CN101189552A

CN101189552A - Radiation-sensitive resin composition, layered product, and process for producing the same

Info

Publication number: CN101189552A
Application number: CNA2006800197117A
Authority: CN
Inventors: 新藤宽明
Original assignee: Nippon Zeon Co Ltd
Current assignee: Zeon Corp
Priority date: 2005-06-01
Filing date: 2006-05-31
Publication date: 2008-05-28
Also published as: JPWO2006129875A1; TW200700911A; WO2006129875A1; KR20080013963A

Abstract

A radiation-sensitive resin composition which comprises a cycloolefin polymer, a radiation-sensitive compound, and 10-60 parts by weight of an alkoxysilane compound per 100 parts by weight of the cycloolefin polymer; a layered product which comprises a base and, superposed thereon, a resinous film formed from the composition; and a process for producing a layered product which comprises the step of forming a resinous film on a base from the composition. The radiation-sensitive resin composition gives a resinous film having excellent high-temperature shape retention. It has a wide temperature margin for melt flowing in forming a patterned resinous film and is suitable for use also as a resist material.

Description

Radiation sensitive resin composition, laminated body and manufacture method thereof

Technical field

The present invention relates to be fit to be used in the radiation sensitive resin composition of electronic units such as making integrated circuit component, liquid crystal display cells, solid-state imager and optics, the resin molding of making by said composition at the substrate superimposed layer and the laminated body that constitutes and the manufacture method of this laminated body.

Background technology

In electronic units such as integrated circuit component, liquid crystal display cells, solid-state imager, colored filter, black matrix", the diaphragm that is used to prevent its deterioration and damage is being set, is being used for, is being used to keep the various resin moldings such as electrical insulating film of electrical insulating property the planarization film of element surface or distribution planarization.In addition, use at the film transistor type liquid crystal in the elements such as display element and integrated circuit component,, the resin molding as interlayer dielectric is being set in order to insulate between the wiring that will be configured to stratiform.

In the past, as the resin material that is used to form these resin moldings, used thermoset resin materials such as epoxy resin usually.But,,, also require exploitation can form the novel radiation sensitive resin composition of electrical characteristics excellences such as fine pattern, low-dielectric for these resin materials along with the densification of wiring or equipment in recent years.

In addition, in forming figuratum resin molding (patterned resin film), not only requiring cross sectional shape is the shape with corner angle (angle Zhang つ), and according to purposes, requires to have the pattern of mild (なだらか) shape.As its example, can enumerate the micro lens that carries the optics material of the image optics class material of colored filter (ォ Application チップカラ one Off ィ Le one) or fiber optics plug connector (コネ Le ) as crystalline substances such as facsimile recorder, electronic copier, solid-state imagers with 2～10 μ m left and right sides lens diameters.

As using radiation sensitive resin composition to form an example of micro lens, can enumerate following method, after forming round dot pattern (De ットパ one Application), make pattern deformation by heat treated, directly use as lens.Such micro lens forms at it in formation operation of peripheral devices such as operation or wiring, carries out hyperthermia and superheating and handles (melt flows).At this moment, when the heat-resisting shape retention of the resin molding that is formed by the radiation-sensitive resin was not enough, the lens shape distortion can not be kept pattern form, becomes sometimes and can not bring into play as the micro lens function.In addition, the heating-up temperature of this resin molding when melt flows do not have in the temperature that departs from optimum temperature, and during broad temperature limit to the degree that can form desired shape, the steady production of goods, yield rate can descend.

In addition, in other resin molding of interlayer dielectric etc., in the time need making the operation of pattern deformation by melt flows, in order stably to form desirable distortion pattern, the heat-resisting shape retention of this film is important.

On the other hand, in the manufacturing of integrated circuit component and liquid crystal indicator etc., at metal film substrates such as silicon substrate, glass substrate, aluminium, molybdenum, chromium, form the film of radiation sensitive resin composition on the various substrates such as ITO metal oxide films such as (tin-doped indium oxides) substrate, by mask pattern to its irradiation ultraviolet radiation isoreactivity radioactive ray after, development treatment, be mask,, form fine pattern by the etch processes substrate with the corrosion-resisting pattern that obtains.In such photoetching process, radiation sensitive resin composition can be used as erosion resistant and uses, and as its characteristic, requires high resolution.

The radiation sensitive resin composition that is developed under above situation, known have various compositions, but as the radiation sensitive resin composition of silicon-containing compound, for example, propose following composition.

The cycloolefin polymer composition that comprises organic silane compound and contain the cycloolefin polymer of silicyl is disclosed in patent documentation 1.In addition, disclose in the cycloolefin polymer composition, when being scaled per 100 parts by weight polymer compositions, the organosilane compounds reaches about 900 weight portions, that is, with respect to this component of polymer, can contain in a large number.

The multipolymer that comprises unsaturated carboxylic acid and/or unsaturated acid anhydride, contain the unsaturated compound of epoxy radicals and olefines unsaturated compound, and specific phenolic compounds and 1 are disclosed in patent documentation 2, the radiation sensitive resin composition of the condensed polymer of 2-naphthoquinones diazido sulfonic acid halide.In addition, disclose and to have used the functional silanes coupling agent as the bonding auxiliary agent that is used to improve with the matrix bonding force, the ratio of the functional silanes coupling agent in the radiation sensitive resin composition, from being suppressed at the residual viewpoint of development the developing procedure, per 100 weight portion multipolymer compositions should be below 20 weight portions.

The radiation sensitive resin composition that is made of inorganic particles such as photoresists such as the polymkeric substance that contains the diazo salt group and cataloids is disclosed in patent documentation 3.Inorganic particles can help the improvement of oxygen plasma patience, thermotolerance, anti-dry ecthing widely, and as inorganic particles, silicon dioxide (cataloid etc.) is particularly suitable for.Disclose in addition in photosensitive polymer combination, be scaled per 100 weight portion photoresists, inorganic particles reaches about 1000 weight portions, that is, can contain in large quantities than this resin.In addition, photoresist is not put down in writing cycloolefin polymer.

In patent documentation 4, also disclose and in the resist that constitutes by alkali soluble resin and alkoxy methyl melamine and acid agent, added the resist composition that cataloid forms.And disclose silicon dioxide gel and can help to improve dry ecthing patience, but do not put down in writing about the use of alkoxy silane.

(patent documentation 1) spy opens the 2002-146145 communique

(patent documentation 2) spy opens the 2004-170566 communique

(patent documentation 3) spy opens flat 11-327125 communique

(patent documentation 4) spy opens flat 5-216232 communique

Summary of the invention

But, the above radiation sensitive resin composition that contains silicon compound, can satisfy every characteristics such as the desired thermotolerance of said composition, the transparency, stickability, pattern formation property, anti-dry ecthing, low-dielectric, characteristic against corrosion to a certain extent, but except the heat-resisting shape retention of resin molding that obtains is insufficient sometimes, when forming the patterned resin film, sometimes the temperature limit during melt flows is narrow, can not expect to carry out patterning and the steady production of the goods that obtain and good yield rate.

