KR101173709B1 - Radiation-sensitive composition, laminate, process for producing the same and electronic part - Google Patents

Abstract

[PROBLEMS] A radiation sensitive composition having excellent electrical properties, high film development sustainability and transparency, and excellent chemical resistance even after high temperature heating, without causing a decrease in film thickness during development or peeling of the developed film. The laminated body which formed the formed resin film on the board | substrate, and the manufacturing method of this laminated body are provided.

[Solution] A radiation sensitive composition comprising a polymer containing a polar group reacting with an epoxy group, a crosslinking agent containing a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, and a radiation sensitive compound. The laminated body which consists of a board | substrate and the resin film formed using this crosslinkable resin composition.

Description

A radiation sensitive composition, a laminated body, a manufacturing method, and an electronic component TECHNICAL FIELD [RADIATION-SENSITIVE COMPOSITION, LAMINATE]

The present invention relates to a laminate having a radiation-sensitive composition and a resin film obtained from the radiation-sensitive composition on a substrate, and more particularly, radiation-sensitive radiation suitable for the production of electronic components such as display elements, integrated circuit elements, and solid-state imaging elements. It relates to a laminate having a composition, a resin film obtained from the radiation-sensitive composition on a substrate, and a method for producing the same.

Electronic components such as display devices, integrated circuit devices, solid-state imaging devices, color filters, and black matrices include protective films for preventing their deterioration and damage, flattening films for flattening the surface and wiring of the elements, and electrical insulation for maintaining electrical insulation. Various resin films are provided as insulating films and the like. Moreover, in order to insulate between the wiring arrange | positioned in layers, the resin film as an interlayer insulation film is provided in elements, such as a thin film transistor type liquid crystal display element and an integrated circuit element.

Conventionally, as a resin material for forming these resin films, thermosetting resin materials, such as an epoxy resin, have been used widely. However, with the recent increase in the density of wirings and devices, there has been a demand for fine patterning and excellent electrical properties of these resin materials.

Several resin materials for responding to these demands have been studied. For example, Patent Document 1 discloses a crosslinking agent having a functional group capable of forming an alkali-soluble cyclic polyolefin resin composition, a 1,2-quinonediazide compound and a crosslinking agent (preferably, glycolurils, and bisphenol A type epoxy, for example). The radiation sensitive composition containing the compound which does not have radical polymerizability which has at least 2 epoxy groups, such as resin, is disclosed. However, when using this radiation sensitive composition, the film thickness at the time of image development, peeling of a developing film may occur, or the shape and transparency may be lost after a heating process. Moreover, since solvent resistance was not enough, the resin film formed from these radiation sensitive compositions was not suitable for apply | coating and laminating | stacking the polyimide for liquid crystal polarizing films with a solution thereon, for example.

In addition, Patent Document 2 discloses a radiation-sensitive composition composed of an alicyclic olefin resin, an acid generator, a crosslinking agent, and a solvent, and using a specific compound as a solvent. However, in this radiation sensitive composition, the film thickness at the time of image development, the peeling of a developing film, the shape and transparency change by a heating process, etc. may arise.

Moreover, the curable composition containing the ring structure containing polymer which has polar groups, such as a carboxyl group, a polyfunctional epoxy resin, and a hardening | curing agent as needed is disclosed (patent document 3). However, the curable composition disclosed herein is not suitable for forming a pattern efficiently by actinic radiation, and in the case where heat resistance shape retention and solvent resistance are highly required, these requirements cannot be sufficiently satisfied.

Patent Document 1: Japanese Patent Application Laid-Open No. 1998-307388

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-156838

Patent Document 3: WO01 / 04213

DISCLOSURE OF INVENTION

Problems to be solved by the invention

The present invention has been made under such a situation, and has excellent electrical properties, does not cause a decrease in the film thickness during development or peeling of the developing film, and has a high shape retention and transparency even after high temperature heating, and also has excellent chemical resistance. It aims at providing the laminated body which formed the resin film which used the radiation sensitive composition on the board | substrate, and the manufacturing method of this laminated body.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, As a result, the polymer which has polar groups, such as a carboxyl group which has reactivity with an epoxy group, the polyfunctional epoxy compound which has an alicyclic structure in a main chain structure, and has three or more epoxy groups, and It has been found that a radiation sensitive composition containing a radiation sensitive compound may be used. Based on these findings, further studies have been conducted to complete the present invention.

According to the present invention, there is provided a polymer containing a polar group reacting with an epoxy group, a crosslinking agent containing a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, and a radiation sensitive composition containing a radiation sensitive compound do.

In the radiation sensitive composition of this invention, it is preferable that the polymer containing the polar group reacting with an epoxy group is a cyclic olefin type polymer which has a polar group reacting with an epoxy group.

Moreover, in the radiation sensitive composition of this invention, it is preferable that the cyclic olefin type polymer which has a polar group which reacts with an epoxy group contains 10-90 weight% of polar group containing cyclic olefin units.

Moreover, in this invention, it is preferable that the polar group which reacts with the said epoxy group is a protic polar group.

Moreover, in this invention, it is preferable that the main chain structure of a polyfunctional epoxy compound has a branched alkylene chain.

Moreover, according to this invention, the laminated body manufactured by laminating | stacking the resin film which consists of said radiation sensitive composition on a board | substrate is provided.

This laminated body can be obtained from the process of forming a resin film on a board | substrate using the said radiation sensitive composition, and then the process of bridge | crosslinking resin as needed.

In the present invention, the resin film may be a patterned resin film.

Moreover, according to this invention, the resin film is laminated | stacked on the board | substrate using the said radiation sensitive composition, this resin film is irradiated with active radiation, a latent flaw pattern is formed in a resin film, and a developing solution is then applied to the resin film. Provided is a method for producing the laminate, wherein the latent image pattern is brought into contact to form a patterned resin on a substrate.

In the manufacturing method of the laminated body of the said invention, after forming patterning resin on a board | substrate, crosslinking reaction of resin can be performed.

Moreover, according to this invention, the electronic component which consists of said laminated body is provided.

