Radiation sensitive composition for forming an insulating film, insulating film and display device Number:6,797,453 from the United States Patent and Trademark Office (PTO) owispatent There is disclosed a radiation sensitive composition containing a silane compound represented by the following formula (1):and a compound which generates an acid or base upon exposure to radiation. The composition is used to form an insulating film for an organic EL display device, and an interlayer insulating film for a liquid crystal display device.<H composition, insulating, Radiation, sensi, 6797453.html, Patent, pto, 6797453

Title: Radiation sensitive composition for forming an insulating film, insulating film and display device

Abstract: There is disclosed a radiation sensitive composition containing a silane compound represented by the following formula (1):and a compound which generates an acid or base upon exposure to radiation. The composition is used to form an insulating film for an organic EL display device, and an interlayer insulating film for a liquid crystal display device.

Patent Number: 6,797,453 Issued on 09/28/2004 to Shiraki, et al.

Inventors: Shiraki; Shinji (Tokyo, JP), Suzuki; Masayoshi (Tokyo, JP), Sasaki; Hirofumi (Tokyo, JP), Niwa; Kazuaki (Tokyo, JP), Nishikawa; Michinori (Tokyo, JP)
Assignee: JSR Corporation (Tokyo, JP)

Appl. No.: 10/349,080

Filed: January 23, 2003

Foreign Application Priority Data


Jan 24, 2002 [JP]			2002-014998
Sep 20, 2002 [JP]			2002-274809
Oct 31, 2002 [JP]			2002-317124

Current U.S. Class: 430/270.1

Field of Search: 430/270.1

References Cited [Referenced By]

U.S. Patent Documents


5385955	January 1995	Tarshiani et al.
5627010	May 1997	Pai et al.
5731126	March 1998	Takemura et al.
5777038	July 1998	Nishikawa et al.
6060130	May 2000	Kim
6087064	July 2000	Lin et al.
6270941	August 2001	Yasunami
6296985	October 2001	Mizutani et al.
6309796	October 2001	Nakashima et al.
6340734	January 2002	Lin et al.
6344305	February 2002	Lin et al.
2001/0012596	August 2001	Kunimoto et al.

Foreign Patent Documents


0 725 106	Aug., 1996	EP
0 965 618	Dec., 1999	EP
1 150 165	Oct., 2001	EP
1 235 104	Aug., 2002	EP
1 296 540	Mar., 2003	EP
04-330444	Nov., 1992	JP
07-098502	Apr., 1995	JP
07-098503	Apr., 1995	JP
07-140648	Jun., 1995	JP
10-153854	Jun., 1998	JP
3003064	Jan., 2000	JP
2000-298352	Oct., 2000	JP
2001-281853	Oct., 2001	JP
2001-281861	Oct., 2001	JP
WO 02/090423	Nov., 2002	WO

Other References

Derwent Abstracts, AN 2002-182008, XP-002260376, JP 2001-300951, Oct. 30, 2001. .
Patent Abstracts of Japan, JP 2001-288364, Oct. 16, 2001. .
Patent Abstracts of Japan, JP 2000-302869, Oct. 31, 2000..

Primary Examiner: Le; Hoa Van
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt, P.C.

Claims

What is claimed is:

1. A radiation sensitive composition which comprises: component (A1), at least one compound selected from the group consisting of a silane compound represented by the following formula (1):

2. The radiation sensitive composition of claim 1, which further comprises a silane coupling agent.

3. The radiation sensitive composition of claim 1, which further comprises a dehydrating agent.

4. A radiation sensitive composition which comprises: component (A1), at least one compound selected from the group consisting of a silane compound represented by the following formula (1):

5. The radiation sensitive composition of claim 4, which further comprises a silane coupling agent.

6. An insulating film for an organic EL display device, formed from the radiation sensitive composition of claim 1.

7. An organic EL display device comprising the insulating film of claim 5.

8. An interlayer insulating film for a liquid crystal display device, formed from the radiation sensitive composition of claim 4.

9. A liquid crystal display device comprising the interlayer insulating film of claim 8.

10. The radiation sensitive composition of claim 2, which further comprises a dehydrating agent.

11. An insulating film for an organic EL display device, formed from the radiation sensitive composition of claim 2.

12. An insulating film for an organic EL display device, formed from the radiation sensitive composition of claim 3.

13. An interlayer insulating film for a liquid crystal display device, formed from the radiation sensitive composition of claim 5.

Description

FIELD OF THE INVENTION

The present invention relates to a radiation sensitive composition for forming an insulating film, an insulating film and a display device. More specifically, it relates to a negative type radiation sensitive composition suitable for the formation of an insulating film using radiation such as ultraviolet rays, deep ultraviolet rays, X-radiation, electron beam, molecular beam, .gamma.-ray, synchrotron radiation or proton beam, an insulating film for a display device formed therefrom, and a display device having the insulating film.

DESCRIPTION OF THE PRIOR ART

An organic EL display device has small dependence on view angle as it emits light by itself and has various advantages such as excellent impact resistance, low voltage drive, low power consumption and high operation stability at a low temperature range as it is a solid device, in comparison with a liquid crystal display device. Since it is highly expected that the organic EL display device will be used particularly for mobile applications such as portable terminals and automobiles due to the above advantages, studies on the organic EL display device are under way energetically.

The production of such an organic EL display device is generally carried out by the following method. A transparent electrode (hole injection electrode) pattern such as a tin-doped indium oxide (ITO) pattern and a hole transport layer pattern are formed on a substrate. Then, an insulating film pattern and a cathode rib pattern are formed, followed by the patterning of an organic EL layer, an electron transport layer and a cathode by deposition in the case of a passive type organic EL display device. In the case of an active type organic EL display device, after an ITO pattern and an insulating film pattern which will become organic EL layer ribs are formed, an organic EL layer pattern is formed by a masking method or ink jet method, followed by the formation of an electron transport layer and a cathode (electron injection electrode).

