KR20060130691A - Radiation-sensitive composition, multilayer body and method for producing same, and electronic component - Google Patents

Abstract

Disclosed is a very safe radiation-sensitive composition having excellent electrical characteristics and good solution stability which is able to form a coating free from unevenness. Also disclosed are a multilayer body wherein a resin film is formed on a substrate by using this radiation-sensitive composition, and a method for producing such a multilayer body. A radiation-sensitive composition containing a cyclic olefin polymer having a polar protic group, a radiation-sensitive compound, a crosslinking agent and a solvent is characterized in that the solvent contains a dialkylene glycol dialkyl ether having two different alkyl groups in one molecule. A multilayer body comprises a substrate and a resin film formed on the substrate using the above-described radiation- sensitive composition.

Description

A radiation sensitive composition, a laminated body, a manufacturing method, and an electronic component TECHNICAL FIELD [RADIATION-SENSITIVE COMPOSITION, MULTILAYER BODY AND METHOD FOR PRODUCING SAME, AND ELECTRONIC COMPONENT}

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. The present invention relates to a laminate having a composition, a resin film obtained from the radiation-sensitive composition, on a substrate, a method for producing the same, and an electronic component including the laminate.

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. Such a resin film requires various properties such as insulation, heat resistance, transparency, water absorption resistance, and chemical resistance.

In recent years, multilayer wiring is performed in such an electronic component, and the material for forming the resin film which can maintain the high insulation between each layer, and has sufficient flatness is requested | required further.

For this reason, the radiation sensitive resin composition containing alkali-soluble cyclic olefin resin which has an ester group, a quinone diazide compound, and crosslinking agents, such as methylol melamine, is proposed (patent document 1). However, although the resin film obtained using this radiation sensitive resin composition is excellent in the characteristics as an insulating film of low dielectric constant, heat resistance, flatness, transparency, and solvent resistance, when the whole board | substrate is seen, the thickness of the formed resin film is not necessarily uniform and also preserve | saved. It turned out that there exists a problem in storage stability, such as a polymer depositing in the air.

Patent Document 2 discloses a radiation sensitive resin composition composed of a resin, a radiation sensitive acid generator, and a specific solvent which have an alicyclic skeleton and become alkali-soluble by the action of an acid. This invention is intended to form a resist film having a uniform thickness which is excellent in characteristics such as sensitivity, resolution, developability, and the like, and particularly excellent in transparency to radiation, by combination of a specific resin and a specific solvent.

In addition, Patent Document 3 proposes a radiation sensitive resin composition wherein the solvent contains at least a specific glycol compound as a radiation sensitive resin composition composed of an alicyclic olefin resin, an acid generator, a crosslinking agent, and a solvent. have.

However, these radiation-sensitive resin compositions have an effect on the higher performance required for the radiation-sensitive resin composition, specifically, the dissolution stability and the optical interference, which affect the uniformity of the resin film, with the recent miniaturization, thinning and high performance of devices. Note cannot fully cope with reduction of coating nonuniformity. At the same time, it is necessary to use a compound that is safer from consideration for the environment. In particular, regarding the solvent contained in a large quantity in a radiation sensitive resin composition, use of the solvent of lower toxicity is called for.

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

Patent Document 2: Japanese Patent Application Laid-Open No. 1998-254139

Patent Document 3: Japanese Patent Publication No. 2003-156838

Disclosure of the Invention

Problems to be Solved by the Invention

SUMMARY OF THE INVENTION The present invention has been made to cope with recent miniaturization, thinning, and improvement of safety, and has excellent electrical properties, good dissolution stability, no coating unevenness, and high safety and practical radiation-sensitive composition, which is radiation-sensitive. It is a subject to provide the laminated body which formed the resin film formed using the composition on the board | substrate, and the manufacturing method of this laminated body.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, in the radiation sensitive composition containing the cyclic olefin type polymer containing a protic polar group, a radiation sensitive compound, a crosslinking agent, and a solvent, 2-heptanone as a solvent, When using a conventionally known solvent such as cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether or diethylene glycol diethyl ether, dissolution stability is not sufficient and coating unevenness is seen. When diethylene glycol ethyl methyl ether is used as the solvent, it is found that a highly sensitive radiation-sensitive composition is obtained with high solubility stability, no coating unevenness, and high stability. Came to complete.