Effects of the Invention

The radiation-sensitive composition of the present invention can be applied to various applications because of its excellent electrical properties, reduced film thickness during development, improved peeling of the developing film, high shape retention even after high temperature heating, and excellent transparency and chemical resistance. have. Moreover, since the laminated body of this invention is excellent in an electrical property, shape retention, transparency, and chemical-resistance, it deteriorates or damages to electronic components, such as a display element, an integrated circuit element, a solid-state image sensor, a color filter, and a black matrix, for example. Protective film for preventing a film, planarizing film for planarizing a device surface or wiring, and an electrical insulating film for maintaining electrical insulation (interlayer insulating film or solder resist film, which is an electrical insulating film of a thin transistor type liquid crystal display device or an integrated circuit device, etc.). ), Microlenses, and spacers are suitable as electronic component materials.

Best Mode for Carrying Out the Invention

The radiation sensitive composition of the present invention is characterized by containing a polymer containing a polar group reacting with an epoxy group, a crosslinking agent containing a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, and a radiation sensitive compound. .

The polar group reacting with the epoxy group is suitably a protic polar group, but may be a polar group (non-protic polar group) other than the protic polar group.

In the present invention, the number of polar groups reacting with the epoxy group contained in the polymer containing the polar group reacting with the epoxy group is not particularly limited in number, and in the case of a plurality, the types may be different from each other.

Protonic polar groups are heteroatoms, preferably atoms of groups 15 and 16 of the periodic table, more preferably atoms of the first and second cycles of groups 15 and 16 of the periodic table, particularly preferably oxygen atoms It is the atomic group which the hydrogen atom couple | bonded directly.

As a specific example of a protic polar group, Polar group which has oxygen atoms, such as a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, a phosphoric acid group, and a hydroxyl group; Polar groups which have nitrogen atoms, such as a primary amino group, a secondary amino group, a primary amido group, and a secondary amido group (imido group); Polar groups which have sulfur atoms, such as a thiol group, etc. are mentioned. Among these, those having an oxygen atom are preferable, and more preferably a carboxyl group.

There is no restriction | limiting in particular in the skeleton of the polymer containing the polar group which reacts with the epoxy group used by this invention, A cyclic olefin type polymer, a linear olefin type polymer, an acrylate polymer etc. are mentioned as the example. Among them, cyclic olefin polymers and acrylate polymers are preferred, and cyclic olefin polymers are particularly preferred because of their excellent dielectric properties.

Although the protic polar group contained in the cyclic olefin type polymer containing a protic polar group may be couple | bonded with the cyclic olefin monomeric unit, and may be couple | bonded with monomer units other than a cyclic olefin monomer, it is preferable that it is couple | bonded with the cyclic olefin monomeric unit. .

The cyclic olefin polymer constituting a part other than the protic polar group of the cyclic olefin polymer containing a protic polar group (hereinafter sometimes referred to as a "base part") is a homopolymer and an air of a cyclic olefin. Any of copolymers and copolymers of cyclic olefins with other monomers may be sufficient, and these may be hydrogenated products.

These cyclic olefin polymers containing a protic polar group can be used individually or in combination of 2 or more which differ in composition, etc., respectively.

Although the cyclic olefin type polymer containing a protic polar group used in this invention is a polymer which consists only of the monomer unit derived from the cyclic olefin monomer (a) containing a protic polar group, the cyclic olefin monomer containing a protic polar group (a It may be a copolymer comprising a monomer unit derived from a) and a monomer unit derived from another monomer copolymerizable with the cyclic olefin monomer (a) containing a protic polar group.

In the cyclic olefin polymer containing a protic polar group used in the present invention, the ratio of monomer units containing a protic polar group to monomer units other than (monomer units / other monomer units containing protic polar groups) is weight ratio. Usually 100/0 to 10/90, preferably 90/10 to 20/80, and more preferably 80/20 to 30/70.

Specific examples of the cyclic olefin monomer (a) containing a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2.2. 1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [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 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4 .0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3 Carboxyl group-containing cyclic olefins such as -ene; 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 ^7,10 ] dodec-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodec-3 and the like hydroxyl group-containing cyclic olefin, such as yen, these, preferred are a carboxyl group-containing cyclic olefin. These protic polar group-containing cyclic olefins may be used alone, or two or more kinds thereof may be used in combination.

As a monomer copolymerizable with the cyclic olefin monomer (a) containing a protic polar group, the cyclic olefin monomer (b) which has polar groups other than a protic polar group, and the cyclic olefin monomer which does not have any polar group ("polar group-containing cyclic olefin monomer") (C), and monomers (d) other than cyclic olefin.

Among these, cyclic olefin monomers (b) containing polar groups other than the protic polar group and cyclic olefin monomers (c) containing no polar group, and more preferably cyclic olefin monomers containing polar groups other than the protic polar group ( b).

Specific examples of polar groups other than the protic polar group include ester groups (collectively referred to as alkoxycarbonyl groups and aryloxycarbonyl groups), N-substituted imido groups, epoxy groups, halogen atoms, cyano groups, and carbonyloxycarbonyl groups (dicarboxylic acids And an acid anhydride residue), an alkoxyl group, a tertiary amino group, an acryloyl group and the like.

Among them, an ester group, an N-substituted imido group and a cyano group are preferable, an ester group and an N-substituted imido group are more preferable, and an N-substituted imido group is particularly preferable.

Examples of the ester group-containing cyclic olefins include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5- Methoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetra Cyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8 -n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3- N, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3- N, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene Etc. can be mentioned.

Examples of the N-substituted imido group-containing cyclic olefins include N-phenyl- (5-norbornene-2,3-dicarboxyimide) and the like.

Examples of the cyano group-containing cyclic olefins include 8-cyanotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene and 8-methyl-8-cyanotetracyclo [4.4.0.1 ^{2 , 5.1 7,10} ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.

As the halogen atom-containing cyclic olefin, for example, 8-chlorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-en etc. are mentioned. The cyclic olefins having polar groups other than these protic polar groups may be used alone, or two or more kinds thereof may be used in combination. Specific examples of the polar group-free cyclic olefin monomer (c) 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-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2- N, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deck-3,7-diene (common name: dicyclopentadiene), tetracyclo [ 8.4.0.1 ^11,14 .0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dec-3-en : Tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10} ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0. 1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a, 5,10,10a Hexahydroanthracene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, tetracyclo [9.2.1.0 ^2,10 .0 ^3,8 ] tetradec-3 , 5,7,12- tetraen (1, 4-meth furnace -1,4,4a, also known as tetrahydro-9a- -9H- fluorene), penta-cyclo [7.4.0.1 ^3,6 .1 ^10,13 .0 ^2,7 ] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadeca-5,12-diene, and the like. . These polar group-free cyclic olefin monomers (c) can be used individually or in combination of 2 or more types, respectively.