In general, the organic EL layer is made from a base material such as Alq.sub.3 or BeBq.sub.3 doped with quinacridone or coumarine and the cathode is mainly made from a material essentially composed of a metal having a low work function such as Mg or Ag.

To meet recent demand for high resolution, an organic EL display device having a larger numerical aperture is now under study.

However, there is definite limitation to the improvement of the numerical aperture for the following reasons.

That is, to improve the numerical aperture of a passive type organic EL display device, the pattern widths of an insulating film and a cathode rib pattern need to be reduced. This requires a certain degree of strength and there is limitation to the reduction of pattern width from the viewpoint of resolution. Accordingly, a sufficiently large numerical aperture could not be obtained.

In an active type organic EL display device, to prevent a short circuit in an ITO pattern for each pixel, a certain space must be formed between pixels, thereby limiting the numerical aperture.

An active type organic EL display device having a structure capable of obtaining a larger numerical aperture is now under study.

This active type organic EL display device is produced by the following method, for example.

A drive terminal is formed on a glass substrate or the like, a first insulating film is formed as a flattening film on the terminal, and then a transparent electrode (hole injection electrode) pattern such as an ITO pattern is formed on the first insulating film. The formation of these patterns is generally carried out by a wet etching method.

A hole transport layer pattern is further formed on the transparent electrode pattern by a masking method. Thereafter, an ITO pattern, a second insulating film pattern which will become ribs for an organic EL layer and an organic EL layer pattern are formed by a masking method or ink jet method, followed by the formation of an electron transport layer and a cathode (electron injection electrode).

At this point, a 1 to 15 .mu.m long through hole or U-shaped depression must be formed in the first insulating film to make the ITO electrode (hole injection electrode) and the drive terminal conductive with each other.

It is known that an organic EL light emissive layer deteriorates quickly and its light emission is impeded when it contacts water even if it is a low-molecular weight light emitting layer or polymer light emitting layer. It is considered that water comes from environment or a trace amount of water adsorbed to an insulating film material permeates an organic EL layer little by little.

Heretofore, there has not been proposed a material capable of forming an insulating film which has resolution high enough to form a through hole or U-shaped depression for realizing a larger numerical aperture, excellent flattening capability and high resistance to a resist remover used for the formation of a transparent electrode and further prevents the permeation of impurities (mainly water) which impede light emission.

A thin film transistor (to be abbreviated as TFT hereinafter) liquid crystal display device is generally produced by opposing a TFT array substrate having TFT's, electrode lines and capacitors formed on a glass substrate to a color filter substrate having a color filter formed on another glass substrate, joining them together using a sealer, injecting liquid crystals into the space between the substrates and sealing up the injection port with a sealer.

The above TFT array substrate is generally produced as follows. TFT elements, display electrodes, scanning lines (gate electrodes), signal lines (drain electrodes) and capacitors are first formed on a glass substrate. Thereafter, an interlayer insulating film is formed on these, a contact hole pattern for interconnecting pixel electrodes and source electrodes is formed, and then transparent pixel electrodes (ITO) are formed on the interlayer insulating film. Thereafter, the transparent pixel electrodes are partitioned for each pixel by etching, and a liquid crystal alignment film is formed and rubbed.

When an end portion of each pixel electrode is placed upon an end portion of a scanning line or signal line to increase the numerical aperture as much as possible, the above interlayer insulating film is formed to insulate them from each other. A radiation sensitive composition from which an interlayer insulating film having a desired pattern shape and excellent flatting capability is obtained from a small number of steps is widely used as a material for the above interlayer insulating film. JP-A 7-98502, JP-A 7-98503 and JP-A 7-140648 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") disclose a combination of a novolak resin or phenolic resin such as polyhydroxystyrene and a quinonediazide-based sensitizer, and Japanese Patent No. 3003064, JP-A 10-153854, JP-A 2001-281853 and JP-A 2001-281861 disclose a combination of an acrylic resin and a quinonediazide-based sensitizer as the materials.

As described above, after such an interlayer insulating film is formed on a substrate, the step of forming a transparent pixel electrode and a liquid crystal alignment film is carried out, and the interlayer insulating film is heated at a high temperature in the above step. Since conventionally known materials for forming an interlayer insulating film are unsatisfactory in terms of heat resistance, they become yellow or brown in the above step with the result of greatly reduced transparency. To avoid this phenomenon, the temperature for heating the transparent electrode film must be set to a certain temperature or lower. If so, the formed transparent electrode film hardly obtains desired electric properties, particularly sufficiently low electric resistance.

After the interlayer insulating film is formed on the substrate, it is supplied to the step of forming an electrode and exposed to organic solvents such as an etchant for the patterning of the electrode and a resist remover. Therefore, the interlayer insulating film needs high solvent resistance so that it is not swollen, deformed or peeled of f from the substrate by these solvents. Further, higher radiation sensitivity and more excellent developability are required from the viewpoint of production yield.

However, there has been unknown a radiation sensitive composition suitable for the formation of an interlayer insulating film for a liquid crystal display device, which has high radiation sensitivity, excellent developability, high heat resistance, high transparency and excellent solvent resistance.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a radiation sensitive composition for forming an insulating film for an organic EL display device, which has resolution high enough to form a through hole or U-shaped depression, excellent flattening capability and high resistance to a resist remover used to form a transparent electrode, and prevents the permeation of impurities (mainly water) which impede light emission.

It is another object of the present invention to provide a radiation sensitive composition which has high radiation sensitivity, excellent developability, high heat resistance, high transparency and excellent solvent resistance and is suitable for the formation of an interlayer insulating film for a liquid crystal display device.

It is still another object of the present invention to provide an insulating film for an organic EL display device or liquid crystal display device formed from the above composition.

