KR860000070B1 - Photo-or radiation-sensitive polymer composition - Google Patents

Abstract

A photosensitive polymer comprises (a) a polymer of formula (I);(b) photosensitive additives, such as C6H4XR5CO2YNR3R4and C6H4 XR5NR3R4; and (c) a sensitizing agent (s) as required. R1 is trior tetra- atomic(sic) organic radical; R2 is a di-atomic(sic ; divalent) organic radical ; M is H, an alkaline metallic ion or an ammonium ion ; n is 0 or 1 ; X is N3 - or N3SO2; Y is H, alkyl, alkoxy, nitro, carboxyl, or sulfonic acid gp. or halogen; R3 is a diatomic organic radical, coupling Ar and R ; R4 and R5 are H or a lower alkyl radical.

Description

Light or radiation sensitive polymer composition

The present invention relates to novel light or radiation sensitive polymer compositions that provide heat resistant polymeric materials.

Amine compounds containing at least one carbon-carbon double bond and at least one amino acid group, which can dimerize or polymerize a polymer having poly (amic acid) which is a precursor of polyimide as a main component, by chemical light, or 4 Polymer compositions obtained by mixing with rapid salts are known as materials that are heat resistant and sensitive to light or radiation, but these materials require long curing times because their sensitivity is low, such as hundreds to thousands of mJ / cm 2.

The present invention is to provide a composition that removes the above-mentioned disadvantages of the prior art and has a storage stability that can be used industrially and has a high sensitivity to light or radiation.

The object of the present invention can be achieved by using a light or radiation-sensitive compound having an amino group and an anti-ark azide or an anti-sulfuryl azide group in one molecule as an amine compound.

Specifically, a large invention includes (a) poly (amic acid) having a repeating unit of the following general formula (I) as a main component;

(b) at least one light or radiation-sensitive compound having an amino group and an oceanic azide group or an oceanic sulfonyl azide group in one molecule, and (c) one or more photosensitizers and / or at least one unsaturated bond, as desired. It provides a light or radiation-sensitive polymer composition consisting of an amine compound and / or (d) one or more compounds having at least two fluorinated bonds in one molecule.

Wherein R ¹ is a trivalent or tetravalent organic group having at least two carbon atoms, R ² is a divalent organic group having at least two carbon atoms, M is hydrogen or ammonium ions, and N is 1 or 2

The materials used in the present invention will now be described.

As the main component of component (a), poly (amic acid) having a repeating unit of formula (1) described above can be converted to polyimide by heating or by the action of a suitable catalyst, which polyimide has high heat resistance.

The poly (amic acid) having the repeating unit (1) as a main component may be a polymer having the repeating unit (1) or a copolymer with the repeating unit (1). There is no limitation on the type of other repeating units used in the copolymer, but it is preferable to select within the limit that the heat resistance of the polyimide obtained by the heat treatment is not greatly reduced.

The heat resistance of the polyimide should be excellent enough to maintain the relief pattern formed even when the polyimide is heated at 250-450 ° C. for 1 hour under a nitrogen stream.

Repeating units used in the copolymerization are particularly preferred when they can be heat resistant polyimides, and representative examples thereof include poly (amic acid) and poly (ester amic acid) [Hara et al. Present State and Tendrncy of Heat Resistant High Polymer (Sekiyu Gakkai Shi 17, 110-120 (1974)), but these repeating units are not limited to these.

In the above general formula (1), R ¹ is a trivalent or tetravalent group having at least two carbon atoms, and in view of the heat resistance of the polyimide, an aliphatic ring or a hetero-aromatic ring is preferable. For example, R ¹ is as follows.

이 있다.In the above formula, the bond line indicates that each is bonded to the carbonyl group of the polymer main body, and the carboxyl group is in the ortho position with respect to the bond line. However, R ¹ is not limited to these. The poly (amic acid) having a repeating unit of the general formula (1) may be a copolymer in which R ¹ includes two or more of the groups described above, and particularly preferably

There is this.

R ² is a divalent organic group having at least two carbon atoms, and an aromatic ring or a heteroaromatic ring is preferable in view of the heat resistance of the polyimide obtained from poly (amic acid). R ^{2 is} for example

There is this. However, R ² is not limited to these.

Formula (1), a repeating unit gateun of the poly (amic acid) is R ² that comprises the above-described geurupreul also includes the above-described group of two or more, and also R ¹ and R ² can not both be a two or more of the above-described group It may be a copolymer which may be a copolymer. These groups may have one or more substituents such as amino groups, amide groups, carboxyl groups, sulfonic acid groups, sulfonamide groups, as long as they do not adversely affect the heat resistance of the polyimide.

As the main component, poly (amic acid) having a repeating unit of formula (1) described above is preferably used, for example, those derived from pyromellitic acid dianhydride and 4,4'-diaminodiphenyl ether; Derived from pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride and 4,4'-diaminodiphenyl ether; pyromellitic acid dianhydride, 3,3 ', 4,4'benzophenonetetracarboxylic acid dianhydride derived from 4,4'-diaminodiphenylate and 4,4'-diaminodiphenylether-3-carbonamide; pyromellitic acid dianone Hydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride 4,4'-diaminodiphenylether, 4,4'-diaminodiphenyl ether-3-carbon amide and bis Derived from (3-aminopropyl) tetramethyldisiloxane; Derived from pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4, 4'-diamino diphenylate and bis (3-aminopropyl) tetradecyldisiloxane Etc.

More preferable examples of the poly (amic acid) having a repeating unit of the general formula (1) described above include the following.

The poly (amic acid) having a repeating unit of the general formula (1) described above is usually obtained by reacting a diamine compound with an almost equivalent amount of dianhydride, as described, for example, in US Pat. Nos. 3,968,14 and 374305. can do. In this case, it is preferable to use a polar solvent in consideration of the solubility of the produced poly (amic acid) as the reaction solvent, and particularly, an aprotic polar solvent is suitable.

Typical examples of aprotic polar solvents include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, N-acetyl- (epsilon) -caprolactam and 1, 3- dimethyl- 2-imidazolidi etc. are mentioned.

The light or radiation sensitivity of the compositions of the present invention is attributed to the sensitivity to light or radiation of component (b), i.e. compounds having amino groups and aromatic azide groups or aromatic sulfonamide groups in one molecule.

Such a compound can bind the amino group of component (b) in the repeating unit of formula (1) by ionic bonding with the carboxyl group in the repeating unit of formula (1). Aromatic azide groups or aromatic sulfonamide groups are relatively excellent in thermal stability, and provide styrene which is active due to light such as ultraviolet rays and radiation such as electron beams and X-rays. In addition to, it causes a double bond, hydrogen absorption reaction. Therefore, the light, radiation, or sensitive compound of (b) bound in the repeating unit of formula (1) is a poly having a repeating unit of formula (1) as a main component through the above-described reactions by irradiation of light or radiation. One pattern can be formed by going to (amic acid) and causing a bond to cause a difference in solubility between the irradiated and unirradiated portions.