According to the present invention, there is provided a radiation-sensitive composition containing a cyclic olefin-based polymer containing a protic polar group, a radiation-sensitive compound, a crosslinking agent and a solvent, wherein the solvent has a diethylene glycol having two different alkyl groups in the same molecule. A radiation sensitive composition is provided which contains a coll dialkyl ether.

In the radiation sensitive composition of the present invention, it is preferable that the dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule is a diethylene glycol dialkyl ether having two different alkyl groups in the same molecule. Do.

In the radiation sensitive composition of the present invention, it is particularly preferable that the diethylene glycol dialkyl ether having two different alkyl groups in the same molecule is diethylene glycol ethyl methyl ether.

Moreover, according to this invention, the laminated body which consists of a board | substrate and the resin film formed using the said radiation sensitive composition on it is provided.

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

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

Moreover, according to this invention, a resin film is formed on a board | substrate using a radiation sensitive composition, this resin film is irradiated with active radiation, a latent flaw pattern is formed in a resin film, and then a developer is contacted with a resin film. The present invention provides a method for producing a laminate comprising a substrate and a patterned resin film formed thereon, wherein the latent image pattern is present to form a patterned resin film on the substrate.

In the manufacturing method of the laminated body of this invention, after forming a patterned resin film 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

ADVANTAGE OF THE INVENTION According to this invention, the radiation sensitive composition which is excellent in melt stability and which can provide the resin film with very few coating nonuniformity is obtained. Since the laminated body in which the resin film was formed on the board | substrate using this radiation sensitive composition is excellent in the electrical characteristic of a resin film, and there is very little application | coating nonuniformity, for example, a display element, an integrated circuit element, a solid-state image sensor, a color filter, a black matrix, etc. Protective film such as a device, a planarization film for planarizing element surfaces and wirings, an insulating film for maintaining electrical insulation (including an interlayer insulation film or a solder resist film, which is an electrical insulation film of a thin transistor type liquid crystal display device or an integrated circuit device) It is suitable as a material for electronic components, such as a microlens and a spacer.

Best Mode for Carrying Out the Invention

The radiation sensitive composition of this invention is a radiation sensitive composition containing a cyclic olefin type polymer containing a protic polar group, a radiation sensitive compound, a crosslinking agent, and a solvent, It is characterized by using a specific compound as a solvent.

In the cyclic olefin polymer containing a protic polar group for use in the present invention, the protic polar group is a heteroatom, preferably atoms of group 15 and 16 of the periodic table, more preferably group 15 and 16 of the periodic table. It is the atomic group which the hydrogen atom couple | bonded with the atom of group 1st and 2nd period, especially preferably oxygen atom directly.

As a specific example of a protic polar group, Polar group which has oxygen atoms, such as a carboxyl 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 a carboxyl group is more preferable.

In the present invention, the number of protic polar groups included in the cyclic olefin polymer containing a protic polar group is not particularly limited in number, and different types of protic polar groups may be included.

In the present invention, the protic polar group contained in the cyclic olefin polymer containing a protic polar group may be bonded to a cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer, but may be bonded to a cyclic olefin monomer unit. It is desirable to do it.

In the present invention, the cyclic olefin polymer constituting a portion other than the protic polar group of the cyclic olefin polymer containing a protic polar group (hereinafter may be referred to as a "base portion") is a cyclic olefin. Any of homopolymers and copolymers of cyclic olefins and cyclic olefins and other monomer copolymers may be used, or may be hydrogenated products thereof.

