TWI427096B - A laminated body, an active matrix substrate, and a planar display device having the substrate - Google Patents

Description

Laminated body, active matrix substrate, and flat display device having the same

The present invention relates to a laminated body, an active matrix substrate, and a flat display device having the same. More specifically, a laminated body in which a resin film composed of a specific radiation-sensitive resin composition is laminated on a substrate, an active matrix substrate, and a flat display device having the substrate are provided.

A liquid crystal display element, an electronic component such as an integrated circuit component or a solid-state imaging device, or a color filter for a liquid crystal display, or the like, is provided with a protective film for preventing deterioration or damage, and flattening the surface of the device or the wiring is flattened. A laminate of a resin film for a functional electronic component such as an electrical insulating film that maintains electrical insulation. Further, in the thin film transistor-shaped liquid crystal display device or the integrated circuit device, a laminate having a resin film for a functional electronic component in which an interlayer insulating film which is insulated between the wirings arranged in a layer is provided is used.

As a radiation sensitive resin composition for forming a resin film for such a laminate, Patent Document 1 discloses a radiation sensitive resin composition containing an alkali-soluble alicyclic olefin resin, an acid generator, a bridging agent, and a solvent. The alkali-soluble alicyclic olefin resin is subjected to ring-opening polymerization of an alicyclic olefin monomer in a tetrahydrofuran solution in the presence of a catalyst, and then injected into a poor solvent hexane to separate the alkali-soluble alicyclic olefin resin, and then dissolving the alicyclic olefin resin. , hydrogenation, re-injection of hexane to solidify, dry.

Further, Patent Document 2 discloses a ring-opening metathesis polymer hydrogenated product in which a ratio of a weight average molecular weight to a number average molecular weight of 1.0 to 2.0 is obtained by ring-opening metathesis polymerization of an aliphatic cyclic hydrocarbon having a specific structure. The ring-opening metathesis polymer used herein or the polymer solution obtained by polymerization in a tetrahydrofuran solution is poured into methanol in a lean solvent to precipitate a polymer, which is dissolved in tetrahydrofuran, hydrogenated, and then methanol is injected to polymerize. The hydride is precipitated, filtered, vacuum dried, etc.

[Patent Document 1] JP-A-2004-212450 (Patent Document 2) JP-A-2001-354756

By using the radiation-sensitive resin composition disclosed in the patent document, various characteristics required for the above-mentioned resin film, particularly, recently, regarding relative dielectric constant, heat-resistant dimensional stability, and solvent resistance Flatness, transparency, heat discoloration, etc. have a certain effect.

However, the laminate in which the resin film composed of the radiation-sensitive resin composition is laminated on the substrate has interlayer insulation and the like, and there is room for improvement.

Accordingly, it is an object of the present invention to provide a laminate having improved interlayer insulation. Further, another object of the present invention is to provide an active matrix substrate and a flat display device using the laminated body.

The inventors of the present invention have studied the above problems by improving the radiation sensitive resin composition. As a result, the following problems were found, and as a result of efforts to solve the problem, it was thought that the invention can be completed by using a radiation-sensitive resin composition obtained by a specific method.

In other words, the conventional radiation sensitive resin composition is solidified after polymerization to remove catalyst residues such as unreacted monomers, polymerization catalysts, or hydrogenation catalysts contained in the polymer, oligomers (low polymers), and the like. The low molecular weight component is used while narrowing the molecular weight distribution. However, in the production of the solution prepared by the coagulation-separation-redissolution, the fine particles of the impurities to be mixed are contained in the polymer between the purification operations of the polymer, or are polymerized in the re-dissolution of the radiation-sensitive resin composition. The particles are not dissolved, and the fine particles which have not been removed by the filtration of the radiation sensitive resin composition solution are removed, and the presence of the fine particles is detected, which greatly affects the decrease in interlayer insulation of the resin film.

The inventors of the present invention have succeeded in researching various problems associated with the production of the conventional radiation-sensitive resin composition as described above, and by using a polymerization catalyst to polymerize an alicyclic olefin in the presence of a specific compound, The polymerizable film obtained by separating the polymer from the polymerization reaction solution and constituting the radiation-sensitive compound constituting the radiation-sensitive resin composition in the polymerization reaction solution can provide a resin film including various characteristics as described above, and is found to include In the laminate of the resin film, the interlayer insulation can be improved as compared with the prior art, and based on this knowledge, the present invention has been completed.

Therefore, according to the invention, there is provided a laminate (hereinafter referred to as a "first laminate") which is obtained by laminating a resin film on a substrate which is subjected to a ring-opening metathesis polymerization catalyst. An alicyclic olefin-containing ring-opening metathesis polymer obtained by polymerizing an alicyclic olefin in a solvent in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups The polymerization reaction solution is composed of a radiation sensitive resin composition obtained by blending a radiation sensitive compound.

Moreover, according to the present invention, there is provided a laminate (hereinafter referred to as a "second laminate") in which a resin film is laminated on a substrate, and the resin film is used in a ring-opening metathesis polymerization catalyst. A polymerization reaction solution containing an alicyclic olefin ring-opening metathesis polymer obtained by polymerizing an alicyclic olefin in a solvent in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups, and introducing hydrogen into the reaction The solution is obtained by hydrogenating a solution of an alicyclic olefin ring-opening metathesis polymer, and a hydrogenation reaction solution containing a condensed cycloolefin metathesis polymer hydride, and a radiation sensitive resin composition obtained by blending a radiation sensitive compound.

The alicyclic olefin ring-opening metathesis polymer for the radiation sensitive resin composition constituting the two laminated bodies has a weight average molecular weight of 2,000 to 10,000, and a content of a component having a number average molecular weight of 1,000 or less is preferably 2% by weight or less. .

Moreover, the radiation sensitive resin composition used in the above-mentioned present invention may be obtained by further blending a bridging agent together with a radiation sensitive compound.

Further, the radiation sensitive resin composition used in the present invention is preferably obtained by using a polar solvent having a boiling point of 150 to 250 ° C as a solvent.

Further, the radiation sensitive resin composition used in the present invention is preferably obtained by using a ring-opening metathesis polymerization catalyst containing ruthenium.

Further, the radiation sensitive resin composition used in the present invention is preferably one obtained by using 1,5-hexadiene as a non-conjugated polyene compound having two or more terminal vinyl groups.

Further, in the laminate of the present invention, the resin film may be a patterned resin film.

Moreover, according to the present invention, there is provided an active matrix substrate which is provided with a gate signal line for driving a gate signal of the switching element and a source signal line for supplying a display signal of the switching element while the switching element is arranged in a matrix. Provided to be mutually intersected, the pixel electrode is partially overlapped with each of the signal lines via the switching element, the interlayer insulating film provided on the gate signal line and the source signal line, and the interlayer insulating film is used for the above-mentioned The inventive radiation sensitive resin composition is formed.

Furthermore, according to the present invention, there is provided a flat display device comprising the above-described active matrix substrate.

According to the present invention, it is possible to obtain a laminate of a resin film having excellent dielectric constant, heat-resistant dimensional stability, solvent resistance, and flatness, excellent transparency and heat discoloration resistance, and excellent interlayer insulation.

The laminate of the present invention is useful as an active matrix substrate. Moreover, by using the active matrix substrate, an excellent flat display device with long life, low power consumption, and high contrast can be obtained.

The laminated body of the present invention is obtained by laminating a resin film on a substrate, and the resin film is composed of a radiation sensitive resin composition obtained by a specific method described below.

The first laminate of the present invention is obtained by laminating a radiation-sensitive resin composition (hereinafter referred to as a "first radiation-sensitive resin composition") on a substrate, and the radiation-sensitive resin composition is obtained. A polymerization reaction solution containing an alicyclic olefin ring-opening metathesis polymer obtained by polymerizing an alicyclic olefin in a solvent in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups using a ring-opening metathesis polymerization catalyst It is obtained by blending a radiation-sensitive compound.

The first radiation sensitive resin composition can be obtained by polymerizing an alicyclic olefin in a solvent in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups by using a ring-opening metathesis polymerization catalyst. A polymerization reaction solution of an olefin ring-opening metathesis polymer obtained by blending a radiation sensitive compound.

In the present invention, an alicyclic olefin ring-opening metathesis polymer (hereinafter referred to as a "ring-opening metathesis polymer") is obtained by ring-opening metathesis polymerization of an alicyclic olefin.

The alicyclic olefin may be a compound having a ring structure having at least one carbon-carbon double bond capable of ring-opening metathesis reaction in the molecule, and the structure of the portion other than the ring structure is not particularly limited.

Further, the number of carbon atoms constituting the alicyclic olefin is not particularly limited. Usually, it is preferably 4 to 25, more preferably 5 to 20, and most preferably 7 to 15.

The alicyclic olefin may be composed of a single ring or a plurality of rings, and the bonding pattern of the plural ring is not limited.

The above alicyclic olefin may be one having a hydrocarbon substituent at any position. Examples of such a substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group; and a methyl group or an ethyl group. a substituent of a propyl group, a butyl group or the like, an aryl group having 6 to 24 carbon atoms such as a phenyl group, a naphthyl group, a tolyl group or a xylyl group; an alkylene group having 1 to 20 carbon atoms such as a methylene group or an ethylene group; a vinyl 2,20 alkenyl group such as a vinyl group, an allyl group or a propenyl group; a cycloalkyl group having a carbon number of 3 to 20 such as a cyclopentyl group, a cyclohexyl group or a norbornyl group; a cyclopentenyl group and a cyclohexene group; A cycloalkenyl group having 3 to 20 carbon atoms such as a group, a norbornene group, a dicyclopentyl group or a dicyclopentenyl group.