Therefore, the object of the present invention is to provide a kind of radiation sensitive resin composition, will be stacked in laminated body and the manufacture method thereof that constitutes on the substrate by the film that said composition is made, described radiation sensitive resin composition, temperature limit when using heat-resisting shape retention excellence, the melt flows when forming the patterned resin film of its resin molding that obtains is wide, and, also be fit to make erosion resistant.

The inventor gos deep into found that of investigation repeatedly for solving above-mentioned problem, adopt following radiation sensitive resin composition to achieve the above object, described composition contains cycloolefin polymer, radiation-sensitive compound and organosilane compounds, particularly alkoxysilane compound containing trialkylsilyl group in molecular structure, than above-mentioned cycloolefin polymer, contain a spot of this alkoxysilane compound containing trialkylsilyl group in molecular structure, particularly, relative this polymkeric substance of 100 weight portions contains this alkoxysilane compound containing trialkylsilyl group in molecular structure of 10～60 weight portions, has finished the present invention based on this opinion.

That is, the present invention relates to:

(1). a kind of radiation sensitive resin composition, said composition comprises:

Cycloolefin polymer,

The radiation-sensitive compound and

With respect to the described cycloolefin polymer of 100 weight portions is the alkoxysilane compound containing trialkylsilyl group in molecular structure of 10～60 weight portions.

(2). according to (1) described radiation sensitive resin composition, it also contains crosslinking chemical.

(3). according to (1) or (2) described radiation sensitive resin composition, wherein, cycloolefin polymer contains the protic polar group.

(4). according to any 1 described radiation sensitive resin composition in (1)～(3), wherein, alkoxysilane compound containing trialkylsilyl group in molecular structure contains the functional group with the reaction of protic polar group.

(5). a kind of laminated body making method, this method comprises: use any 1 described radiation sensitive resin composition in (1)～(4), form the operation of resin molding on substrate.

(6). according to (5) described laminated body making method, this method also comprises:

Resin molding is shone active radioactive ray, in resin molding, form the sub-image pattern operation and

By making resin molding contact developer solution, make the sub-image pattern development, with the operation of resin molding patterning.

(7). according to (6) described laminated body making method, this method also comprises: heating is formed on the patterned resin film on the substrate, makes the operation of pattern form distortion.

(8). according to any 1 described laminated body making method in (5)～(7), this method also comprises the crosslinked operation of resin molding that will be formed on the substrate.

(9). a kind of laminated body, its substrate superimposed layer by (1)～(4) in the resin molding made of any 1 described radiation sensitive resin composition form.

(10). according to (9) described laminated body, wherein, resin molding is the resin molding of patterning.

(11). a kind of electronic unit or optics, it comprises (9) or (10) described laminated body.

Embodiment

Radiation sensitive resin composition of the present invention contains cycloolefin polymer, radiation-sensitive compound and is 10～60 weight portion alkoxysilane compound containing trialkylsilyl group in molecular structure with respect to the above-mentioned cycloolefin polymer of 100 weight portions.

One of feature of radiation sensitive resin composition of the present invention is to contain organosilane compounds, particularly alkoxysilane compound containing trialkylsilyl group in molecular structure with above-mentioned ormal weight.Infer that because have such formation (Si-O-Si-), this cross-linked structure helps the formation of the best cross-linked structure of resin molding so can generate the cross-linked structure that is caused by alkoxysilane compound containing trialkylsilyl group in molecular structure in the resin molding of being made by said composition.Consequently, think and to obtain the desirable effect of the present invention.

In this manual, sometimes cycloolefin polymer is called " resin ", the film that will contain cycloolefin polymer is called " resin molding ".

In addition, in this manual, so-called " heat-resisting shape retention excellence " is meant, the patterned resin film (a patterned resin film) that the resin molding patterning is obtained carries out melt flows, make the pattern form distortion, when forming patterned resin film (secondary pattern resin molding), pattern form originally is excessive deformation not, and can form desirable pattern form easily; In addition, after the secondary pattern resin molding forms, during the above temperature of the temperature when this film is exposed to melt flows, at this moment, the distortion of desirable pattern form is had tolerance, synthetically be called the heat control height of pattern form.Here, so-called " distortion " is meant, when the contrast patterns shape of the heating front and back of patterned resin film, pattern form takes place can discern degree change with range estimation.On the other hand, so-called " temperature limit is wide " is meant that patterned resin film is carried out the optimum temperature of melt flows when forming the secondary pattern resin molding be the heating-up temperature amplitude broad at center.These character of radiation sensitive resin composition of the present invention can be according to the method evaluation of putting down in writing in aftermentioned embodiment.In addition, in this manual, in " patterned resin film ", short of special situation then comprises patterned resin film and secondary pattern resin molding.

So-called cycloolefin polymer among the present invention is meant, makes the cycloolefin monomers polymerization and obtains and have the polymkeric substance of this monomeric unit as structural unit.It is structural unit that such cycloolefin polymer also can have with the monomeric unit beyond the cycloolefin monomers.Object lesson as cycloolefin polymer, can enumerate, the ring opening copolymer thing of the ring-opening polymerization polymer of cycloolefin monomers or cycloolefin monomers (below, with both and be called open loop (being total to) polymkeric substance of cycloolefin monomers), cycloolefin monomers and vinyl alicyclic ring family hydrocarbon monomer (clicyclic hydrocarbon) with vinyl or with the addition copolymer of vinyl aromatic hydrocarbon monomer (aromatic hydrocarbon), and these hydrogenation thing with vinyl.

In addition, though do not contain the cycloolefin monomers unit is structural unit, but has polymkeric substance with the structural unit of the same structure in cycloolefin monomers unit, also can be used in radiation sensitive resin composition of the present invention, to replace cycloolefin polymer, also can access desirable effect thus.Object lesson as such polymkeric substance, can enumerate the polymkeric substance of vinyl alicyclic ring family hydrocarbon monomer or the multipolymer of vinyl alicyclic ring family hydrocarbon monomer (below, with both and be called (being total to) polymkeric substance of vinyl alicyclic ring family hydrocarbon monomer), the multipolymer of vinyl alicyclic ring family's hydrocarbon monomer and other monomer and these hydrogenation thing; And the hydrogenation thing of the multipolymer of the polymkeric substance of vinyl aromatic hydrocarbon monomer or vinyl aromatic hydrocarbon monomer (below, with both and be called (being total to) polymkeric substance of vinyl aromatic hydrocarbon monomer), also has the hydrogenation thing of the multipolymer of vinyl aromatic hydrocarbon monomer and other monomer.These polymkeric substance also can be any one in ring-opening polymerization polymer and the addition polymer.