A linear olefin is mentioned as a representative example of monomer (d) other than cyclic olefin. Examples of the chain olefins include ethylene; Propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl- 1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, C2-C20 alpha olefins, such as 1-dodecene, 1- tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; And non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene. . These monomers can be used individually or in combination of 2 types or more, respectively.

As a preferable manufacturing method of the cyclic olefin type polymer containing a protic polar group, the method of superposing | polymerizing a cyclic olefin monomer (a) containing a protic polar group and performing hydrogenation as needed is mentioned.

The cyclic olefin monomer (a) containing a protic polar group can be copolymerized with the monomer copolymerizable with this (monomer (b), (c) or (d) mentioned above) as needed.

In the production method of the protic polar group-containing cyclic olefin polymer, the protic polar group may be a precursor thereof, and it is preferable to convert the precursor into a protic polar group by chemical reaction such as decomposition or hydrolysis by light or heat. For example, in the case where the protic polar group is a carboxyl group, the protic polar group-containing cyclic olefin polymer can be obtained by hydrolysis using a cyclic olefin containing an ester group instead of the protic polar group.

The protic polar group-containing cyclic olefin polymer can also be obtained by introducing a protic polar group into a cyclic olefin polymer containing no protic polar group by a known method and then hydrogenating as necessary. Hydrogenation may be performed with respect to the polymer before introduction of a protic polar group.

The cyclic olefin polymer which does not contain a protic polar group can be obtained using the said monomers (b)-(d). At this time, of course, you may use together the monomer containing a protic polar group.

As a modifier for introducing a protic polar group, a compound having a carbon-carbon unsaturated bond reactive with the protic polar group in one molecule is usually used. Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassidic acid, maleic acid, Unsaturated carboxylic acids such as fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid and cinnamic acid; Allyl alcohol, methylvinyl-methanol, crotyl alcohol, metalyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1-ol, 3-butene-2-ol , 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-butene-2-ol, 2-methyl-3-buten-1-ol, 4 And unsaturated alcohols such as -penten-1-ol, 4-methyl-4-penten-1-ol, and 2-hexen-1-ol. The modification reaction is in accordance with conventional methods and is usually carried out in the presence of a radical generator.

The polymerization method of each said monomer may be according to a conventional method, and a ring-opening polymerization method and an addition polymerization method are employ | adopted, for example.

As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are suitably used. These polymerization catalysts can be used individually or in combination of 2 types or more, respectively. The amount of the polymerization catalyst is usually in the range of 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000, more preferably 1: 1,000 to 1: 500,000 in a molar ratio of metal compound: cyclic olefin in the polymerization catalyst.

Hydrogenation of the polymer is usually carried out using a hydrogenation catalyst.

As a hydrogenation catalyst, what is generally used in hydrogenation of an olefin compound can be used, for example. Specifically, a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst and the like can be used. Among these hydrogenation catalysts, noble metal complex catalysts such as rhodium and ruthenium are preferable, because side reactions such as functional groups are not modified and carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated. Particularly preferred is a ruthenium catalyst in which a woman has a high nitrogen-containing heterocyclic carbene compound or phosphines.

The acrylate polymer having a polar group reacting with the epoxy group may be an acrylate copolymer having a protic polar group, but at least one monomer selected from a carboxylic acid having an acrylic group, a carboxylic anhydride having an acrylic group, or an epoxy group-containing acrylate compound Preferred are homopolymers or copolymers as essential components.

As a specific example of the carboxylic acid which has an acryl group, (meth) acrylic acid, maleic acid, a fumaric acid, a citraconic acid, a mesaconic acid, glutamic acid, etc .; As a specific example of the carboxylic anhydride which has an acryl group, maleic anhydride, a citraconic anhydride, etc .; Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, glycidyl α-butyl acrylate, and acrylic acid. -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl Etc. can be mentioned. Among these, (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferable.

In addition, in this invention, "(meth) acryl" means "acryl" and / or "methacryl".

The acrylate polymer may be a copolymer of at least one monomer selected from unsaturated carboxylic acids, unsaturated carboxylic anhydrides or epoxy group-containing unsaturated compounds with other acrylate monomers or copolymerizable monomers other than acrylates. As another acrylate monomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acryl Late, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth ) Acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate Alkyl (meth) acrylates such as dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;

Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate; Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl ( Alkoxyalkyl (meth) acrylates such as meth) acrylate; Polyethylene glycol mono (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy Polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, nonyl Polyalkylene glycol (meth) acrylates such as phenoxy polypropylene glycol (meth) acrylate; Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate Cycloalkyl (meth) acrylates such as carbonyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecaneyl (meth) acrylate; Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. Among these, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.

The copolymerizable monomers other than the acrylate are not particularly limited as long as they are copolymerizable with the carboxylic acid having an acryl group, the carboxylic acid anhydride having an acrylic group, or the epoxy group-containing acrylate compound, but for example vinylbenzyl methyl ether, vinyl glycidyl ether, and sty. And vinyl group-containing radically polymerizable compounds such as lene, α-methylstyrene, butadiene, and isoprene.

These compounds can be used individually or in combination of 2 or more types.

The weight average molecular weight (Mw) of the polymer containing the polar group which reacts with the epoxy group used by this invention is 1,000 to 1,000,000 normally, Preferably it is 1,500-100,000, More preferably, it is the range of 2,000-10,000.

The molecular weight distribution of the polymer containing the polar group reacting with the epoxy group used by this invention is 4 or less normally, Preferably it is 3 or less, More preferably, it is 2.5 or less by weight average molecular weight / number average molecular weight (Mw / Mn) ratio.

The iodine value of the polymer containing the polar group which reacts with an epoxy group used by this invention is 200 or less normally, Preferably it is 50 or less, More preferably, it is 10 or less. When the iodine value of the polymer containing the polar group reacting with an epoxy group exists in this range, the resin film formed using the radiation sensitive composition obtained is excellent in heat resistance, and is suitable.

In this invention, the polymer containing the polar group which reacts with an epoxy group may be used individually by 1 type, and may use two or more types together.

The crosslinking agent used in the present invention contains a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, preferably an epoxy group bonded to the alicyclic structure portion directly or through a divalent linking group. It contains the epoxy compound which has more than two pieces. The alicyclic structure may be obtained by hydrogenating an aromatic ring.