Specific examples of the non-polar alicyclic olefin include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo[2.2.1] hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylene-bicyclo[2.2.1]hept-2-ene, 5-methylene-bicyclo[2.2.1]hept-2 - alkene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 ^{2 , 5} ]decene-3,7-diene (common name: dicyclopentadiene), Tetracyclic [7.4.0.1 ^{1 0 , 1 3} .0 ^{2 , 7} ] thirteen carbon-2,4,6,11-tetraene (alias, 1,4-methylene-1,4,4a,9a-four Hydroquinone), tetracyclo[8.4.0.1 ^{1 1 , 1 4} .0 ^{2 , 8} ] fourteen carbon-3,5,7,12-tetraene, tetracyclo[8.4.0.1 ^{1 1 , 1 4} .0 ^{3 , 7} ] fifteen carbon-3,5,7,12,11-pentene, tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] dodeca-3-ene (common name: four ring ten Diene), 8-methyl-tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methylene-tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-ethylene-tetracyclic [4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] twelve carbon 3-ene, 8-vinyl-tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] dodec-3-ene, pentacyclo[6.5.1.1 ^{3 , 6} .0 ^{2 , 7} .0 ^{9 , 1 3} ] pentadec-3,10-diene, pentacyclo[7.4. 0.1 ^{3 , 6} .1 ^{1 0 , 1 3} .0 ^{2 , 7} ] fifteen carbon-4,11-diene, pentacyclic [9.2.1.1 ^{4 , 7} .0 ^{2 , 1 0} .0 ^{3 , 8} ] Penta-5,12-diene, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl )-1-cyclohexene, cyclooctene, 3a,5,6,7a-tetrahydro-4,7-methylene-1H-indole, cycloheptene, vinylcyclohexene, vinylcyclohexane, Cyclopentadiene, cyclohexadiene, 5-phenyl-bicyclo[2.2.1]hept-2-ene, 1,4-methylene-1,4,4a,5,10,10a-hexahydroindole, Tetracyclic [6.6.0.1 ^{2 , 5} .1 ^{8 , 1 3} ] fourteen carbon-3,8,10,12-tetraene, tetracyclo[9.2.1.0 ^{2 , 1 0} .0 ^{3 , 8} ] fourteen carbon -3,5,7,12-tetraene (also known as 1,4-methylene-1,4,4a,9a-tetrahydro-9H-indole), 8-phenyl-tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] dodeca-3-ene, etc.

Further, the alicyclic olefin may have a functional group.

Such a functional group may be a protic polar group or a polar group other than the above.

The so-called protic polar group is a group of hydrogen atoms directly bonded to a hetero atom. The hetero atom is preferably an atom of Groups 15 and 16 of the periodic table, and more preferably atoms of the first and second periods of Groups 15 and 16 of the periodic table are further preferably an oxygen atom.

Specific examples of the protic polar group include a polar group having an oxygen atom such as a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, a phosphoric acid group or a hydroxyl group; a primary amino acid, a secondary amino acid, a primary amidino group, and a secondary group; A polar group having a nitrogen atom such as a mercapto group (methyleneamine); a polar group having a sulfur atom or the like, such as a thiol group. Among these, those having an oxygen atom are preferred, and the carboxyl group is more preferred.

Further, a group which can form a carboxyl group by hydrolysis such as a nitrile group, an ester group, a guanamine group or an acid anhydride group can be preferably used.

Among the alicyclic olefin ring-opening metathesis polymers of the present invention, those having a protic polar group are alkali-soluble, and the alkali-soluble ones are useful for radiation sensitive compositions. Further, in the case of having a protic polar group, a bridging resin can be imparted when the composition is blended with a bridging agent.

Specific examples of the alicyclic olefin having a protic polar group include 5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5-hydroxycarbonylmethyl-5-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene, 8 -hydroxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] dodecene-3-ene, 8-exo-9-endo-8-hydroxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]carboxyl-3-ene carboxyl group containing lipid Cycloolefin; 5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 8-(4-Hydroxyphenyl)tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methyl-8-(4-hydroxyphenyl)tetracyclo[ 4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] The hydroxyl group such as dodeca-3-ene contains an alicyclic olefin or the like, and among these, the carboxyl group contains an alicyclic olefin.

Specific examples of the polar group other than the protic polar group, an ester group (a general term for an alkoxycarboxy group and an aryloxycarboxy group), an N-substituted amidino group, a cyano group, a halogen atom, an ether group (-O-), and a ring. An oxy group, a carbonyloxycarbonyl group (an acid anhydride residue of a dicarboxylic acid), an alkoxy group, a tertiary amine, an acrylonitrile or the like. Among these, an ester group, an N-substituted guanamine group and a cyano group are preferred, and an oxime group is substituted with an ester group and an N- group.

The ester group contains an alicyclic olefin, and examples thereof include 5-ethyloxybicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, and 5-methyl group. 5-5-methoxybicyclo[2.2.1]hept-2-ene, 8-vinyloxytetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methyl Oxycarbonyl tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-ethoxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]12 carbon 3-ene, 8-n-propoxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-isopropyloxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-n-butoxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methyl- 8-methoxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8- Methyl 8-isopropyloxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4 .0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodec-3-ene, 8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] dodec-3-ene, 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodeca-3 - alkene, 2-methoxy-1-methylethylbicyclo[2.2.1]hept-5-ene-2-carboxylate, 2-methoxy-1-methylethyl-2-methylbicyclo[ 2.2.1] Hept-5-ene-2-carboxylate and the like.

The N-substituted guanamine group contains an alicyclic olefin, and examples thereof include N-phenyl-(5-formylbornene-2,3-dicarboxyliminium) and N-(2-ethylhexyl)bicyclo[2.2. .1]hept-5-ene-2-carboxydecylamine, N-(2-ethylpentyl)bicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-(2-ethyl Butyl)bicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-(2-methylbutyl)bicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N -butylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-isobutylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-(2-ethyl Hexyl)-2-methylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-(2-ethylpentyl)-2-methylbicyclo[2.2.1]hept-5- Alkene-2-carboxydecylamine, N-(2-ethylbutyl)-2-methylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, 2-methyl-N-(2 -Methylbutyl)-2-methylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-butyl-2-methylbicyclo[2.2.1]hept-5-ene- 2-carboxydecylamine, N-isobutyl-2-methylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N -(2-ethylhexyl)-N-methylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-(2-ethylpentyl)-N-methylbicyclo[2.2. 1]hept-5-ene-2-carboxydecylamine, N-(2-ethylbutyl)-N-methylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-A --N-(2-methylbutyl)bicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-butyl-N-methylbicyclo[2.2.1]hept-5-ene 2-carboxydecylamine, N-isobutyl-N-methylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-(2-ethylhexyl)-N,2-dimethyl Bicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-(2-ethylpentyl)-N,2-dimethylbicyclo[2.2.1]hept-5-ene-2 -Carboxylimine, N-(2-ethylbutyl)-N,2-dimethylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N,2-dimethyl N- (2-methylbutyl)bicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, N-butyl-N,2-dimethylbicyclo[2.2.1]hept-5-ene- 2-carboxydecylamine, N-isobutyl-N,2-dimethylbicyclo[2.2.1]hept-5-ene-2-carboxydecylamine, 4-[4-(2-ethylhexyloxy) Phenyl]-4-azatricyclo[5.2.1.0. ^{2 , 6} ]decen-8-ene-3,5-dione, 3-[4-(2-ethylhexyloxy)benzene 4-azatricyclo[5.2.1.0. ^{2 , 6} ]decen-8-ene-3,5-dione, 2-[4-(2-ethylhexyloxy)phenyl]- 4-Azatricyclo[5.2.1.0. ^{2 , 6} ] Decen-8-ene-3,5-dione, dimethyl 5-(3,5-dioxo-4-azatricyclo[5.2 .1.0. ^{2 , 6} ] Deca-8-en-4-yl)isophthalate, dimethyl 4-(3,5-dioxo-4-azatricyclo[5.2.1.0. ^{2 , 6} ] Deca-8-en-4-yl) phthalate, dimethyl 3-(3,5-dioxo-4-azatricyclo[5.2.1.0. ^{2 , 6} ] Carbon-8-en-4-yl)phthalate, dimethyl 2-(3,5-dioxo-4-azatricyclo[5.2.1.0. ^{2 , 6} ] decacarbon-8- Alkene-4-yl)terephthalate or the like.

The cyano group contains an alicyclic olefin, and examples thereof include 8-cyanotetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodeca-3-ene, 8-methyl-8-cyanotetracycline. [4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] dodec-3-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, 5-cyano-5-methylbicyclo[2.2 .1] Hept-2-ene and the like.

The alicyclic olefin containing a halogen atom may, for example, be 8-chlorotetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodeca-3-ene, 8-methyl-8-chlorotetracyclo [ 4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ] dodeca-3-ene.

The ether group contains an alicyclic olefin, and, for example, 5-{[(2-ethylhexyl)oxy]methyl}bicyclo[2.2.1]hept-2-ene, 5-{[(2-ethylpentyl) Alkyloxy]methyl}bicyclo[2.2.1]hept-2-ene, 5-{[(2-ethylbutyl)oxy]methyl}bicyclo[2.2.1]hept-2-ene, 5-(Butoxymethyl)bicyclo[2.2.1]hept-2-ene, 5-[(2-methylbutoxy)methyl]bicyclo[2.2.1]hept-2-ene, 5-( Isobutoxymethyl)bicyclo[2.2.1]hept-2-ene, 2-ethylhexyl (2-methylbicyclo[2.2.1]hept-5-en-2-yl)methyl ether, 2- Ethylpentyl (2-methylbicyclo[2.2.1]hept-5-en-2-yl)methyl ether, 2-ethylbutyl (2-methylbicyclo[2.2.1]hept-5- Alken-2-yl)methyl ether, 5-(butoxymethyl)-5-methylbicyclo[2.2.1]hept-2-ene, (2-methylbicyclo[2.2.1]hept-5- Alken-2-yl)methyl-2-methylbutyl ether, 5-(isobutoxymethyl)-5-methylbicyclo[2.2.1]hept-2-ene, and the like.

These alicyclic olefins may be used alone or in combination of two or more.

Among these alicyclic olefins, those having an original borneol skeleton are preferred.

In the case of obtaining the alicyclic olefin ring-opening metathesis polymer used in the present invention, a non-alicyclic olefin may also be used in combination.

Specific examples of such non-alicyclic olefinic fats include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl-1-pentyl Alkene, 3-methyl-1-hexene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-di Methyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, An ethylene or an α-olefin having 2 to 20 carbon atoms such as 1-hexadecene, 1-octadecene or 1-eicosene.

The ring-opening metathesis polymer used in the present invention is obtained by using a ring-opening metathesis polymerization catalyst.

The ring-opening metathesis polymerization catalyst is a complex compound in which a transition metal atom is used as a central atom and a plurality of ions, atoms, polyatomic ions or compounds are bonded. The bond of the above ions or the like may be an ionic bond or a covalent bond or a coordination bond. For the transition metal atom, atoms of Groups 5, 6 and 8 of the periodic table are used. Among these, it is preferable to use the 钌 or 第 of the 8th group, especially 钌.

Among the ruthenium ring-opening metathesis polymerization catalysts, a ruthenium carbene catalyst is preferred. The ruthenium carbene catalyst is stable to oxygen or moisture and is not easily deactivated, and has good catalytic activity.

The ruthenium carbene catalyst is represented by the following formula (1) or formula (2).

In the formulae (1) and (2), R ¹ and R ² are independently represented by a hydrogen atom, a halogen atom, or a carbon which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a ruthenium atom. A hydrocarbon group of 1 to 20 carbon atoms. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ and L ² are preferably a neutral electron-donating compound, and at least one of them is a carbene compound containing a hetero atom. Further, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded to each other to form a polydentate chelating ligand.

