JPS59160140A - Polymer composition sensitive to chemical ray - Google Patents

Abstract

PURPOSE:To improve the sensitivity to chemical rays by blending a polymer consisting essentially of specified structural units with a compound polymerizable under chemical rays and a specified amino compound. CONSTITUTION:The titled composition is formed by blending a polymer consisting essentially of structural units represented by the formula with a compound dimerizable or polymerizable under chemical rays and having an unsatd. bond and an amino group or its quaternized salt and an aromatic secondary or tertiary amino compound having saponifiable >C=O not bonding directly to the aromatic ring having a bonded secondary or tertiary amino group. In the formula, R<1> is a ter- or quater-valent org. group having plural carbon atoms, the preferred group has a structure in which as atom in the aromatic or aromatic heterocyclic ring bonds directly to each carbonyl group in the principal chain of the polymer in respect of the heat resistance of the polyimide polymer, R<2> is a bivalent org. group having plural carbon atoms, the preferred group has a structure in which an atom in the aromatic or aromatic heterocyclic ring bonds directly to each amido group in the principal chain of the polymer, R<3> is H, an alkali metallic ion or an ammonium ion.

Description

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

[Prior art]

The following are known as polyimide base compositions imparted with actinic radiation, particularly photosensitivity, which have been developed for use in semiconductor insulating layers and passivation layers.

(a) Compositions consisting of polyamic acid and 1 to 5 parts by weight of dichromate (e.g. USP ~3623870) (
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, 15,
957,51 2. usp4,04 mouth, 851
).

(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
．． -145794).

All of these were dissolved in an appropriate organic solvent and applied to the substrate in a face state, 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 film of the patterned polyimide precursor 1 is further subjected to an appropriate heat treatment to form a polyimide film having heat resistance.

However, such conventional compositions have the following drawbacks: they cannot be directly patterned with light. 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.

In (b), the polymer is mainly polymerized by reacting a diamine with a compound having 9 photosensitive groups and a diacid chloride group, and the manufacturing process is not only complicated, but also desalinated □acid Since chlorine ions generated by the process remain in the film, there is a possibility that reliability may be adversely affected in semiconductor applications.

The materials described in (C) are materials that have improved these drawbacks, but even in these materials, the sensitivity is still only several hundred mJ.
The diameter is as low as 7 cm, which is insufficient for processing with exposure equipment commonly used in the semiconductor industry.

[Purpose of the invention]

The present invention solves the drawbacks of the prior art described in section 2.

It is an object of the present invention to provide a polymer composition that is superior in sensitivity to actinic radiation as a heat-resistant polymer.

[Structure of the invention]

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

(]) (a) A polymer whose main component is the structural unit [I] represented by the general formula (%) (wherein R'' in formula 9 is a hexavalent or tetravalent compound having at least 2 or more carbon atoms). organic group.

R' represents a divalent organic group having at least two carbon atoms, and R' represents hydrogen, an alkali metal ion or an ammonium ion. n is 1 or 2).

(b) Compounds containing unsaturated bonds and amine groups or quaternized salts thereof that can be dimerized or polymerized by actinic radiation (III
and.

an actinic radiation-sensitive polymer composition consisting of an aromatic secondary or 6th class amine compound [■] which is not
The present invention is characterized by an actinic radiation-sensitive polymer composition obtained by mixing the aromatic azide compound [I■] with the composition of item ().

What is the polymer having structural units C and IE (hereinafter referred to as a polyimide polymer precursor) in the present invention?

It has a structure represented by the above ML general formula, and can be turned into a polymer (hereinafter referred to as a polyimide polymer) having an imide ring or other cyclic structure by heating or using a suitable catalyst.

2 Structural unit [■] Medium size R1 is a trivalent or tetravalent organic group having at least two or more carbon atoms. From the viewpoint of heat resistance of the polyimide polymer, R1 preferably has a structure in which bonding to the carbonyl group of the polymer main chain is directly carried out through an aromatic ring or an aromatic heterocycle. Therefore, R1 is preferably a group containing an aromatic ring or an aromatic heterocycle, having a carbon number of 6 to 0, and having a valence or tetravalence.

A preferable specific example of R'' is as follows.

CH, CF3 (in the formula, the bond is the bond f with the carbonyl group of the polymer main chain)
:fi, the carboxyl group is located at the ortho position to the bond, but this bond is not shown in the above structural formula).

Examples include, but are not limited to, these.

In the polymer having the oxda structural unit [I], R1 may be composed of only one of these.

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

What's particularly impressive about R1?