On the light-sensitive side, the preferred compound is 100 mJ / cm 2 or less (measured at 365 mm using a 500w Xe-Hg lamp) at an ultraviolet irradiation amount at which the standardized film thickness after development is 0.5 to the thickness of the coating peeling. Are compounds with sensitivity.

Light or radiation sensitive compounds having an amino group and an aromatic azide group or an aromatic sulfonyl azide group in one molecule are compounds represented by the following general formulas (2) to (7), which are used alone or in combination of two or more of these compounds. It can be mixed and used.

Wherein X is -N ₃ or -SO ₂ N ₃ , Y is preferably an alkylene group having up to 5 carbon atoms, and R ³ , R ⁴ and R ⁵ are independently hydrogen or lower alkyl groups .

Wherein X is -N ₃ or -SO ₂ N ₃ : R ³ , R ⁴ and R ⁵ are independently hydrogen or lower alkyl group.

Wherein X is -N ₃ or -SO ₂ N ₃ , R ³ , R ⁴ and R ⁵ are independently hydrogen or lower alkyl group,

또는-CH₂이다.R ⁶ is

Or -CH ₂ .

Wherein X is -N ₃ or -SO ₂ N ₃ : R ⁷ is hydrogen or lower alkyl group;

Wherein X is -N ₃ or -SO ₂ N ₃ , R ⁵ ′ is a monovalent group or atom selected from nitro group, halogen, hydrogen, lower alkyl group, lower alkoxy group and cyano group, R ⁷ Is a hydrogen or lower alkyl group, R ⁸ is a monovalent group or atom selected from hydrogen, a cyano group lower alkyl group and halogen, and R ⁹ is a divalent organic group linking an unsaturated bond to an amino group,

또는

이고, R³및 R⁴는 독립적으로 수소 또는 저급 알킬그룹이고, m은 1 내지 3의 정수이다 ;For example,

or

R ³ and R ⁴ are independently hydrogen or a lower alkyl group, and m is an integer of 1 to 3;

Wherein Ar is an aromatic group selected from an aromatic ring and a heteroaromatic ring, X is -N ₃ or -SO ₂ N ₃ , R ¹¹ is hydrogen, lower alkyl group, lower alkoxy group nitro group, carboxyl group, sulfonic acid Monovalent group or atom selected from the group and halogen, R ¹⁰ is a divalent organic group bonding Ar to N, and R ³ and R ⁴ are independently hydrogen or lower alkyl group having up to 5 carbon atoms.

Examples of Ar include the following:

이며, 여기에서 R¹²는 알킬렌 또는 탄소-탄소 불포화 결합을 갖는 2가 탄화수소 그룹이다.R ¹⁰ is for example alkylene,

Wherein R ¹² is a divalent hydrocarbon group having an alkylene or carbon-carbon unsaturated bond.

Lower in the alkyl group in the general formulas (2) to (7) described above means that the number of carbon atoms is preferably 5 or less.

In the compound stocks of the general formulas (2) to (7) described above, the compounds of the general formulas (2), (6) or (7) are preferred, and the compounds of the general formulas (6) or (7) are particularly preferred. However, in the case of the compound of formula (6), the aromatic ring is paired with a carbon-carbon double bond to shift the wavelength range for photosensitivity to a wavelength range of 300 nm or more, and in the case of the compound of the formula (7), The conversion to paired polycyclic rings allows the use of cheap photo masks made with soda glass or emelzone coating.

Examples of such compounds are as follows:

Among the compounds of formula (2), compounds in which R ³ and R ⁴ are not independently C ₂ H ₅ are novel compounds, and compounds of formula (6) are also novel compounds.

The compound of formula (2) or (6) is synthesized according to the following process, for example. That is, a carboxylic acid having an aromatic azide group is reacted with thionyl clyde to synthesize an acid chloride having an aromatic azide group, and then reacted with dialkylaminoalcohol or dialkylamino amine to form an ester bond or an amide bond. Hydrochlorides of dialkylamines are synthesized. This compound can then be reacted with an aqueous alkali solution such as NaOH, KOH or the like to give general formula (2) or (6).

The light or radiation sensitive compound of component (b) is 0.05 to 5 times, preferably 0.05 to 3 times, more preferably 0.4 to 3 times, most preferably the total COOM group of repeating units of formula (1) Is preferably added in an amount of 0.4 to 2 times. If the added amount is out of the above-mentioned maximum range, the light or radiation sensitivity is degraded or there are many limitations on developing performance. Particularly high bonding rates adversely affect the heat resistance of the polyimide produced after the final heat treatment.

The light or radiation sensitive composition of the present invention is typically a varnish prepared by dissolving a poly (amic acid) (a) having a repeating unit of formula (1) as a main component and a compound of the aforementioned component (b) in a suitable organic solution. Use in form. The solvent used in this case is preferably capable of dissolving both a poly (amic acid) having a repeating unit of formula (1) and a compound of component (b). For this reason, mainly a polar solvent is used preferably, More preferably, it is an aprotic polar solvent. Examples of polar solvents include N-methyl N-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethyl formamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphor Triamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, and the like, which can be used alone or as a mixture thereof.

The solvent used is a total amount of component (a), the photosensitive compound of component (b), and the components (c) and (d) used as necessary, which is a poly (amic acid) having a repeating unit of formula (1). 100 to 10,000 parts by weight are preferred, and 200 to 5,000 parts by weight are more preferred based on the weight parts. Too much or too little solvent adversely affects film forming properties.

The light or radiation sensitive composition of the present invention may optionally contain one or more unsaturated amines, photosensitizers, crosslinks, in addition to components (a) and component (b), which are poly (amic acids) having repeating units of the general formula (1) as main components. A binding aid and an adhesive improvement agent can be contained further.

The photosensitizer (component (c)) improves the radiation sensitivity by extending the wavelength range for photosensitivity of the photosensitive group or by efficiently applying light energy to the photosensitive group. Since unsaturated amines are mixed as reaction aids of photosensitive groups of components other than the photo-sensitive compound, when both unsaturated amines of the photosensitizer are used, they can be used alone or in combination.

Examples of the photosensitizer include anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, benzoquinone, 1,4naphthoquinone, 1,2-benzoanthraquinone, benzophenone, P, P'-dimethylbenzophenone and fine water. Ruquetone, 2-nitrofluorane, 5-nitroacetonaphthene, 4-nitro-1-naphthylamine, anthrone, 1,9-benzanthrone, dibenzalacetone, benzoin ether, 4,4'- Bis (diethylamiro) benzophenone, acridine, cyanoacridine, nitropyrene, 1,8-dinitropyrene, pyrene-1, 6-quinone, 9-fluorenone, anthrone, 2-chloro -1, 2-benz anthraquinone, 2-bromobenz anthraquinone, 2-chloro-1, 8-phthaloyl naphthalene, etc. are mentioned.