The hetero atom refers to an atom of Groups 15 and 16 of the periodic table, and specific examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of a stable carbene compound, N, O, P, and S atoms are preferred, and N atoms are particularly preferred.

The hetero atom contains a carbene compound, and is preferably bonded to a hetero atom adjacent to both sides of the carbene carbon, and further preferably a carbene carbon atom and a hetero atom containing a hetero atom on both sides thereof. Further, it is preferred that the hetero atom adjacent to the carbene carbon has a high substituent.

Examples of the hetero atom containing a carbene compound include compounds represented by the following formula (3) or formula (4).

In the formula, R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may have a carbon atom which may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a halogen atom, and may have a halogen atom or another substituent. Further, R ³ to R ⁶ may be bonded to each other in any combination to form a ring.

Specific examples of the compound represented by the above formula (3) and formula (4) include 1,3-distributyltolyl imidazolidine-2-ylidene and 1,3-bis(1-adamantyl). Imidazolidin-2-ylidene, 1-cyclohexyl-3-mestilyleneimidazolidin-2-ylidene, 4,5-dichloro-1,3-distributylimidazolidine-2-ylidene , 4,5-dibromo-1,3-distributylmethylimidazolidine-2-ylidene, 1,3-distributylmethylidazolidin-2-ylidene, 1,3-diisopropyl Imidazoline-2-ylidene, 1,3-bis(1-phenylethyl)imidazolin-2-ylidene, 4,5-dichloro-1,3-distributylimidazolidin-2- Subunit, 4,5-dibromo-1,3-distributylimidazolidin-2-ylidene, 1,3-distributyltolyl octahydrobenzimidazole-2-ylidene, 1,3 -distributyltolyl-2,3-dihydrobenzimidazole-2-ylidene and the like.

Further, in addition to the compounds represented by the above formulas (3) and (4), 1,3,4-trimethyl-2,3,4,5-tetrahydro-1H-1,2 may also be used. 4-triazol-5-subunit, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N,N,N',N'-tetraisopropylcarbamamine subunit, 1,3, 4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-ylidene, 3-(2,6-diisopropylphenyl)-2,3-dihydrothiazole- The hetero atom such as the 2-subunit contains a carbene compound.

In the above formulas (1) and (2), the anionic ligands X ¹ and X ² are a negatively charged ligand when the central metal ion is pulled apart. Specific examples thereof include a halogen atom such as fluorine, chlorine, bromine or iodine, a diketo acid group, a substituted cyclodienyl group, an alkoxy group, an aryloxy group, a carboxyl group, a decyl group, an alkylsulfonyloxy group, and an aromatic group. Sulfosulfonyloxy and the like. Among these, a halogen atom is preferred, and a chlorine atom is more preferred.

Further, the neutral electron-donating compound may be any of the ligands having a neutral charge when the central metal is detached. Specific examples thereof include a carbene compound, a carbonyl group, an amine, an ether, a nitrile, an ester, a phosphine, a thioether, an aromatic compound, an olefin, an isocyano group, and a thiocyanate. Among these, a carbene compound, phosphine or pyridine is preferred, and a carbene compound and a trialkylphosphine are more preferred.

The complex compound represented by the above formula (1) may, for example, be (4,5-dibromo-1,3-distributylmethylidazolidin-2-ylidene)tricyclohexylphosphorus benzylidene Bismuth dichloride, (4,5-dichloro-1,3-distributylimidazolidin-2-ylidene) (tricyclohexylphosphoryl)benzylidene dichloride, (1,3-di) Mesitylene imidazolin-2-ylidene) (tricyclohexylphosphine) benzalchloride ruthenium dichloride, (1,3-dimesamethylidazolidin-2-yl) (tricyclohexylphosphine) Benzylidene ruthenium dichloride, (1,3-dimesamethylidene imidazol-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphoryl) Benzyl ruthenium dichloride, benzylidene (1,3-distributyltolyl-octahydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) benzalkonium dichloride, [1,3 - bis(1-phenylethyl)-4-imidazolin-2-ylidene](tricyclohexylphosphine)benzylidene ruthenium dichloride, (1,3-dimesityl-2,3- Dihydrobenzimidazole-2-ylidene (tricyclohexylphosphine)benzylidene dichloride, (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5- Tetrahydro-1H-1,2,4-triazole-5-ylidene)benzylidene dichloride, (1,3-diisopropyl-6) Hydropyrimidin-2-ylidene)(ethoxymethylene)(tricyclohexylphosphine)benzylidene ruthenium dichloride, (1,3-distributyltolyl imidazolidine-2-ylidene)pyridinium bromide a hetero atom such as ruthenium dichloride containing a ruthenium compound in which a carbene compound and a neutral electron-donating compound are bonded; bis(1.3-dicyclohexamethylene imidazol-2-ylidene)benzylidene ruthenium dichloride Two hetero atoms such as bis(1,3-diisopropyl-4-imidazolin-2-ylidene)benzylidene ruthenium dichloride include a ruthenium complex compound in which a carbene compound is bonded.

Further, the complex compound represented by the above formula (2) may, for example, be (1.3-dimethylimidazolidin-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (Third butyl vinylene) (1,3-diisopropyl-4-imidazolin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, bis(1.3-dicyclohexyl-4- Imidazoline-2-ylidene)phenylvinylidene dichloride or the like.

Such a ruthenium complex compound can be produced, for example, by the method described in Org. Lett., 1999, Vol. 1, p. 953, Tetrahedron. Lett., 1999, Vol. 40, p. 2247.

The amount of the ring-opening metathesis polymerization catalyst used is (mole ratio of metal atom in the catalyst: alicyclic olefin), usually 1:1,000 to 1:1,000,000, preferably 1:2,000 to 1:500,000, and 1 : The range of 3,000~1:300,000 is better.

In the present invention, ring-opening metathesis polymerization of an alicyclic olefin is carried out in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups.

Specific examples of the non-conjugated polyene compound having two or more terminal vinyl groups include compounds represented by the following formula (5).

In the above formula (5), R ⁷ and R ⁸ are each a vinyl group which may have a substituent; R ⁹ to R ¹² are each a hydrogen atom or an alkyl group; X is a divalent organic group; m and n are respectively 0 or a positive integer. However, when X is a group having C=Q (Q is an atom which can form a double bond with a carbon atom), m and n are positive integers.

The substituent of the vinyl group of R ⁷ and R ⁸ may, for example, be an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group. The alkyl group of R ⁹ to R ¹² may, for example, be an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group. Specific examples of X include an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an ether group, a vinylidene group (the above Q is a carbon atom), a carbonyl group (the above Q is an oxygen atom), and sulfur. a carbonyl group (the above Q is a sulfur atom), an imido group (the above Q is a nitrogen atom), an oxycarbonyl group [-C(=O)O-], a carbonate group [-OC(=O)-O-], etc. The substituent may have a substituent such as a methyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group.

The non-conjugated polyene compound having two or more terminal vinyl groups is preferably one having a boiling point of 175 ° C or less at normal pressure in consideration of purification removal after polymerization or the like.

Specific examples of the non-conjugated polyene compound having two or more terminal vinyl groups include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, and 1,7-. a non-conjugated diene compound such as octadiene, 1,8-decadiene or 1,9-decadiene; or a lipid such as 1,3-dipropenylcyclohexane or 1,3-dipropenylcyclopentane a cyclopropenyl compound; a propenyl ketone compound such as a dipropenyl ketone or the like.

Among these, non-conjugated diene compounds are preferred, and aliphatic The conjugated diene compound is more preferable. Among the aliphatic non-conjugated diene compounds, 1,5-hexadiene is particularly preferred.

The amount of the non-conjugated polyene compound having two or more terminal vinyl groups is usually 0.1 to 20% by mole for the alicyclic olefin, preferably 0.5 to 15% by mole, and more preferably 1 to 10% by mole. good.

In the present invention, after ring-opening metathesis polymerization of an alicyclic olefin, since the polymer is not separated from the polymerization reaction solution, the radiation-sensitive resin composition is prepared, so that the same solvent as that used for the radiation-sensitive resin composition is used. A polymerization solvent is preferred. Thereby, environmental pollution caused by solvent removal can be suppressed, and since the steps of separation, drying, and re-dissolution of the polymer can be omitted, the productivity of the radiation-sensitive resin composition can be improved.

Specific examples of such a solvent include a monoalkylene glycol solvent; a polyalkylene glycol solvent; a monoalkylene glycol alkyl ester solvent; a polyalkylene glycol alkyl ester solvent; a monoalkylene glycol alkanediester solvent; a polyalkylene glycol; Alkanediester solvent.

Examples of the monoalkylene glycol solvent include monoalkylene glycols such as ethylene glycol and propylene glycol; monoalkylene glycols such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Monoalkyl ether; monoalkylene glycol dialkyl ether such as ethylene glycol diethyl ether or propylene glycol diethyl ether.

Examples of the polyalkylene glycol solvent include polyalkylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether. , dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and other polyalkylene glycol monoalkane; diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether And a polyalkylene glycol dialkyl ether such as triethylene glycol methyl ethyl ether or tripropylene glycol methyl ethyl ether.

Specific examples of the monoalkylene glycol alkyl ester solvent include propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, and propylene glycol monoisobutylene. Ethyl acetate, propylene glycol monobutyl ether acetate, propylene glycol monobutyl ether acetate, and the like.

Specific examples of the polyalkylene glycol alkyl ester solvent include diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol monomethyl ether. Acetate and the like.

Specific examples of the monoalkylene glycol alkane diester solvent include ethylene glycol diacetate and propylene glycol diacetate.

Specific examples of the polyalkylene glycol alkanediester solvent include diethylene glycol diacetate, dipropylene glycol diacetate, and triethylene glycol diacetate.

Other than these, a high-boiling ketone solvent such as 2-heptanone, cyclohexanone or 4-hydroxy-4-methyl-2-pentanone; 3-methoxy-3-methylbutanol, 3 - high boiling point alcohol solvent such as methoxybutanol; ethyl lactate, n-propyl lactate, isopropyl lactate, 3-methoxybutyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid High-boiling ester solvent such as ethyl ester, ethyl hydroxyacetate, ethyl 3-ethoxypropionate or γ-butyrolactone; N-methylformamide, N,N-dimethylformamide, N- A guanamine solvent such as methyl-2-pyrrolidone, N-methylacetamide or N,N-dimethylacetamide; dimethyl hydrazine or the like.

Among these, a preferred solvent is a polyalkylene glycol solvent, a monoalkylene glycol alkyl ester solvent, and a polyalkylene glycol alkyl ester solvent, preferably having a boiling point of 150 ° C or higher, and having a boiling point of 150 to 250 ° C. Better.

