence of inorganic ions adversely affects reliability.

(+)), the polymer mainly contains photosensitive groups and 2
Polymerization is achieved by reacting a compound with an acid chloride group with a diamine, and the manufacturing process is not complicated, but the chlorine ions produced by dehydrochlorination remain in the film, making it reliable for semiconductor applications. It could have a negative impact on sexuality.

The materials listed in (C) are materials that have improved these drawbacks, but even in these materials, the sensitivity is still only several hundred Jm/m.
cm", which is insufficient for processing with exposure equipment commonly used in the semiconductor industry.

[Purpose of the invention]

The present invention eliminates the drawbacks of the prior art described above.

It is an object of the present invention to provide a polymer composition having excellent sensitivity to actinic radiation as a precursor for a heat-resistant polymer.

[Structure of the invention]

In order to achieve the above object, the present invention has the following configuration.

Group (a) A polymer whose main component is the structural unit CII represented by the general formula - A divalent organic group having at least 2 or more carbon atoms.

R1 represents hydrogen or ammonium ion.

n is 1-4:, or 2).

(b) A compound (I['
l and.

(c) With an aromatic secondary or 6th class amino compound [■] which is insensitive to actinic radiation.

(d) An actinic radiation-sensitive polymer composition comprising an orthoquinone diazide compound [: IV ].

A polymer having the structural unit [I] in the present invention (hereinafter referred to as
What is a polyimide polymer precursor?

It has a structure represented by the above general formula, and has a diimide ring or other cyclic structure formed by heating or a suitable catalyst. It can be used as a polymer (hereinafter referred to as polyimide polymer).

In the above structural unit [l], R1 is a hexavalent or tetravalent organic group having at least two or more carbon atoms. In view of the heat resistance of the polyimide polymer, R' preferably has a structure in which the bond to the carbonyl group in the main chain of the polymer is directly formed from an aromatic ring or an aromatic heterocycle. Therefore, R1 contains an aromatic ring or an aromatic heterocycle,
And a trivalent or tetravalent group having 6 to 30 carbon atoms is preferred.

More preferable specific examples of R1 include:

CI(,CF.

(In the formula, the bond represents a bond with the carbonyl group of the polymer main chain, and the carboxyl group is located at the ortho position to the bond; however, this bond is not shown in the above structural formula).

Examples include, but are not limited to, the following.

Further, in the polymer having the structural unit CI), 9R' may be composed of only one of these types.

A copolymer composed of two or more types may also be used.

What is particularly desirable as R1?

(However, the definition of the bond in the formula is the same as above).

In the above structural unit CI), R2 is a divalent organic group having at least two or more carbon atoms, but from the viewpoint of heat resistance when used as a polyimide polymer, the bond with the amide group of the polymer main chain is Those having a structure directly formed from an aromatic ring or an aromatic heterocycle are preferred. Therefore, R2 contains an aromatic ring or an aromatic heterocycle and has 6 carbon atoms.
-3o divalent groups are preferred.

Preferred specific examples of R2 include:

O CH.

CH,,CH.

In formula C, the bond represents a bond with an amide group in the main chain). Further, these may have a nuclear substituent such as an amino group, an amide group, a carboxyl group, a sulfonamide group, etc., within a range that does not adversely affect the heat resistance of the polyimide polymer. Particularly preferred examples of those having these nuclear substituents include:

In the polymer having the structural unit [I], R2 may be composed of only one type among these, or may be a copolymer composed of two or more types.

Furthermore, in order to improve the adhesiveness of the polyimide polymer, it is also possible to copolymerize an aliphatic group having a siloxane structure as R2 within a range that does not reduce the heat resistance. CHCH as a preferred example.

Pyromellitic dianhydride and 4,4'-diaminodiphenyl ether.

Pyromellitic dianhydride and 3.3/, 4.4/-
Benzophenone tetracarboxylic acid and 4,41-diaminodiphenyl ether.

3, 3/, 4.4/-benzophenone tetracarboxylic dianhydride and 4+4'-diaminodiphenyl ether.

3, 3/, 4.4/-biphenyltetracarboxylic dianhydride, 4.4/-diaminodiphenyl ether.

3,6',4.4r-biphenyltetracarboxylic dianhydride and 3.3/,4.4/-penzophenonetetracarboxylic dianhydride and 4+4'-diaminodiphenyl ether.

Pyromellitic dianhydride and 6,3'-diaminodiphenylsulfone.

6. pyromellitic dianhydride and 6da,4,4'-benzophenonetetracarboxylic dianhydride; Dar (or 4
．． 4/-) diaminodiphenylsulfone.