The amount of the photosensitizer added as necessary is preferably 0.01 to 10% by weight, more preferably 1 to 10% by weight based on the total amount of components (a), (b) and (c). Too much amount will limit the developing ability or adversely affect the heat resistance of the final product polyimide.

Typical examples of adhesion-improving agents include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyl Organosilicon compounds such as triethoxysilane and the like; Aluminum monoethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetate), aluminum tris (malonic acid ethylate), aluminum diethylacetonate monoisopropylate, aluminum diacetylacetonate mono Isopropylate, aluminum monomethyl acetoacetate diisopropylate, aluminum dimethylaceto acetate monoisopropylate, aluminum tris (methylacetoacetate), aluminum monopropylacetoacetate diisopropylate, aluminum dipropylaceto acetate monoisopropylate Aluminum chelate compounds, and the like.

Examples of the amine compound (component (c)) include unsaturated amines having the following general formula.

=3이고, k=1내지 3이다.Wherein R ¹⁴ is hydrogen or methyl group, R ¹⁵ is hydrogen, lower alkyl group or vinyl group, k +

= 3 and k = 1 to 3.

Wherein R ¹⁶ is hydrogen or phenyl group: R ¹⁷ is hydrogen or lower alkyl group, R ¹⁸ is a molar or unsubstituted hydrocarbon group, R ¹⁹ and R ²⁰ are independently substituted or unsubstituted lower alkyl Group.

Wherein R ²¹ is a substituted or unsubstituted lower alkyl group.

"Lower" in the above means that no more than five carbon atoms are preferred.

Specific examples of the unsaturated amines are as follows.

The proportion of the amine is usually from 0.05 to 2 moles, preferably from 0.1 to 1 mole and more preferably from 0.1 to 0.5 mole per mole of light or radiation-sensitive compound of (b) described above. The total amount of the light or radiation sensitive compound of (b) and the amine compound (c) is no more than three times the COOM group equivalent of compound (a). If the ratio is out of the above-described range, there is a limit on developing power or a bad effect on the heat resistance of the final product polyimide.

Also, if desired, as component (d), one or more compounds having at least two unsaturated bonds in one molecule (except the unsaturated amines described above) may be used as crosslinking aids, and examples of such compounds include have.

Wherein R ²² is hydrogen or a methyl group and k is an integer from 1 to 3.

In which R is²³, R²⁴, R²⁶And R²⁷Is independently hydrogen or methyl group, R²⁵Is a lower alkyl group, 1 + m is 4, 1 is an integer from 2 to 4;

In which R ²⁸ is CH ₂ ═CH—CH ₂ — and P is an integer from 1 to 10;

이다.Wherein R ²⁹ is

to be.

Specific examples of the compound include the following.

As the support that can be used for light or radiation sensitive polymer composition of the present invention may for example deulsu a metal, a glass, a semiconductor metal oxide insulator _{(for. TiO 2, Ta 2 O 5} , SiO 2 , etc.), silicon nitride round.

The light or radiation sensitive polymer composition of the present invention can be molded using, for example, conventional micro-processing methods using ultraviolet light.

In order to coat the above-described support with a light or radiation-sensitive polymer composition, methods such as spin coating using spinners, dipping, spraying, printing, and the like may be used, and these methods may be appropriately selected according to the purpose. The thickness of the coating film can be adjusted according to the coating method, the solids content of the composition and the viscosity of the varnish.

The optical or radiation-sensitive composite composition of the present invention formed as a coating film on the support may be exposed to light and then dissolve the unexposed portions and removed with a developer to obtain a desired image. The light source is not limited to ultraviolet rays, and may use visible light, X-rays, electron beams, and the like.

-카프로락탐등과 같은 아프로틱 극성용매를 단독으로 또는 메탄올, 에탄올, 이소프로필알콜, 벤젠, 톨루엔, 크실렌, 메틸셀로솔브 등과의 혼합용액 형태로 사용할 수 있다.As the developing solution, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and dimethylimidazoli which are solvents of the polymer composition. Dinon, N-benzyl-2-pyrrolidone, N-acetyl-

Aprotic polar solvents such as caprolactam may be used alone or in the form of a mixed solution with methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve and the like.

The relief pattern formed by the development is rinsed with a washing solution to remove the developing solvent. Suitable examples of washes include methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methylcellosolve, which can be mixed well with the developer.

The polymer having a relief pattern formed by the above-described treatment is a precursor of a heat resistant polyamide, and is converted to a heat resistant polymer having an imide ring or another ring by heat treatment at 150 to 450 ° C.

The light or radiation-sensitive polymer composition of the present invention can be used to make semiconductors, antifreeze films, internal laminated films of multilayer integrated circuits, soldering protective films for printed circuits, orientation adjusting films for liquid crystal displays, and also utilizes high heat resistance. It may be used as a dry-etch resistant photoresist and a dry-etch resistant radio resist.

The invention is illustrated by the following examples.

Example 1

In a nitrogen stream, 100 g (0.5 mol) of 4,4'-diaminodiphenyl ether was dissolved in 79 g of N-methyl-2-pyrrolidone to prepare an amine solution, and then the temperature of the amine solution was cooled to ice-cooling. 109 g (0.5 mole) of powdered pyromellitic acid dianhydride is added while stirring at about 15 ° C. The resulting mixture is further reacted at 15 ° C. for about 3 hours to obtain a solution A having a viscosity of 30 poises (30 ° C.).

After dissolving 2.34 g (0.01 mol) of 2- (N, N-dimethylamino) ethyl p-azidobenzoate in 20 g of (A) solution, the resulting solution was filtered through a 5 μm mesh filter under pressure. .

The obtained solution is applied to a silicon wafer by a spin-coating method using a spinner and dried at 90 ° C. for 30 minutes to obtain a 2.6 탆 thick coating film. The coating film is flat and uniform and adheres well to the substrate.

The coating film is covered with a strip mask and then irradiated with ultraviolet light from a 500 WXe-Hg lamp.

The ultraviolet intensity on the exposed surface is 25 mW / cm ² in the wavelength range of 365 nm. The coating film is developed with a mixed solution containing dimethylacetamide and ethanol (4: 1 in capacity) and then rinsed with a washing solution (ethanol) to obtain a relief pattern. The sensitivity was calculated to be 18 mJ / cm ² when the exposure dose at which the standard value of the residual film thickness was 0.5 was measured by measuring the change in residual film thickness over time. A relief pattern with a sharp end surface was obtained when exposed at an exposure amount of 72 mJ / cm ² , which is four times the sensitivity, and the pattern did not become cloudy even when heated at 400 ° C. for 60 minutes.

Example 2

1.17 g (0.05 mole) of 2- (N, N-dimethylamino) ethyl p-azidobenzoate and 0.28 g (0.05 mole) of ethylamine were added to 20 g of the solution (A). , Exposure, development and washing are carried out in the same manner as in Example 1. The sensitivity was 20 mJ / cm ^2, and decomposability and heat resistance comparable to those of the pattern obtained in Example 1 were obtained.