In the present invention, when the alicyclic olefin is subjected to ring-opening metathesis polymerization, the polymerization conditions are not particularly limited.

The polymerization temperature is not particularly limited, but is usually -50 to +150 ° C, preferably 0 to 100 ° C.

The polymerization time may be appropriately determined depending on the polymerization temperature, the amount of the catalyst used, and the like, and is usually from 1 minute to 24 hours.

The polymerization atmosphere is not particularly limited, and the ring-opening metathesis polymerization catalyst may be carried out in the air at a timing, and it is preferably carried out in an inert gas atmosphere such as nitrogen, carbonic acid gas or rare gas.

The alicyclic olefin ring-opening metathesis polymer thus obtained is preferably a polystyrene-reduced weight average measured by gel permeation chromatography using tetrahydrofuran (THF) as a dissolving solution from the viewpoint of patterning property or developability. The content of the oligomer component having a molecular weight of 2,000 to 10,000 and a number average molecular weight of 1,000 or less is 2% by weight or less. Further, the ring-opening metathesis polymer preferably has a weight average molecular weight/number average molecular weight ratio of 1.80 or less. The content of the oligomer of the present invention is a value calculated from the peak area measured by a gel permeation chromatography-low angle laser light scattering luminosity (GPC-LALLS) method. Such an alicyclic olefin ring-opening metathesis polymer can be easily produced in accordance with suitable polymerization conditions as described above.

Generally, a low weight average molecular weight obtained by ring-opening metathesis polymerization, particularly a ring-opened metathesis polymer having a weight average molecular weight of 10,000 or less, contains a considerable amount of a low molecular oligomer. Therefore, in order to remove the oligomer after polymerization, a step of solidification, separation, and drying is required. The ring-opening metathesis polymer obtained by such a production step needs to be dissolved in a solvent in order to make it a radiation sensitive resin composition, but the time required for dissolution is extremely long.

In this regard, the alicyclic olefin ring-opening metathesis polymer used in the present invention can be obtained only by a polymerization step, in other words, after the polymerization step, without the need for separation, drying, redissolution, or the like of the polymer.

The method for preparing the first radiation-sensitive resin composition is advantageous in terms of equipment, environmental safety, and energy, without dissociating the polymer once.

The second laminate of the present invention is obtained by laminating a resin film on a substrate which is in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups using a ring-opening metathesis polymerization catalyst. Hydrogenation of a alicyclic olefin-containing ring-opening metathesis polymer obtained by polymerizing an alicyclic olefin in a solvent, and hydrogenating the alicyclic olefin-containing ring-opening metathesis polymer contained in the reaction solution to obtain an alicyclic olefin A radiation-sensitive reaction solution of a ring-opening metathesis polymer hydride, and a radiation sensitive resin composition obtained by blending a radiation sensitive compound (hereinafter referred to as a "second radiation sensitive resin composition").

The second radiation sensitive resin composition can be obtained by polymerizing an alicyclic olefin in a solvent in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups by using a ring-opening metathesis polymerization catalyst. a hydrogenation reaction solution in which a polymerization reaction solution of an olefin ring-opening metathesis polymer is introduced into hydrogen, and a hydrogenation reaction solution containing an alicyclic olefin olefin ring-opening metathesis polymer hydride is obtained by hydrogenating an alicyclic olefin ring-opening metathesis polymer contained in the reaction solution. It is obtained by blending a radiation sensitive compound.

That is, the second radiation sensitive resin composition is a hydrogenation reaction of an alicyclic olefin ring-opening metathesis polymer, which is directly subjected to a polymerization reaction solution obtained by ring-opening polymerization, and the obtained alicyclic olefin-containing ring-opening metathesis polymer hydride is obtained. The hydrogenation reaction solution is obtained by blending a radiation sensitive compound.

Further, the ring-opening polymerization may be carried out in the same manner as in the first radiation sensitive resin composition. The suitable conditions are also the same.

The alicyclic olefin ring-opening metathesis polymer hydride obtained by the hydrogenation is preferably a polystyrene-equivalent weight average molecular weight of 2,500 to 15,000 as measured by a gel permeation chromatograph (further, 3,000 to 12,000) Preferably, the content of the oligomer component having a number average molecular weight of 1,000 or less is 2% by weight or less, and further, the ratio of the weight average molecular weight/number average molecular weight of the ring-opened metathesis polymer hydride is 1.80 or less.

As the hydrogenation catalyst, for example, it is generally used in the hydrogenation of an olefin compound. Specifically, a Ziegler-type homogeneous catalyst, a noble metal complex catalyst, and a supported noble metal-based catalyst can be used. Among these hydrogenation catalysts, a side reaction such as denaturation of a functional group which does not cause a protic polar group or the like is carried out, and a palladium catalyst or a noble metal catalyst such as ruthenium or osmium is preferably supported by carbon, and a nitrogen-containing impurity having high electron supply property is preferable. A cyclic carbene compound or a phosphorus-coordinated rhodium catalyst is particularly preferred.

The hydrogenation catalyst may be added with activated carbon or the like to the hydrogenation reaction solution after the hydrogenation reaction, and is insoluble in the porous solid component of the reaction liquid, and after the catalyst is adsorbed thereto, it is removed by filtration. When the catalyst is adsorbed to the porous solid fraction, the adsorption of the catalyst can be efficiently carried out by dissolving hydrogen in the hydrogenation reaction solution.

When the first and second radiation sensitive resin compositions are prepared, the excess solvent may be distilled off from the polymerization reaction solution or the hydrogenation reaction solution, or the solvent may be replenished.

The radiation-sensitive compound for the first and second radiation-sensitive resin compositions is a compound which can absorb radiation of ultraviolet rays or electron rays and cause a chemical reaction. When the ring-opening metathesis polymer having a protic polar group or a hydride thereof is used in the present invention, it is preferred to control the alkali solubility.

The radiation-sensitive compound may, for example, be an azide compound such as an acetophenone compound, a triarylsulfonate or a quinonediazide compound, preferably an azide compound, and particularly preferably a rhodium-diazonium compound.

The hydrazine diazonium compound is bonded to a protonic polar group of a ring-opening metathesis polymer or a hydride thereof to control the solubility of the alkali developing solution, and the acid generating compound is irradiated by active radiation. As the diazonium compound, for example, an ester compound of a sulfonium halide and a compound having a phenolic hydroxyl group can be used.

醌 heavy sulfonium halide, which can be 1,2-naphthoquinonediazol-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonium chloride, 1,2-benzoquinonediazepine-5-sulfonate Chlorine and so on.

Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane and 4,4'-[1-[ 4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol.

Other compounds having a phenolic hydroxyl group other than this include 2,3,4-trihydroxybenzophenone, 2,3,4,4,-tetrahydroxybenzophenone, 2-bis(4-hydroxybenzene) Propane, tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxy-3-methylphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl) An oligomer of an alkane or a phenol resin, an oligomer obtained by copolymerizing a compound having one or more phenolic hydroxyl groups, and dicyclopentadiene.

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

The amount of the photosensitive compound to be used is usually 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, per 100 parts by weight of the ring-opening metathesis polymer or the hydride thereof. When the amount of the radiation-sensitive compound used is in this range, when the resin film formed on the substrate is patterned, the difference in solubility between the radiation-irradiated portion and the non-irradiated portion of the radiation is large, and patterning by development is easy, and the radiation sensitivity is also improved. It is getting better.

The radiation sensitive resin composition used in the present invention is added with a radiation sensitive compound and an anterior bridging agent.

The bridging agent which can be used in the present invention can form a bridging structure between the bridging agent molecules by heating, or react with a ring-opening metathesis polymer or a hydride thereof to form a bridge between the ring-opening metathesis polymers or their hydrides. Constructor.

The bridging agent can be used for two or more functional groups having a functional group capable of reacting with a protonic polar group or an unsaturated bond of a ring-opened metathesis polymer or a hydrogenated product thereof, and preferably having three or more. . When the ring-opening metathesis polymer or a hydride thereof contains a protic polar group, preferred functional groups include, for example, an amine group, a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group, an amine group, an epoxy group, and an isocyanate group. More preferably, the epoxy group is particularly preferred.

Such bridging agents include aliphatic polyamines such as hexamethyldiamine; aromatic polyamines such as 4,4'-diaminodiphenyl ether and diaminodiphenyl hydrazine; 2,6- Azide such as bis(4'-azidobenzylidene)cyclohexanone or 4,4'-diazophenyl hydrazine; nylon, polyhexamethylenediamine-p-xylamine, polyhexamethylene Polyamides such as benzyl phthalimide; melamines such as N, N, N', N', N", N"-(hexahydrooxymethyl) melamine; N, N', N" , lactic acid compounds such as N'"-(tetraalkoxymethyl) glycoluril; acrylate compounds such as ethylene glycol (meth) acrylate: hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate Isocyanate compound such as polyisocyanate, toluene diisocyanate polyisocyanate or hydrobiphenylmethane diisocyanate; 1,4-bis-(hydroxymethyl)cyclohexane, 1,4-bis-(hydroxymethyl)norbornene ; 1,3,4-trihydroxycyclohexane; various polyfunctional epoxy compounds and the like.

Further specific examples of the polyfunctional epoxy compound include an epoxy compound having two or more epoxy groups, an alicyclic skeleton, a cresol novolac skeleton, a phenol novolac skeleton, and a bisphenol A skeleton. Those who have a naphthalene skeleton and the like.

Among these, it has good compatibility with a ring-opening metathesis polymer or a hydride thereof, and particularly has an alicyclic structure and has two or more epoxy groups, and has three or more more polyfunctional epoxides. It is better.

Specific examples of the polyfunctional epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, and ring. An aliphatic epoxy resin, an aliphatic glycidyl ether, an epoxy acrylate polymer, or the like.

These bridging agents may be used alone or in combination of two or more.

The amount of bridging agent can be appropriately selected according to the purpose of use. For 100 parts by weight of the ring-opening metathesis polymer or its hydride, it is usually 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, and 10 to 100 parts by weight. Better. When the amount used is in this range, the heat resistance of the formed resin film can be highly improved.

The molecular weight of the bridging agent is not particularly limited, but is usually from 100 to 100,000, preferably from 500 to 50,000, more preferably from 1,000 to 10,000. The molecular weight in this range is preferably determined by the stability at the time of heating or the efficiency of gelation.

Further, the bridging agent is a polymerization reaction solution containing an alicyclic olefin ring-opening metathesis polymer obtained by polymerizing an alicyclic olefin or a hydride containing a cycloaliphatic ring-opening metathesis polymer obtained by hydrogenating the polymer. The hydrogenation reaction solution may be used, and it may be combined with the radiation sensitive compound at the same time.