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.

The cyclic olefin polymer containing a protic polar group used in the present invention is a cyclic olefin monomer containing a protic polar group even if the polymer is composed of only monomer units derived from a cyclic olefin monomer (a) containing a protic polar group (a It may be a copolymer made of a monomer unit derived from a) and a monomer unit derived from another monomer copolymerizable with the cyclic olefin monomer (a) containing the 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-free cyclic olefin monomer") (C), and monomers (d) other than cyclic olefin.

Among these, the cyclic olefin monomer (b) containing a polar group other than a protic polar group and the cyclic olefin monomer (c) containing no polar group are preferable, and the cyclic olefin monomer (b) containing a polar group other than a protic polar group is more preferable. Do.

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 Acid anhydride residues), alkoxy groups, carbonyl groups, tertiary amino groups, sulfone groups, acryloyl groups 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 which have polar groups other than these protic polar groups can be used individually, or can be used in combination of 2 or more type.

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-butyl-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-tetraene (also known as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [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, etc. have. These nonpolar cyclic olefins 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 used in this invention, 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 addition, the protic polar group-containing cyclic olefin polymer used in the present invention is introduced into a cyclic olefin polymer containing no protic polar group by a known method and then hydrogenated as necessary. It can also be obtained by Hydrogenation may be performed with respect to the polymer before introduction of a protic polar group.

In the production method of the protic polar group-containing cyclic olefin polymer, the protic polar group may be a precursor thereof, and the precursor can be converted into a protic polar group by chemical reaction such as decomposition or hydrolysis by light or heat. For example, when the protic polar group is a carboxyl group, an ester group may be used instead of the 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, and in view of being capable of selectively hydrogenating carbon-carbon unsaturated bonds in the polymer without causing side reactions such as modification of functional groups, and electron donating. Particularly preferred is a ruthenium catalyst to which this high nitrogen-containing heterocyclic carbene compound or phosphines are coordinated.

The weight average molecular weight (Mw) of the cyclic olefin polymer containing a protic polar group used in the present invention is usually in the range of 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10,000.

The molecular weight distribution of the cyclic olefin polymer containing a protic polar group used in the present invention is usually 4 or less, preferably 3 or less, more preferably 2.5 or less in a weight average molecular weight / number average molecular weight (Mw / Mn) ratio. .

The iodine value of the cyclic olefin polymer containing a protic polar group used in the present invention is usually 200 or less, preferably 50 or less, and more preferably 10 or less. When the iodine number of the cyclic olefin polymer containing a protic polar group exists in this range, it is especially excellent in heat resistance and is suitable.

The radiation sensitive compound used in the present invention is a compound capable of absorbing radiation such as ultraviolet rays or electron beams to cause a chemical reaction, and can also control the alkali solubility of the cyclic olefin polymer having a protic polar group used in the present invention. It is.

Examples of such radiation-sensitive compounds include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, and the like, but are preferably azide compounds, 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 chloride, 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 cyclic olefin polymer containing a protic polar group. When the amount of the radiation-sensitive compound used is within this range, when the resin film formed on the substrate is patterned, the solubility difference between the radiation irradiated portion and the non-irradiated portion becomes large, patterning by development is easy, and radiation sensitivity is also preferable. .

In the present invention, as the crosslinking agent, those having two or more, preferably three or more, functional groups capable of reacting with the protic polar groups of the cyclic olefin polymer containing a protic polar group are used. As a functional group which can react with a protic polar group, an amino group, a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group, etc. are mentioned, For example, Amino group, an epoxy group, and an isocyanate group are more preferable. Preferably an epoxy group.