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

In the above structural unit [1], 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, it is necessary to combine R2 with the amide group of the main chain of the polyimide polymer. Those having a structure in which the bond is 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 to 6 carbon atoms.
60 divalent groups are preferred.

Preferred specific examples of R2 include:

0 CH, CH.

(In the formula, the bond represents a bond with an amide group in the main chain.). Further, examples thereof include amine groups, amide groups, carboxyl groups, and sulfo groups as long as they do not adversely affect the heat resistance of the polyimide polymer.

In the polymer having the structural unit [1], R' may be composed of only one of these units, or may be a copolymer composed of two or more types.

Additionally, it is also possible to copolymerize an aliphatic group having a shiq-kizan structure as R1 within a range that does not reduce heat resistance. A preferred example is -CHCHCH-8i-0
-8i-CHCHCI(-1 CH,CH.

Examples include.

As a specific example of a polymer whose main component is structural unit [I].

Pyromellisotonic dianhydride and 4,41-diaminodiphenyl ether.

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

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

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

3,3',4.4/-biphenyltetracarboxylic dianhydride and 3.3',4.4/-benzophenonetetracarboxylic dianhydride and 4,47-diaminodiphenyl ether.

Pyromellitic dianhydride and 6,3'-diaminodiphenylsulfone.

Pyromellitic dianhydride and 3.5', 4.4/
-benzophenonetetracarboxylic dianhydride and 3,3/
-(ll:4.4'-)diaminodiphenylsulfone.

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

3, 3/, 4.4/-biphenyltetracarboxylic dianhydride and 6. (or 4,4/-)diaminodiphenylsulfone.

6, da, 4.47-biphenyltetracarboxylic dianhydride and 3,3/, 4.4/-benzophenonetetracarboxylic anhydride and 3.3/-(or 4.4/
-) Diaminodiphenylsulfone.

Pyromellitic dianhydride, 4,41-diaminodiphenyl ether and bis(6-aminopropyl)tetramethyldisiloxane.

Pyromellitic dianhydride and 3.3/, 4.4/
-benzophenonetetracarboxylic dianhydride and 4,4/
- Diaminodiphenyl ether and bis(6-aminopropyl)tetramethyldisiloxane.

5,5/, 4.41-benzophenonetetracarboxylic dianhydride, 4.4'-diaminodiphenyl ether and bis(6-aminopropyl)tetramethyldisiloxane.

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

3,3/,4.4'-biphenyltetracarboxylic dianhydride and 3.3/,4.4/-hensiphenotetracarboxylic anhydride and 4,4'-diaminodiphenyl ether and bis(6- aminopropyl)tetramethyldisiloxane.

Pyromellitic dianhydride and 3,3/- (or 4,4/-
) Diaminodiphenylsulfone and bis(6-aminopropyl)tetramethyldisiloxane.

Pyromellitic dianhydride and 6. da, 4.4/-benzophenonetetracarboxylic dianhydride and 3.3'-(
Also [4,4/-)diaminodiphenylsulfone and bis(6-aminopropyl)tetramethyldisiloxane.

3, s; 4.4'-benzophenone tetracarboxylic dianhydride and 3,5/- (or 4,4/-) diaminodiphenylsulfone and bis(6-aminopropyl)tetramethyldisiloxane.

3, 5/, 4.4/-biphenyltetracarboxylic dianhydride and 6. di(or 4,4/-)diaminodiphenylsulfone and bis(3-aminopropynolitetramethyldisiloxane).

3,3',4.4/-biphenyltetracarboxylic dianhydride and 3.3/,4.4/-benzophenonetetracarboxylic dianhydride and 3,3/-(or 4,4
/-) A polyamic acid synthesized from diaminodiphenylsulfone and bis(3-aminopropyl)tetramethyldisiloxane is preferably used.

The polymer having the structural unit [1:l as a main component] may be composed only of the structural unit [1], or may be a copolymer with other structural units. The type and amount of structural units used in the copolymerization are desirably selected within a range that does not significantly impair the thermal properties of the polyimide polymer obtained by the final heat treatment. Typical examples include structural units of polyamic acid and polyesteramic acid, but are not limited thereto.

A compound [11] containing an unsaturated bond and an amino 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 amino group or a quaternized amine group in one molecule. It is a compound containing.

The following general formula [A] \8 (where R4 is hydrogen or a phenyl group, R5 is hydrogen or a lower alkyl group having 1 to 2 carbon atoms, R& is a substituted or unsubstituted hydrocarbon group having 2 to 12 carbon atoms, R' , R' represents a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms) and 9 General formula CBI (where R9 represents an unsubstituted or substituted alkyl group having 1 to 2 carbon atoms).