The radiation sensitive resin composition used in the present invention may contain a nonionic interface such as polyoxyethylene lauryl ether or polyoxyethylene dilauryl ether for the purpose of preventing streaks (coating streaks) and improving developability. Active agent; new EPATOP series manufactured by Akita Chemical Co., Ltd., MEGAFAC series manufactured by Dainippon Ink Chemical Industry Co., Ltd., FLUORAD series manufactured by Sumitomo 3M Co., Ltd., ASAHIGURAD series manufactured by Asahi Glass Co., Ltd., etc.; organic oxirane polymer manufactured by Shin-Etsu Chemical Co., Ltd. A decane-based surfactant such as KP series; various surfactants such as an acrylic copolymer copolymer such as POLYFLOW series manufactured by Kyoei Oil & Fat Chemicals Co., Ltd.

The surfactant is preferably used in an amount of not less than 2 parts by weight, and preferably not more than 1 part by weight, based on 100 parts by weight of the solid content of the radiation sensitive resin composition.

In the radiation sensitive resin composition used in the present invention, a functional oxime coupling agent such as γ-glycidylpropyl methoxy decane may be added as a secondary auxiliary agent for the purpose of improving the adhesion to the substrate. The amount of the auxiliary agent is usually 20 parts by weight or less per 100 parts by weight of the ring-opening metathesis polymer or the hydride thereof, preferably 0.05 to 10 parts by weight, particularly preferably 1 to 10 parts by weight.

Further, the radiation sensitive resin composition used in the present invention may contain a charge preventing agent, a storage stabilizer, an antifoaming agent, a pigment, a dye, an aging preventive agent, a sensitizer, and the like as needed.

The solid content concentration of the radiation sensitive resin composition used in the present invention may be arbitrarily set in consideration of the thickness of the resin film required or the coating method, and is usually from 5 to 40% by weight from the viewpoint of workability.

The radiation-sensitive resin composition to be prepared is preferably used after being removed by using a filter of 0.1 to 5 μm or the like.

The radiation-sensitive resin composition obtained as described above can be suitably used as a protective film such as a display display element or an integrated circuit, or a protective film such as a color filter for liquid crystal display, and a flattening film for flattening the surface or wiring of the device. A material having a laminated body of various resin pattern films for electronic parts, such as an insulating film (including an interlayer insulating film or a solder resist film of an electric insulating film of a thin film transistor) or an integrated circuit, which is electrically insulating.

The laminate of the present invention comprises: a substrate; and a resin film formed using the first or second radiation sensitive resin composition.

In the present invention, for example, a printed circuit board, a tantalum wafer substrate, a glass substrate, a plastic substrate, or the like can be used. Further, it can be suitably used in the field of displays, and a thin film transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed on a glass substrate or a plastic substrate.

The thickness of the resin film is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, and more preferably 0.5 to 30 μm.

In the laminate of the present invention, after the resin film is formed on the substrate by using the first or second radiation sensitive resin composition, the resin film is bridged as needed.

The method of forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used. The coating method is, for example, a method in which a radiation sensitive resin composition is applied to a substrate, followed by heating and drying to remove the solvent. The method of applying the radiation sensitive resin composition to the substrate may be, for example, a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, or screen printing. Various methods such as law. The heating and drying conditions vary depending on the type of each component or the blending ratio, and are usually 30 to 150 ° C, preferably 60 to 120 ° C, usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and 1 to 30 minutes. Better.

The film layer method is, for example, a method in which a radiation-sensitive resin composition is dispersed or dissolved in a solvent, and is applied onto a substrate such as a resin film or a metal film, and then the solvent is removed by heat drying to obtain a B-base film, followed by B. A method in which a substrate film is laminated on a substrate. The heating conditions vary depending on the type of each component or the blending ratio, and are usually 30 to 150 ° C, preferably 60 to 120 ° C, usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and 1 to 30 minutes. good. The film layer can be formed using a press machine such as a pressure laminator, a stamping machine, a vacuum laminator, a vacuum embossing, a roll laminator, or the like.

The resin film may be patterned by forming a laminate of a substrate and a resin mold formed on the substrate with a radiation-sensitive resin composition.

The patterning of the resin film formed on the substrate can be performed, for example, by forming a latent image pattern by irradiating the active film with the resin film, and then bringing the developer into contact with the resin film having the latent image pattern to visualize the pattern. A laminate in which a patterned resin film is formed on a substrate is used as various electronic components.

The actinic radiation is not particularly limited as long as it can activate the sensitizing radioactive compound and change the alkali solubility of the bridging composition containing the radiation sensitive compound. Specifically, light of a single wavelength such as ultraviolet rays, g-line or i-line, KrF excimer laser light, ArF excimer laser light, or the like; a particle line such as an electron beam, or the like can be used.

The method of selectively irradiating the active radiation to a pattern to form a latent image pattern may be carried out in accordance with a conventional method. For example, ultraviolet light, g-line or i-line, or KrF may be used by reducing a projection exposure apparatus or the like. The method of irradiating light such as molecular laser light, ArF excimer laser light, or the like through a desired mask pattern, and drawing by a particle line such as an electron beam.

When light is used as the active radiation, it may be a single wavelength light or a mixed wavelength light. The irradiation conditions can be appropriately selected according to the active radiation used. For example, when the wavelength is 200 to 450 nm, the irradiation amount is usually 10 to 1,000 mJ/cm 2 and the range is 50 to 500 mJ/cm 2 . Preferably, it is determined according to the irradiation time and illuminance. After the active radiation is irradiated in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C for 1 to 2 minutes as needed.

Next, the latent image pattern formed on the resin film is developed to be manifested. In the present invention, such a step is referred to as "patterning", and the patterned resin film is referred to as a "patterned resin film".

For the developer, an aqueous solution of a basic compound is usually used. As the basic compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The basic compound may be an inorganic compound or an organic compound.

Specific examples of such compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, and sodium metasilicate; aqueous ammonia; primary amines such as ethylamine and n-propylamine; and diethylamine. a secondary amine such as di-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabromoammonium hydroxide, choline, etc. Ammonium salt; ammonium alkoxide such as dimethylethanolammonium or triethanolammonium; pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[ 4.3.0] a cyclic amine such as anthracene-5-ene or N-methyl-2-pyrrolidone. These basic compounds may be used alone or in combination of two or more.

As the aqueous medium of the aqueous alkali solution, water; a water-soluble organic solvent such as methanol or ethanol can be used. The aqueous alkaline solution may also be added with an appropriate amount of a surfactant.

A method of bringing the developer into contact with the resin film having the latent image pattern, for example, a stirring method, a spraying method, a dipping method, or the like is used. Development, usually at 0 to 100 ° C, preferably 5 to 55 ° C, preferably in the range of 10 to 30 ° C, usually in the range of 30 to 180 seconds.

After the desired patterned resin film is formed on the substrate, the development residue on the substrate, the substrate back surface, and the substrate end portion can be removed as needed, and the substrate can be rinsed with a conventional rinse liquid such as ultrapure water. After the rinsing treatment, the remaining rinsing liquid is removed with compressed air or compressed nitrogen.

Further, in order to inactivate the radiation sensitive compound, the substrate having the patterned resin film may be entirely irradiated with active radiation as needed. The irradiation of the active radiation can be utilized for the method exemplified by the formation of the above-described latent image pattern. The resin film may be heated simultaneously with or after the irradiation. The heating method may, for example, be a method in which the substrate is heated in a hot plate or in an oven. The temperature is usually 100 to 300 ° C, preferably in the range of 120 to 200 ° C.

In the present invention, after the patterned resin film is formed on the substrate, a bridging reaction of the resin can be performed.

The bridging of the resin film formed on the substrate may be carried out by heating according to the type of the bridging agent. The heating method can be carried out, for example, using a heating pan, an oven, or the like. The heating temperature is usually 180 to 250 ° C, and the heating time is appropriately selected depending on the size or thickness of the resin film and the use of a machine. For example, when a heating plate is used, it is usually 5 to 60 minutes, and when an oven is used, it is usually 30 to 90 minutes. range.

Heating can also be carried out under an inert gas atmosphere as needed. The inert gas may be any one that does not contain oxygen and does not oxidize the resin film, and examples thereof include nitrogen, argon, helium, neon, krypton, xenon, and the like. Among these, nitrogen and argon are preferred, and nitrogen is particularly preferred. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly preferably nitrogen. These inert gases may be used alone or in combination of two or more.

The laminate of the present invention may have a resin layer composed of one or two or more kinds of conventional resins between the substrate and the resin film formed using the first or second radiation-sensitive resin composition. Further, the resin film formed using the above-mentioned radiation-sensitive resin composition on the substrate may further have a resin layer composed of one or two or more kinds of conventional resins. Specific examples of the laminated body of the present invention include a matrix substrate or the like in addition to the active matrix substrate to be described later.

The active matrix substrate can be produced by using the above first or second sensitized radioactive resin composition in accordance with a conventional method.

That is, the active matrix substrate of the present invention is provided with a switching element in a matrix form, and a gate signal line for supplying a gate signal for driving the switching element and a source signal line for supplying a display signal of the switching element to each other Providing the pixel electrode to be partially overlapped between each of the signal lines via the switching element, the interlayer insulating film provided on the gate signal line and the source signal line, and the interlayer insulating film is used for the first or the first The second-sensing radiation resin composition is formed.

An example of the active matrix substrate of the present invention will be described with reference to FIGS. 1 and 2. Fig. 1 is a plan view showing an example of a flat display device of the present invention to be described later, and Fig. 2 is a cross-sectional view taken along line X-Y.

In FIG. 1 and FIG. 2, on the active matrix substrate 101, a gate signal line 203 for driving a gate signal of a TFT (thin film transistor) 201 as a switching element is supplied to an insulating substrate, and a signal is supplied to the TFT 201. The source signal lines 204 of the (source signals) are disposed to intersect each other (here orthogonally), and a TFT 201 is provided in the vicinity of the intersection of the two signal lines, via which the first or second sensitized resin composition is placed. The pixel electrode 202 is provided between the interlayer insulating films 104 which are formed so as to partially overlap the two signal lines. The interlayer insulating film 104 constituting the active matrix substrate is formed by the above method using the above first or second sensitized radioactive resin composition. Further, the pixel electrode 202 and the drain electrode of the TFT 201 are connected by a contact hole (not shown) of the interlayer insulating film 104. Further, an alignment film 111 is provided on the interlayer insulating film 104.

On the other hand, the two signal lines extend beyond the frame region, and the signal voltage for driving the TFT 201 can be input to the gate signal line 203 via the input terminal 108 of the terminal region provided outside, and the display data can be input to the source signal line 204. The signal voltage. The electrode pattern 105 is formed on the outer peripheral region of the interlayer insulating film 104, and is extended to the terminal region, and a signal from the driving circuit can be input.