The proportion of the polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups in the crosslinking agent is preferably 50% by weight or more, and more preferably 70% by weight or more.

By using this crosslinking agent, it is excellent in the electrical property of the resin film formed from the radiation sensitive composition of this invention, it does not cause the fall of the film thickness at the time of image development, or peeling of a developing film, and its shape retention property and transparency are high even after high temperature heating, and It is excellent in chemical resistance. Moreover, when the main chain structure of a polyfunctional epoxy compound further has a branched alkylene chain, it is suitable because each said characteristic is highly balanced. Here, the alkylene chain which has a branched chain means what has a tertiary or quaternary carbon in an alkylene chain. Although the number of epoxy groups in a polyfunctional epoxy compound is essential three or more, Preferably it is 4-100, More preferably, it is 5-50, Most preferably, it is 10-30.

Examples of such epoxy compounds include hydrogenated bisphenol-type epoxy resins, hydrogenated novolac-type epoxy resins, glycidyl esters of alicyclic polyhydric carboxylic acids, epoxides of alicyclic olefins, and the like, having three or more epoxy groups (trifunctional or higher). It can be mentioned.

As a specific example of the polyfunctional epoxy compound which has alicyclic structure in a principal chain structure, and has three or more epoxy groups, the trifunctional epoxy compound (brand name "XD-1000") which has dicyclopentadiene as frame | skeleton. Nippon Kayaku Product). Moreover, as an example of the polyfunctional epoxy compound which has an alicyclic structure and branched alkylene chain in a main chain structure, and has three or more epoxy groups, the 1, 2- epoxy-4 of [2, 2-bis (hydroxymethyl) 1-butanol -(2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name "EHPE3150", manufactured by Daicel Chemical Co., Ltd.), epoxidized 3-cyclohexene -1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin. Trade name "Epolead GT301" manufactured by Daicel Chemical Industries, Ltd.), epoxidized butane Tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified (epsilon) -caprolactone (aliphatic cyclic tetrafunctional epoxy resin. Brand name "Eporide GT401".

The molecular weight of the polyfunctional epoxy compound having an alicyclic structure in the main chain structure used in the present invention and having three or more epoxy groups is not particularly limited, but is usually 500 to 50,000, preferably 1,000 to 10,000, more preferably 1,500 to 5,000, Especially preferably, it is 2,000-5,000. If it is the molecular weight of this range, it is suitable at the point of stability at the time of heating, or a gelation efficiency.

The polyfunctional epoxy compound having an alicyclic structure in these main chain structures and having three or more epoxy groups may be used alone or in combination of two or more thereof, and the amount of use thereof is appropriately selected according to the purpose of use, but the polar groups reacting with the epoxy group may be used. It is 1-200 weight part normally with respect to 100 weight part of polymers containing, Preferably it is 10-100 weight part, More preferably, it is 20-50 weight part. When the amount of use is within this range, the heat resistance (heat resistance shape retention and heat resistance transparency) of the resin film to be formed is highly improved and suitable.

In the present invention, as the crosslinking agent, other crosslinking agents may be used in addition to the polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups.

As a crosslinking agent which can be used together, the epoxy compound which has 3 or more epoxy groups but does not have an alicyclic structure in a principal chain structure, the epoxy compound of which the number of epoxy groups contains is two, the crosslinkable group which has reactivity like 1 or less epoxy groups and / or an epoxy group in total The crosslinking agent which has two or more is mentioned.

Examples of the epoxy compound having three or more epoxy groups but no alicyclic structure in the main chain structure include an epoxy compound having a cresol-novolak structure in the main chain structure and two or more epoxy groups and a phenol-novolak structure in the main chain structure and two or more epoxy compounds. Epoxy compound having an epoxy group, Epoxy compound having a bisphenol A structure in the main chain structure and two or more epoxy groups, Epoxy compound having a naphthalene structure in the main chain structure and two or more epoxy groups, Trimethylolpropane type having two or more epoxy groups Epoxy compound etc. are mentioned.

As a crosslinking agent which has two or more reactive crosslinkable groups, such as one or less epoxy groups and / or an epoxy group in total, the crosslinking agent which has two or more amino groups, a carboxyl group, a hydroxyl group, an isocyanate group, etc. can be mentioned. have. As the specific example, Aliphatic polyamines, such as hexamethylenediamine; Aromatic polyamines such as 4,4'-diaminodiphenyl ether and diaminodiphenyl sulfone; Azide compounds such as 2,6-bis (4'-azidobenzal) cyclohexanone and 4,4'-diazidodiphenyl sulfone; Polyamides such as nylon, polyhexamethylene diamine terephthalamide, polyhexamethylene isophthalamide and the like; Melamines such as N, N, N ', N', N ", N"-(hexaalkoxymethyl) melamine; Glycolurils such as N, N ', N ", N"'-(tetraalkoxymethyl) glycoluril; Acrylate compounds such as ethylene glycol di (meth) acrylate and epoxy acrylate polymers; Isocyanate compounds such as hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate and tolylene diisocyanate polyisocyanate; Hydrogenated diphenylmethane diisocyanate-based polyisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornene, 1,3,4-trihydroxycyclohexane, etc. are mentioned. Among these, those having an amino group or an isocyanate group are preferable. These crosslinkable groups may be the same or different.

The radiation sensitive compound used in the radiation sensitive composition of the present invention is a compound that can cause a chemical reaction by absorbing radiation such as ultraviolet rays or electron beams. It is preferable to be able to control the alkali solubility of the polymer which has a polar group reacting with the epoxy group used by this invention, especially the cyclic olefin type polymer which has a protic polar group.

Examples of the radiation-sensitive compound include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds. Preferably, they are azide compounds, and particularly preferably quinonediazide compounds.

As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used.

As quinone diazide sulfonic-acid halide, a 1, 2- naphthoquinone diazide-5-sulfonic acid chloride, a 1, 2- naphthoquinone diazide- 4-sulfonic acid chloride, a 1, 2- benzoquinone diazide-5 -Sulfonic acid chlorochloride, etc. are mentioned.

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

Examples of the compound having a phenolic hydroxyl group other than these include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 2-bis (4-hydroxyphenyl) Propane, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, The oligomer etc. which are obtained by copolymerizing the oligomer of a novolak resin, the compound which has at least one phenolic hydroxyl group, and dicyclopentadiene are mentioned.

These radiation sensitive compounds can be used individually or in combination of 2 types or more, respectively.