As the cycloolefin polymer that uses in the present invention, the hydrogenation thing of (being total to) polymkeric substance of open loop (being total to) polymkeric substance of wherein preferred cycloolefin monomers and the addition copolymer of hydrogenation thing, cycloolefin monomers and vinyl alicyclic ring family's hydrocarbon monomer or vinyl aromatic hydrocarbon monomer and hydrogenation thing and vinyl aromatic hydrocarbon monomer, more preferably the hydrogenation thing of the open loop of cycloolefin monomers (being total to) polymkeric substance.

Be used to obtain the cycloolefin monomers of cycloolefin polymer, there is no particular limitation promptly to have the olefinic monomer of ring structure, as the 1st group, can enumerate the cycloolefin monomers (a) that does not have polar group.Norborene), 5-ethyl-two ring [2.2.1] hept-2-ene", 5-butyl-two ring [2.2.1] hept-2-ene", 5-ethidine-two ring [2.2.1] hept-2-ene", 5-methene base-two ring [2.2.1] hept-2-ene", 5-vinyl-two ring [2.2.1] hept-2-ene", three ring [4.3.0.1 as its object lesson, can enumerate two ring [2.2.1] hept-2-ene"s (common first names: ^2,5] last of the ten Heavenly stems-3, bicyclopentadiene), Fourth Ring [8.4.0.1 7-diene (common first names: ^11,14.0 ^3,7] 15 carbon-3,5,7,12,11-pentaene, Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] last of the ten Heavenly stems-tetracyclododecane), 8-methyl-Fourth Ring [4.4.0.1 3-alkene (common first names: ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-ethyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methene base-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-ethidine-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-vinyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-propenyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, five rings [6.5.1.1 ^3,6.0 ^2,7.0 ^9,13] 15 carbon-3,10-diene, cyclopentene, cyclopentadiene, 1,4-endo-methylene group-1,4,4a, 5,10,10a-six hydrogen anthracenes, 8-phenyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, Fourth Ring [9.2.1.0 ^2,10.0 ^3,8] 14 carbon-3,5,7,12-tetraene (being also referred to as 1,4-endo-methylene group-1,4,4a, 9a-tetrahydrochysene-9H-fluorenes), five rings [7.4.0.1 ^3,6.1 ^10,13.0 ^2,7] 15 carbon-4,11-diene, five rings [9.2.1.1 ^4,7.0 ^2,10.0 ^3,8] 15 carbon-5,12-diene etc.These cycloolefin monomers both can have been distinguished use separately, also can make up more than 2 kinds and use.

The 2nd group of cycloolefin monomers can be enumerated the cycloolefin monomers with polar group.These cycloolefin monomers with polar group both can have been distinguished use separately, also can make up more than 2 kinds and use.

Polar group can be distinguished and be expressed as protic polar group and polar group in addition.Therefore, the cycloolefin monomers with polar group can be distinguished the cycloolefin monomers (c) that is expressed as the cycloolefin monomers (b) with protic polar group and has protic polar group polar group (non-proton property polar group) in addition.

In this manual, so-called protic polar group is meant, the atomic group of Direct Bonding hydrogen atom on the atom beyond the carbon atom.Here,, preferably belong to the atom of periodic table the 15th family and the 16th family, more preferably belong to periodic table the 15th family and the 16th family the 1st and the atom in the 2nd cycle, more preferably oxygen atom, nitrogen-atoms or sulphur atom, preferred oxygen atom especially as the atom beyond the carbon atom.

As the object lesson of protic polar group, can enumerate, carboxyl (hydroxycarbonyl group), sulfonic group, phosphate, hydroxyl etc. have the polar group of oxygen atom; Primary amino radical, secondary amino group, primary amide base, secondary amide base (imide) etc. have the polar group of nitrogen-atoms; Mercapto (チォ one Le base) etc. has the polar group of sulphur atom etc.Wherein, preferably has the polar group of oxygen atom, more preferably carboxyl.

As the object lesson of the cycloolefin monomers with protic polar group (b), can enumerate 5-hydroxycarbonyl group two ring [2.2.1] hept-2-ene"s, 5-methyl-5-hydroxycarbonyl group two ring [2.2.1] hept-2-ene"s, 5-ethyloic-5-hydroxycarbonyl group two ring [2.2.1] hept-2-ene"s, 5-outer-6-in-dihydroxy carbonyl two ring [2.2.1] hept-2-ene"s, 8-hydroxycarbonyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-8-hydroxycarbonyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-are outer-9-in-dihydroxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene etc. has the cycloolefin of carboxyl; 5-(4-hydroxy phenyl) two ring [2.2.1] hept-2-ene"s, 5-methyl-5-(4-hydroxy phenyl) two ring [2.2.1] hept-2-ene"s, 8-(4-hydroxy phenyl) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-(4-hydroxy phenyl) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene etc. has the cycloolefin of hydroxyl etc.Wherein, the cycloolefin that preferably has carboxyl.

Object lesson as non-proton property polar group; can enumerate ester group (general name alkoxy carbonyl group and aryloxy carbonyl), N-substituted imides base, epoxy radicals, halogen atom, cyano group, carbonyl oxygen carbonyl (the acid anhydrides residue of dicarboxylic acid), alkoxy, carbonyl, uncle's amino, sulfo group, halogen atom, acryloyl group etc.Wherein, preferred ester group, N-substituted imides base, cyano group and halogen atom are more preferably ester group and N-substituted imides base.Preferred especially N-substituted imides base.

As the object lesson of the cycloolefin monomers (c) with non-proton property polar group, particular instantiation is in following.

As cycloolefin, for example, can enumerate 5-acetoxyl group two ring [2.2.1] hept-2-ene"s, 5-methoxycarbonyl two ring [2.2.1] hept-2-ene"s, 5-methyl-5-methoxycarbonyl two ring [2.2.1] hept-2-ene"s, 8-acetoxyl group Fourth Ring [4.4.0.1 with ester group ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methoxycarbonyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-carbethoxyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, the positive third oxygen carbonyl Fourth Ring [4.4.0.1 of 8- ^2,5.1 ^7,10] 12 carbon-3-alkene, the different third oxygen carbonyl Fourth Ring [4.4.0.1 of 8- ^2,5.1 ^7,10] 12 carbon-3-alkene, the positive butoxy carbonyl of 8-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-8-methoxycarbonyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-8-carbethoxyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, the positive third oxygen carbonyl Fourth Ring [4.4.0.1 of 8-methyl-8- ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-8-isopropoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, the positive butoxy carbonyl of 8-methyl-8-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-(2,2,2-trifluoro carbethoxyl group) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-8-(2,2,2-trifluoro carbethoxyl group) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene etc.