The active matrix substrate as described above can be manufactured as follows. That is, after the TFT 201 is formed on the substrate in accordance with a conventional method, the interlayer insulating film 104 composed of the first or second radiation-sensitive resin composition is formed thereon by, for example, a spin coating method at a thickness of 3 μm. The interlayer insulating film 104 forms a contact hole (not shown). Next, a pixel electrode 202 formed of, for example, ITO (Indium Tin Oxide) is patterned by sputtering, and the gate electrode and the pixel of the TFT 201 are connected via a contact layer of the interlayer insulating film 104. Electrode 202. At this time, the electrode pattern 105 is simultaneously formed by the ITO constituting the pixel electrode 202. Thereafter, the alignment film 111 is formed to obtain the active matrix substrate 101 by the alignment treatment such as brushing treatment.

The active matrix substrate of the present invention is excellent in suppressing generation of leakage current and preventing deterioration of characteristics of the interlayer insulating film, and is useful for a flat display device of the present invention to be described later.

The flat display device of the present invention is characterized by comprising the active matrix substrate of the present invention. Since the flat display device of the present invention is formed by using the substrate, it is long-lived, and suppresses generation of leakage current and consumes low power, and is a flat display device excellent in high contrast. Specific examples of the device include an active matrix liquid crystal display device and an active matrix organic electroluminescence (EL) display device.

The active matrix liquid crystal display device is configured such that one of the pair of substrates is disposed opposite to each other with the optical control member interposed therebetween, and the substrate of one of the pair of substrates is a planar display device comprising the active matrix substrate of the present invention. . A substrate (hereinafter referred to as a "opposing substrate") that is disposed opposite to the active matrix substrate may, for example, be a color filter substrate or a microlens substrate. The term "optical control member" as used herein refers to a member that changes in optical properties such as a liquid crystal material or a film-like liquid crystal by voltage or current.

Further, in a modification of the liquid crystal display device including the active matrix substrate and the color filter substrate, the color filter material layer is directly provided on the pixel electrode of the active matrix substrate, and the color filter is not provided on the opposite substrate. A liquid crystal display device or a liquid crystal display device having a conductive color filter material and forming a pixel electrode of an active matrix substrate without a color filter on the opposite substrate.

Fig. 1 is a plan view showing an example of an active matrix liquid crystal display device produced by using the active matrix substrate of the present invention, and Fig. 2 is a cross-sectional view taken along line X-Y. In this aspect, the active matrix substrate 101 including the pixel electrode 202 and the color filter substrate 102 including the opposite electrode 206 are disposed opposite to each other across the liquid crystal layer 110, and the opposite portions of the pixel electrode 202 and the opposite electrode 206 are disposed. Become a pixel. A seal member 103 is provided on the outer periphery of the display region composed of pixels, and an electrode pattern 105 exists in a region between the display region and the seal member 103. Further, in the color filter substrate 102, a counter electrode 206 is provided on the color filter layer 207 having the black matrix 208, and an alignment film 111 is provided thereon. On the active matrix substrate 101, a gate signal line 203 for supplying a gate signal for driving the TFT 201 as a switching element and a source signal line 204 for supplying a source signal of the TFT 201 are provided orthogonally to each other. A TFT 201 is provided in the vicinity of the intersection of the two signal lines, and the pixel electrode 202 is provided on the organic signal via the organic protective film 104 so as to partially overlap the two signal lines. Further, a contact electrode (not shown) of the organic protective film 104 is connected to the pixel electrode 202 and the drain electrode of the TFT 201. Further, an alignment film 111 is disposed opposite to the organic protective film 104.

On the other hand, the gate signal line 203 and the source signal line 204 extend beyond the frame region, and the signal voltage for driving the TFT 201 is input to the gate signal line 203 via the input terminal 108 of the terminal region provided outside. The pole signal line 204 inputs the signal voltage of the display data. The electrode pattern 105 is formed on the outer peripheral region of the organic protective film 104, further extended to the terminal region, and inputs a signal from the driving circuit. The above liquid crystal display device can be produced by a method known in the art, for example, in JP-A-2003-005215.

The active matrix type organic EL display device is characterized in that each pixel formed in a matrix array on the active matrix substrate of the present invention has at least one organic EL element and a display for driving at least two TFTs of the organic EL element. Device.

The organic EL device is not particularly limited, and for example, a structure (SH-A structure) in which a hole transport layer and a light-emitting material layer are formed between a hole injection electrode serving as an anode and an electron injection electrode serving as a cathode is used. a structure in which a light-emitting material layer and an electron transport layer are formed between the hole injection electrode and the electron injection electrode (SH-B structure), or between the hole injection electrode layer and the electron injection electrode to form a hole transport layer and a light-emitting material The structure of the layer and the electron transport layer (DH structure). In the case of any configuration, the organic EL element is a hole injected from a hole injection electrode (anode) and an electron injected from an electron injection electrode (cathode), at an interface between a light-emitting layer material and a hole (or electron) transport layer, And the principle of recombination in the luminescent material layer to emit light.

Fig. 3 shows a typical configuration example of an organic EL element of an active matrix organic EL display device which can be fabricated using the active matrix substrate of the present invention. The organic EL device shown in FIG. 3 is composed of an active matrix substrate [including a pixel electrode as a lower electrode layer (anode)] 301, a light-emitting material layer 302, and an upper electrode layer (cathode) 303. Further, an encapsulation film 304 is provided as the outermost layer. In the configuration of one pixel of the organic EL display device, generally, at least two TFTs for driving the EL element, that is, a driving transistor and a writing transistor, are required for at least one organic EL element, but the configuration example of FIG. Omit the two transistors. The transistors are present in the active matrix substrate of the present invention.

In the active matrix substrate of the present invention, the pixel electrode as the anode is connected to the drain electrode of the TFT. An example of a circuit on the active matrix substrate of the present invention is shown in FIG. 4, in which the TFT 402 (write transistor) is turned on by a voltage applied sequentially to the scan electrodes 401 connected to the horizontal drive circuit. The capacitor 404 accumulates the amount of charge in accordance with the display signal from the data electrode 403 connected to the vertical drive circuit. The TFT 405 (drive transistor) is operated by the amount of charge accumulated in the capacitor 404, and a current is supplied to the organic EL element 406 to turn on the organic EL element. This lighting state is maintained until a voltage is applied to the scan electrode 401. The organic EL display device described above can be produced, for example, according to a conventional method described in JP-A-2002-333846.

[Examples]

The invention is further illustrated by the following examples. In addition, the part and % in each case are the mass basis unless otherwise mentioned.

Furthermore, the definition and evaluation methods of each characteristic are as follows.

[Polymerization conversion rate]

The residual amount of the monomer was measured using a gas chromatograph.

[Hydration rate]

The ratio of the carbon number of the hydrogenated carbon-carbon double bond to the molar number of carbon-carbon double bonds before hydrogenation was determined by ¹ H-NMR spectroscopy.

[molecular weight]

The molecular weight in terms of polystyrene was calculated using a gel permeation chromatography (product name "HLC-8020", manufactured by TOSO Corporation). Further, the developing solvent used tetrahydrofuran.

[Amount of oligomer]

The ratio of the component having a molecular weight of 1,000 or less was calculated by a gel permeation chromatography-low angle laser light scattering method (GPC-LALLS) method. The measurement conditions are as follows.

Column: TSKgel GMHHR-H+G2500HHR+G1000HHR 1 each (inner diameter 7.8 mm × length 300 mm × 3) Dissolution: tetrahydrofuran flow 0.8 ml / min Detector: RI + LALLS column temperature: 40 ° C sample concentration: 1.0% (weight / Volume) Injection volume: 200 microliters

[solid content concentration]

The amount of residual solvent of the solid fraction obtained by vacuum-drying the resin solution at 0.5 gram at 140 ° C was calculated by gas chromatography.

[Manufacture of active matrix substrate]

The active matrix substrate as shown in FIGS. 1 and 2 was fabricated in accordance with the following steps.

(Step 1: Coating film forming step) After the active matrix circuit including the TFT element as the switching element is formed on the transparent glass substrate by a conventional method, the radiation-sensitive resin composition is applied onto the glass substrate by a spin coating method. The film was pre-baked at 85 ° C for 2 minutes on a hot plate to form a film having a film thickness of about 1.2 μm.

(Step 2: Exposure Step) The surface region of the formed coating film was irradiated with ultraviolet rays (exposure amount: 190 mJ/cm 2 ) in a state where the slit mask was shielded from light, and subjected to exposure treatment to perform pattern formation.

(Step 3: Development step), after developing for 40 seconds at 23 ° C in tetramethylammonium hydroxide 0.4% aqueous solution using a liquid-filling method, water-washing treatment with pure water for 30 seconds, and drying by spin drying. deal with.

(Step 4: Post-baking step) Next, baking was carried out by heating at 230 ° C for 15 minutes in an oven to obtain an interlayer insulating film having a desired pattern.

(Step 5: pixel electrode forming step) The glass substrate on which the interlayer insulating film is formed is moved to a vacuum chamber, and through a mask, electrons are injected into the metal layer by DC sputtering to form an In-Sn- film having a thickness of 200 nm. O-based amorphous transparent conductive layer (pixel electrode). Thereby, an active matrix substrate is obtained.

Further, the conditions of the DC sputtering are as follows: the sputtering gas is a mixed gas of argon and oxygen (volume ratio: 1000:5), the pressure is 0.3 Pascal, and the DC output is 40 watts.

[Interlayer insulation (leakage current measurement method)]

The radiation sensitive resin composition was applied to a P-type germanium wafer (resistance value of 1 ohm or less), and then heated in an oven at 230 ° C for 15 minutes to cure the resin film. The film thickness of the resin cured film was 150 nm.

Current-voltage characteristics were evaluated using a mercury probe (Four Dimensions Inc. CV map 92A), and the current value flowing through the resin film at an applied voltage of 1 million volts/cm was measured.

The interlayer insulating film, the current value is less than 3.0 × 10 ^{- 1 0} Amps / dm well as, 3.0 × 10 ^- while above ¹⁰ Amps / dm poor.

[Manufacture of liquid crystal display device]

A liquid crystal display device is obtained by enclosing a liquid crystal display device in which a color filter substrate provided with a counter electrode and a filter substrate are provided on the outer periphery. The liquid crystal display device thus obtained was driven by a gate driving voltage of 60 volts and a source driving voltage of 15 volts.