The amount of the radiation-sensitive compound is usually in the range of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight based on 100 parts by weight of the polymer containing the polar group reacting with the epoxy group. When the usage-amount of a radiation sensitive compound exists in this range, when the resin film formed on the board | substrate is patterned, the solubility difference of a radiation irradiation part and an unirradiation part becomes large, patterning by image development becomes easy, and radiation sensitivity is also suitable.

The radiation sensitive composition of this invention may contain resin components (other resin component), other compounding agents, etc. other than the polymer containing the polar group which reacts with an epoxy group as needed.

Examples of other resin components include styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polycarbonate resins, polyester resins, and polyamide resins that do not contain polar groups that react with epoxy groups. And polyether sulfone resins, polysulfone resins, polyimide resins, rubbers and elastomers.

Examples of other compounding agents include sensitizers, surfactants, latent acid generators, antioxidants, light stabilizers, adhesion aids, antistatic agents, antifoaming agents, pigments, dyes, and the like.

Examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazine-3 (4H)-warms and 10H-pyrido- (3,2-b) -1,4-benzo Thiazines, urazoles, hydantoin, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimide, and the like are preferable.

Surfactants are used for the purpose of preventing striation (coating streak), improving developability, and the like, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like. Polyoxyethylene alkyl ethers; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine-based surfactants; Silicone surfactants; (Meth) acrylic acid copolymer type surfactant etc. are mentioned.

Potential acid generators are cationic polymerization catalysts which are used for the purpose of improving the heat resistance shape retention and chemical resistance of the radiation-sensitive composition of the present invention, for example, to generate acids by heating, and include sulfonium salts, benzothiazolium salts, ammonium salts, phospho And other salts may be mentioned. Among these, sulfonium salt and benzothiazolium salt are preferable.

As antioxidant, a phenolic antioxidant, phosphorus antioxidant, sulfur antioxidant, lactone antioxidant, etc. which are used for a normal polymer can be used. For example, as a phenol antioxidant, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl 3- (3 ', 5'-di-t-butyl- 4'-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5 ' -Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thio-bis (3 -Methyl-6-t-butylphenol), alkylated bisphenol, etc. are mentioned. Examples of the phosphorus antioxidant include triphenyl phosphite, trisphosphite (nonylphenyl), and thiodipropionic acid dilauryl. Among these, phenolic antioxidants are preferable from the viewpoint of yellowing at the time of heating, and among these, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is preferable. Do.

Light stabilizers include ultraviolet absorbers such as benzophenone series, salicylic acid ester series, benzotriazole series, cyanoacrylate series, and metal complex salt series; Anything, such as a trapped amine system (HALS) and the like which capture | acquires the radical generate | occur | produced by light, may be sufficient. Among these, HALS is a compound which has a piperidine structure, and since it is a little coloring and the stability is good with respect to the composition of this invention, it is preferable. As a specific compound, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2 , 3,4-butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

Examples of the adhesion aid include a functional silane coupling agent, and specific examples thereof include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and vinyltrimethoxysilane. Phosphorus, γ-isocyanatopropyl triethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The radiation sensitive composition of the present invention can be obtained by using a polymer having a polar group reacting with the epoxy group, a crosslinking agent, and a radiation sensitive compound as essential components, and adding other components as necessary, and usually dissolving or dispersing them in a solvent. .

The solvent usable in the present invention is not particularly limited, and examples thereof include alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol Alkylene glycol monoethers such as coll monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;

Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol Alkylene glycol dialkyl ethers, such as ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, and tripropylene glycol ethyl methyl ether ; Propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether Acetates, propylene glycol mono-n-butyl ether acetates, propylene glycol mono-i-butyl ether acetates, propylene glycol mono-sec-butyl ether acetates, propylene glycol mono-t-butyl ether acetates and the like Alkylene glycol monoalkyl ether esters of; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and cyclopentanone; Alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methylbutanol; Cyclic ethers such as tetrahydrofuran and dioxane; Cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate;

Aromatic hydrocarbons such as benzene, toluene and xylene; Ethyl acetate, butyl acetate, ethyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetic acid, 2-hydroxy-3-methyl moiety Esters such as methyl carbonate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and γ-butyrolactone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide and N, N-dimethylacetamide; Dimethyl sulfoxide and the like.

These solvents can be used individually or in combination of 2 or more types, respectively. The amount of the solvent used is usually in the range of 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts by weight based on 100 parts by weight of the polymer having a polar group reacting with the epoxy group.

The method for mixing the radiation-sensitive composition and the solvent of the present invention may be carried out according to a conventional method, for example, stirring using a stirrer and a magnetic stirrer, a high speed homogenizer, a disperser, a planetary stirrer, a biaxial stirrer, a ball mill, a three roll mill, and the like. You can do it using

After the radiation sensitive composition of this invention is dissolved or dispersed in a solvent, it is preferable to provide for use, for example, after filtering using a filter etc. which have a pore size of about 0.5 micrometer.

Solid content concentration at the time of melt | dissolving or disperse | distributing the radiation sensitive composition of this invention in a solvent is 1-70 weight% normally, Preferably it is 5-50 weight%, More preferably, it is 10-40 weight%. When solid content concentration exists in this range, the coating property on a board | substrate, the film thickness uniformity of the resin film formed, flatness, etc. are highly balanced and suitable.

The laminated body of this invention is manufactured by laminating | stacking the resin film which consists of a radiation sensitive composition on a board | substrate. In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used. Moreover, the thing in which a thin transistor type liquid crystal display element, a color filter, a black matrix, etc., etc. which are used in the display field, etc. are formed suitably is used suitably.

The thickness of a resin film is 0.1-100 micrometers normally, Preferably it is 0.5-50 micrometers, More preferably, it is the range of 0.5-30 micrometers.

The laminated body of this invention can be obtained by crosslinking a resin film as needed, after forming a resin film on a board | substrate using the radiation sensitive composition of this invention.

The method of forming a resin film on a board | substrate is not specifically limited, For example, methods, such as a coating method and a film lamination method, can be used. A coating method is a method of apply | coating a radiation sensitive composition on a board | substrate, for example, and heat-drying to remove a solvent. As a method of apply | coating a radiation sensitive composition on a board | substrate, various methods, such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a rotation coating method, a bar coating method, and a screen printing method, are employ | adopted, for example. Can be. Heat-drying conditions vary depending on the type and blending ratio of each component, but usually at 30 to 150 ° C, preferably at 60 to 120 ° C, usually for 0.5 to 90 minutes, preferably for 1 to 60 minutes, more preferably 1 to It is good to carry out for 30 minutes.