General formula [S10 (CH, = c-CH-'j- N-H'
Csn ] (Here, R represents hydrogen or a methyl group.

n10)=3, n=1 to 5).

The quaternized salts of these salts are preferably used.

As a preferred specific example (　CH　　　　　＞　　e CH, = Cl - CH, NH,.

(cH,=CH-CH,)2NH An amino compound having an acrylic group or a methacryl group is desirable.

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

In the case of compounds in which the amine group is quaternized, the structural unit [
It is desirable that R' in [I] be combined with an alkali metal ion or an ammonium ion. In this case, inorganic compounds such as alkali metal chlorides may precipitate in the solution, but it is desirable to remove them by filtration or the like.

Compound (II) is mixed with the polymer in an amount of at least 0.05 equivalents, preferably at least 0.3 equivalents, and at most twice the amount of light, of all carboxyl groups (or salts thereof) of the patented polymer characterized by the structural unit [■]. It is desirable to have one.

If it is outside this range, there is a risk that the photosensitivity may deteriorate or the permissible range of development conditions such as development time and temperature may be narrowed, so care must be taken.

Group secondary or 6th class amine compounds [■] have an amine group 9 directly bonded to an aromatic nucleus, an alkylene group with 1 or more amino acids, a giant amine compound (others) C;O and an aromatic nucleus. It is an aromatic secondary or tertiary amino compound that is bonded via a divalent group that inhibits the conjugation of the compound.

As shown in Japanese Unexamined Patent Publication No. 54-145794, it is difficult to achieve the desired sufficient improvement in sensitivity.

The aromatic nucleus referred to here refers to benzene nucleus, naphthalene nucleus, etc. These aromatic nuclei include alkyl groups, alkoxy groups,
・Substituents such as rogene groups, ie.

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. For example, it can be said that a substituent such as an unsaturated bond that can be easily dimerized or polymerized by actinic radiation does not naturally exist in the molecule. Also, -CH,- group, -
It may be bonded to another substituted or unsubstituted aromatic nucleus via a simple divalent group such as so, - group, -o- group, etc. It usually has 6 to 50 carbon atoms, preferably 6 to 15 carbon atoms.

The alkyl group bonded to the amino 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 6 are used.

Preferred specific examples of the amine compound [■] include N
-phenylethylamine, N-phenyldiethylamine, lJ-phenyl-N-ethylbenzylamine, N-
Phenylmorpholine, 3-ethylamino-1]-cresol, N-phenyl-N-(2-cyanoethyl)ethylamine, N-phenylethanolamine, N-phenyl-N-methylethanolamine, N-phenyl-N-ethyl Ethanolamine, N-phenyldiethanolamine.

N-('5-methylphenyl)jetanolamine.

N-(4-methylphenyl)siethanolamine.

Examples include N-phenyldiisopropanolamine.

Aromatic secondary compound having an amino group to which the above alkyl group is bonded
Among class- or tertiary amine compounds, those having a polar substituent on the alkyl group are more preferable, and in particular, amine compounds having a hydroxyl group as a polar substituent, that is,
Most preferred are aromatic amino compounds in which at least one hydrogen of the amine group is substituted with an alkyl group having a hydroxyl group.

It is desirable that the compound [■] is mainly composed of the structural unit [I] and is mixed in an amount of 01 weight percent or more based on the weight of the winter polymer, more preferably a 05 weight percent or more and a 20 weight percent based on the weight of the polymer. It is best to mix them in the following proportions. If it is outside this range, there is a risk that the photosensitivity may deteriorate or the permissible range of development conditions such as development time and temperature may be narrowed, so care must be taken.

The preparation of 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 CIl as a main component was obtained.

Next, the compounds [■] and [■] and, if necessary, other additives can be dissolved and prepared in this solution. In addition, as the above-mentioned polymer, a solid polyamic acid polymer or a polymer separated and purified from the solution after two reactions may be redissolved and used.

As the solvent used in the above production method, polar solvents are preferably used from the viewpoint of polymer solubility, and aprotic polar solvents are particularly suitable. As an aprotic polar solvent,
N-methyl-2-vinyl 1)), N,N-dimethylformamide, 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.

When the amount of compound [11t) mixed is 0.5 to 10% by weight, Mihira ketone, 4,4/-bis(diethylamino)benzophenone, etc. are preferably used as the sensitizer. By adding a sensitizer.

The actinic radiation sensitivity of the compositions of the invention can be further improved.