Example 3

The conditions such as the mixing ratio of the sample, the reaction solvent, the developer, and the like, and the results of the coating properties, the sensitivity, and the heat resistance are shown in Nos. Marked 1 to 33. Other reaction conditions and operations are as follows.

The diamine compound is dissolved in an aprotic polar solvent at about 15 ° C. under a stream of nitrogen to prepare a diamine solution.

The powdered acid dianhydride is added while stirring while maintaining the reaction temperature at 15 ° C. under a nitrogen stream.

After the addition, the obtained mixture was further reacted at 15 ° C. for 3 hours to prepare a poly (amic acid) solution.

To the prepared poly (amic acid) solution is added a light or radiation sensitive compound. When unsaturated amines and / or photosensitizers are added, these materials are dissolved again in the solution described above to obtain a homogeneous solution. This solution is then filtered under pressure through a 5 μm mesh filter.

In the eggs for the photosensitive additives in Tables 1, 3 and 5 and in the eggs for the unsaturated amines in tables 2, 4 and 6, the "equivalent based on polymer COOH" is added to the total carboxyl group of poly (amic acid) It means the number of equivalents of a compound. In the columns for photosensitizers in Tables 2, 4 and 6, the "weight percent" value is obtained by dividing the weight of the photosensitive agent by the total amount of diamines, acid dianhydrides, light or radiation sensitive compounds, unsaturated amines and photosensitizers, and multiplying by 100 it means.

The photo- or radiation-sensitive polymer composition prepared by the above-described method was applied onto various substrates by spin-coating using spinners, respectively, and then dried at 90 ° C. for 30 minutes to prepare a coating film, and then into a strip. Ultraviolet light of 500 W Xe-Hg ramplob is irradiated through the photomask, developed, rinsed with ethanol and cured at 350 ° C. for 1 hour. Sensitivity is expressed as "good" when 100 mJ / cm ² or less at the exposure amount (measured at 365 nm) where the standardized film thickness after development is 0.5 with the applied film thickness, and "bad" when 100 mJ / cm ^{2 or} more. It was. The heat resistance is hardened for 1 hour at 350 ° C. and then heated for 1 hour at 300 ° C., and the weight loss is 1% or less. If the pattern is not blurred, it is “good”, and if the weight loss is 1% or more, it is “bad”. It was.

TABLE 1

TABLE 2

Example 4

The conditions such as the mixing ratio of the sample, the reaction solvent, and the developer, and the results regarding coating properties, sensitivity, and heat resistance are shown in Tables 7 and 8. 34-38. The light or radiation-sensitive polymer composition was prepared under the same conditions and operation as in Example 3 except for the conditions described above.

The polymer composition prepared by the above method is applied to the substrate by the spin coating method, respectively, and then dried at 90 ° C. for 30 minutes to form a coating film. The sample is irradiated with an electron beam of 15 volts of accelerated bolt. The exposure is locally different, and the irradiated portion is made insoluble and then developed with a developer. Electron-sensitivity curves were obtained by plotting the change in film thickness after development with respect to the dosage. Sensitivity is expressed as "good" when the exposure amount that the standardized film thickness after development is 0.5 to the applied film thickness is 6 × 10 ^-6 coulomb / cm ² or less, and is 6 × 10 ^-6 coulomb / cm or more It was marked as "bad". The heat resistance was marked as "good" when the pattern did not blur when heated at 350 ° C.

TABLE 3

TABLE 4

When an amine compound containing at least one carbon-carbon double bond and at least one amino or quaternary row thereof which can be dimerized or polymerized by ultraviolet rays is added to the same poly (amic acid) as used in Example 1 as a main component. The experimental results obtained in the following are described as comparative examples.

Comparative Example 1

An amine solution is prepared by dissolving 110 g of 4,4'-diaminodiphenyl ether in 278 g of N-methylpyrrolidone under a nitrogen stream. 120 g of pyromellitic dianhydride is dispersed in 308 g of dimethylacetamide to obtain a poly (amic acid) solution (B).

Di dissolved by dissolving 10.2 g (equivalent to 0.055 mole poly (amic acid) total carboxyl groups) in 1.15 g of myrrhketone and 10 g of dimethylacetamide added to 50 g of (B) solution, 30 g of dimethylacetamide. The solution obtained by mixing ethylamino ethyl methacrylate to a homogeneous solution is filtered under pressure through a 5 μm mesh filter.

The solution obtained above was applied to a silicon wafer by a spin coating method using a spinner, and then dried at 100 ° C. for 5 minutes to obtain a coating film having a thickness of 2 μm. The coating film is covered with a strip mask and then irradiated with ultraviolet light from a 5000 W Xe-Hg lamp. The ultraviolet intensity on the exposed surface was 25 mW / cm ² in the wavelength region of 365 mu m. After exposure, the coating film is developed with a mixed solution of dimethyl formamide and methanol (volume 5: 2) and then rinsed in ethanol to obtain a peel pattern. This pattern was retained even when heated at 400 ° C. for 60 minutes. Sensitivity Example 1 1/10 or less of the sensitivity (18mJ / cm ²⁾ of the composition shown in the lower extent 310mJ / cm ^2.

Comparative Example 2

12 g (0.055 moles, equivalent to the total carboxyl group of poly (amic acid)) dissolved in 50 g of (B) solution, 1.15 g of a micromirror ketone added to 30 g of dimethyl acetamide and 10 g of dimethyl acetamide were dimethylamino The ethyl cinnamate solution was mixed to become a homogeneous solution, and the resulting solution was filtered under pressure through a 5 μm mesh filter.

The obtained solution was applied to a silicon wafer by a spin-coating method using a spinner, and then dried at 100 ° C. for 5 minutes to obtain a 2.2 μm thick coating film. The coating film is exposed and developed under the same conditions as in Comparative Example 1 and then washed to obtain a relief pattern. This pattern remained unchanged even when heated at 400 ° C. for 60 minutes, but the photosensitivity was as low as 1,500 mJ / cm ² , which is 1/15 of the photosensitivity in all compositions tested in the present invention.

Example 5

Dissolve 100 g (0.5 mol) of 4,4'-diaminodiphenyl ether in 1,791 g of N-methyl-2-pyrrolidone under a stream of nitrogen to prepare an amine solution, and then cool the solution by ice cooling. 109 g (0.5 mol) of powdered pyromellitic dianhydride was added while stirring at 15 ° C. while stirring, and the reaction mixture was further reacted at about 15 ° C. for 3 hours to obtain a solution having a viscosity of 60 poises (at 60 ° C.). C) is obtained.

5.2 g (0.02 mol) of 2- (N, N-dimethylamino) ethyl p-azidocinnamate was dissolved in 200 g of solution (C) and the resulting solution was filtered through a 5 μm mesh filter under pressure.