It is a further object of the present invention to provide an organic EL display device or liquid crystal display device having the above insulating film.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, firstly, the above objects and advantages of the present invention are attained by a radiation sensitive composition which comprises: (A1) at least one compound selected from the group consisting of a silane compound represented by the following formula (1):

According to the present invention, secondly, the above objects and advantages of the present invention are attained by a radiation sensitive composition which comprises (A1) at least one compound selected from the group consisting of a silane compound represented by the above formula (1), a hydrolyzate thereof and a condensate of the hydrolyzate, and (A2) a compound which generates an acid or base upon exposure to radiation, and (B) which is used to form an interlayer insulating film for a liquid crystal display device.

According to the present invention, thirdly, the above objects and advantages of the present invention are attained by an insulating film for an organic EL display device or a liquid crystal display device, which is formed from the above radiation sensitive composition of the present invention.

According to the present invention, in the fourth place, the above objects and advantages of the present invention are attained by an organic EL display device or liquid crystal display device having the above insulating film.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The radiation sensitive composition of the present invention will be described hereinbelow.

Component (A1)

The component (A1) contained in the radiation sensitive composition for forming an insulating film for an organic EL display device and the radiation sensitive composition for forming an insulating film for a liquid crystal display device of the present invention is at least one compound selected from the group consisting of a silane compound represented by the following formula (1), a hydrolyzate thereof and a condensate of the hydrolyzate:

wherein R.sup.1 is an unhydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3.

The hydrolyzable group represented by X is generally a group capable of forming a silanol group when it is hydrolyzed by heating at room temperature (25.degree. C.) to 100.degree. C. without a catalyst in the presence of excess water or a group capable of forming a siloxane bond when it is further condensed. Examples of the-hydrolyzable group include hydrogen atom, halogen atom, alkoxyl group having 1 to 12 carbon atoms, amino group and acyloxyl group having 2 to 12 carbon atoms.

Examples of the unhydrolyzable organic group having 1 to 12 carbon atoms represented by R.sup.1 include alkyl group having 1 to 12 carbon atoms, aryl group having 6 to 12 carbon atoms and aralkyl group having 7 to 12 carbon atoms. They may be linear, branched or cyclic and may be existent in combination when a plurality of R.sup.1 's are existent in the same molecule.

R.sup.1 may contain a structural unit having a hetero atom. Examples of the structural unit include ether, ester and sulfide.

Unhydrolyzability required for R.sup.1 means the property of being existent stably under a condition that the hydrolyzable group X is hydrolyzed.

The above p is an integer of 0 to 3, preferably 0 to 2, particularly preferably 1.

The silane compound represented by the above formula (1) is, for example, a saline compound substituted by four hydrolyzable groups, a silane compound substituted by one unhydrolyzable group and three hydrolyzable groups, a silane compound substituted by two unhydrolyzable groups and two hydrolyzable groups, or a silane compound substituted by three unhydrolyzable groups and one hydrolyzable group.

Illustrative examples of these silane compounds include silane compounds substituted by four hydrolyzable groups, such as tetrachlorosilane, tetraminosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenziloxysilane and tetrapropoxysilane; silane compounds substituted by one unhydrolyzable group and three hydrolyzable groups, such as methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, d3-methyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane and trifluoromethyltrimethoxysilane; silane compounds substituted by two unhydrolyzable groups and two hydrolyzable groups, such as dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane diphenyldimethoxysilane and dibutyldimethoxysilane; and silane compounds substituted by three unhydrolyzable groups and one hydrolyzable group such as trimethylchlorosilane, hexamethyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane and tributylethoxysilane.

Out of these, silane compounds substituted by one unhydrolyzable group and three hydrolyzable groups are preferred, and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane and butyltrimethoxysilane are particularly preferred.

These silane compounds may be used alone or in combination of two or more.

The component (A1) used in the present invention is at least one compound selected from the group consisting of the above silane compound, a hydrolyzate thereof and a condensate of the hydrolyzate, preferably a hydrolyzate of a silane compound or a condensate of the hydrolyzate.

The conditions for hydrolyzing or condensing the above silane compound are not particularly limited. The hydrolysis or condensation of the silane compound can be carried out by the following step, for example.

The above silane compound and predetermined amounts of water and a suitable solvent are placed in a vessel equipped with a stirrer and stirred in an air atmosphere at a temperature of 0.degree. C. to the boiling point of the solvent or silane compound for 1 to 24 hours. During stirring, the reaction mixture may be concentrated by distillation as required, or the solvent may be newly added.

The solvent used is not limited to a particular kind but generally a solvent identical to a solvent used for the preparation of the radiation sensitive composition which will be described hereinafter. When the solvent is used, its amount is preferably 1,000 parts or less by weight based on 100 parts by weight of the silane compound.

To hydrolyze or condense the above silane compound, a catalyst may be used. The catalyst is a metal chelate compound, organic acid, inorganic acid, organic base or inorganic base.

The metal chelate compound used as the catalyst is preferably a titanium chelate compound, zirconium chelate compound or aluminum chelate compound.