As cycloolefin, for example, can enumerate N-(4-phenyl)-(5-norborene-2,3-dicarboxyl acid imide) etc. with N-substituted imides base.

As cycloolefin, for example, can enumerate 8-cyano group Fourth Ring [4.4.0.1 with cyano group ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-8-cyano group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 5-cyano group two ring [2.2.1] hept-2-ene"s etc.

As cycloolefin, for example, can enumerate 8-chlorine Fourth Ring [4.4.0.1 with halogen atom ^2,5.1 ^7,10] 12 carbon-3-alkene, 8-methyl-8-chlorine Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene etc.

In addition, as the example of above-mentioned alicyclic vinyl ring type hydrocarbon monomer (d), can enumerate vinyl cycloalkanes such as vinyl trimethylene, vinyl cyclo-butane, vinyl cyclopentane, vinyl cyclohexane, vinyl cycloheptane; 3-methyl isophthalic acid-vinyl cyclohexane, 4-methyl isophthalic acid-vinyl cyclohexane, 1-phenyl-2-vinyl trimethylene, 1, the vinyl cycloalkanes that 1-diphenyl-alkyl such as 2-vinyl trimethylene replace etc.

As the example of vinyl aromatic hydrocarbon monomer (e), can enumerate the vinyl aromatic same clans such as styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 3-vinyl naphthalene; The vinyl aromatic same clan that alkyl such as 3-methyl styrene, 4-propylstyrene, 4-cyclohexyl benzene ethene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4-(phenyl butyl) styrene replace; Between divinylbenzene, to polyfunctional vinyl aromatic classes such as divinylbenzene, two (4-ethenylphenyl) methane etc.

As alicyclic vinyl ring type hydrocarbon monomer (d) and vinyl aromatic hydrocarbon monomer (e) in addition, can with the representative example of the monomer of cycloolefin copolymerization, can enumerate olefine (f).Example as olefine (f), can enumerate ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4, the alpha-olefin of carbon numbers 2～20 such as 4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene; 1,4-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 1, non-conjugated dienes such as 7-octadiene etc.These monomers can be distinguished use more than 2 kinds alone or in combination.In addition, olefine (f) also can be used as and can use with the monomer of vinyl alicyclic ring family hydrocarbon monomer (d) and vinyl aromatic hydrocarbon monomer (e) copolymerization.

The polymerization of above-mentioned each monomer can for example adopt ring-opening polymerization method and addition polymerization method according to usual method.As polymerization catalyst, for example, preferably use the metal complex of molybdenum, ruthenium and osmium etc.These polymerization catalysts can be distinguished use more than 2 kinds alone or in combination.For example, when the open loop that is used to obtain cycloolefin monomers (being total to) polymkeric substance, with the metallic compound in the polymerization catalyst: the molar ratio computing of cycloolefin monomers, the amount of polymerization catalyst normally 1: 100～1: 2,000,000, preferred 1: 500～1: 1,000,000, more preferably 1: 1,000～1: 500,000 scope.

Cycloolefin polymer by above-mentioned polymerization obtains can carry out hydrogenation according to hope.Hydrogenation makes spent hydroprocessing catalyst carry out usually.As hydrogenation catalyst, for example, can utilize normally used hydrogenation catalyst when the hydrogenation of olefin(e) compound.Particularly, can utilize homogeneous System Catalyst, noble metal coordination compound catalyzer and the solid supported noble metal class catalyzer etc. of Ziegler-type.In these hydrogenation catalysts, never can cause subsidiary reactions such as functional group's generation sex change such as protic polar group, and can be to the viewpoint of hydrogenation optionally of the carbon-to-carbon unsaturated bond in the polymkeric substance, the coordination compound catalyzer of noble metals such as preferred rhodium and ruthenium, more preferably coordination the high nitrogen heterocyclic ring carbene compound of electron donability or the ruthenium catalyst of phosphine class.In addition, preferred more than 80% as the hydrogenation ratio of cycloolefin polymer, more preferably more than 90%.

In the present invention, cycloolefin polymer can be used singly or in combination different polymkeric substance such as composition more than 2 kinds respectively.

As the cycloolefin polymer that uses in the present invention, preferably has the cycloolefin polymer of polar group.There is no particular limitation for polar group number contained in having the cycloolefin polymer of polar group, and polar group can comprise the polar group of identical or different kind.In addition, polar group both can be combined on the cycloolefin monomers unit, also can be combined on the cycloolefin monomers monomeric unit in addition, but preferred combination was on the cycloolefin monomers unit.

In the present invention, cycloolefin polymer especially preferably has the cycloolefin polymer of protic polar group.Have the cycloolefin polymer (below, be sometimes referred to as " cycloolefin polymer that contains the protic polar group ") of protic polar group by use, the radiation sensitive resin composition that obtains improves the susceptibility of radioactive ray, therefore is fit to.The cycloolefin polymer that contains the protic polar group can be used singly or in combination different polymkeric substance such as composition more than 2 kinds respectively.

In the cycloolefin polymer that contains the protic polar group, the ratio (monomeric unit/this monomer monomeric unit in addition that contains the protic polar group) that contains the monomeric unit and the monomeric unit beyond this monomer of protic polar group, usually, weight ratio is 100/0～10/90, preferred 90/10～20/80, more preferably 80/20～30/70 scope.

As the preferred manufacture method of the cycloolefin polymer that contains the protic polar group that uses among the present invention, can enumerate cycloolefin monomers (b) that polymerization has the protic polar group, carry out the method for hydrogenation according to hope.According to hope, have the protic polar group cycloolefin monomers (b) can with can with monomer (for example, above-mentioned monomer (a), (c)～(the f)) copolymerization of its copolymerization.

In addition, the cycloolefin polymer that contains the protic polar group of Shi Yonging can behind the importing protic polar group, according to hope, carry out the method for hydrogenation by known method in the cycloolefin polymer that does not have the protic polar group in the present invention.Polymkeric substance before hydrogenation also can import the protic polar group carries out.

Modifier as being used for importing to the cycloolefin polymer that does not have the protic polar group protic polar group can use to have the compound that has reactive carbon-to-carbon unsaturated bond with the protic polar group usually in a part.As the object lesson of such compound, can enumerate unsaturated carboxylic acids such as acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassidic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid, cinnamic acid; Unsaturated alcohols such as allyl alcohol, methyl ethylene methyl alcohol, butenol, methallyl alcohol, 1-styrene-1-alcohol, 2-propylene-1-alcohol, 3-butene-1-alcohol, 3-butene-2-alcohol, 3-methyl-3-butene-1-alcohol, 3-methyl-2-butene-1-alcohol, 2-methyl-3-butene-2-alcohol, 2-methyl-3-butene-1-alcohol, 4-amylene-1-ol, 4-methyl-4-amylene-1-ol, 2-hexen-1-ol etc.Modified-reaction can carry out in the presence of free radical generating agent usually according to usual method.These modifier can be distinguished use separately or use simultaneously more than 2 kinds.