In the film lamination method, for example, a mixture of a radiation-sensitive composition and a solvent 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 stage film. It is a method of laminating on a phase. Heat-drying conditions vary depending on the type and blending ratio of each component, but usually at 30 to 150 ° C, preferably at 60 to 120 ° C, usually for 0.5 to 90 minutes, preferably for 1 to 60 minutes, more preferably 1 to It is good to carry out for 30 minutes. Film lamination can be performed using crimping machines, such as a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator, and the like.

In the laminated body which consists of a resin film formed on the board | substrate and the radiation sensitive composition of this invention on the board | substrate, the resin film may be patterned.

The laminated body of this invention, especially the laminated body in which the patterned resin film was formed on the board | substrate is useful as various electronic components. As an electronic component, a display element, an integrated circuit element, a solid-state image sensor, a color filter, a black matrix, etc. are mentioned.

The patterned resin film formed on the substrate can be obtained by, for example, irradiating active radiation to the resin film to form a latent image pattern, and then presenting the pattern by bringing the developer into contact with the resin film having the latent image pattern.

The actinic radiation is not particularly limited as long as it can activate the radiation sensitive compound and change the alkali solubility of the radiation sensitive composition containing the radiation sensitive compound. Specifically, light rays such as single wavelength ultraviolet rays such as g-rays and i-rays, mixed ultraviolet rays thereof, and far ultraviolet rays such as KrF excimer laser light and ArF excimer laser light; Particle beams, such as an electron beam, can be used. As a method of forming a latent image pattern by selectively irradiating these active radiations in a pattern shape, it is a conventional method, for example, the method of irradiating light rays, such as an ultraviolet-ray or far-ultraviolet rays, with a reduced projection exposure apparatus etc. through a desired mask pattern, or The method of drawing by particle beams, such as an electron beam, etc. can be used. When using a light ray as active radiation, it may be single wavelength light or mixed wavelength light. The irradiation conditions are appropriately selected depending on the active radiation used, but for example, when using a light having a wavelength of 200 to 450 nm, the irradiation amount is usually in the range of 10 to 1,000 mJ / cm ² , preferably 50 to 500 mJ / cm ² , and the irradiation It depends on the time and the intensity of illumination. After irradiating active radiation in this way, the resin film is heat-processed for about 1 to 2 minutes at the temperature of about 60-130 degreeC as needed.

Next, the latent image pattern formed in the resin film is developed and made to present. In this invention, such a process is called "patterning" and the patterned resin film is called "patterning resin film." As the developing solution, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, alkali metal salts, amines and ammonium salts can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline; Alcohol amines such as dimethylethanolamine and triethanolamine; Pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, N-methylpyrrolidone and the like And cyclic amines. These alkaline compounds can be used individually or in combination of 2 types or more, respectively.

As an aqueous medium of the aqueous solution of an alkaline compound, it is water; Or water-soluble organic solvents, such as methanol and ethanol, can be used. The aqueous solution of the alkaline compound may be obtained by adding an appropriate amount of a surfactant and the like.

As a method of bringing a developing solution into contact with the resin film which has a latent image pattern, methods, such as a paddle method, a spray method, and a dipping method, are used, for example. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.

In this way, after forming the target patterned resin film on a board | substrate, a board | substrate can be rinsed with a rinse liquid in order to remove the developing residue on the board | substrate, the back surface of a board | substrate, and a board | substrate edge part as needed. After the rinse treatment, the remaining rinse liquid is removed by compressed air or compressed nitrogen.

Moreover, in order to deactivate the radiation sensitive compound as needed, active radiation can also be irradiated to the whole board | substrate with a patterned resin film. For the irradiation of active radiation, the method exemplified for the formation of the latent image pattern can be used. The resin film may be heated at the same time as or after the irradiation. As a heating method, the method of heating a board | substrate in a hotplate or oven, for example is mentioned. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

In this invention, after forming a patterned resin film on a board | substrate, resin which comprises the said film can be bridge | crosslinked.

The crosslinking of the resin is preferably carried out by appropriately selecting the method according to the kind of the crosslinking agent, but is usually carried out by heating. A heating method can be performed using a hotplate, oven, etc., for example. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the resin film, the equipment used, and the like. Range.

Heating may be performed in an inert gas atmosphere as needed. As an inert gas, what is necessary is just to contain oxygen and not to oxidize a resin film, for example, nitrogen, argon, helium, neon, xenon, krypton, etc. are mentioned. Among these, nitrogen and argon are preferable, and nitrogen is especially preferable. In particular, an inert gas having an oxygen content of 0.1 vol% or less, preferably 0.01 vol% or less, in particular nitrogen, is suitable. These inert gases can be used individually or in combination of 2 or more types, respectively.

The present invention will be described in more detail with reference to Synthesis Examples and Examples below. In addition, the part and% in each example are a mass reference | standard unless there is particular notice.

In addition, each characteristic was evaluated by the following method.

[Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer]

It is calculated | required as molecular weight of polyisoprene conversion using gel permeation chromatography (The product made from Toso, product name "HLC-8020").

[Hydrogenation rate]

The hydrogenation rate is calculated | required as a ratio with respect to the number of moles of carbon-carbon double bond before hydrogenation of the number of hydrogenated carbon-carbon double bond moles by ¹ H-NMR spectrum.

[Iodine]

Measured according to JIS K0070B.

[Formation of Patterned Resin Film]

Spin-coating the radiation-sensitive composition on a glass substrate (Corning Corporation, product name "Corning 1737 glass"), drying at 95 ° C. for 120 seconds using a hot plate, and forming a film so that the film thickness after drying is 2.0 μm. do.

The resin film is irradiated with ultraviolet light having a light intensity of 5 mW / cm ² at 365 nm for 40 seconds through a mask having a 5 μm line-and-space pattern. Subsequently, the development treatment was carried out at 25 ° C. for 60 to 90 seconds using a tetramethylammonium hydroxide 0.3% solution, followed by rinsing with ultrapure water for 30 seconds to form a positive 5 μm line-and-space To form a patterned resin film.