The obtained solution was applied to a silicon wafer by a spin coating method using a spinner, and then dried at 80 ° C. for 30 minutes to obtain a 0.5 μm thick coating film. The coating film was flat and uniform and adhered well to the substrate.

The coating film is covered with a strip mask made of soda glass and then irradiated with ultraviolet light from a 500 W Xe-Hg lamp. The ultraviolet intensity on the exposed surface was 10 mW / cm ² in the wavelength region of 365 nm. After exposure, the coating film is developed with a mixed solution of N-methyl-2-pyrrolidone and ethanol (4: 1 in capacity), followed by washing with a washing solution (ethanol) to obtain a relief pattern. The change of residual film thickness over time is measured and the irradiation characteristic curve is made. Sensitivity was calculated as 50 mJ / cm ² when the exposure amount at which the standard value of the residual film was 0.5 was applied as the applied film thickness. A relief pattern with a sharp end surface was obtained upon exposure with an exposure dose of 200 mJ / cm ² , which is four times the sensitivity, and the pattern was not blurred even when heated at 400 ° C. for 60 minutes.

Example 6

To 100 g of solution (C) obtained in Example 5, 10.4 g (0.4 mol) of 2- (N, N-dimethylamino) ethyl p-azido cinnamate was added to prepare a solution. Coating, drying, exposure, development and cleaning.

The sensitivity was 60 mJ / cm ² and the degradability and heat resistance of the pattern were comparable to those obtained in Example 5.

Example 7

To 200 g of solution (C) obtained in Example 5, 5.2 g (0.2 mol) of 2- (N, N-dimethylamino) ethyl p-azidocinnamate and 1.1 g (0.02 mol) of allylamine were added. It is prepared and subjected to coating, dry exposure, development and washing in the same manner as in Example 5. The sensitivity was 50 mJ / cm ² and the decomposition and heat resistance comparable to those obtained in Example 5 were obtained.

Example 8

Dissolve 100 g (0.5 mol) of 4,4'-diaminodiphenyl ether in N-methyl-2-pyrrolidone under nitrogen stream to prepare an amine solution, and then keep the solution at about 15 ° C. in an ice bath. 109 g (0.5 mole) of pyromellitic acid dianhydride was added with stirring, and the resulting mixture was further reacted at about 15 ° C for 3 hours to obtain a poly (amic acid) solution (D) having the following general formula repeating unit. The viscosity of the solution is 60 poise at 30 ° C.

The solution obtained by adding 2.68 g (0.01 mol) of 2- (N, N-dimethylamino) ethyl 4-azidonaphthylketone to 20 g of solution D was filtered under pressure through a 5 μm mesh filter. . The obtained solution was applied to a silicon wafer by spin coating using a spinner, and then dried at 70 ° C. for 30 minutes to obtain a 0.3 μm thick coating film. The coating film is covered with a strip photo mask and then irradiated with ultraviolet light from a 500 W Xe Hg lamp. The ultraviolet intensity on the exposed surface was 10 mW / cm ² in the wavelength region of 365 nm. After exposure, the coating film is developed with a mixed solution of N-methyl-2-pyrrolidone and ethanol (5: 1 in capacity) and then washed with a washing solution (ethanol) to obtain a relief pattern. The change in residual film thickness over time was measured. The sensitivity was 20 mJ / cm ² at an exposure amount at which the standardized residual film thickness was 0.5 with the applied film thickness. A relief pattern with a sharp end surface was obtained at an exposure dose three times the sensitivity, and this relief pattern did not fade even when heated at 400 ° C. for 60 minutes.

Example 9

A solution obtained by adding 0.27 g (0.001 mol) of 2- (N, N-dimethylamino) ethyl 4'-azidonaphthyl ketone to 20 g of the solution (D) obtained in Example 8 was filtered using a 5 μm mesh filter. Filter under pressure through.

The resulting solution was applied onto a silicon wafer by spin coating using a spinner and then dried at 70 ° C. for 30 minutes to obtain a 1.0 μm thick coating film. The coating film was covered with a strip photomask and then irradiated with ultraviolet light from a 500 W high pressure mercury arc lamp. The ultraviolet intensity on the exposed surface was 8 mW / cm ² (at 365 nm). After exposure, the coating film was developed with a mixed solution containing N, N-dimethyl acetamide and ethanol (4:10 by volume) and then washed with a washing solution (ethanol) to obtain a relief pattern. The sensitivity was 140 mJ / cm ² and obtained. One relief pattern did not become cloudy when heated at 400 ° C. for 60 minutes.

Example 10

Two obtained solutions obtained by adding 5.36 g (0.02 mole) of 2- (N, N-dimethylamino) ethyl 4'-azidonaphthylketone to 20 g of (D) solution obtained in Example 8 were filtered with a 5 µm mesh filter. Filter under pressure through.

The obtained solution was applied to a silicon wafer by spin coating using a spinner, and then dried at 70 ° C. for 30 minutes to obtain a coating film having a thickness of 3.2 μm. The coating film was covered with a strip photomask and then irradiated with ultraviolet light from a 500 W high pressure mercury arc lamp. The ultraviolet intensity on the exposed surface was 8 mW / cm ² (at 365 nm). After exposure, the coating film is developed with a mixed solution of dimethylformamide and ethanol (3: 2 by volume) and then washed with a washing solution to obtain a relief pattern. The sensitivity was 21 mJ / cm ² and the pattern was not blurred even when heated at 400 ° C. for 60 minutes.

Example 11

90 g (0.45 mole) of 4,4'-diaminodiphenyl ether and 11.4 g (0.05 mole) of 4,4'-diaminodiphenyl ether-3-in 1,764 g of N-methyl-2-pyrrolidone The amine solution was prepared by adding carbon amide, and then 54.5 g (0.15 mole) of pyromellitic dianhydride and 80.5 g (0.25 mole) of 3,3 ', 4 were prepared while maintaining the temperature of the amine solution at 15 DEG C in an ice bath. , 4'-benzophenone tetracarboxylic dianhydride is added by stirring. After the addition was completed, the obtained mixture was further reacted at 15 ° C for 3 hours to obtain a solution (E) of poly (amic acid) having a viscosity of 55 poises (at 30 ° C) and a repeating unit of the following general formula.

Percentages)

(E) A solution obtained by dissolving 2.84 g (0.01 mol) of 2 '-(N, N-dimethylamino) ethyl-4-azido-1-naphthalenecarboxylate in a solution was pressurized through a 5 µm filter. Under filtration.

The resulting solution was applied to a silicon wafer using a spinner and then dried at 70 ° C. for 30 minutes to obtain a 2.4 μm thick coating film. The coating film is covered with a strip photomask and irradiated with ultraviolet light from a 500 WXe-Hg lamp. The ultraviolet intensity on the exposed surface was 8 mW / cm ² (at 365 nm). After exposure, the coating film is developed with a mixed solution of N-methyl-2-pyrrolidone and ethanol (5: 1 in capacity), followed by washing with a washing solution (ethanol) to obtain a relief pattern. The sensitivity was 15 mJ / cm ² and the relief pattern was not blurred even when heated at 400 ° C. for 60 minutes.