In the method for making of the cycloolefin polymer that contains above-mentioned protic polar group, the protic polar group that is present in this polymkeric substance also can be its precursor, at this moment, chemical reactions such as decomposition that can be by adopting light and heat to cause, hydrolysis are transformed to the protic polar group.For example, when the protic polar group in the cycloolefin polymer that will contain the protic polar group is made carboxyl, can use the precursor of ester group, then be transformed to suitable carboxyl as the protic polar group.

The cycloolefin polymer that does not have the protic polar group, for example, can be according to usual method, use above-mentioned monomer (a), (c)～(f) obtain.

In the present invention the weight average molecular weight of the cycloolefin polymer of Shi Yonging (Mw) normally 1,000～1,000,000, preferably 1,500～100,000, be more preferably 2,000～10,000 scope.

In the present invention the molecular weight distribution of the cycloolefin polymer of Shi Yonging in weight-average molecular weight/number-average molecular weight (Mw/Mn) than, normally below 4, preferably below 3, be more preferably below 2.5.

The iodine number of the cycloolefin polymer of Shi Yonging is normally below 200, preferred below 50 in the present invention, more preferably below 10.If the iodine number of cycloolefin polymer is in this scope, the heat-resisting shape retention of the resin molding of being made by radiation sensitive resin composition of the present invention is excellent especially, so suitable.

The radiation-sensitive compound of Shi Yonging is to absorb ultraviolet ray and electronics line isoradial in the present invention, causes the compound of chemical reaction.In the present invention, when use has the cycloolefin polymer of protic polar group, preferably can control the cycloolefin polymer of the alkali dissolution of this cycloolefin polymer.In the present invention, as the radiation-sensitive compound, preferably use photoacid generator (Guang Suan development to give birth to drug).

As the radiation-sensitive compound, for example, can enumerate azido cpds such as acetophenone compound, triarylsulfonium salt and quinone diazido compound etc., preferred azido cpd, preferred especially quinone diazido compound.

As quinone diazido compound, for example, can use quinone diazido sulfonic acid halide and ester compounds with compound of phenol hydroxyl.As quinone diazido sulfonic acid halide, can enumerate 1,2-naphthoquinones diazido-5-sulfonic acid halide, 1,2-naphthoquinones diazido-4-sulfonic acid halide, 1,2-benzoquinones diazido-5-sulfonic acid halide etc.As the representative example of compound, can enumerate 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl with phenol hydroxyl] phenyl] ethidine] bis-phenol etc.As the compound beyond these with phenol hydroxyl, can enumerate 2,3,4-trihydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, two (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) methane, 1,1 of 2-, 1-three (4-hydroxy-3-methyl phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethane, the oligomer of novolac resin, the compound that will have 1 above phenol hydroxyl and bicyclopentadiene copolymerization and oligomer of obtaining etc.

As photoacid generator; except that quinone diazido compound; can use salt, halogenated organic compounds, α, known compounds such as α '-two (sulfonyl) diazomethane compounds, alpha-carbonyl-α '-sulfonyl diazomethane compounds, sulfo group compound, organic acid esters compound, organic acid amide compound, organic acid imide compound.

These radiation-sensitive compounds can be distinguished alone or in combination and use more than 2 kinds.

Relative 100 weight portion cycloolefin polymers, the consumption of radiation-sensitive compound is 1～100 weight portion normally, preferred 5～50 weight portions, the more preferably scope of 10～40 weight portions.If the consumption of radiation-sensitive compound is in this scope, to being formed at resin molding on the substrate when carrying out patterning, radiation exposure part and the radioactive ray not poor solubility to developer solution of illuminated portion become big, easy by the patterning that development causes, and the radioactive ray susceptibility also uprises, so preferred.

In radiation sensitive resin composition of the present invention, except that mentioned component, also contain alkoxysilane compound containing trialkylsilyl group in molecular structure, relative 100 weight portion cycloolefin polymers, the content of this compound is 10～60 weight portions.

Especially, as the consumption of alkoxysilane compound containing trialkylsilyl group in molecular structure, relative 100 weight portion cycloolefin polymers are preferably greater than 20 weight portions and below 60 weight portions, are more preferably greater than 20 weight portions and below 50 weight portions.

Alkoxysilane compound containing trialkylsilyl group in molecular structure of the present invention is not particularly limited, for example, can have functional groups such as halogen atom, vinyl, amino, carboxyl, sulfydryl, epoxy radicals, isocyanate group, metacryloxy, propenyloxy group, urea groups, thioether group (ス Le Off ィ De base), oxetanyl arbitrarily.Alkoxysilane compound containing trialkylsilyl group in molecular structure can be distinguished use separately or use simultaneously more than 2 kinds.

As the object lesson of alkoxysilane compound containing trialkylsilyl group in molecular structure, can enumerate tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane; Methyltrimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, the isopropyl trimethoxy silane, the isopropyl triethoxysilane, the normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, the n-pentyl trimethoxy silane, the n-hexyl trimethoxy silane, the n-heptyl trimethoxy silane, the n-octyl trimethoxy silane, positive decyl trimethoxy silane, to the styryl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-chloropropyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane, 3,3,3-trifluoro propyl triethoxysilane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, just-2-(amino-ethyl)-3-TSL 8330, just-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene, just-phenyl-3-TSL 8330,2-hydroxyethyl trimethoxy silane, 2-hydroxyethyl triethoxysilane, 2-hydroxypropyl trimethoxy silane, 2-hydroxypropyl triethoxysilane, 3-hydroxypropyl trimethoxy silane, 3-hydroxypropyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, 3-ethyl (trimethoxysilyl propoxyl group methyl) oxetanes, 3-ethyl (triethoxysilyl propoxyl group methyl) oxetanes, 3-triethoxysilyl-just-(1,3-dimethyl-Ding pitches base) propylamine, trialkoxysilanes such as two (triethoxysilylpropyltetrasulfide) tetrasulfide; Dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, the diethyl diethoxy silane, di dimethoxy silane, the di diethoxy silane, diisopropyl dimethoxy silane, the diisopropyl diethoxy silane, di-n-butyl dimethoxy silane, the di-n-butyl diethoxy silane, two n-pentyl dimethoxy silane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxy silane, the di-n-hexyl diethoxy silane, two n-heptyl dimethoxy silane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxy silane, the di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxy silane, two positive cyclohexyl diethoxy silanes, dimethoxydiphenylsilane, the diphenyl diethoxy silane, 3-glycidoxy propyl group methyldiethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloxy propyl group methyldiethoxysilane, just-2-(amino-ethyl)-dialkoxy silicane classes such as 3-aminopropyl methyl dimethoxysilane, and methyl triacetoxysilane, dimethyl diacetoxy silane etc.In addition, in this manual, so-called (methyl) acryloyl group, expression propionyl thiazolinyl or methacryl.