5,3', 4,4'-benzophenone tetracarboxylic dianhydride and 3.3/-(or 4,4'-)diaminodiphenylsulfone.

Ro, Ot, 4.4t-biphenyltetracarboxylic dianhydride Toro3/ (or 4.4/ -) diaminodiphenylsulfone.

3, 3/, 4.4/-biphenyltetracarboxylic dianhydride and 3.3/, 4.4/-benzophenone tetracarboxylic acid and i, 3/ - (or 4.4/
-,) diaminodiphenylsulfone.

Pyromellitic dianhydride, 4,41-diaminodiphenyl ether and bis(3-aminopropyl)tetramethyldisiloxane.

Pyromellitic dianhydride and 3.3', 4.4/-
Benzophenone tetracarboxylic dianhydride and 4.4'-
Diaminodiphenyl ether and bis(3-aminopropyl)tetramethyldisiloxane.

6. Filter, 4.4t-benzophenone tetracarboxylic dianhydride, 4.4'-diaminodiphenyl ether and bis(6-aminopropyl)tetramethyldisiloxane.

3,3/,4.4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether and bis(6-aminopropyl)tetramethyldisiloxane.

3,3/,4.4/-biphenyltetracarboxylic dianhydride and 3.3/,4.4/-benzophenonetetracarboxylic acid dianhydride and 4,41-diaminodiphenyl ether and bis(6-aminopropyl) Tetramethyldisiloxane.

Pyromellitic dianhydride and 3.3/- (or 4.4t
-) diaminodiphenylsulfone and bis(6-aminopropyl)tetramethyldisiloxane.

Pyromellitic dianhydride and 3.3', 4.4'-
Hensiphenotetracarboxylic dianhydride and 3,3/-
(or 4,4/-)diaminodiphenylsulfone and bis(3-aminopropyl)tetramethyldisiloxane.

3/, 4.4'-benzophenonetetracarboxylic dianhydride and 3.3'-(or 4.4/-)diaminodiphenylsulfone and bis(3-aminopropyl)
Tetramethyldisiloxane.

Ro, da, 4,4/-biphenyltetracarboxylic dianhydride! = 3.3/-(or 4.4/-)diaminodiphenylsulfone and bis(6-aminopropyl)
Tetramethyldisiloxane.

Ro, Ro/, 44/-biphenyltetracarboxylic dianhydride and 6.6',4,4'-benzophenonetetracarboxylic dianhydride and 3.3/- (or 4.4/-)
Polyamic acid synthesized from diaminodiphenylsulfone, bis(6-aminopropyl)tetramethyldisiloxane, etc. is preferably used.

A polymer whose main component is structural unit [I] is 9 structural units [
I], or may be a copolymer with other structural units. 11 used in copolymerization
The type and amount of the four-structured units are typically exemplified by the heat resistance of the polyimide polymer obtained by the final heat treatment, but are not limited thereto.

Compound (II) containing an unsaturated bond and an amine group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation is a compound containing a carbon-carbon double bond and an amine group or a quaternized salt thereof in one molecule. It is a compound containing an amino group.

In the following general formula [A] R', R4 is hydrogen or a phenyl group, R5 is hydrogen or a lower methyl group having 1 to 2 carbon atoms, R6 is a substituted or unsubstituted hydrocarbon group having 2 to 2 carbon atoms, R" and R" each represent a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms).

General formula [E] (where R7 represents an unsubstituted or substituted alkyl group having 1 to 2 carbon atoms).

General formula [C] R1゜(CH,=C-CH1+N-I() [C] (where 9R10 represents hydrogen or a methyl group.

n+1 = 3, n = 1 to 5) or their quaternized salts are preferably used.

As a preferred specific example CH,=CH-CH,NH2.

CH.

CH,=C-CH,NH,.

(CH,=CH-CH3), NH Examples include, but are not limited to, the following.

From the viewpoint of actinic radiation sensitivity, amino compounds having an acrylic or methacrylic group as an unsaturated group are particularly desirable.

In the case of a compound in which the amino group is not quaternized, it is preferable to combine the structural unit [I] with one in which R' is hydrogen.

In the case of compounds in which the amino group is quaternized, the structural unit C
It is desirable that R″ in I) be combined with that of ammonia/ion.

Compound CII) is 005 equivalent or more of all carboxyl groups (or salts thereof) of the polymer mainly composed of structural unit [I],
Preferably, it is mixed with the polymer in an amount of 3 equivalents or more and 2 times the equivalent or less.

If it is outside this range, there is a risk that the sensitivity to actinic radiation will deteriorate (9) or that the allowable range of development conditions such as development time and temperature will be narrowed, so care must be taken.