Example 12

5 µm mesh solution obtained by dissolving 3.16 g (0.01 mol) of 5-azido-1-naphthyl-2 '(N, N-dimethylamino) ethylsulfone in 20 g of (E) solution obtained in Example 11 It is filtered under pressure through a filter of.

The obtained solution was applied to a silicon wafer by spin coating using a spinner, and then dried at 70 ° C. for 30 minutes to obtain a coating film having a thickness of 2.7 μm. The coating film is covered with a strip photo mask and irradiated with UV light from a 500 W high pressure mercury arc lamp. The ultraviolet intensity on the exposed surface was 9 mW / cm ² (at 365 nm). The exposed coating film is developed with a mixture of N-methyl-2-pyrrolidone and ethanol (5: 1 in volume) and then washed with a washing solution (ethanol) to obtain a relief pattern with a sharp end surface. The sensitivity was 25 mJ / cm ^2, and the pattern was not blurred even when heated at 400 ° C. for 60 minutes.

Example 13

In 20 g of (E) solution obtained in Example 11, 3.34 g (0.01 mol) of 2- (N, N-dimethylamino) ethyl-9-azido-10-naphthalenecarboxylate was dissolved. Filter through a filter of micrometer mesh.

The obtained solution was applied to a silicon wafer by spin-coating using a spinner, and then dried at 70 ° C. for 30 minutes to obtain a 2.2 μm thick coating film. The coating film was covered with a strip photomask and then irradiated with ultraviolet light from a 500 W high pressure mercury arc lamp. The UV intensity on the exposed surface was 9 mW / cm ² (at 365 nm), and after exposure the coating film was developed with a mixed solution of N-ethyl-2-pyrrolidone and ethanol (5: 1 in volume) and then washed with ethanol. ) To obtain a relief pattern with an edged end surface. The sensitivity was 18 mJ / cm ^2, and the pattern was not blurred even when heated at 400 ° C. for 60 minutes.

Comparative Example 3

As a comparative example, an amine compound containing at least one carbon-carbon double bond and at least one amino group or a quaternary salt thereof, which can be dimerized or polymerized by ultraviolet rays, is added to a polymer having poly (amic acid) as a main component. The experimental results obtained are described below.

Dissolve 1.57 g (0.01 mole) of 2- (N, N-dimethylamino) ethyl methacrylate in 20 g of solution D obtained in Example 8 and filter the resulting solution under pressure through a 5 μm mesh filter. do. The obtained solution was applied to a silicon wafer by spin-coating using a spinner, and then dried at 70 ° C. for 30 minutes to obtain a coating film having a thickness of 3.2 μm. The coating film is covered with a strip photomask and then irradiated with ultraviolet light from a 500 W high pressure mercury arc lamp.

After exposure, the coating film is developed with a mixed solution of N, N-methylacetamide and ethanol (5: 1 in volume), followed by washing with ethanol to obtain a relief pattern. The sensitivity was 3200 mJ / cm ² , which was lower than in Examples 8 to 13.

Example 14

1,791 g of N-methyl-2-pyrrolidone was dissolved in 100 g (0.5 mol) of 4,4'-diaminodiphenyl ether under a stream of nitrogen to obtain an amine solution. The temperature of the solution was then changed to about 15 ° C. in an ice bath. Add 100 g (0.5 mole) of powdered phytomellitic dianhydride while maintaining. After the addition is complete, the resulting mixture is further reacted at about 15 ° C. for 3 hours to obtain a solution (F) having a viscosity of 60 poises (at 30 ° C.).

A solution obtained by dissolving 11.7 g (0.05 mol) of 2- (N, N-dimethylamino) ethyl p-azidobenzoate and 2 g (0.01 mol) of ethylene glycol dimethacrylate in 100 g of (F) solution. Is filtered under pressure through a 5 μm mesh filter. The resulting solution was applied to a silicon wafer by spin-coating using a spinner, and then dried under vacuum at 2 nmHg for 1 hour to obtain a coating film having a thickness of 1.5 탆. The coating film was flat and uniform and adhered well to the substrate. The coating film was covered with a strip mask and irradiated with ultraviolet light from a 500 W high pressure mercury arc lamp. The ultraviolet intensity on the exposed surface was 15 mW / cm ² in the wavelength region of 365 nm. The post-exposure coating film is developed with a mixed solution of N-methyl-2-pyrrolidone and ethanol (4: 1 in capacity) and then washed with a washing solution (ethanol) to obtain a relief pattern. Sensitivity was calculated as 20 mJ / cm ² when the change in the residual film thickness over time was measured and the exposure amount at which the standard value of the residual film thickness was 0.5 was applied as the applied film thickness. At an exposure dose of 100 mJ / cm ² , which is five times the sensitivity, the relief pattern with a minimum width of 3 μm and a sharp end surface did not become cloudy even when heated at 400 ° C. for 60 minutes.

Example 15

Experiment with the (F) polymer solution obtained in Example 14 and changing the compound (d) having an unsaturated bond with the photosensitive compound (b). The materials tested and the results are listed in Tables 9-11, 39-62, and in the column for photosensitive compounds (b) in the table, "Equivalent based on polymer COOH" refers to the total carboxyl group of polymer (a). The equivalent number of compound (b) added is meant. In the table, "moles" described in the column for compound (d) having an unsaturated bond means the number of moles added to the photosensitive compound (d). The light or radiation sensitive polymer composition prepared by the above method is coated on a support by a spin coating method using a spinner and then dried under vacuum at 2 nmHg for 1 hour to obtain a coating film. The coating film was developed by irradiating ultraviolet rays through a photomask formed by stripping a 500W high pressure mercury silver arc lamp, washing with ethanol and curing at 350 ° C for 1 hour. Sensitivity was expressed as "good" at 100 mJ / cm ² at an exposure amount (measured at 365 nm) that the film thickness after development was standardized to 0.5 with the applied film thickness, and "bad" when 100 mJ / cm ^{2 or} more. .

Heat resistance was shown as "good" when the weight loss after 1 hour at 350 ℃, heating at 300 ℃ 1% or less and "bad" when 1% or more.

In Tables 9 to 11, when the addition amount of the photosensitive compound (b) was 0.4 equivalent or less based on the polymer COOH group, the sensitivity was bad, and when the equivalent amount was 3 equivalent or more, the heat resistance was lowered.

TABLE 5

As a comparative example, the same polyamines as those used in Example 14 containing an amine compound containing at least one carbon-carbon double bond and at least one quaternary salt thereof, which can be double-polymerized or polymerized by UV light The experimental results obtained by addition to the mic acid polymer will be described next.