Monomaleimide, polymaleimide, or substituted products thereof are preferably used as the copolymerizable monomer, but the copolymerization monomer is not limited thereto.

8. The present invention is characterized by the actinic radiation-sensitive polymer composition as described above, and by adding an aromatic and compound [:IVI] to this composition.

Furthermore, a composition with excellent actinic radiation sensitivity can be obtained.

An example of a method for producing the composition in this case is a method in which an aromatic and compound is further added and dissolved in the production of the actinic radiation-sensitive composition described in 2.

An aromatic and compound [■] is a compound in which an azide group (N, -) is directly bonded to an aromatic nucleus, and the aromatic nucleus here refers to Hensen nucleus, naphthalene nucleus, anthracene nucleus, naphthoquinone nucleus, anthraquinone nucleus. Refers to the nucleus, etc. These aromatic nuclei are lower alkyl groups.

Alkoxy group, carboxyalkyl group, 21.

It may be substituted with a halogen group, etc.
group, -c- group, -s○2- group, -CH2- group.

1 CH= cI (substituted through a divalent group such as -C- group or 1 may be combined with another unsubstituted aromatic nucleus. Therefore, the number of carbon atoms is usually 6 to 50. Preferably 6 to 21. There may be one azide group in the molecule (hereinafter,
(hereinafter referred to as an aromatic bisazide compound), the aromatic nucleus to which an azide group is bonded may be further bonded by a 21111i group as described above, and there may be two azide groups in the molecule (hereinafter referred to as an aromatic bisazide compound) · in particular.

Aromatic monoazide compounds such as 0 0, and CH.

Preferably used are aromatic bisazidized metals such as, but not limited to, these.

Aromatic monoacid compounds are particularly preferred because of the solubility of the azide compound, the ease of selecting the sensitive wavelength range, and the ease of production.

It is desirable that the aromatic and compound [:IVI] be added in an amount of 0.01 weight or more based on the weight of the polymer whose main component is the structural unit [I], and more preferably 0.5 weight percent or more based on the weight of the polymer.
It is preferably added in a proportion of 30% or more by weight.

If it is outside this range, there is a risk that the developability and storage stability of the composition will be adversely affected, so care must be taken.

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 concentration of the coating means 9 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 and the support after heat treatment, a 7" run, a--'lysidoxypropyltrimethoxysilane, γ-aminopropyltriethoxy Silane.

Organosilicon compounds such as r-methacryloxyglobyltrimethoxysilane, aluminum chelate compounds such as aluminum monoethyl lycetoacetate diisopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), or titanium bis( Titanium chelate compounds such as acetylacetonate) are 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, and visible light. However, ultraviolet rays and short wavelength visible rays, that is, in the wavelength range of 200 nm to 500 nm are preferred.

Then, a relief pattern is obtained by dissolving and removing the unirradiated areas 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.

Non-solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, etc. alone or compositions such as methanol, ethanol, isopropyl alcohol, water, methylcalpitol, ethylcalpitol, etc. It can be used as a mixture with In many cases, aqueous ammonia or other alkaline aqueous solutions can also 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, etc. 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 an imide 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.
Secondary development was performed by irradiating the film with light from a high-pressure mercury lamp through a high-pressure mercury lamp (2215TEPS), and the film was evaluated based on the number of layers remaining with 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 to 1/7 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, soldering protective films for printed circuits, alignment films for liquid crystals, etc. It is offered. Furthermore, it can be applied to gold as a highly heat-resistant photoresist.

〔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
) and an aromatic secondary or 6th class amine compound [13], the actinic radiation-sensitive composition was composed of a well-known sensitizer [9], although its mechanism of action has not yet been elucidated. Compared to the composition used, the unexpected effect of significantly improving sensitivity was obtained.

In addition, polymers and compounds whose main component is the structural unit CI) [
]II and the compound ClID of the present invention, if an aromatic and compound, preferably an aromatic monoazide compound, is added, the sensitivity is further improved. In particular, when irradiated with ultraviolet rays, the actinic radiation reaches deep into the film, which is advantageous for patterning thick films.

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 with 2DD'O in a nitrogen atmosphere for 1 hour.

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

Example 1 68 g of diaminodiphenyl ether was dissolved in 600 g of N-methyl-2-pyrrolidone to obtain a polymer solution (A) of 4 amine-soluble amines.

40 g of solution (A) and 5.6 g of diethylaminoethyl methacrylate [! 'jc mixed, then a solution dissolved in 0.6 gf of N-phenyldiethanolamine, mixed with 45 g of N-methylpyrrolidone, and filtered.The resulting solution was spin-coated onto silicone sea urchin/S using a spinner, It was dried for 1 hour at 'a' to obtain a coating film of 5μ. This coating film is even at normal temperatures.