9 as a monomer that can be copolymerized with the compound [■].
For example, it is preferable to use monomaleimide, polymaleimide, or a combination of substituted substances thereof, since the sensitivity to actinic radiation is improved.

Actinic radiation-insensitive aromatic secondary or 6th-class amino compounds 14] are compounds that cause direct chemical changes (1), such as photochemical changes, due to actinic radiation at an irradiation dose sufficient to achieve the purpose of the present invention. It is made with a compound that does not have any Examples of such compounds include unsaturated bonds that can be easily dimerized or polymerized by actinic radiation.

A ketonic carbonyl group conjugated to an aromatic nucleus with an amino group can naturally be said to be a compound that does not exist in the molecule. The actinic radiation-insensitive aromatic secondary or quaternary amine compound [■] according to the present invention has an aromatic nucleus and an amine group directly bonded to the aromatic nucleus, and at least one of the amine groups Refers to a compound in which hydrogen is replaced with a substituted or unsubstituted alkyl group.

The aromatic nucleus referred to here refers to benzene nucleus, naphthalene nucleus, etc. These aromatic nuclei include substituents such as alkyl groups, alkoxy groups, and halogen groups.

It may be substituted with a substituent that does not cause a photochemical change such as trimerization at the irradiation dose normally used for exposure of this type of photosensitive composition.

Further, it may be bonded to another substituted or unsubstituted aromatic nucleus via a simple divalent group such as -CH, - group, -so, - group, ÷ group. Normally carbon number is 6 to 60°, preferably 6
~15. The alkyl group bonded to the amine group may be chain-like.

Cyclic (oxygen in the ring) containing the nitrogen atom of the amino group.

may contain a heteroatom such as sulfur or nitrogen), and may have a polar substituent.

And usually has 1 to 12 carbon atoms. Preferably, those of 1 to B are used.

Preferred specific examples of the amino compound CI) include N
-phenylethylamine, N-phenyldiethylamine, N-phenyl-N-ethylbenzylamine, N-phenylmorpholine, 3-ethylamino-p-cresol,
N-phenyl-N, -(cyanoethyl)ethylamine, N-phenylethanolamine, N-phenyl-N
-Methylethanolamine, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine.

N-(,3-methylphenyl)jetanolamine.

N-(4-methylphenyl)jetanolamine.

Examples include N-phenyldiisopropazuramine.

Aromatic secondary compound having an amine group to which the above alkyl group is bonded
Of the primary or tertiary amino compounds, those having a polar substituent on the alkyl group are particularly preferred.Amino compounds having a hydroxyl group as a polar substituent, that is, those in which at least one hydrogen of the amino group is replaced by a hydroxyl group, are preferred. Most preferred are aromatic amino compounds substituted with an alkyl group.

Specifically, N-phenylethanolamine, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, N-(3-methylphenyl)jetanolamine, 'N-(4-methylphenyl)jetanolamine, etc. Can be mentioned.

It is desirable that the compound (1) be mixed in an amount of O11 based on the weight of the polymer containing the structural unit [■] as a main component, and preferably in an amount of 05 or more and 20 or less based on the weight of the polymer. It is best to mix them in the following proportions. If you deviate from this range, the sensitivity to actinic radiation may deteriorate, the development time may
Care must be taken because the allowable range of developing conditions such as temperature may be narrowed.

The orthoquinonediazide compound [■] is a compound containing one or more orthoquinonediazide groups in one molecule.

The orthoquinonediazide group is benzene-based.

Naphthalene type, quinoline type, etc. are used. Benzoquinone diazide or naphthoquinone diazide is preferably used, but (1,2)-naphthoquinone-(
2)-diazide group is particularly preferably used.

As the orthoquinonediazide compound CIV).

Usually, an orthoquinonediazide sulfonic acid amide compound consisting of the sulfonic acid derivative of orthoquinonediazide and an amino compound, or an orthoquinonediazide sulfonic acid ester consisting of a hydroxy compound is preferably used.

for example.

(1,2)-naphthoquinone-(2)-diazide-(4)
-sulfonic acid or.

(1,2)-naphthoquinone-(2)-diazide-(5)
- Sulfonic acid, ammonia, methylamine, ethanolamine, aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, 2,6-
Dihydroxyaniline.

2. A sulfonic acid amide compound consisting of an amino compound selected from 5-dihydroxyaniline, 0-amino-p-cresol, p-aminobenzoic acid, 3-amino-4-hydroxy-diphenyl, etc.

or.

and the naethoquinonediazide sulfonic acid derivative.

Ethylene glycol, glycerol, phenol.