Examples of the metal chelate compound include titanium chelate compounds such as triethoxy.cndot.mono(acetylacetonato)titanium, tri-n-propoxy.cndot.mono(acetylacetonato)titanium, tri-i-propoxy.cndot.mono(acetylacetonato)titanium, tri-n-butoxy.cndot.mono(acetylacetonato)titanium, tri-sec-butoxy.cndot.mono(acetylacetonato)titanium, tri-t-butoxy.cndot.mono(acetylacetonato)titanium, diethoxy.cndot.bis(acetylacetonato)titanium, di-n-propoxy.cndot.bis(acetylacetonato)titanium, di-i-propoxy.cndot.bis(acetylacetonato)titanium, di-n-butoxy.cndot.bis(acetylacetonato)titanium, di-sec-butoxy.cndot.bis(acetylacetonato)titanium, di-t-butoxy.cndot.bis(acetylacetonato)titanium, monoethoxy.cndot.tris(acetylacetonato)titanium, mono-n-propoxy.cndot.tris(acetylacetonato)titanium, mono-i-propoxy.cndot.tris(acetylacetonato)titanium, mono-n-butoxy.cndot.tris(acetylacetonato)titanium, mono-sec-butoxy.cndot.tris(acetylacetonato)titanium, mono-t-butoxy.cndot.tris(acetylacetonato)titanium, tetrakis(acetylacetonato)titanium, triethoxy.cndot.mono(ethylacetoacetate)titanium, tri-n-propoxy.cndot.mono(ethylacetoacetate)titanium, tri-i-propoxy.cndot.mono(ethylacetoacetate)titanium, tri-n-butoxy.cndot.mono(ethylacetoacetate)titanium, tri-sec-butoxy.cndot.mono(ethylacetonato)titanium, tri-t-butoxy.cndot.mono(ethylacetonato)titanium, diethoxy.cndot.bis(ethylacetoacetate)titanium, di-n-propoxy.cndot.bis(ethylacetoacetate)titanium, di-i-propoxy.cndot.bis(ethylacetoacetate)titanium, di-n-butoxy.cndot.bis(ethylacetoacetate)titanium, di-sec-butoxy.cndot.bis(ethylacetoacetate)titanium, di-t-butoxy.cndot.bis(ethylacetoacetate)titanium, monoethoxy.cndot.tris(ethylacetoacetate)titanium, mono-n-propoxy.cndot.tris(ethylacetoacetate)titanium, mono-i-propoxy.cndot.tris(ethylacetoacetate)titanium, mono-n-butoxy.cndot.tris(ethylacetoacetate)titanium, mono-sec-butoxy.cndot.tris(ethylacetoacetate)titanium, mono-t-butoxy.cndot.tris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonato)tris(ethylacetoacetate)titanium, bis(acetylacetonato)bis(ethylacetoacetate)titanium and tris(acetylacetonato)mono(ethylacetoacetate)titanium; zirconium chelate compounds such as triethoxy.cndot.mono(acetylacetonato)zirconium, tri-n-propoxy.cndot.mono(acetylacetonato)zirconium, tri-i-propoxy.cndot.mono(acetylacetonato)zirconium, tri-n-butoxy.cndot.mono(acetylacetonato)zirconium, tri-sec-butoxy.cndot.mono(acetylacetonato)zirconium, tri-t-butoxy.cndot.mono(acetylacetonato)zirconium, diethoxy bis(acetylacetonato)zirconium, di-n-propoxy.cndot.bis(acetylacetonato)zirconium, di-i-propoxy.cndot.bis(acetylacetonato)zirconium, di-n-butoxy.cndot.bis(acetylacetonato)zirconium, di-sec-butoxy.cndot.bis(acetylacetonato)zirconium, di-t-butoxy.cndot.bis(acetylacetonato)zirconium, monoethoxy tris(acetylacetonato)zirconium, mono-n-propoxy.cndot.tris(acetylacetonato)zirconium, mono-i-propoxy.cndot.tris(acetylacetonato)zirconium, mono-n-butoxy.cndot.tris(acetylacetonato)zirconium, mono-sec-butoxy.cndot.tris(acetylacetonato)zirconium, mono-t-butoxy.cndot.tris(acetylacetonato)zirconium, tetrakis(acetylacetonato)zirconium, triethoxy.cndot.mono(ethylacetoacetate)zirconium, tri-n-propoxy.cndot.mono(ethylacetoacetate)zirconium, tri-i-propoxy.cndot.mono(ethylacetoacetate)zirconium, tri-n-butoxy.cndot.mono(ethylacetoacetate)zirconium, tri-sec-butoxy.cndot.mono(ethylacetoacetate)zirconium, tri-t-butoxy.cndot.mono(ethylacetoacetate)zirconium, diethoxy.cndot.bis(ethylacetoacetate)zirconium, di-n-propoxy.cndot.bis(ethylacetoacetate)zirconium, di-i-propoxy.cndot.bis(ethylacetoacetate)zirconium, di-n-butoxy.cndot.bis(ethylacetoacetate)zirconium, di-sec-butoxy.cndot.bis(ethylacetoacetate)zirconium, di-t-butoxy.cndot.bis(ethylacetoacetate)zirconium, monoethoxy.cndot.tris(ethylacetoacetate)zirconium, mono-n-propoxy.cndot.tris(ethylacetoacetate)zirconium, mono-i-propoxy.cndot.tris(ethylacetoacetate)zirconium, mono-n-butoxy.cndot.tris(ethylacetoacetate)zirconium, mono-sec-butoxy.cndot.tris(ethylacetoacetate)zirconium, mono-t-butoxy.cndot.tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato)tris(ethylacetoacetate)zirconium bis(acetylacetonato)bis(ethylacetoacetate)zirconium and tris(acetylacetonato)mono(ethylacetoacetate)zirconium; aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum.

Illustrative examples of the organic acid used as the catalyst include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid.

Illustrative examples of the inorganic acid used as the catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid and phosphoric acid.

Examples of the organic base used as the catalyst include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene and tetramethylammnoium hydroxide.

Examples of the inorganic base used as the catalyst include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide.

Out of these, metal chelate compounds, organic acids and inorganic acids are preferred, and titanium chelate compounds and organic acids are more preferred as the catalyst.

These compounds may be used alone or in combination of two or more as the catalyst.

The amount of the catalyst is preferably 10 parts or less by weight, more preferably 0.001 to 10 parts by weight, much more preferably 0.01 to 10 parts by weight based on 100 parts by weight of the silane compound.