Wherein, as alkoxysilane compound containing trialkylsilyl group in molecular structure, preferably has the functional group of reacting, particularly with the protic polar group, when cycloolefin polymer has the protic polar group, the functional group of the protic polar group reaction that more preferably has with this cycloolefin polymer.As the protic polar group, can enumerate above-mentioned protic polar group.As with the functional group of protic polar group reaction, for example, can enumerate amino, carboxyl, epoxy radicals, isocyanate group etc., preferred epoxy radicals, isocyanate group.It is generally acknowledged, if alkoxysilane compound containing trialkylsilyl group in molecular structure has the functional group with the reaction of protic polar group, in the functional group and the reaction of protic polar group of alkoxysilane compound containing trialkylsilyl group in molecular structure, polycondensation reaction takes place between the alkoxysilane compound containing trialkylsilyl group in molecular structure, can access the effect of alkoxysilane compound containing trialkylsilyl group in molecular structure performance resin cross-linking agent effect thus.As with alkoxysilane compound containing trialkylsilyl group in molecular structure in the number of functional group of protic polar group reaction there is no particular limitation, normally 1～2.In alkoxysilane compound containing trialkylsilyl group in molecular structure, can have the identical or different functional group with protic polar group reaction, in addition, also can exist with can with different types of functional group of functional group of protic polar group reaction.

In the present invention, as alkoxysilane compound containing trialkylsilyl group in molecular structure, preferred especially 3-glycidoxypropyltrime,hoxysilane (γ-glycidoxypropyltrime,hoxysilane), 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-isocyanate group propyl trimethoxy silicane and 3-isocyanate group propyl-triethoxysilicane.

In addition, if in the scope of not damaging desirable effect of the present invention, then can in radiation sensitive resin composition of the present invention, contain alkoxysilane compound containing trialkylsilyl group in molecular structure organosilane compounds in addition.

From the viewpoint that the heat-resisting shape retention that makes resin molding improves, radiation sensitive resin composition of the present invention preferably also contains crosslinking chemical.As crosslinking chemical, can use at molecule contain more than 2, preferred more than 3 can with the crosslinking chemical of the functional group of cycloolefin polymer reaction.As long as the functional group of crosslinking chemical can react with functional group or the unsaturated link in the cycloolefin polymer, there is no particular limitation.When cycloolefin polymer has the protic polar group, as can with the preferred functional group of this polar group reaction, for example can enumerate amino, carboxyl, hydroxyl, epoxy radicals, isocyanate group etc., more preferably amino, epoxy radicals, isocyanate group, especially preferably epoxy radicals.

As the object lesson of such crosslinking chemical, can enumerate aliphatic polyamine classes such as hexamethylene diamine; 4, aromatic polyamine classes such as 4 '-diaminodiphenyl ether, diamino-diphenyl sulfone; 2,6-two (4 '-azido benzal base) cyclohexanone, 4, nitrine base class such as 4 '-diazido diphenylsulphone; Benzenedicarboxamide etc. is polyamide-based between nylon, polyhexamethylene diamino terephthalamide, polyhexamethylene; N, N, N ', N ', N ", N "-melamine class such as (six alkoxy methyls) melamine; N, N ', N ", N "-glycoluril classes such as (four alkoxy methyls) glycoluril; Acrylate compounds such as ethylene glycol bisthioglycolate (methyl) acrylate; Isocyanate ester compounds such as hexamethylene diisocyanate class polyisocyanates, isophorone diisocyanate class polyisocyanates, toluene diisocyanate class polyisocyanates, hydrogenation methyl diphenylene diisocyanate; 1,4-two (methylol) cyclohexane, 1,4-two (methylol) norbornane; 1,3,4-trihydroxy cyclohexane; Various multi-functional epoxy compounds etc.

As above-mentioned multi-functional epoxy compound, be epoxy compound with 2 above epoxy radicals, preferred 3 above epoxy radicals, can enumerate have the ester ring type structure, that have cresols novolaks skeleton, that have phenol novolaks skeleton, that have the bisphenol-A skeleton, have the naphthalene skeleton etc.Wherein, from the good degree of the intermiscibility of cycloolefin polymer, particularly suitable is to have the ester ring type structure, and have more than 2, the multi-functional epoxy compound of preferred 3 above epoxide groups.

In the present invention, as crosslinking chemical, the above-mentioned multi-functional epoxy compound of preferred use, as the object lesson of this epoxy compounds, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylic ester polymer etc.

These crosslinking chemicals can be used alone or in combination of two or more kinds respectively.The consumption of crosslinking chemical is suitably selected according to application target, relative 100 weight portion cycloolefin polymers, normally 1～1,000 weight portion, preferred 5～500 weight portions, more preferably 10～100 weight portions.If consumption is in this scope, the thermotolerance of formed resin molding is highly improved, so preferred.

There is no particular limitation for the molecular weight of the crosslinking chemical of Shi Yonging in the present invention, normally 100～100,000, preferred 500～50,000, be more preferably 1,000～10,000.If the molecular weight of this scope, the stability during from heating or the efficient of gelation consider it is preferred.

In addition, as long as in the scope that does not hinder the desired effect that shows of the present invention,, also can in radiation sensitive resin composition of the present invention, contain other compositions such as resinous principle beyond the cycloolefin polymer or other compounding ingredient according to hope.

As the resinous principle beyond the cycloolefin polymer, for example, can enumerate styrene resin, vinyl chloride resin, acrylic resin, polyphenylene oxide resin, polyarylene sulfide resin, polycarbonate resin, vibrin, polyamide, polyethersulfone resin, polysulfone resin, polyimide resin, rubber and elastic body etc.

As other compounding ingredient, for example, can enumerate sensitizer, surfactant, potential type acid agent (potential De Suan development is given birth to drug), antistatic agent, antioxidant, bonding auxiliary agent, defoamer, pigment, dyestuff etc.

As sensitizer, for example, can enumerate 2H-pyrido-(3,2-b)-1,4- piperazine-3 (4H)-ketone, 10H-pyrido-(3,2-b)-1,4-benzo thiazides, urazole class, hydantoins, barbital acids, glycine anhydride class, I-hydroxybenzotriazole class, alloxan class, maleimide etc.