[Residual Residual Rate]

The remaining film rate after development for 70 seconds is measured by defining the remaining film rate = 100 x (film thickness after development) / (film thickness after prebaking). It determines with the following reference | standard according to the result of a measurement.

A: Residual rate is over 95% (best)

B: 90% or more but less than 95% (good)

C: 85% or more but less than 90% (slightly inferior)

D: less than 85% (deteriorated)

[Developing margin (with or without peeling of the pattern film at the time of development)]

The presence or absence of the pattern peeling at the time of developing time 70, 80, 90, and 100 second is observed and it determines with the following reference | standard.

A: There is no pattern peeling in all development time (best).

B: The pattern is peeled off (good) at 100 seconds.

C: The pattern is peeled off (slightly inferior) at 90 seconds.

D: The pattern is peeled off (falling off) at 80 seconds.

[Heat Resistant Shape Resin of Resin Film]

The front surface of the patterned resin film was irradiated with ultraviolet light having a light intensity of 5 mW / cm ² at 365 nm for 60 seconds in air, and then the glass substrate on which this pattern was formed was heated at 160 ° C. for 2 minutes using a hot plate for the first time. Processing (sometimes referred to as "middle-baking"). The cross section of the obtained pattern was observed with an electron microscope, and the width a of the lower end of the pattern was measured. Next, about the glass substrate which performed the 1st heat processing (middle baking), the 2nd heat processing (it is called "post-baking") for 1 hour at 220 degreeC using a clean oven. Case). The cross section of the pattern subjected to the second heat treatment was observed with an electron microscope to evaluate the shape of the upper end of the pattern, and the lower end width b of the pattern was measured. The percentage ratio (b / a) of the lower end width b of the pattern after the second heating treatment (post-baking) to the lower end width a of the pattern after the first heating treatment (middle-baking) was determined and determined based on the following criteria. do.

A: No roundness is recognized at the top, and the ratio is 110% or less (best).

B: The top is rounded, but the ratio is 120% or less (good).

C: The top is rounded and the ratio is over 120% (slightly inferior).

D: The pattern is completely melted and fused with the adjacent pattern (deteriorated).

[Evaluation of Heat Transparency]

The transmittance of the patterned resin film is measured at a wavelength of 400 nm to 700 nm using a spectrophotometer (Nippon Bunkoh Co., Ltd. product name "V-560"). The measured value was converted into a transmittance of 2 µm in accordance with the Lambert-Beer equation, and evaluated according to the following criteria.

A: The lowest transmittance is 90% or more (best)

B: 85% or more but less than 90% (good)

C: 80% or more but less than 85% (slightly inferior)

D: less than 80% (deteriorated)

[Solvent resistance]

The swelling ratio of the film when the patterned resin film is immersed in N-methyl-2-pyrrolidone (NMP) at 40 ° C. for 1 hour is defined as follows.

Swelling rate (%) of film = 100 * (film thickness after NMP immersion / film thickness after post-baking) -100

Using this numerical value, it determines according to the following criteria.

A: 2% or less swelling ratio (best)

B: 2% or more but less than 5% (good)

C: 5-10% or less (slightly inferior)

D: 10% or more (deteriorated)

[Dielectric Properties of Resin Membrane]

After the radiation-sensitive composition was applied on an aluminum substrate using a spinner (manufactured by Mikasa), the film was dried at 95 ° C. for 120 seconds with a hot plate to give a tack-sensitive film thickening agent (manufactured by Tencor, P-10 '') is formed so as to have a thickness of 3 µm. The film was immersed in a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 100 seconds without being exposed to light, followed by developing for 1 minute, followed by rinsing with ultrapure water for 1 minute. UV radiation of / cm ² to inactivate the radiation-sensitive compound. Then, it heats with a 220 degreeC hotplate for 1 hour. A 0.3 micrometer aluminum film is formed on this resin film, and the dielectric constant of 1 MHz is measured in 23 degreeC environment. Based on this dielectric constant, it determines with the following reference | standard.

A: dielectric constant is less than 3 (good)

D: dielectric constant is 3 or more (deteriorated)

Synthesis Example 1

62.5 parts of 8-hydroxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 37.5 parts of N-phenyl- (5-norbornene-2,3-dicarboxyimide) , 1.3 parts of 1-hexene, 0.05 parts of 1,3-dimethylimidazolidine-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride, and 400 parts of tetrahydrofuran in a nitrogen-containing glass pressure reactor Reaction was carried out at 70 ° C. for 2 hours with input and stirring to obtain Polymer Solution A (solid content concentration: about 20%).

A part of this polymer solution A was transferred to an autoclave with a stirrer, and dissolved in hydrogen at a pressure of 4 MPa at 150 ° C. for 5 hours to react. Polymer solution B containing a hydrogenated polymer (hydrogenation rate of 100%) (solid content concentration: about 20 %) Was obtained.

The heat-resistant container which added 1 part activated carbon powder to 100 parts of polymer solution B was put into the autoclave, and hydrogen was dissolved at 150 degreeC by the pressure of 4 MPa for 3 hours, stirring. Subsequently, the solution was taken out and filtered through a fluorine resin filter having a pore size of 0.2 μm to separate activated carbon to obtain a polymer solution. Filtration could be performed without clogging. The polymer solution was poured into ethyl alcohol to coagulate, and the resulting crumb was dried to obtain polymer (1). Mw of polyisoprene conversion of the obtained polymer (1) was 5,500, and Mn was 3,200. Also iodine was one.

[Synthesis Example 2]

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene 100 parts, 1-hexene 1.3 parts, 1,3-dimethylimidazolidine 0.05 parts of -2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride and 400 parts of toluene were introduced into a nitrogen-substituted glass pressure reactor, followed by polymerization and hydrogenation in the same manner as in Synthesis Example 1. A polymer was obtained. Mw of the obtained hydrogenated polymer was 5,300 and Mn was 3,200. Iodine was one.

100 parts of hydrogenated polymer, 100 parts of N-methylpyrrolidone, 500 parts of propylene glycol, and 84.5 parts of aqueous potassium hydroxide solution (85%) were put into a reactor, and it stirred at 190 degreeC for 4.5 hours by heating. The obtained reaction solution was poured into a mixed solution of a large amount of water, tetrahydrofuran and hydrochloric acid to coagulate the hydrolyzate. The coagulated polymer was washed with water, dried and hydrolyzed to obtain a hydrolyzed polymer (2) in which a methoxycarbonyl group was converted to a carboxyl group. The hydrolysis rate of the obtained hydrolysis polymer was 95%.