The weight average molecular weight of the hydrolyzate of the silane compound or the condensate of the hydrolyzate is preferably 15,000 or less, more preferably 500 to 15,000, much more preferably 1,000 to 12,000.

When the weight average molecular weight is within the above range, a composition whose film forming properties and radiation sensitivity are well balanced can be obtained.

It should be understood that the above weight average molecular weight is measured in terms of polystyrene by gel permeation chromatography (may be abbreviated as GPC hereinafter).

(A2) Compound which Generates an Acid or Base upon Exposure to Radiation

The component (A2) used in the present invention is a radiation sensitive acid generator or radiation sensitive base generator.

The radiation sensitive acid generator is a compound which can generate an acidic substance capable of curing (crosslinking) the component (A1) upon exposure to radiation such as ultraviolet radiation. The radiation sensitive acid generator is, for example, a trichloromethyl-s-triazine, diaryliodonium salt, triarylsulfonium salt, quaternary ammonium salt or sulfonic acid ester. Out of these, a diaryliodonium salt and triarylsulfonium salt are preferred.

Examples of the above trichloromethyl-s-triazine include 2,4,6-tris(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-.beta.-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3-methoxy-.beta.-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2-methoxy-.beta.-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4,5-trimethoxy-.beta.-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methylthio-p-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3-methylthio-.beta.-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3-methylthio-.beta.-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis (trichloromethyl)-s-triazine and 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis (trichloromethyl)-s-triazine.

Examples of the above diaryl iodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonato, diphenyliodonium trifluorbacetate, diphenyliodonium-p-toluenesulfonato, diphenyliodonium butyltris(2,6-difluorophenyl)borate, diphenyliodonium hexyltris(p-chlorophenyl)borate, diphenyliodonium hexyltris (3-trifluoromethylphenyl) borate, 4-methxoyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonato, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonato, 4-methoxyphenylphenyliodonium butyltris(2,6-difluorophenyl)borate, 4-methoxyphenylphenyliodonium hexyltris(p-chlorophenyl)borate, 4-methoxyphenylphenyliodonium hexyltris(3-trifluoromethylphenyl)borate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluoroarsenate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonato, bis(4-tert-butylphenyl)iodonium trifluoroacetate, bis(4-tert-butylphenyl)iodonium-p-toluenesulfonato, bis(4-tert-butylphenyl)iodonium butyltris(2,6-difluorophenyl)borate, bis(4-tert-butylphenyl)iodonium hexyltris(p-chlorophenyl)borate, bis(4-tert-butylphenyl)iodonium hexyltris(3-trifluoromethylphenyl)borate, phenyl 4-(2'-hydroxy-1'-tetradecaoxy)phenyliodonium tetrafluoroborate, phenyl 4-(2'-hydroxy-1'-tetradecaoxy)phenyliodonium trifluoromethanesulfonate, phenyl 4-(2'-hydroxy-1'-tetradecaoxy)phenyliodonium hexafluoroantimonato and phenyl 4-(2'-hydroxy-1'-tetradecaoxy)phenyliodonium hexafluoroantimonato.

Examples of the above triaryl sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonato, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonato, triphenylsulfonium butyltris(2,6-difluorophenyl)borate, triphenylsulfonium hexyltris(p-chlorophenyl)borate, triphenylsulfonium hexyltris(3-trifluoromethylphenyl)borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonato, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonato, 4-methoxyphenyldiphenylsulfonium butyltris(2,6-difluorophenyl)borate, 4-methoxyphenyldiphenylsulfonium hexyltris(p-chlorophenyl)borate, 4-methoxyphenyldiphenylsulfonium hexyltris(3-trifluoromethylphenyl)borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonato, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonato, 4-phenylthiophenyldiphenylsulfonium butyltris(2,6-difluorophenyl)borate, 4-phenylthiophenyldiphenylsulfonium hexyltris(p-chlorophenyl)borate, 4-phenylthiophenyldiphenylsulfonium hexyltris(3-trifluoromethylphenyl)borate, 4-hydroxy-1-naphthalenyl dimethylsulfonium tetrafluoroborate, 4-hydroxy-1-naphthalenyl dimethylsulfonium hexafluorophosphonate, 4-hydroxy-1-naphthalenyl dimethylsulfonium hexafluoroarsenate, 4-hydroxy-1-naphthalenyl dimethylsulfonium trifluoromethanesulfonato, 4-hydroxy-1-naphthalenyl dimethylsulfonium trifluoroacetate, 4-hydroxy-1-naphthalenyl)dimethylsulfonium-p-toluenesulfonato, 4-hydroxy-1-naphthalenyl dimethylsulfonium butyltris(2,6-difluorophenyl)borate, 4-hydroxy-1-naphthalenyl dimethylsulfonium hexyltris(p-chlorophenyl)borate and 4-hydroxy-1-naphthalenyl dimethylsulfonium hexyltris(3-trifluoromethylphenyl)borate.