Moreover, it was in sufficient contact with the substrate. A striped mask was placed on top of this coating film, and ultraviolet rays were irradiated for 2 seconds using a 2DOW high-pressure mercury lamp. The intensity of ultraviolet rays on the exposed surface was 10 mw/cm'' in the 365 nm wavelength range, that is, 20 mJ/cm.
cm” exposed. Dimethylacetamide (5 parts) after exposure.
A relief pattern was obtained by developing with a mixed solvent of and methanol (2 parts) and then washing with a rinse solution (isopropanol). The pattern had sharp edges and a thickness of 35μ. Conventional compositions contain hundreds of 6+ J/
The composition of the present invention has excellent sensitivity in that a pattern can be obtained with a small exposure of 2[] m J/Cm', compared to the exposure of 9 cm'.This pattern was heat-treated at 650"C for 260 minutes. By doing so, a heat-resistant relief pattern was obtained. 200 copies of this pattern
Even after heat treatment at °C for 1 hour, the pattern did not burn or lose heat.

Comparative Example 1 40 g of the polymer solution (A) obtained in Example 1 and Mihira.
Ketones and diethylaminoethyl methacrylate5.
A composition obtained by mixing 4.5 g of 1N-methylpyrrolidone with 4.5 g of molten pyrrolidone and filtering the mixture was tested in the same manner as in Example 2. Mihira Rito/ amount from 0009g to 0
I tested it by adjusting it to 9g.

The improvement in the sensitizing effect reached a plateau when about 0.02 g was added. The minimum number of exposure steps at which the film remained after development, that is, the sensitivity was 4 steps.

Examples 2 to 16 In Examples 2 to 16, the sensitivities of solutions prepared by changing the types and amounts of aromatic amino compounds, aromatic azide compounds, and sensitizers were evaluated using a gray scale method. The results are shown in Table 1.

In the table, 9% by weight is the value obtained by dividing the weight of the added compound by the weight of the polyester, which is one digit of 100.

Solution Preparation 9 Sensitivity testing was conducted as follows.

Diethylaminoethyl methacrylate was completely mixed into the solution (A) obtained in Example 1, and then an aromatic amine compound (i7
The solution 'e' dissolved in N-methylpyrrolidone (if an aromatic and compound and a sensitizer were added, the bath liquid in which these were further dissolved) were mixed together and filtered.

Using the obtained i'' solution, a coating film was formed on a silicon wafer in the same manner as in Example 1. Instead of a striped pattern, a gray scale was adhered and irradiated with ultraviolet rays for 10 seconds using the same mercury lamp.Development. The minimum number of exposure steps at which the post-coating remains, ie, the sensitivity, was determined.

As is clear from Table 1, Examples 2 to 8 show that the aromatic secondary and 6th class amino compounds have two effects on sensitivity and are excellent.

Example 9 shows that when a small amount of an aromatic amine compound is used, the sensitivity improvement effect is amplified by using Mihira ketone, which is a representative example of a well-known sensitizer, in combination.

Examples 10 to 15 show that using an aromatic azide compound instead of a well-known sensitizer can improve sensitivity to the same level as or even more than the combination of 8 well-known sensitizers.

Example 16 shows that when an aromatic amino compound and an aromatic azide compound are used together with a well-known sensitizer such as Mihira Ketone, the sensitivity can be further improved.

Claims (1)

[Claims] (1) (a) A polymer whose main component is a structural unit [■] represented by the general formula 7 (% formula %) (in formula 9, R1 is a hexavalent or tetravalent organic group, R2 is a divalent organic group having at least 2 carbon atoms, R' is hydrogen, an alkali metal ion or an ammonium ion; n is 1 or 2). (b) Compound (II) containing an unsaturated bond that can be dimerized or polymerized by actinic radiation and an amine group or a quaternized salt thereof
and. An actinic radiation-sensitive polymer composition comprising an aromatic secondary or 6th class amine compound [■]. (21(a) General/Formula%Formula%) A polymer whose main component is the structural unit CII (wherein R1 is a hexavalent or tetravalent organic group having at least 2J or more carbon atoms, and R2 is (b) dimerizable or polymerizable by actinic radiation; A chemical compound containing an unsaturated bond and an amino group or a quaternized salt thereof (Cl0)
and. Aromatic secondary or tertiary amino compound CI[+
]and. (d) An actinic radiation-sensitive polymer composition comprising an aromatic azide compound (IV).