Surfactant is in order to prevent striped (coating striped vestige (Tu cloth muscle あと)), improve development etc. and use, for example, can enumerate polyethylene oxide alkyl ethers classes such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether; Polyoxyethylene such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylplenyl ether aryl ethers; Non-ionics such as polyoxyethylene dialkyl esters such as polyoxyethylene two lauryls, polyoxyethylene distearyl ester; Fluorine class surfactant; Polysiloxane-based surfactant; Methacrylic acid copolymer class surfactant, acrylic copolymer class surfactant etc.

The potential type acid agent is to use for the thermotolerance that improves radiation sensitive resin composition of the present invention and resistance to chemical reagents, for example, by heating acidic cationic polymerization catalyst, can enumerate sulfonium salt, benzothiazole  salt, ammonium salt,  salt etc.Wherein, preferred sulfonium salt and benzothiazole  salt.

As other above-mentioned compounding ingredient, use known compounding ingredient arbitrarily.

Radiation sensitive resin composition of the present invention usually with cycloolefin polymer, radiation-sensitive compound and alkoxysilane compound containing trialkylsilyl group in molecular structure and crosslinking chemical optionally or the dissolving of other composition or be dispersed in the solvent, obtains solution or dispersion liquid.Radiation sensitive resin composition of the present invention preferably uses with the form of such solution or dispersion liquid.

In addition, radiation sensitive resin composition of the present invention both can be simply mixing and the formation of each constituent with solid shape, also removed to desolvate the composition that can obtain from the form with solution or dispersion liquid to form.

As the solvent that uses in the present invention, there is no particular limitation, for example, can enumerate aklylene glycol classes such as ethylene glycol, propylene glycol, diglycol, triethylene glycol, tetraethylene glycol; Alkylene glycol mono ethers such as ethylene glycol monoethyl ether, ethylene glycol ether, glycol monomethyl uncle butyl ether, dihydroxypropane single-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 list ether, triethylene glycol monomethyl ether, triethylene glycol list ether, tripropylene glycol monomethyl ether, tripropylene glycol list ether; Aklylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl-methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl-methyl ether, triglyme, triethylene glycol diethyl ether, triethylene glycol ethyl-methyl ether, tripropylene glycol ethyl-methyl ether; Alkylene glycol monoalkyl ethers ester classes such as propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list positive propyl ether acetic acid esters, propylene glycol list isopropyl ether acetic acid esters, propylene glycol mono-n-butyl ether acetic acid esters, propylene glycol list isobutyl ether acetic acid esters, the secondary butyl ether acetic acid esters of propylene glycol list, propylene glycol list uncle butyl ether acetic acid esters; Ketones such as MEK, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2 pentanone, cyclohexanone, cyclopentanone; Methyl alcohol, ethanol, propyl alcohol, butanols, 3-methoxyl-alcohols such as 3-methyl butanol; Cyclic ethers classes such as tetrahydrofuran, two  alkane; Cellosolve such as methylcellosolve acetate, ethyl cellosolve acetate ester class; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based; Ester classes such as ethyl acetate, butyl acetate, ethyl lactate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxacetic acid ethyl ester, 2-hydroxy-3-methyl methyl butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters, gamma-butyrolacton; N-NMF, N, amide-types such as dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, N-methylacetamide, N,N-dimethylacetamide; Dimethyl sulfoxide (DMSO) etc.

These solvents can be distinguished use separately or use simultaneously more than 2 kinds.Relative 100 weight portion cycloolefin polymers, the consumption of solvent are 20～10,000 weight portion, preferred 50～5,000 weight portion, the more preferably scope of 100～1,000 weight portion normally.

Dissolving or dispersion constitute the method for the various compositions of radiation sensitive resin composition of the present invention in solvent, can be according to usual way, for example, can use the stirring of agitator (Stir mixes son) and magnetic stirrer or high speed homogenizer, decollator, planetary mixer, biaxial rneader, bowl mill, three-roller etc. to carry out.In addition, in solvent the dissolving or disperse each composition after, for example, can use the filtering membrane (Off ィ Le one) about the 0.5 μ m of aperture to filter.

As the solid component concentration of radiation sensitive resin composition of the present invention, normally 1～70 weight %, preferably 5～50 weight %, be more preferably 10～40 weight %.If solid part concentration is in this scope, steady dissolution, can the height balance to the film thickness uniformity of the resin molding of the coating of substrate and formation and flatness etc.

The wide characteristic of temperature limit when radiation sensitive resin composition of the present invention has heat-resisting shape retention excellence, the melt flows when forming the patterned resin film of the resin molding that obtains.Therefore, as an embodiment of the invention, the method of using radiation sensitive resin composition of the present invention to improve the heat-resisting shape retention of resin molding also can be provided, or the method for the temperature limit when enlarging melt flows when forming the patterned resin film.

The resin molding that laminated body of the present invention is made by radiation sensitive resin composition of the present invention at the substrate superimposed layer forms.Thickness of resin film normally 0.1～100 μ m, preferred 0.5～50 μ m, be more preferably the scope of 0.5～30 μ m.

In the present invention, substrate for example can use printed circuit substrate, silicon wafer substrate, glass substrate, plastic base etc.In addition, the preferred parts that form thin type transistor type liquid crystal display cells, colored filter, black matrix" etc. on the glass substrate that in field of display, uses or the plastic base etc. that use.

The laminated body of the present invention resin molding that normally direct lamination is made by radiation sensitive resin composition of the present invention on substrate forms, and for example, also can be that the lamination resin molding forms indirectly by other films such as planarization films.In addition, laminated body of the present invention also comprises by substrate and resin molding, looks the multilayer laminate that other film of hope constitutes except the 2 layer laminate bodies that are made of substrate and resin molding.

In addition, resin molding also can be patterned.Laminated body of the present invention, the particularly laminated body of formation patterned resin film on substrate can be used for the various opticses of aftermentioned, electronic unit.

Laminated body of the present invention, radiation sensitive resin composition that for example can the application of the invention forms resin molding and makes on substrate.

As the method that forms resin molding on substrate, there is no particular limitation, for example, can use methods such as rubbing method and film lay-up method.For example, rubbing method is behind the radiation sensitive resin composition of coating solution on the substrate or dispersion liquid form, and heat drying removes the method for desolvating.Method as coating radiation sensitive resin composition on substrate, for example, can adopt spray-on process, method of spin coating (スピ Application コ one ト), roller rubbing method, mould rubbing method, scrape the whole bag of tricks such as the skill in using a kitchen knife in cookery, method of spin coating (returning translocation Tu cloth method), scraping article rubbing method (バ one Tu cloth method), silk screen print method.Heat drying is according to the kind of each composition or cooperation ratio and difference, and normally 30～150 ℃, preferred 60～120 ℃, usually at 0.5～90 minute, preferred 1～60 minute, more preferably to carry out under 1～30 minute the condition.