A hydroxy compound selected from catechol, human 90 quinone, p-human 90 xybenzoic acid, p-hydroxybenzamide, p-hydroxybenzenesulfonamide, 2.3.4'-) hydroxybenzophenone, etc. Although the following sulfonic acid ester compounds are preferably used, the present invention is not limited thereto.

These orthoquinonediazide 9 sulfonic acid amide compounds or orthoquinonediazide sulfonic acid ester compounds are usually composed of an acid chloride of orthoquinonediazide sulfonic acid and an amino compound or.

Produced by condensation reaction of hydroxy compounds.

The orthoquinonediazide compound (IV) has the structural unit [
It is desirable to add 01 parts by weight or more to the weight of the polymer whose main component is I], and more preferably in a ratio of 05 parts to more than 60 parts by weight to the weight of the polymer. If it is out of this range, it may adversely affect the developability and stability of the composition, so care must be taken.

Only one type of compound [■] may be used, or two or more types may be used in combination.

One method for producing the composition of the present invention will be explained.

First, a diamine compound and an acid dianhydride are reacted in a solvent,
A polymer containing the structural unit [white] as the main component was obtained.

Next, compounds CI[], CHI) and [■] were added to this solution.
, can be manufactured by dissolving and blending other additives as necessary. In addition, as the above-mentioned polymer, a solid polyamic acid polymer or a polymer separated and purified from the solution after 9 reactions may be redissolved and used.

As the solvent used in the above production method, polar solvents are preferably used from the viewpoint of solubility of the polymer, and aprotic polar solvents are particularly suitable. As an aprotic polar solvent,
N-methyl-2-pyrrolidone, N,N-dimethylformamide I-,N,N-dimethylacetamide, dimethylsulfoxide.

Preferably used are hexamethylphosphorotriamide, t-butyrolactone, and the like.

As other additives, a sensitizer, a copolymer monomer, or an adhesion improver with the substrate may be included as long as the sensitivity and heat resistance are not significantly reduced.

Next, a method of using the composition of the present invention will be explained. The compositions of the present invention can be patterned using well-known microfabrication techniques using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Application methods include rotation coating using a spinner, spray coating using a spray coater, and dipping.

Means such as printing, roll coating, etc. are possible. The coating film thickness is the solid content concentration of the coating means 1 composition.

It can be adjusted by viscosity.

Examples of materials for the support to which the composition of the present invention is applied include metals, glass, semiconductors, metal oxide insulators (e.g.
Tie, Ta, O, Sin, etc.), silicon nitride, and the like.

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after heat treatment and the support, an adhesion aid may be used as appropriate.

As an adhesion aid, oxypropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane.

Organosilicon compounds such as γ-methacryloxypropyltrimethoxysilane, aluminum chelate compounds such as aluminum monoethylacetoacetate diimpropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), or titanium bis(acetylacetonate). A titanium chelate compound such as Nate) is preferably used.

Next, the composition of the present invention, which has become a coating film on the support, is irradiated with actinic radiation in a desired pattern. Examples of actinic radiation include X-rays, electron beams, ultraviolet rays, visible light, etc., but ultraviolet rays and short-wavelength visible rays, that is, wavelengths in the range of 300 nm to 500 nm are preferred.

Then, a sill relief pattern is obtained by dissolving and removing the unirradiated area with a developer. An appropriate developer is selected depending on the structure of the polymer.

The developing solution is N-methyl-2-pyrrolidone and N-acetyl-2-pyrrolidone, which are the solvents of this composition.

N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, etc. alone or in a composition of methanol, ethanol, inpropyl alcohol, water, methylcalpitol, ethylcalpitol, etc. It can be used as a mixed solution with a non-solvent of the product.Also, aqueous ammonia and other alkaline aqueous solutions can often be used.

For development, the above developer is sprayed onto the coating surface.

Alternatively, immerse it in a developer. Alternatively, it can be carried out by a method such as applying ultrasonic waves while being immersed.

The relief pattern formed by development.

It is then preferable to wash with a rinsing liquid.

The rinse solution is methanol, which has good miscibility with the developer.

Ethanol, isopropyl alcohol, butyl acetate, and the like are preferably used.

The relief pattern polymer obtained by the above treatment is a precursor of a heat-resistant polyimide polymer, and by heat treatment becomes a heat-resistant polymer having a diimide ring or other cyclic structure.

The degree of actinic radiation sensitivity (sensitivity) of the composition of the present invention is determined by measuring the gray scale (Kodak Photographic 5tep tablet) on the coating formed on the support substrate.
Light from a high-pressure mercury lamp was irradiated through the Nα221BTEPE).