As a specific example of such a crosslinking agent, Aliphatic polyamines, such as hexamethylenediamine; Aromatic polyamines such as 4,4'-diaminodiphenyl ether and diaminodiphenylsulfone; Azides, such as 2, 6-bis (4'-azidobenzal) cyclohexanone and a 4,4'- diazido diphenyl 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; Hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate Isocyanate compounds; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1,3,4-trihydroxycyclohexane; An epoxy compound having an alicyclic skeleton and having at least two epoxy groups, an epoxy compound having a cresol-novolak skeleton and having at least two epoxy groups, an epoxy compound having a phenol-novolak skeleton and having at least two epoxy groups, and a bisphenol Polyfunctional epoxy compounds, such as an epoxy compound which has A frame | skeleton, and has two or more epoxy groups, and an epoxy compound which has a naphthalene skeleton and has two or more epoxy groups, etc. are mentioned. Among these, a polyfunctional epoxy compound is preferable, and since a coating film formation property is especially favorable, the polyfunctional epoxy compound which has alicyclic skeleton and has 2 or more epoxy groups, More preferably, 3 or more is preferable.

These crosslinking agents can be used individually or in combination of 2 types or more, respectively. The amount of the crosslinking agent used is usually 1 to 100 parts by weight, preferably 10 to 70 parts by weight, more preferably 20 to 50 parts by weight based on 100 parts by weight of the cyclic olefin polymer containing a protic polar group. When the crosslinking agent is in this range, the heat resistance is highly improved.

In the radiation-sensitive composition of the present invention, it is essential to use, as a solvent, dialkylene glycol dialkyl ethers having two different alkyl groups in the same molecule. By using a dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule as the solvent, dissolution stability is improved, and application unevenness can be reduced.

The alkyl group in the dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule is preferably in the range of 1 to 4 carbon atoms, more preferably in the range of 1 to 3 carbon atoms.

Moreover, it is preferable that carbon number of one alkylene chain in the dialkylene glycol dialkyl ether which has two different alkyl groups in the same molecule exists in the range of 1-4, More preferably, it is 2-3. Range.

Specific examples of diethylene glycol dialkyl ethers having two different alkyl groups in the same molecule include diethylene glycol ethyl methyl ether, diethylene glycol methyl propyl ether, diethylene glycol butyl methyl ether, di Diethylene glycol dialkyl ethers having two different alkyl groups in the same molecule such as ethylene glycol ethyl propyl ether, diethylene glycol butyl ethyl ether, diethylene glycol butyl propyl ether, and the like; Dipropylene glycol ethyl methyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl propyl ether, dipropylene glycol butyl ethyl ether, dipropylene glycol And dipropylene glycol dialkyl ethers having two different alkyl groups in the same molecule such as butyl propyl ether.

Of these, diethylene glycol dialkyl ethers having two different alkyl groups in the same molecule are preferred, and diethylene glycol ethyl methyl ether is particularly preferred.

The amount of dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule is usually 20 to 10,000 parts by weight, preferably 50 to about 100 parts by weight of the cyclic olefin polymer containing a protic polar group. 5,000 weight part, More preferably, it is the range of 100-1,000 weight part.

In the present invention, a dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule may be used in combination with another solvent.

As a solvent which can be used together, Chain and cyclic ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl- 2-pentanone; Alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methylbutanol; Cyclic ethers such as tetrahydrofuran and dioxane;

Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; Monoalkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Monoalkylene glycol monoalkyl ether esters (monoalkylene glycol monoether acetate) such as ethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

Ethylene glycol dimethyl ether, ethylene glycol diethyl ether; Monoalkylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Dialkylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether; Dialkylene glycol dialkyl ethers having the same two alkyl groups in the same molecule, such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; Trialkylene glycol monoalkyl ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; Triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether; Trialkylene glycol dialkyl ethers such as tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol ethyl methyl ether, and the like;

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-butyl-2-pyrrolidone, N-methylacetamide and N, N-dimethylacetamide; Dimethyl sulfoxide and the like.

These other solvents can be used individually or in combination of 2 or more types, respectively, The use amount is suitably selected in the range which does not impair the effect of this invention.