Examples of the above quaternary ammonium salt include tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphonate, tetramethylammonium hexafluoroarsenate, tetramethylammonium trifluoromethanesulfonato, tetramethylammonium trifluoroacetate, tetramethylammonium-p-toluenesulfonato, tetramethylammonium butyltris(2,6-difluorophenyl)borate, tetramethylammonium hexyltris(p-chlorophenyl)borate, tetramethylammonium hexyltris(3-trifluoromethylphenyl)borate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphonate, tetrabutylammonium hexafluoroarsenate, tetrabutylammonium trifluoromethanesulfonato, tetrabutylammonium trifluoroacetate, tetrabutylammonium-p-toluenesulfonato, tetrabutylammonium butyltris(2,6-difluorophenyl)borate, tetrabutylammonium hexyltris(p-chlorophenyl)borate, tetrabutylammonium hexyltris(3-trifluoromethylphenyl)borate, benzyltrimethylammonium tetrafluoroborate, benzyltrimethylammonium hexafluorophosphonate, benzyltrimethylammonium hexafluoroarsenate, benzyltrimethylammonium trifluoromethanesulfonato, benzyltrimethylammonium trifluoroacetate, benzyltrimethylammonium-p-toluenesulfonato, benzyltrimethylammonium butyltris(2,6-difluorophenyl)borate, benzyltrimethylammonium hexyltris(p-chlorophenyl)borate, benzyltrimethylammonium hexyltris(3-trifluoromethylphenyl)borate, benzyldimethylphenylammonium tetrafluoroborate, benzyldimethylphenylammonium hexafluorophosphonate, benzyldimethylphenylammonium hexafluoroarsenate, benzyldimethylphenylammonium trifluoromethanesulfonato, benzyldimethylphenylammonium trifluoroacetate, benzyldimethylphenylammonium-p-toluenesulfonato, benzyldimethylphenylammonium butyltris(2,6-difluorophenyl)borate, benzyldimethylphenylammonium hexyltris(p-chlorophenyl)borate, benzyldimethylphenylammonium hexyltris(3-trifluoromethylphenyl)borate, N-cinnamylideneethylphenylammonium tetrafluoroborate, N-cinnamylideneethylphenylammonium hexafluorophosphonate, N-cinnamylideneethylphenylammonium hexafluoroarsenate, N-cinnamylideneethylphenylammonium trifluoromethanesulfonato, N-cinnamylideneethylphenylammonium trifluoroacetate, N-cinnamylideneethylphenylammonium-p-toluenesulfonato, N-cinnamylideneethylphenylammonium butyltris(2,6-difluorophenyl)borate, N-cinnamylideneethylphenylammonium hexyltris(p-chlorophenyl)borate and N-cinnamylideneethylphenylammonium hexyltris(3-trifluoromethylphenyl)borate.

Examples of the above sulfonic acid ester include .alpha.-hydroxymethylbenzoin-p-toluenesulfonic acid ester, .alpha.-hydroxymethylbenzoin-trifluoromethanesulfonic acid ester, .alpha.-hydroxymethylbenzoin-methanesulfonic acid ester, pyrogallol-tri(p-toluenesulfonic acid)ester, pyrogallol-tri(trifluoromethanesulfonic acid)ester, pyrogallol-trimethanesulfonic acid ester, 2,4-dinitrobenzyl-p-toluenesulfonic acid ester, 2,4-dinitrobenzyl-trifluoromethanesulfonic acid ester, 2,4-dinitrobenzyl-methanesulfonic acid ester, 2,4-dinitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester, 2,6-dinitrobenzyl-p-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, 2,6-dinitrobenzyl-methanesulfonic acid ester, 2,6-dinitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester, 2-nitrobenzyl-p-toluenesulfonic acid ester, 2-nitrobenzyl-trifluoromethanesulfonic acid ester, 2-nitrobenzyl-methanesulfonic acid ester, 2-nitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester, 4-nitrobenzyl-p-toluenesulfonic acid ester, 4-nitrobenzyl-trifluoromethanesulfonic acid ester, 4-nitrobenzyl-methanesulfonic acid ester, 4-nitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester, N-hydroxynaphthalimido-p-toluenesulfonic acid ester, N-hydroxynaphthalimido-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimido-methanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimido-p-toluenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimido-trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimido-methanesulfonic acid ester, 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazido-4-sulfoni c acid ester and 1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazido-4-sulfonic acid ester.

Out of these compounds, 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy-.beta.-styryl)-bis(4,6-trichloromethyl)-s-triazine, 2-piperonyl-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-bis.(4,6-trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-bis(4,6-trichloromethyl)-s-tr iazine and 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine are preferred as trichloromethyl-s-triazines; diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonato, 4-methoxyphenylphenyliodonium trifluoromethanesulfonato, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl 4-(2'-hydroxy-1'-tetradecaoxy)phenyliodonium trifluoromethanesulfonato, phenyl 4-(2'-hydroxy-1'-tetradecaoxy)phenyliodonium hexafluoroantimonato and phenyl 4-(2'-hydroxy-1'-tetradecaoxy)phenyliodonium-p-toluenesulfonato are preferred as diaryliodonium salts; triphenylsulfonium trifluoromethanesulfonato, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonato, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonato and 4-phenylthiophenyldiphenylsulfonium trifluoroacetate are preferred as triarylsulfonium salts; tetramethylammonium butyltris(2,6-difluorophenyl)borate, tetramethylammonium hexyltris(p-chlorophenyl)borate, tetramethylammonium hexyltris(3-trifluoromethylphenyl)borate, benzyldimethylphenylammonium butyltris(2,6-difluorophenyl)borate, benzyldimethylphenylammonium hexyltris(p-chlorophenyl)borate and benzyldimethylphenylammonium hexyltris(3-trifluoromethylphenyl)borate are preferred as quaternary ammonium salts; and 2,6-dinitrobenzyl-p-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimido-p-toluenesulfonic acid ester and N-hydroxynaphthalimido-trifluoromethanesulfonic acid ester are preferred as sulfonic acid esters.

The above radiation sensitive base generator is a compound which can generate a basic substance capable of curing (crosslinking) the component (A1) upon exposure to radiation such as ultraviolet radiation.

Radiation sensitive base generators disclosed by JP-A 4-330444, "Polymer", pp. 242-248, vol. 46, No. 6 (1997) and U.S. Pat. No. 5,627,010 are advantageously used. However, any radiation sensitive base generator is acceptable if it generates a base upon exposure to radiation as function.