[Manufacturing Example 1]

8-Hydroxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodeca-3-ene 60-part, N-phenyl-(5-formylbornene-2,3-dicarboxyl 40 parts of decylamine, 2.8 parts of 1,5-hexadiene, 0.05 parts of (1,3-dimesylimidazolidin-2-ylidene) (tricyclohexylphosphine)benzylidene dichloride 400 parts of diethylene glycol ethyl methyl ether was placed in a nitrogen-substituted pressure-resistant glass reactor, and polymerization was carried out at 80 ° C for 2 hours with stirring to obtain a polymerization reaction solution containing the ring-opening metathesis polymer 1A. The polymerization conversion ratio was 99.9% or more. The polymer 1A had an average molecular weight of 3,200, a number average molecular weight of 1,900, a molecular weight distribution of 1.68, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 1.35%.

Next, 0.1 part by weight of bis(tricyclohexylphosphine) ethoxy methylene dichloride as a hydrogenation catalyst was added to the polymerization reaction solution, and hydrogen was dissolved at a pressure of 4 million Pascals for 5 hours to carry out hydrogenation reaction. Thereafter, one portion of the activated carbon powder was added, and the mixture was placed in a high-pressure reactor and stirred at 150 ° C for 3 hours at a pressure of 4 MPa. Next, the solution was taken out and the activated carbon was separated by filtration using a fluororesin filter having a pore size of 0.2 μm to obtain a hydrogenation reaction solution 476 containing the hydride 1B of the ring-opening metathesis polymer 1A. Filtration can be carried out without stagnation. Here, the solid content concentration of the hydrogenation reaction solution containing the hydride 1B was 20.6%, and the yield of the hydride 1B was 98.1. The obtained hydride 1B had a weight average molecular weight of 4,430, a number average molecular weight of 2,570, a molecular weight distribution of 1.72, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 0.91%. The hydrogenation rate was 99.9%.

The hydrogenation reaction solution of the hydride 1B thus obtained was concentrated by a rotary concentrator to adjust the solid content concentration to 35.0% to obtain a solution of the hydride 1C. The yield before and after concentration, the weight average molecular weight of the hydride, the number average molecular weight, the molecular weight distribution, and the ratio of the oligomer component having a molecular weight of 1,000 or less did not change.

Further, in the above description, the hydride 1B and the hydride 1C are described separately, and the description is only for convenience, and the two hydrides are the same. Hereinafter, the hydride 2B and the hydride 2C, and the hydride 3B and the hydride 3C are also the same.

These results are shown in Table 1.

[Manufacturing Example 2]

The amount of 1,5-hexadiene was changed to 2.3 instead of (1,3-distributylmethylidazolidin-2-ylidene) (tricyclohexylphosphine)benzylidene dichloride (4, 5-dibromo-1,3-distributylimidazolin-2-ylidene) (tricyclohexylphosphine)benzylidene dichloride, the amount of diethylene glycol ethyl methyl ether is 200 In the same manner as in Production Example 1, a polymerization reaction solution containing the ring-opening metathesis polymer 2A was obtained. The polymerization conversion ratio was 99.9% or more. The polymer 2A had a weight average molecular weight of 3,970, a number average molecular weight of 2,450, a molecular weight distribution of 1.62, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 0.90%.

Then, in the same manner as in Production Example 1, except that the hydrogenation catalyst was not added, a hydrogenation reaction solution 286 containing the hydride 2B of the ring-opening metathesis polymer 2A was obtained. Filtration can be carried out without stagnation. Here, the solid content concentration of the hydrogenation reaction solution containing the hydride 2C was 34.1%, and the yield of the hydride 2B was 97.5 parts. The obtained hydride 2B had a weight average molecular weight of 5,470, a number average molecular weight of 3,310, a molecular weight distribution of 1.65, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 0.62%. The hydrogenation rate was 99.9%.

These results are shown in Table 1.

[Manufacturing Example 3]

A polymerization reaction solution containing the ring-opening metathesis polymer 3A was obtained in the same manner as in Production Example 2 except that the 1,3-diene was used in part 2.3. The polymerization conversion ratio was 99.9% or more. The polymer 3A had a weight average molecular weight of 3,450, a number average molecular weight of 2,000, a molecular weight distribution of 1.73, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 1.15%.

This polymer 3A was hydrogenated in the same manner as in Production Example 2 to obtain a hydrogenation reaction solution 279 containing the hydride 3B of the ring-opening metathesis polymer 3A. Filtration can be carried out without stagnation. Here, the solid content concentration of the hydrogenation reaction solution containing the hydride 3C was 34.2%, and the yield of the hydride 3B was 95.4 parts. The obtained hydride 3B had a weight average molecular weight of 4,760, a number average molecular weight of 2,700, a molecular weight distribution of 1.76, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 0.78%. The hydrogenation rate was 99.9%.

These results are shown in Table 1.

[Comparative Manufacturing Example 1]

8-Hydroxycarbonyltetracyclo[4.4.0.1 ^{2 , 5} .1 ^{7 , 1 0} ]dodeca-3-ene 60-part, N-phenyl-(5-formylbornene-2,3-dicarboxyl 40 parts of decylamine, 3.9 parts of 1-hexene, (1,3-di-tris-tolyl imidazolidine-2-ylidene) (tricyclohexylphosphine), benzylidene dichloride ruthenium 0.05 and diethyl 2 400 parts of alcohol ethyl methyl ether was placed in a nitrogen-substituted pressure-resistant glass reactor, and polymerization reaction was carried out at 80 ° C for 2 hours with stirring to obtain a polymerization reaction solution containing a ring-opening metathesis polymer C1A. The polymerization conversion ratio was 99.9% or more. The polymer C1A had a weight average molecular weight of 3,080, a number average molecular weight of 1,640, a molecular weight distribution of 1.88, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 1.79%.

Next, 0.1 part of (tricyclohexylphosphine) ethoxy methylene dichloride as a hydrogenation catalyst was added to the polymerization reaction solution to carry out a hydrogenation reaction, thereby obtaining a solution containing the hydride C1B of the ring-opening metathesis polymer C1A. The obtained hydride-containing C1B had a weight average molecular weight of 4,400, a number average molecular weight of 2,140, a molecular weight distribution of 2.06, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 1.31%. The hydrogenation rate was 99.9%.

To the hydrogenation reaction solution containing the hydride C1B thus obtained, one portion of activated carbon powder was placed, and the mixture was placed in a high-pressure reactor and stirred at 150 ° C for 3 hours at a pressure of 4 MPa. Next, the solution was taken out and the activated carbon was separated by filtration through a fluororesin filter having a pore size of 0.2 μm, and then 2,500 parts of n-hexane were placed to analyze the solid form. The solid fraction was filtered and dried to obtain a hydride C1C 91.0 portion. The hydride C1C had a weight average molecular weight of 4,430, a number average molecular weight of 2,320, a molecular weight distribution of 1.91, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 1.15%. The yield of hydride C1C was 91.0 parts.

These results are shown in Table 1.

[Comparative Manufacturing Example 2]

In the same manner as in Comparative Production Example 1, except that 1,000 parts of n-hexane were used, the hydrogenated C2C of the ring-opening metathesis polymer was obtained in the same manner as in Comparative Example 1. The polymer C2C had a weight average molecular weight of 4,460, a number average molecular weight of 2,620, a molecular weight distribution of 1.70, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 0.90%.

These results are shown in Table 1.

[Comparative Manufacturing Example 3]

In the same manner as in Comparative Production Example 2, 57.1 parts of the ring-opening metathesis polymer hydride C3C was obtained, except that the amount of n-hexane was changed to 500 parts. The polymer C3C had a weight average molecular weight of 4,790, a number average molecular weight of 3,280, a molecular weight distribution of 1.46, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 0.61%.

These results are shown in Table 1.

[Comparative Manufacturing Example 4]

A hydrogenation reaction solution containing a polymerization reaction solution of a ring-opening metathesis polymer C4A and a hydride C4B containing a ring-opening metathesis polymer C4A was obtained in the same manner as in Comparative Production Example 1 except that the amount of 1-hexene was 2.6. The polymer C4A had a weight average molecular weight of 3,920, a number average molecular weight of 2,120, a molecular weight distribution of 1.85, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 1.38%. Further, the hydride C4B had a weight average molecular weight of 5,460, a number average molecular weight of 2,700, a molecular weight distribution of 2.02, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 1.08%. The hydrogenation rate was 99.9%.

A solution of the obtained hydride C4B was put into 1,000 parts of cyclohexane to analyze the solid form. The solid fraction was filtered and dried to obtain 89.8 parts of a ring-opening metathesis polymer hydride C4C. The hydride C4C had a weight average molecular weight of 5,490, a number average molecular weight of 3,190, a molecular weight distribution of 1.72, and a ratio of an oligomer component having a molecular weight of 1,000 or less of 0.60%.

These results are shown in Table 1.

[Example 1]

100 parts of a hydrogenation reaction solution (solid content: 35.0%) containing a hydride 1C obtained in Production Example 1 and an alicyclic structure mixed as a bridging agent containing a polyfunctional epoxy compound (molecular weight of about 2,700, epoxy group number 15, product name) "EHPE3150", manufactured by DAICELL Chemical Industry Co., Ltd., as 1, 1, 3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) as a radiation sensitive compound And 25 parts by weight of a condensate of 1,2-naphthoquinonediazol-5-sulfonyl chloride (2.5 mol) as an anti-aging agent (1,2,2,6,6-pentamethyl-4- Piperidine/trimethyl)-1,2,3,4-butane tetracarboxylate 5, γ-glycidylpropyltrimethyldecane as a secondary auxiliary agent 5 and silicone surfactant (Product name "KP341", manufactured by Shin-Etsu Chemical Co., Ltd.), 0.05 parts, and further added 92 parts of diethylene glycol ethyl methyl ether and 8 parts of N-methyl-2-pyrrolidone. The mixture became a homogeneous solution within 5 minutes. This solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm to prepare a radiation sensitive resin composition (1D).

The obtained radiation sensitive resin composition (1D) was spin-coated on a glass substrate (product name "CORNING 1737 Glass", manufactured by CORNING Co., Ltd.), and then prebaked at 85 ° C for 2 minutes using a hot plate to form a resin film having a thickness of 1.2 μm. .

The resin film was irradiated with ultraviolet rays having a light intensity of 5 mW/cm 2 at 365 nm for 40 seconds through a photomask of a pattern of 5 μm in space. Subsequently, development treatment was carried out at 25 ° C for 90 seconds using a 0.4% aqueous solution of tetramethylammonium hydroxide, followed by rinsing with ultrapure water for 30 seconds to form a spatially aligned pattern. A good pattern with a residual film ratio of 90% or more was obtained.

Moreover, the active matrix substrate was produced using the composition as an interlayer insulating film material while evaluating the interlayer insulating property of the resin film formed by the radiation sensitive resin composition (1D). Further, a liquid crystal display device using the substrate is manufactured.