The radiation sensitive composition of this invention may contain resin components other than the cyclic olefin type polymer containing a protic polar group, other compounding agents, etc. as needed.

As other resin components, for example, a cyclic olefin polymer, a styrene resin, a vinyl chloride resin, an acrylic resin, a polyphenylene ether resin, a polyarylene sulfide resin, a polycarbonate resin, a polyester resin, and a poly that does not have a protic polar group Amide resins, polyether sulfone resins, polysulfone resins, polyimide resins, rubbers and elastomers, and the like. These other resin components can be used individually or in combination of 2 types or more, respectively, The compounding quantity is suitably selected in the range which does not impair the effect of this invention.

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 used for the purpose of improving the heat resistance and chemical resistance of the radiation-sensitive composition of the present invention and are, for example, cationic polymerization catalysts that generate acids by heating, and include sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, and the like. Can 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 phenolic 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), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, alkylated bisphenol, etc. are mentioned. . Examples of the phosphorus antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Thiodipropionic acid dilauryl etc. are mentioned as a sulfur type antioxidant. Among them, from the viewpoint of yellowing at the time of heating, a phenolic antioxidant is preferable, and among them, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Is preferred.

The light stabilizer captures radicals generated by light, such as ultraviolet absorbers such as benzophenone, salicylic acid ester, benzotriazole, cyanoacrylate, and metal complex salts, and hindered amines (HALS). It may be anything such as a thing. Among these, HALS is a compound which has a piperidine structure, and since it has little coloring and the stability is good with respect to the radiation sensitive 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-butane-tetracarboxylate, 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-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The radiation-sensitive composition of the present invention is a dialkyl having two different alkyl groups in the same molecule by adding cyclic olefin-based polymers containing a protic polar group, a radiation-sensitive compound and a crosslinking agent as essential components, and adding other components as necessary. It can be prepared by dispersing or dissolving in a solvent containing ethylene glycol dialkyl ether. The method of dissolving or dispersing each component in the solvent is in accordance with conventional methods, for example, by stirring using a stirrer and a magnetic stirrer, or a high speed homogenizer, a disperser, a planetary stirrer, a biaxial stirrer, a ball mill, a three roll It can be performed using a mill or the like. 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 of the radiation sensitive composition of this invention 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, dissolution stability is favorable and further, application | coating nonuniformity is reduced.

The laminated body of this invention consists of a resin film formed on the board | substrate and the radiation sensitive composition of this invention on it.

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 the thin transistor type liquid crystal display element, a color filter, a black matrix, etc. were formed in the glass substrate or plastic substrate used for a display field is used suitably.

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

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, heat-drying to remove a solvent, and then crosslinking as needed. 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 are usually 0.5 to 90 minutes, preferably 1 to 60 minutes, more preferably 1 to 60 ° C at 30 to 150 ° C, preferably 60 to 120 ° C. You can do it for 30 minutes.

The film lamination method is a method of, for example, applying a radiation-sensitive composition on a substrate such as a resin film or a metal film to remove the solvent by heat drying to obtain a B stage film, and then laminating the B stage film on a substrate. . 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 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 present invention, the resin film may be a patterned resin film (hereinafter referred to as a "patterned resin film").

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.

The resin film patterned on the board | substrate can be formed as follows.

First, actinic radiation is irradiated to the resin film formed on the board | substrate as mentioned above, and the latent image of a desired pattern is formed. The actinic radiation is not particularly limited as long as it can activate the radiation sensitive compound to change the alkali solubility of the radiation sensitive composition. Specifically, ultraviolet rays, such as ultraviolet rays of a single wavelength such as g-rays or i-rays, KrF excimer laser light, ArF excimer laser light, etc .; Particle beams, such as an electron beam, can be used. In order to form a latent image pattern by selectively irradiating these active radiations in a pattern shape, conventional methods may be used, for example, ultraviolet rays, g-rays, i-rays, KrF excimer laser light, ArF excimer laser light, etc., by a reduced projection exposure apparatus or the like. The method of irradiating a light ray through a desired mask pattern, the method of drawing by particle beams, such as an electron beam, etc. can be used. When using a light ray as active radiation, a light ray 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. 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 alkaline aqueous solution, it is water; Water-soluble organic solvents, such as methanol and ethanol, can be used. The alkaline aqueous solution 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 developing conditions are 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.