Examples of the radiation sensitive base generator (A2) which can be preferably used in the present invention include compounds represented by the following formulas (2) to (12): ##STR1##

wherein R.sup.2 is an alkyl group having 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbon atoms, dialkylamino group having two alkyl groups with 1 to 6 carbon atoms, piperidyl group, nitro group, hydroxy group, mercapto group, alkenyl group or alkynyl group having 2 to 6 carbon atoms, aryl group having 6 to 20 carbon atoms, fluorine atom, chlorine atom or bromine atom, a is an integer of 0 to 5, R.sup.3 is a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and R.sup.4 and R.sup.5 are each independently a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group or benzyl group having 6 to 20 carbon atoms, or R.sup.4 and R.sup.5 may be bonded together to form a cyclic structure having 5 to 6 carbon atoms with a nitrogen atom bonded thereto, ##STR2##

wherein R.sup.6 is an alkyl group having 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbon atoms, dialkylamino group having two alkyl groups with 1 to 6 carbon atoms, piperidyl group, nitro group, hydroxy group, mercapto group, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, R.sup.7 is a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and R.sup.8 and R.sup.9 are each independently a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group or benzyl group having 6 to 20 carbon atoms, or R.sup.8 and R.sup.9 may be bonded together to form a cyclic structure having 5 to 6 carbon atoms with a nitrogen atom bonded thereto, ##STR3##

wherein R.sup.10 is an alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and R.sup.11 and R.sup.12 are each independently a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group or benzyl group having 6 to 20 carbon atoms, or R.sup.11 and R.sup.12 may be bonded together to form a cyclic structure having 5 to 6 carbon atoms with a nitrogen atom bonded thereto, ##STR4##

wherein R.sup.13 and R.sup.14 are each independently an alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, ##STR5##

wherein R.sup.15, R.sup.16 and R.sup.17 are each independently an alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, ##STR6##

wherein R.sup.18 is an alkyl group having 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbon atoms, dialkylamino group having two alkyl groups with 1 to 6 carbon atoms, piperidyl group, nitro group, hydroxy group, mercapto group, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, R.sup.9 is a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and R.sup.20, R.sup.21 and R.sup.22 are each independently a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group or benzyl group having 6 to 20 carbon atoms, ##STR7##

wherein R.sup.23 is an alkyl group having 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbon atoms, dialkylamino group having two alkyl groups with 1 to 6 carbon atoms, piperidyl group, nitro group, hydroxy group, mercapto group, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, R.sup.24 and R.sup.25 are each independently a hydrogen atom, hydroxyl group, mercapto group, cyano group, phenoxy group, alkyl group having 1 to 6 carbon atoms, fluorine atom, chlorine atom, bromine atom, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and R.sup.26 and R.sup.27 are each independently a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group or benzyl group having 6 to 20 carbon atoms, or R.sup.26 and R27 may be bonded together to form a cyclic structure having 5 to 6 carbon atoms with a nitrogen atom bonded thereto, ##STR8##

wherein R.sup.28 and R.sup.29 are each independently an alkyl group having 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbon atoms, dialkylamino group having two alkyl groups with 1 to 6 carbon atoms, piperidyl group, nitro group, hydroxy group, mercapto group, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, R.sup.30 to R.sup.33 are each independently a hydrogen atom, hydroxyl group, mercapto group, cyano group, phenoxy group, alkyl group having 1 to 6 carbon atoms, fluorine atom, chlorine atom, bromine atom, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and A.sup.1 is a divalent atomic group formed by excluding two hydrogen atoms bonded to one or two nitrogen atoms of a monoalkylamine, piperazine, aromatic diamine or aliphatic diamine, ##STR9##

wherein R.sup.34 and R.sup.35 are each independently an alkyl group having 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbon atoms, dialkylamino group having two alkyl groups with 1 to 6 carbon atoms, piperidyl group, nitro group, hydroxy group, mercapto group, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, R.sup.36 and R.sup.37 are each independently a hydrogen atom, hydroxyl group, mercapto group, cyano group, phenoxy group, alkyl group having 1 to 6 carbon atoms, fluorine atom, chlorine atom, bromine atom, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, R.sup.38 to R.sup.41 are each independently a hydrogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group or benzyl group having 6 to 20 carbon atoms, or R.sup.38 and R.sup.39, or R.sup.40 and R.sup.41 may be bonded together to form a cyclic structure having 5 to 6 carbon atoms with a nitrogen atom bonded thereto, and A.sup.2 is an alkylene group having 1 to 6 carbon atoms, cyclohexylene group, phenylene group or single bond, ##STR10##

wherein R.sup.42 to R.sup.44 are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, alkyl group having 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and b, c and d are each independently an integer of 0 to 5,

wherein L is at least one ligand selected from the group consisting of ammonia, pyridine, imidazole, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, propylenediamine, 1,2-cyclohexanediamine, N,N-diethylethylenediamine and diethylenetriamine, e is an integer of 2 to 6, R.sup.45 is an alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, and R.sup.46 is an alkyl group having 1 to 18 carbon atoms.

In all the above formulas (2) to (12), the alkyl group can be linear, branched or cyclic. Examples of the alkenyl group include vinyl group and propylenyl group, and examples of the alkynyl group include acetylenyl group. Examples of the aryl group include phenyl group, naphthyl group and anthracenyl group.

Also what are obtained by substituting a hydrogen atom contained in the above groups by a fluorine atom, chlorine atom, bromine atom, haloalkyl group, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, azido group, dialkylamino group, alkoxyl group or thioalkyl group are included in the above examples.

Out of these radiation sensitive base generators, preferred are 2-nitrobenzylcyclohexyl carbamate, triphenyl methanol, o-carbamoylhydroxylamide, o-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate) and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.

The amount of the component (A2) in the present invention is preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight based on 100 parts by weight of the component (A1). When the amount of the component (A2) is within the above range, a composition having excellent radiation sensitivity is obtained. An insulating film obtained from the composition has excellent alkali resistance, solvent resistance and heat resistance.