Comparative Example 4

The solution obtained by dissolving 7.85 g (0.05 mole) of 2- (N, N-dimethylamino) ethylmethacrylate in 100 g of the polymer solution (F) obtained in Example 14 was subjected to pressurization through a 5 μm mesh filter. Filtered. The obtained solution was coated on a silicon wafer by a spin coating method using a spinner, and then dried at 70 ° C. for 30 minutes to obtain a coating film having a thickness of 1.8 μm. The coating film is covered with a photomask made of soda glass and then irradiated with ultraviolet light from a 500 W high pressure mercury arc lamp. After exposure, the coating film is developed with a mixed solution of N-methyl-2-pyrrolidone and ethanol (5: 1 in capacity) and then washed with ethanol to obtain a relief pattern. The sensitivity was 2,500 mJ / cm ^{2, which} is lower than that of 39 to 62 in Tables 9 to 11.

Example 16

Synthesis of N, N-dimethylamino-N '-(p-azidobenzylideneacetyl) ethyllemdiamine

To 17 g (90 mmol) of p-azidocinnamic acid is added 53 g (150 mmol) of thionyl chloride and the resulting solution is heated to reflux. Reflux was stopped when generation of SO2 gas was stopped, excess thionyl chloride was distilled off under reduced pressure, and 14.8 g of p-azidocinnamic acid chloride was obtained as a distillation residue. A solution obtained after dissolving 8.5 g (40 mmol) of p-azido cinnamic acid chloride in chloroform and adding 4.8 g (40 mmol) of N, N-diethyl aminoethylenediamine at a reaction temperature of 10 to 20 ° C. Let react for 1 hour more. Chloroform is distilled off under reduced pressure, 100 ml of water is added to the oily residue, and a solution of 1.7 g of sodium hydroxide is dissolved in 20 ml of water in an ice bath.

The separated organic layer is extracted with chloroform, the extract is washed with water, dried over anhydrous sodium sulfate and the solvent is distilled off to obtain 11 g of oily substance as distillation residue. This oily substance decomposes at 130 ° C., forming bubbles and generating heat. This oily substance was found to be a compound of the present invention by analysis using the following spectrum.

Nuclear Magnetic Resonance (NMR): Chemical shifts measured in deuterated chloroform are given below in ppm, in parentheses in the order of pattern, binding constant, integral ratio and corresponding symbol. 1.1 (triple, 6Hz, 6Ha, a), 2.7 (quadrant and triplet 6Hz, 6H, b and c), 3.5 (quadrant, 6Hz, 4H, d), 6.45 (doublet, 16Hz, 1H, f ), 7.0 (doublet and singlet, 10Hz, 3H, o and h), 7.5 (doublet, 10Hz, 2H, i), 7.65 (doublet, 16Hz, 2H, g).

Infrared absorption spectrum (IR); The main maximum absorption measured by the liquid film method is given below in cm ⁻¹ units, and their designations are indicated in parentheses. 2,130 (azide group), 1,650 (double bond), 1,620 (carbyl group). Since the compound of the present invention has a maximum ultraviolet absorption region at 305 nm and its absorption end reaches a long wavelength of 380 nm, the compound is sensitive to the desired ultraviolet light in the long wavelength region.

Example 17

Synthesis of 2- (N, N-diethylamino) ethyl p-azidocinnamate

To 80 g of chloroform, 6.2 g (30 mmol) of p-azidocinnamic acid chloride obtained in Example 16 and 3.5 g (30 mmol) of 2-diethylamino ethanol were added dropwise at a temperature of 10 to 20 ° C. The obtained mixture is left to react for another 1 hour. After evaporating the chloroform under reduced pressure, 100 ml of water was added to the oily residue and 1.3 g of sodium hydroxide solution dissolved in 20 ml of water was added in an ice bath. The separated organic layer is extracted with chloroform, the extract is washed with water, dried over anhydrous sodium sulfate and the solvent is evaporated to give 7.2 g of oily substance as distillation residue. This oily substance decomposes at 130 ° C., producing bubbles and generating heat. This oily water proved to be a compound of the present invention by analysis using the following spectrum.

Nuclear Magnetic Resonance (NMR): The chemical shifts measured in deuterated chloroform are given below in ppm and in parentheses in the order of pattern, binding constant, integral ratio and corresponding symbol.

1.1 (triple, 6 Hz, 6H, a), 2.75 (quartet and triplet, 6 Hz, 6H, b and c), 4.35 (triple, 6 Hz, 2H, d), 6.45 (doublet, 16 Hz, 1H, e), 7.08 (doublet, 8Hz, 2H, g), 7.52 (doublet, 8Hz, 2h, h), 7.63 (doublet, 16Hz, 1H, f).

Infrared Absorption Spectrum (IR): The main maximum absorption measured in the liquid film method is given below in cm ⁻¹ , and their designations are indicated in parentheses.

2,120 (azido group), 1,710 (carbonyl group), 1,640 (olefin group).

Since the compound of the present invention has a maximum ultraviolet absorption region at 314 nm and its absorption end reaches a long wavelength of 370 nm, the compound is sensitive to a desired ultraviolet ray in the long wavelength region.

Example 18

Synthesis of 2- (N, N-diethylamino) ethyl p-azido cinnamate

Obtained by dissolving 14 g (70 mmol) of p-azidocinnamic acid chloride obtained in Example 16 in carbon tetrachloride and then dropwise addition of 6 g (70 mmol) of 2-dimethylaminomethanol at 10 ° to 20 ° C in the solution. One mixture is further reacted for 1 hour. The precipitated material is recovered by filtration and 100 ml of water is added thereto. Participate in a solution obtained with 2.8 g of sodium hydroxide solution dissolved in 50 ml of water in an ice bath, extract the separated organic layer with chloroform, and then wash the extract with water, dry over anhydrous sodium sulfate, and evaporate the solvent. An oily substance is obtained. The oily material decomposes at 125 ° C. with foaming and generation of heat. The oily substance was identified as a compound of the present invention by analysis using the following spectrum.

Nuclear Magnetic Resonance (NMR): The chemical shifts measured in chloroform are given below in ppm, in parentheses in the order of pattern, binding constant, integral ratio and corresponding symbol.

2.4 (Singlet, 6H, a), 2.7 (Triple, 8Hz, 2H, b), 4.4 (Triple, 8Hz, 2H, c), 6.45 (Dual, 16Hz, 1H, d), 7.05 (Dual , 8 Hz, 2H, f), 7.57 (doublet, 8Hz, 2H, e), 7.72 (doublet, 16Hz, 1H, e).

Infrared Absorption Spectrum (IR): The main maximum absorptions measured by the liquid film method are given below in cm-1 and their designations are indicated in parentheses.

2,140 (azido group), 1,720 (carbonyl group), 1,630 (double bond).

The compound of the present invention has an infrared absorption maximum region at 315 nm and its absorption end reaches a long wavelength of 370 nm, so the compound is sensitive to infrared rays in the long wavelength region.