After forming a patterned resin film on a board | substrate, you may crosslink resin.

Although crosslinking of the patterned resin film formed on the board | substrate is suitably selected suitably according to the kind of crosslinking agent, it is normally performed 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, for example, when using a hot plate, usually 5 to 60 minutes, and when using an oven, usually 30 to 90 minutes. 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 case 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 polyisoprene conversion molecular weight using gel permeation chromatography.

[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 bonds by ¹ H-NMR spectrum.

[Iodine]

It measures in accordance with JIS K0070B.

[Solvent safety]

The following criteria are judged by the LD ₅₀ values obtained in the acute toxicity test by oral administration of the solvent to rats. In addition, a numerical value is based on the product safety data sheet (The Daicel Chemical company regarding propylene glycol monomethyl ether acetate, the Toho Chemical company publication about other solvents).

○: 5,000 mg / kg or more

×: less than 5,000 mg / kg

[Dissolution Stability]

The radiation-sensitive composition is stored for 1 day separately under -20 ° C and 5 ° C, respectively, and the presence or absence of a precipitate is determined based on the following criteria.

(Circle): A deposit is not seen after storage under either environmental conditions of -20 degreeC and 5 degreeC.

(Triangle | delta): A precipitate is seen after storage under -20 degreeC environmental conditions, but a deposit is not seen after storage under 5 degreeC environmental conditions.

X: A deposit was seen in both after storage under -20 degreeC environmental conditions, and after storage under 5 degreeC environmental conditions.

[Formation and Coating Unevenness of the Radiation-Resistant Composition Resin Film]

50 ml of the radiation-sensitive composition was added dropwise onto a glass substrate with a low reflection Cr film of 550 × 650 × 0.7 mm and spin-coated, followed by drying for 2 minutes at 95 ° C. on a hot plate to form a coated substrate having a thickness of 3 μm. do. Interference pattern inspection, etc. The light of HCN052NA (manufactured by Toshiba Corporation) is irradiated to the coating substrate, and the "drop trace" in which the trace of dripping the solution remains by the state of the interference fringe, and the stripe unevenness generated when the solution spreads during spin coating The presence or absence of streaks nonuniformity ”is observed and the following criteria are determined. All of these nonuniformities show a slight film thickness difference in a region that cannot be detected as a film thickness system.

(Circle): Neither nonuniformity is observed.

(Triangle | delta): Only a dripping trace is observed.

X: Both the dripping trace and the stripe unevenness are observed.

[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 using a hot plate, followed by P-10 (Tencor). It is formed so that it becomes 3 micrometers when measured by). 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, followed by 365 nm on the entire surface of the resin film. Irradiated with ultraviolet rays having a light intensity of 5 mW / cm ² to deactivate the radiation-sensitive compound. Then, it heats with a 230 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. It determines with the following reference | standard according to this dielectric constant.

○: The dielectric constant is less than 3.

X: dielectric constant is 3 or more.

Synthesis Example 1

60 parts of 8-hydroxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 40 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 portion 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. and reacted for 5 hours to give a 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 of activated carbon powder to 100 parts of polymer solution B was put into the autoclave, and hydrogen was melt | 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 done without clogging. The polymer solution was poured into ethyl alcohol to solidify and the resulting crumb was dried to give a polymer. Mw of polyisoprene conversion of the obtained polymer was 5,500 and Mn was 3,200. Also iodine was one.