Example 1

100 parts of the polymer (1) obtained in Synthesis Example 1, 200 parts of propylene glycol monoethyl ether acetate, 100 parts of diethylene glycol ethyl methyl ether and 100 parts of N-methyl-1-pyrrolidone, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mole) and 1,2-naphthoquinonediazide-5-sulfonic acid as quinonediazide compounds 25 parts of a condensate of chloride (1.9 moles), 25 parts of a tetrafunctional epoxy resin (molecular weight 400, product name "Eporide GT400", manufactured by Daicel Chemical Industries, Ltd.) having an alicyclic structure in the main chain as a crosslinking agent, γ-letter as an adhesive aid. 5 parts of lycidoxypropyltrimethoxysilane, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant (Ciba Specialty Chemical) product, product name "Irganox 1010") 1 part, and silicone type surfactant as surfactant (Shin-Etsu (Shin-etsu) Products and Chemicals, Inc., product name "KP341") was dissolved in a mixture of 0.05 parts, by filtration with a Millipore (Millipore) filter having a pore size 0.45㎛ to prepare a radiation-sensitive composition.

The residual film ratio, development margin, heat retaining shape after middle-baking and post-baking, heat transparency after post-baking, solvent resistance and dielectric properties were evaluated for this radiation-sensitive composition. The results are shown in Table 1.

[Example 2]

In Example 1, the radiation sensitive composition was changed in the same manner as in Example 1 except that the crosslinking agent was changed to a 15-functional epoxy compound having an alicyclic structure in the main chain (molecular weight about 2700, manufactured by Daicel Chemical Industries, product name "EHPE3150"). It prepared and performed the same evaluation as Example 1 about this radiation sensitive composition. The results are shown in Table 1.

[Referential Example 1]

In Example 1, the radiation sensitive composition was prepared like Example 1 except having used the hydrolysis polymer (2) instead of the polymer (1).

The residual film ratio, development margin, heat retaining shape after middle-baking and post-baking, heat transparency after post-baking, solvent resistance and dielectric properties were evaluated for this radiation-sensitive composition. The results are shown in Table 1.

[Reference Example 2]

A radiation sensitive composition was prepared in the same manner as in Example 3 except that the crosslinking agent was changed to that used in Example 2.

The residual film ratio, development margin, heat retaining shape after middle-baking and post-baking, heat transparency after post-baking, solvent resistance and dielectric properties were evaluated for this radiation-sensitive composition. The results are shown in Table 1.

Comparative Example 1

The crosslinking agent is used in a main chain except for changing the solvent to 400 parts of cyclohexanone using a bifunctional epoxy compound (molecular weight 352, product of Dai-Nippon Ink, product name "EXA7015") having an alicyclic structure. A radiation sensitive composition was prepared in the same manner as in Example 1.

The residual film ratio, development margin, heat retaining shape after middle-baking and post-baking, heat transparency after post-baking, solvent resistance and dielectric properties were evaluated for this radiation-sensitive composition. The results are shown in Table 1.

Comparative Example 2

A radiation sensitive composition was prepared in the same manner as in Comparative Example 1 except that the crosslinking agent was changed to an aromatic amine type tetrafunctional epoxy compound (manufactured by Toto Chemical Company, product name "H-434").

The residual film ratio, development margin, heat retaining shape after middle-baking and post-baking, heat transparency after post-baking, solvent resistance and dielectric properties were evaluated for this radiation-sensitive composition. The results are shown in Table 1.

Comparative Example 3

A radiation sensitive composition was prepared in the same manner as in Comparative Example 1 except that the crosslinking agent was changed to a bifunctional bisphenol A epoxy compound (molecular weight 340, manufactured by Dainippon Ink, Inc., product name "EXA850CRP").

The residual film ratio, development margin, heat retaining shape after middle-baking and post-baking, heat transparency after post-baking, solvent resistance and dielectric properties were evaluated for this radiation-sensitive composition. The results are shown in Table 1.

From the results of Table 1, in the embodiment of the present invention using a polyfunctional epoxy compound having an alicyclic structure in the main chain structure as a crosslinking agent and having three or more epoxy groups, the heat resistance after development residual film ratio, development margin, middle-baking and post-baking It can be seen that the shape retaining properties, heat resistance transparency after post-baking, solvent resistance and dielectric properties are excellent.

In contrast, the case where a bifunctional epoxy resin is used as the crosslinking agent but has a bifunctional epoxy resin (Comparative Example 1) and a tetrafunctional epoxy compound but the alicyclic structure is not used in the main chain structure (Comparative Example 2) are used. When the performance is inferior, and bifunctional and further with no alicyclic structure is used, it turns out that it is remarkably inferior in these various characteristics.

Claims (11)

A cyclic olefin polymer containing a cyclic olefin monomer unit having a protic polar group and a monomer unit containing an N-substituted imide group, a crosslinking agent containing a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, And a radiation sensitive composition comprising a radiation sensitive compound. The method of claim 1, A radiation sensitive composition wherein the cyclic olefin polymer containing a cyclic olefin monomer unit having a protic polar group and a monomer unit containing an N-substituted imide group contains 10 to 90% by weight of a cyclic olefin monomer unit having a protic polar group. . delete The method of claim 1, A radiation sensitive composition wherein the main chain structure of the polyfunctional epoxy compound has a branched alkylene chain. The laminated body manufactured by laminating | stacking the resin film which consists of a radiation sensitive composition of Claim 1 on a board | substrate. 6. The method of claim 5, The laminated body whose resin film is a patterned resin film. The manufacturing method of the laminated body which consists of a board | substrate and the resin film formed on it which has a process of forming a resin film on a board | substrate using the radiation sensitive composition of Claim 1. The method of claim 7, wherein After forming a resin film on a board | substrate, the manufacturing method of the laminated body which further has a process of bridge | crosslinking resin. The resin film is laminated on a substrate using the radiation-sensitive composition according to claim 1, the actinic radiation is irradiated to the resin film to form a latent image pattern in the resin film, and then the developer is brought into contact with the resin film to present the latent image pattern. The manufacturing method of the laminated body of Claim 6 which forms a patterned resin film on a board | substrate. The method of claim 9, After forming a patterned resin film on a board | substrate, the manufacturing method of the laminated body which further has a process of performing crosslinking reaction of resin. Electronic component consisting of the laminate according to claim 5.