Claims (21)

a) a poly (amic acid) having a repeating unit of the following general formula (1) as a main component, and b) having an amino group and an aromatic azide group or an aromatic sulfonyl azide group in one molecule To at least one light or radiation sensitive compound selected from the compounds of (7) to 0.05 to 5 times the equivalent of the total COOM groups of repeating units in the general formula (1) of component (a). Or radiation sensitive polymer composition

In the above formula, R ₁ is a trivalent or tetravalent organic group having at least two carbon atoms, R ² is a divalent organic group having at least two carbon atoms, and R ³ , R ⁴ and R ⁵ are independently hydrogen or lower alkyl groups , R ⁵ 'is hydrogen, halogen, nitro group, lower alkoxy group, lower alkyl group or cyano group, R ⁷ is hydrogen or lower alkyl group, R ⁸ is hydrogen, halogen, cyano group or lower alkyl group , R ⁹ is a divalent organic group bonded to a residue having N atoms and unsaturated bonds, R ¹⁰ is a divalent organic group bonded to Ar and N atoms, R ¹¹ is hydrogen, a halogen, a lower alkyl group, a lower alkoxy Group, nitro group, carboxyl group, or sulfonic acid group, M is hydrogen or ammonium, n is an integer of 1 or 2, m is an integer of 1 to 3, X is -N3 or -SO ₂ N ₃ , Y is an alkylene group, Ar is a benzene ring and hetero Aromatic group selected in the cyclic ring. The method according to claim 1, wherein 0.01 to 10% by weight of one or more photosensitizers and / or 0.05 to 2 moles per mole of (b) component, based on the total weight of the components (c), (a), (b) and (c). A light or radiation sensitive polymer composition further comprising an amine compound having an unsaturated bond (wherein the total amount of the amine of component (b) and component (c) is three times the equivalent of the COOM group of component (a)). Heim). The light or radiation sensitive polymer composition according to claim 1, further comprising (d) at least one compound having at least two unsaturated bonds in one molecule. A compound according to claim 1 comprising (c) at least one photosensitizer and / or an amine compound having at least one unsaturated bond and (d) at least one compound having at least two unsaturated bonds in one molecule other than the amine compound (c) described above. A light or radiation sensitive polymer composition, further comprising. The light or radiation sensitive polymer composition according to claim 1, 2 or 3, wherein the repeating unit of the general formula (1) is as described below.

The light or radiation sensitive polymer composition according to claim 1, 2, 3 or 4, wherein component (b) is a compound of formula (2).

In the above formula, X is —N ₃ or —SO ₂ N ₃ , Y is an alkylene group having 5 or less carbon atoms, and R ³ , R ⁴ and R ⁵ are independently hydrogen or a lower alkyl group. The light or radiation sensitive polymer composition according to claim 1, 2, 3 or 4, wherein component (b) is a compound of formula (c).

In the above formula, X is -N ₃ or -SO ₂ N ₃ ; R ³ , R ⁴ and R ⁵ are independently hydrogen or lower alkyl group. The light or radiation sensitive polymer composition according to claim 1, 2, 3 or 4, wherein component (b) is a compound of the following general formula (4).

In the above formula, X is -N ₃ or -SO ₂ N ₃ , R ³ , R ⁴ and R ⁵ are independently hydrogen or lower alkyl group, R ⁶ is

-O-or-CH _2- . The light or radiation sensitive polymer composition according to claim 1, 2, 3 or 4, wherein component (b) is a compound of the following general formula (5).

In the above formula, X is -N ₃ or -SO ₂ N ₃ and R ⁷ is hydrogen or lower alkyl group. The light or radiation sensitive polymer composition according to claim 1, 2, 3 or 4, wherein component (b) is a compound of the following general formula (6).

In the above formula, X is -N ₃ or -SO ₂ N ₃ , R ³ and R ⁴ are independently hydrogen or lower alkyl group, R ⁵ ′ is hydrogen, halogen, nitro, lower alkoxy, lower alkyl or cyano group, R ⁷ Is a hydrogen or lower alkyl group, R ⁸ is a hydrogen, halogen, cyano or lower alkyl group, R ⁹ is a divalent organic group bonded to a residue having N atoms and unsaturated bonds, m is an integer of 1 to 3 to be. The light or radiation sensitive polymer composition according to claim 1, 2, 3 or 4, wherein component (b) is a compound of the following general formula (7).

In the above formula, X is -N ₃ or -SO ₂ N ₃ , Ar is an aromatic group selected from benzene ring and heterocyclic ring which can be fused, R ³ and R ⁴ are independently hydrogen or lower alkyl group, R ¹⁰ is Ar And a divalent organic group bonded to an N atom, R ¹¹ is hydrogen, halogen, lower alkyl group, lower alkoxy group, nitro group, carboxyl or sulfonic acid group. The light or radiation sensitive polymer composition according to claim 6, wherein the compound of formula (2) is represented by the following general formula.

Wherein P is 2 or 3. The light or radiation sensitive polymer composition according to claim 10, wherein the compound of formula (6) has the following structural formula.

11. A light or radiation sensitive polymer composition according to claim 10, wherein the compound of formula (6) has the following structural formula.

The photoconductor of component (c) is N, N'-tetramethyl-4, 4'-diaminobenzophenone or N, N'-tetraethyl-4, 4'-diamino. Light or radiation sensitive polymer composition, characterized in that benzophenone. The light or radiation sensitive polymer composition according to claim 3 or 4, wherein the unsaturated bond in component (d) is an acryloyl or methacryloyl group. A method of forming a relief pattern on a substrate using the composition of claims 1, 2, 3 or 4. The acid chloride compound obtained by reacting the carboxylic acid of formula (II) with thionyl chloride and the compound of formula (III) are reacted with an alkali solution, and the compound of formula (2) How to manufacture.

In the above formula, X is -N ₃ or -SO ₂ N ₃ , Y is an alkylene group having 5 or less carbon atoms, and R ³ , R ⁴ and R ⁵ are independently hydrogen or a lower alkyl group. The method according to claim 18, wherein the prepared compound is a compound having the following structural formula.

The acid chloride compound obtained by reacting carboxylic acid and thionyl chloride of formula (IV) is reacted with a compound of formula (V) and then treated with an alkali solution to prepare a compound of formula (6). How to.

In the above formula, X is -N ₃ or -SO ₂ N ₃ , R ³ and R ⁴ are independently hydrogen or lower alkyl group, R ⁵ ′ is hydrogen, halogen, nitro, lower alkyl, lower alkoxy or cyano group, R ⁷ is hydrogen or lower alkyl group, R ⁸ is hydrogen, halogen, cyano or lower alkyl group, R ⁹ is a divalent organic group bonded to a residue having N atom and unsaturated bond, m is 1 to 3 Integer and W is hydroxy or amino. The preparation method according to claim 20, wherein the prepared compound is a compound having the following structural formula.