Example 1

100 parts of the polymer obtained in Synthesis Example 1, 550 parts of diethylene glycol ethyl methyl ether as solvent, and 4,4 '-[1- [4- [1- [4-hydroxy as 1,2-quinonediazide compound 25 parts by weight of a condensate of phenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.5 mol), an alicyclic structure as a crosslinking agent 20 parts of containing polyfunctional epoxy compound (molecular weight 2,700, number of epoxy groups, 15, manufactured by Daicel Chemical Industries, EHPE3150), 1 part of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, and a silicone surfactant (Shin-Shin (Shin- 0.05 parts of etsu) Chemical Co., Ltd. product, KP-341) were mixed and dissolved, and it filtered with the polytetrafluoroethylene filter of 0.45 micrometer of pore diameters, and prepared the radiation sensitive composition. Dissolution stability, coating nonuniformity, and dielectric constant were evaluated about this radiation sensitive composition. The results are shown in Table 1.

[Comparative Examples 1 to 4]

Instead of diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate (comparative example 1), diethylene glycol dimethyl ether (comparative example 2), diethylene glycol diethyl ether (comparative example 3) The radiation sensitive composition was prepared like Example 1 except having used the 1: 4 (weight ratio) mixed solvent (comparative example 4) of diethylene glycol monoethyl ether and propylene glycol monoethyl ether, respectively. Dissolution stability, coating nonuniformity, and dielectric constant were evaluated about this radiation sensitive composition. The results are shown in Table 1.

Footnotes in Table 1

* 1 DEGEME: diethylene glycol ethyl methyl ether

    PGMEA: Propylene Glycol Monomethyl Ether Acetate

    DEGDME: diethylene glycol dimethyl ether

    DEGDEE: diethylene glycol diethyl ether

    DEGEE: diethylene glycol monoethyl ether

    PGEE: Propylene Glycol Monoethyl Ether

* 2 Melt stability was bad, and an insoluble matter existed in the coating film.

From the results in Table 1, when diethylene glycol ethyl methyl ether, which is a dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule, is used as a solvent, there is no problem in safety, It is understood that the radiation-sensitive composition having excellent and uneven coating is obtained, and the resin film obtained by using this is excellent in dielectric properties.

In contrast, when other solvents are used, it can be seen that the obtained radiation-sensitive composition has a problem in safety or an unsatisfactory result in either dissolution stability or uneven coating.

Claims (10)

A radiation sensitive composition comprising a cyclic olefin polymer containing a protic polar group, a radiation sensitive compound, a crosslinking agent and a solvent, wherein the solvent is a dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule. A radiation sensitive composition comprising: The method of claim 1, A radiation sensitive composition wherein the dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule is a diethylene glycol dialkyl ether having two different alkyl groups in the same molecule. The method of claim 2, A radiation sensitive composition wherein the diethylene glycol dialkyl ether having two different alkyl groups in the same molecule is diethylene glycol ethyl methyl ether. The laminated body which consists of a board | substrate and the resin film formed on it using the radiation sensitive composition of any one of Claims 1-3. The method of claim 4, wherein 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 thereon which consists of forming a resin film on a board | substrate using the radiation sensitive composition in any one of Claims 1-3. The method of claim 6, The manufacturing method of the laminated body which crosslinks resin after forming a resin film on a board | substrate. The resin film is formed on a board | substrate using the radiation sensitive composition of any one of Claims 1-3, and this resin film is irradiated with active radiation, a latent image pattern is formed in a resin film, and then a developing solution is applied to the resin film. The manufacturing method of the laminated body of Claim 5 which consists of a board | substrate and the patterned resin film formed on it, which is made to contact and present a latent image pattern to form a patterned resin film on a board | substrate. The method of claim 7, wherein After forming a patterned resin film on a board | substrate, the manufacturing method of the laminated body which performs a crosslinking reaction of resin. An electronic component composed of the laminate according to claim 4.