Next, the film was developed and judged based on the number of layers that remained on the film under the minimum amount of light.

In the above gray scale, each time the number of stages increases by one stage, the amount of transmitted light decreases by 17.7FK of the previous stage. Therefore, the larger the number of stages, the higher the sensitivity.

The actinic radiation-sensitive polymer composition of the present invention can be used to form passivation films for semiconductors, interlayer insulating films for multilayer integrated circuits, interlayer insulating films for hybrid integrated circuits, solder shielding films for printed circuits, alignment films for liquid crystals, etc. It is offered to In addition, as a highly heat-resistant photoresist, it can be used for metal adhesion, printing, etching, etc.
Application to processes is also possible. It can be applied to other known uses of polyimide.

〔Effect of the invention〕

As described above, the present invention relates to a polymer having the structural unit [I] as a main component, and a compound containing an unsaturated bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation
), an aromatic node, a secondary or 6th class amino compound [■], and an orthoquinonediazide compound [I■] to form an actinic radiation-sensitive composition. The unexpected effect was that the sensitivity was significantly improved compared to the previous composition.

Note that the terms used in the present invention are defined as follows.

Heat resistance means that there is almost no blurring or thermal loss of the formed relief pattern even when heated at 200° C. for 1 hour in a nitrogen atmosphere.

Next, embodiments of the present invention will be described based on Examples.

Example 1 Diaminodiphenyl ether 68 gfN-methyl-2
- An amine bath solution was prepared by dissolving pyrotodone in 600 g. Benzophenone tetracarboxylic diacid anhydride 108g
was added and dispersed, and then reacted at 50°C for 6 hours to obtain a polymer solution (A) of 20 poise at 30°C.

40 g of solution (A) and 5.6 g of diethylaminoethyl methacrylate were mixed, and then 03 g of N-phenyldiethanolamine and (1,2)-naphthoquinone-
A solution of 03 g of (2)-diazide-(5)-sulfo(4'-hydroxy)anilide dissolved in 4.5 g of N-methylpyrrolidone was mixed and filtered for 175 minutes.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 80° C. for 1 hour to obtain a coating film of 5 μm. This coating is flat and even.

Moreover, it was in sufficient contact with the substrate.

Sensitivity was investigated using the gray scale method. Exposure was performed using a high pressure mercury lamp for 10 seconds. The intensity of the ultraviolet rays was 10 mW/cm'' in the wavelength range of 665 nm.Development was carried out using a mixed solvent of dimethylacetamide (5 parts) and methanol (2 parts), followed by washing with a rinse solution.

The minimum number of exposure steps at which the film remained, that is, the sensitivity was 11 steps.

Comparative Example 1 40 g of the polymer solution (A) obtained in Example 1 and Mihira.
Ketones and diethylaminoethyl methacrylate5.
A composition prepared by dissolving 6 g of N-methylpyrrolidone in 45 g of N-methylpyrrolidone was mixed and filtered and tested in the same manner as in Example 1. When the amount of Mihira Ketone was adjusted from 0.009 B to 0.9 g, the improvement in the sensitizing effect reached a plateau when approximately 0.2 g was added. The minimum number of exposure steps at which the film remained after development, that is, the sensitivity was 4 steps.

Example 2 40 g of the polymer solution (A) obtained in Example 1 and 5.6 g of dimethylamine ethyl methacrylate were mixed, and then 06 g of N-phenyldiethanolamine and (1,
2)-naphthoquinone-(2)-diazide-(5)-sulfo(4'-hydroxy)anilide" 0.2 g was added to N
- A solution dissolved in 5 g of methylhydrolidone was mixed and filtered.

A coating film was formed on a silicon wafer in the same manner as in Example 1, and then a striped pattern mask was placed on top of this coating film, exposed for 4 seconds in the same manner as in Example 1, and developed and rinsed. , a relief pattern with sharp edges was obtained. This pattern was heat treated with 3511MC for 30 minutes to obtain a heat resistant relief pattern. Even when this pattern was heat-treated at 200°C for 1 hour, there was no pattern blurring or thermal loss.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] (1) (a) A polymer whose main component is a structural unit [■] represented by the general formula %) (wherein R1 is a hexavalent or tetravalent organic compound having at least 2 or more carbon atoms) group, R' is a divalent organic group having at least 2 carbon atoms, R8 is hydrogen or ammonium ion, n is 1 or 2). (b) A compound [■] containing an unsaturated bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation. (c) an aromatic secondary or tertiary amine compound [■] that is insensitive to actinic radiation; (d) An actinic radiation-sensitive polymer composition comprising an orthoquinonediazide compound CIV.