Other Additives

The radiation sensitive composition for forming an insulating film for an organic EL display device of the present invention comprises the above components (A1) and (A2) as essential ingredients and may contain other additives as required.

The other additives include a silane coupling agent, dehydrating agent, acid diffusion control agent, sensitizer, surfactant, shelf stabilizer and antifoaming agent.

Silane Coupling Agent

The above silane coupling agent may be used to improve adhesion between an insulating film formed from the radiation sensitive composition of the present invention and a substrate.

The silane coupling agent is preferably a functional silane coupling agent, for example, a silane coupling agent having a reactive substituent such as a carboxyl group, methacryloyl group, vinyl group, isocyanate group, epoxy group or amino group. Examples of the silane coupling agent include trimethoxysilylbenzoic acid, methyldimethoxysilylbenzoic acid, .gamma.-methacryloxypropyltrimethoxysilane, .gamma.-methacryloxypropylmethyldimethoxysilane, .gamma.-methacryloxyethyltrimethoxysilane, .gamma.-methacryloxyethylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, .gamma.-isocyanatopropyltrimethoxysilane, .gamma.-isocyanatopropylmethyldimethoxysilane, .gamma.-isocyanatoethyltrimethoxysilane, .gamma.-isocyanatoethylmethyldimethoxysilane, .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropylmethyldimethoxysilane, .beta.-glycidoxyethyltrimethoxysilane, .beta.-glycidoxyethylmethyldimethoxysilane, .beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, .beta.-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, .gamma.-(3,4-epoxycyclohexyl)propyltrimethoxysilane, .gamma.-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane and 3-aminopropylmethyldiethoxysilane.

Commercially available products of the silane coupling agent include Sila-Ace S210, S220, S310, S320, S330, S510, S520, S530 and S710 (of Chisso Corporation), A-151, A-171, A-172, A-174, Y-9936, A-186, A-187, A-1100, A-1110, A-1120, A-1122, Y-9669 and A-1160 (of Nippon Unicar Co., Ltd.), and SH6020, SZ6023, SH6026, SZ6030, SZ6032, SH6040, SZ6050, SZ6070, SZ6072, SZ6075, SZ6083 and SZ6300 (of Toray Dow Corning Silicone Co., Ltd.).

Out of these, silane coupling agents having an epoxy group are preferred, and .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropylmethyldimethoxysilane, .beta.-glycidoxyethyltrimethoxysilane, .beta.-glycidoxyethylmethyldimethoxysilane, .beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, .beta.-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, .gamma.-(3,4-epoxycyclohexyl)propyltrimethoxysilane and .gamma.-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane are particularly preferred.

The amount of the silane coupling agent is preferably 50 parts or less by weight, more preferably 2 to 50 parts by weight, much more preferably 5 to 30 parts by weight based on 100 parts by weight of the component (A1).

Dehydrating Agent

The dehydrating agent which can be added to the radiation sensitive composition of the present invention can convert water into another substance through a chemical reaction or can trap water by physical adsorption or inclusion. By containing the dehydrating agent in the radiation sensitive composition of the present invention, the influence of water coming from environment or water generated from the component (A1) upon exposure to radiation in the step of forming an insulating film which will be described hereinafter can be reduced. Therefore, it is assumed that the dehydrating agent contributes to the improvement of the radiation sensitivity of the composition.

At least one compound selected from the group consisting of a carboxylic acid ester, acetal (including ketal) and carboxylic anhydride is preferably used as the dehydrating agent.

The above carboxylic acid ester is preferably an orthocarboxylic acid ester or carboxylic acid silyl ester.

Examples of the orthocarboxylic acid ester include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl orthopropionate and ethyl orthopropionate. Out of these orthocarboxylic acid esters, orthoformic acid esters are particularly preferred.

Examples of the carboxylic acid silyl ester include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate and trimethylsilyl oxalate.

Examples of the acetal include reaction products between a ketone and an alcohol, reaction products between a ketone and a dialcohol, and ketene silyl acetals. Example of the reaction products between a ketone and an alcohol include dimethyl acetal, diethyl acetal and dipropyl acetal.

Examples of the above carboxylic anhydride include formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride and antic-benzoic anhydride. Out of these, acetic anhydride and succinic anhydride are preferred because they are particularly excellent in dehydrating effect.

The amount of the dehydrating agent used in the present invention is preferably 100 parts or less by weight, more preferably 0.1 to 100 parts by weight, much more preferably 0.5 to 50 parts by weight, particularly preferably 1 to 10 parts by weight based on 100 parts by weight of the component (A1).

Beyond the above range, the effect of the dehydrating agent is not further enhanced.

Acid Diffusion Control Agent

In the present invention, the acid diffusion control agent may be used when a compound which generates an acid upon exposure to radiation (radiation sensitive acid generator) is used as the component (A2). The agent controls the diffusion of an acidic substance generated by exposing the radiation sensitive acid generator to radiation in the coating film of the composition and suppresses a curing reaction in an unexposed area.

By adding such an acid diffusion control agent, a radiation sensitive composition having excellent pattern accuracy can be obtained.

Examples of the acid diffusion control agent include a compound (to be referred to as "nitrogen-containing compound (I) hereinafter) represented by the following formula (13), diamino compound having two nitrogen atoms in the same molecule (to be referred to as "nitrogen-containing compound (II)" hereinafter), nitrogen-containing compound having three or more nitrogen atoms (to be referred to as "nitrogen-containing compound (III)" hereinafter), amido group-containing compound, urea compound and nitrogen-containing heterocyclic compound: ##STR11##

wherein R.sup.47, R.sup.48 and R.sup.49 are each independently a hydrogen atom, alkyl group having 1 to 6 carbon a