The results are shown in Table 2.

[Embodiment 2]

In the same manner as in Example 1, except that 293 portions of the hydrogenation reaction solution (solid content: 34.1%) of the hydride 2C obtained in Production Example 2 were used, and the amount of addition of diethylene glycol ethyl methyl ether was changed to 6.9. Ingredients, the mixture became a homogeneous solution within 5 minutes. This was filtered in the same manner as in Example 1 to obtain a radiation sensitive resin composition (2D).

The radiation sensitive resin composition (2D) was patterned to obtain a good pattern having a residual film ratio of 90% or more.

Moreover, the active matrix substrate was produced using the composition as an interlayer insulating film material while evaluating the interlayer insulating property of the resin film formed by the radiation sensitive resin composition (2D). Further, a liquid crystal display device using the substrate is manufactured.

The results are shown in Table 2.

[Example 3]

In the same manner as in Example 1, except that 292 parts of the hydrogenation reaction solution (solid content: 34.2%) containing the hydride 3C obtained in Production Example 3 were changed to 7.9 parts. Ingredients, the mixture became a homogeneous solution within 5 minutes. This was filtered in the same manner as in Example 1 to obtain a radiation sensitive resin composition (3D).

The radiation sensitive resin composition (3D) was patterned to obtain a good pattern having a residual film ratio of 90% or more.

Moreover, the active matrix substrate was produced using the composition as an interlayer insulating film material while evaluating the interlayer insulating property of the resin film formed by the radiation sensitive resin composition (3D). Further, a liquid crystal display device using the substrate is manufactured.

The results are shown in Table 2.

[Comparative Examples 1 to 4]

The hydride-containing C1C-C4C100 portion obtained in Comparative Production Examples 1 to 4 was mixed with a polyfunctional epoxy compound (product name "EHPE 3150", manufactured by DAICELL Chemical Co., Ltd.) in an alicyclic structure as a bridging agent, and used as a radiation. Compound 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2-naphthoquinonediazol-5-sulfonyl chloride (2.5 mol) of the condensate 25 parts by weight, as an anti-aging agent (1,2,2,6,6-pentamethyl-4-piperidine/tridecyl)-1,2,3,4- 5 parts of butane tetracarboxylate, 5 parts of γ-glycidylpropyltrimethyl decane as a secondary auxiliary agent, and 0.05 type of surfactant (product name "KP341", manufactured by Shin-Etsu Chemical Co., Ltd.). Further, 100 parts of propylene glycol monoethyl ether acetate, 200 parts of diethylene glycol ethyl methyl ether, and 100 parts of N-methyl-2-pyrrolidone were mixed and stirred to obtain a solution. Table 2 shows the time when the mixture became a homogeneous solution.

This solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm to prepare a radiation sensitive resin composition (C1D) to (C4D). The radiation sensitive resin composition (C1D) to (C4D) was patterned to obtain a good pattern having a residual film ratio of 90% or more.

Moreover, the active matrix substrate was produced using the composition as an interlayer insulating film material while evaluating the interlayer insulating properties of the resin film formed of the radiation sensitive resin composition (C1D) to (C4D). Further, a liquid crystal display device using the substrate is manufactured.

The results are shown in Table 2.

The following cases are known from Tables 1 and 2.

That is, in Production Examples 1 to 3, in the polymerization step, a ratio of a polymer component having a weight average molecular weight of 2,000 to 10,000 in terms of polystyrene and a number average molecular weight of 1,000 or less was obtained in an amount of 2.0% or less, and a weight average molecular weight/ A polymerization reaction solution of an alicyclic olefin ring-opening metathesis polymer having a number average molecular weight of 1.80 or less. Further, the yield of the ring-opening metathesis polymer is more than 95%. Since the polymer has the above characteristics, it is not necessary to separate the polymer for the purpose of removing the oligomer component or the like. The hydrogenation reaction solution containing the alicyclic olefin ring-opening metathesis polymer hydride, which is obtained by hydrogenating the alicyclic olefin ring-opening metathesis polymer contained in the polymerization solution, by introducing hydrogen into the polymerization solution, and modulating the radiation-sensitive compound, A uniform radiation sensitive resin composition (Examples 1 to 3) was obtained in a short time by blending.

On the other hand, in Comparative Production Example 1 and Comparative Production Example 4, a polymer having a desired polymer property could not be obtained only by a polymerization step, and the low molecular weight component was removed by solidification of the polymer to obtain desired The polymer of the characteristics is required to have a large amount of solvent (7 times or more in Production Example 1 in Comparative Production Example 1 and 3.5 times in Production Example 1 in Comparative Production Example 4). When the amount of the solvent is to be reduced, the yield of the polymer is largely lowered (Comparative Production Examples 2 and 3). Further, when the alicyclic olefin olefin ring-opening metathesis polymer obtained by the solidification and redissolution steps after the polymerization is used, it takes a very long time until the ring-opening metathesis polymer is dissolved and homogenized, and it is found that the productivity is poor (Comparative Example) 1~4).

Further, as a result of comparing the results of Examples 1 to 3 and Comparative Examples 1 to 4, it was found from the results of evaluation of interlayer insulation that the interlayer insulation property was good with respect to the use of the first or second radiation sensitive resin composition. (The leakage current is small), and when the radiation sensitive resin composition obtained by the polymer obtained by the method of removing the low molecular weight component by the solidification process after the polymerization is used, the interlayer insulation is not good (the leakage current is large).

The reason for this is not clear, and the fine particles which have been removed by filtration in the case where the radiation-sensitive linear resin composition cannot be modulated by the prior art remain in the composition, and it is considered that it greatly affects the decrease in the insulating property of the interlayer insulating film. In other words, it is considered that when there is an impurity in the interlayer insulating film, leakage current is generated to lower the performance of the interlayer insulating film, power consumption is increased, or the transistor is inoperable to lower the reliability, so that the first or second radiation sensitive resin is used. The composition can remarkably reduce impurities in the interlayer insulating film, suppress generation of leakage current, and prevent deterioration of characteristics of the interlayer insulating film.

101. . . Active matrix substrate

102. . . Color filter substrate

103. . . Sealing material

104. . . Interlayer insulating film

105. . . Electrode pattern

108. . . Input terminal

110. . . Liquid crystal layer

111. . . Orientation film

201. . . TFT

202. . . Pixel electrode

203. . . Gate signal line

204. . . Source signal line

206. . . Counter electrode

207. . . Color filter layer

208. . . Black matrix

301. . . Active matrix substrate

302. . . Luminescent material layer

303. . . Upper electrode layer (cathode)

304. . . Encapsulation film

401. . . Scanning electrode

402. . . Thin film transistor (TFT)

403. . . Data electrode

404. . . Capacitor

405. . . Thin film transistor (TFT)

406. . . Organic EL element

Fig. 1 is a plan view showing an example of an active matrix type liquid crystal display device of the present invention.

2 is a cross-sectional view showing the X-Y of the active matrix type liquid crystal display device of FIG. 1.

Fig. 3 is a view showing a typical configuration example of an organic EL element of an active matrix type organic EL display device of the present invention.

Fig. 4 is an explanatory view showing an example of a circuit on the active matrix substrate of the present invention in the active matrix type organic EL display device of the present invention.

101. . . Active matrix substrate

102. . . Color filter substrate

103. . . Sealing material

105. . . Electrode pattern

108. . . Input terminal

203. . . Gate signal line

204. . . Source signal line

Claims (9)

A laminate obtained by laminating a resin film on a substrate, which is polymerized in a solvent in the presence of a non-conjugated diene compound having two or more terminal vinyl groups using a split ring metathesis polymerization catalyst. An alicyclic olefin (wherein the amount of the oxime metathesis polymerization catalyst is such that the ruthenium atom: the molar ratio of the alicyclic olefin to be polymerized is from 1:1,000 to 1:1,000,000, the non-conjugated diene compound a polymerization reaction solution containing an alicyclic olefin ring-opening metathesis polymer in an amount of 0.1 to 20 mol% for the alicyclic olefin to be polymerized, and blending from a weight of 0.5 to 100 parts of the ring-opening metathesis polymer A composition of a radiation-sensitive resin composition obtained by selecting a radiation-sensitive compound of 100 parts by weight of an azide compound. A laminated body obtained by laminating a resin film on a substrate, which is obtained by polymerizing a solvent in a solvent in the presence of a non-conjugated diene compound having two or more terminal vinyl groups using a split ring metathesis polymerization catalyst. a cyclic olefin (wherein the amount of the rhodium-opening metathesis polymerization catalyst is such that the molar ratio of the argon atom: the alicyclic olefin to be polymerized is from 1:1,000 to 1:1,000,000, the non-conjugated diene compound The amount of the alicyclic metathesis polymer to be polymerized is 0.1 to 20 mol%), and the polymerization reaction solution containing the alicyclic olefin ring-opening metathesis polymer is introduced into hydrogen, and the alicyclic olefin contained in the polymerization reaction solution is subjected to ring-opening metathesis. The hydrogenation reaction solution containing the hydride of the alicyclic olefin ring-opening metathesis polymer obtained by hydrogenating the polymer, and modulating the radiation selected from the azide compound having a weight of 0.5 to 100 parts by weight for 100 parts by weight of the ring-opening metathesis polymer Sensible radiation The composition of the resin composition. The laminate according to claim 1 or 2, wherein the alicyclic olefin ring-opening metathesis polymer has a weight average molecular weight of 2,000 to 10,000, and a content of a component having a number average molecular weight of 1,000 or less is 2% by weight or less. The laminate according to claim 1 or 2, wherein the radiation sensitive resin composition is obtained by further blending a bridging agent together with the azide compound. The laminate according to claim 1 or 2, wherein the radiation sensitive resin composition is obtained by using a polar solvent having a boiling point of 150 to 250 ° C as a solvent. The laminate according to claim 1 or 2, wherein the radiation sensitive resin composition uses 1,5-hexadiene as a non-conjugated diene compound having two or more terminal vinyl groups. Winner. The laminate according to claim 1 or 2, wherein the resin film is a patterned resin film. An active matrix substrate is provided with a switching element arranged in a matrix, and a gate signal line for supplying a gate signal for driving the switching element and a source signal line for supplying a display signal of the switching element are disposed to cross each other through the switching element And a pixel electrode in which a plurality of signal lines are partially overlapped between the interlayer signal lines on the gate signal line and the source signal line, and the interlayer insulating film is a radiation sensitive unit according to claim 1 or 2. A resin composition former. A flat display device for aligning an optical control member A flat display device comprising a pair of substrates, wherein one of the pair of substrates is the active matrix substrate according to claim 8 of the patent application.