The film lay-up method is following method: for example, behind the radiation sensitive resin composition of coating solution on the base materials such as resin molding or metal film or dispersion liquid form, heat drying removes and desolvates, and obtains B stage film, then at this B stage film of substrate superimposed layer.Heat drying is according to the kind of each composition or cooperation ratio and difference, normally 30～150 ℃, preferred 60～120 ℃, usually 0.5～90 minute, preferred 1～60 minute, more preferably carry out under 1～30 minute the condition.The film lamination can use pressing machines such as pressure level press, pressing machine, vacuum laminator, vacuum press, roll laminating machine to carry out.

The laminated body that forms the patterned resin film and form on substrate of the present invention can be made by the following method, for example, use radiation sensitive resin composition of the present invention at substrate superimposed layer resin molding, this resin molding is shone active radioactive ray, in resin molding, form the sub-image pattern, then make developer solution contact pressure resin film, the sub-image pattern is obviously changed, with the resin molding patterning on the substrate.

The resin molding of being made by radiation sensitive resin composition of the present invention at the substrate superimposed layer can carry out according to the method described above.As the active radioactive ray that the resin molding that forms is shone, so long as make the radiation-sensitive compound activityization, and the active radioactive ray of the alkali-soluble variation of the crosslinkable composite that comprises the radiation-sensitive compound are got final product, there is no particular limitation.Particularly, can use the light such as ultraviolet ray, KrF excimer laser, ArF excimer laser of single wavelengths such as ultraviolet ray, g line or i line; The particle ray that electron ray is such etc.Form sub-image method of patterning as optionally on resin molding, shining these active radioactive ray, can be according to usual method, for example, by reduced projection exposure device etc., the method of light such as the mask pattern irradiation ultraviolet radiation of adopt wishing, g line, i line, KrF excimer laser, ArF excimer laser, or by the draw method etc. of (drawing) of particle lines such as electron ray.When using light as active radioactive ray, both can be single wavelength light, also can be mixed wavelengths light.Illuminate condition is suitably selected according to the active radioactive ray that use, and for example, when using the light of wavelength 200～450nm, exposure is 10～1000mJ/cm normally ², preferred 50～500mJ/cm ²Scope, according to the decision of irradiation time and illumination.Like this behind the active radioactive ray of irradiation, according to hope, under the temperature about 60～130 ℃ with the resin molding heat treated about 1～2 minute.

Then, the sub-image pattern development with being formed on the resin molding makes it obviousization, in this manual, such operation is called " patterning ", the resin molding that is patterned is called " patterned resin film ".Developer solution can use the aqueous solution (buck solution) of alkali compounds usually.Alkali compounds can use for example alkali metal salt, amine, ammonium salt.Alkali compounds both can be mineral compound, also can be organic compound.As the object lesson of these compounds, can enumerate.Alkali metal salts such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate; Ammonia; Primary amine such as ethamine, n-propylamine; Secondary amine such as diethylamine, di-n-propylamine; Tertiary amine such as triethylamine, methyl-diethyl-amine; Quaternary ammonium salts such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium, choline; Hydramine such as dimethylethanolamine, triethanolamine; Pyrroles, piperidines, 1,8-diazonium two ring [5.4.0] 11 carbon-7-alkene, 1, cyclic amines such as 5-diazonium two rings [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N-Methyl pyrrolidone etc.These alkali compounds can be used alone or in combination of two or more kinds respectively.

The aqueous medium of alkalescence aqueous solution can use to comprise in water, methyl alcohol and the ethanol etc. at least a kind water-miscible organic solvent.Buck solution also can be the buck solution that has added appropriate amount surfactant etc.

As making the developer solution contact be formed with the method for the resin molding of sub-image pattern, for example, can use methods such as scraper plate method (パ De レ method), spray-on process, infusion process.Normally 0～100 ℃, preferred 5～55 ℃ of development conditions, more preferably 10～30 ℃ scope are suitably selected 30～180 seconds scope usually.

By above method, can on substrate, form the patterned resin film (a patterned resin film) of target.Then, according to hope, for remove on the substrate, the development residue of substrate back and substrate end, can be with washing fluids such as ultrapure water flushing substrate.Flushing can be removed residual washing fluid by pressurized air and compressed nitrogen after handling.In addition, according to desired, in order to make radiation-sensitive compound inactivation, also can be to the active radioactive ray of irradiation on the whole base plate with patterned resin film.In the irradiation of active radioactive ray, can utilize illustrative method in the formation of above-mentioned sub-image pattern.In irradiation or after the irradiation, can heat resin molding.As heating means, for example, can be set forth in the method for heated substrates in electric hot plate or the baking oven.Normally 100～300 ℃ of temperature, preferred 120～200 ℃ scope, the time is 1～120 minute scope normally.

In addition, obtain this film behind the patterned resin film one time, can obtain making the secondary pattern resin molding of the preceding pattern form distortion of this film heating by heating.By distortion, for example, the pattern form that makes cross sectional shape have corner angle is changed to the pattern of the mild shape that does not have angle.Particularly, for example, when on resin molding, forming the round dot pattern, this resin molding is supplied with melt flows, make pattern be deformed into the hemisphere shape from examples of dot shaped.Therefore, the present invention also comprises the method for following manufacturing laminated body, and this method also comprises heating and is formed on patterned resin film on the substrate, makes the operation of pattern form distortion.The manufacture method of such laminated body for example can be used in the manufacturing of micro lens etc.

When making the secondary pattern resin molding, pattern at a patterned resin film is heated fusion, when formation has the secondary pattern resin molding of pattern form of hope, balance is carried out the crosslinked of resin molding well, can form the cross-linked structure that the pattern form institute that keeps the secondary pattern resin molding must degree.Therefore, according to radiation sensitive resin composition of the present invention, can easily form the secondary pattern resin molding, on the other hand by melt flows, even the temperature more than the secondary pattern resin molding that obtains exposes to the open air when melt flows also can be brought into play the tolerance to the pattern form distortion.In addition, the temperature limit in the time of can enlarging melt flows can be made the secondary pattern resin molding efficiently.

In addition, the flowability of the resin molding the during melt flows of the resin molding of being made by radiation sensitive resin composition of the present invention (for example patterned resin film) can be estimated according to the MV minium viscosity that method of record in (4) of aftermentioned embodiment (evaluation of radiation sensitive resin composition) is measured.We can say that this viscosity is big more, the flowability of the resin molding during melt flows is more little.The MV minium viscosity of the resin molding during melt flows among the present invention normally 2.5 * 10 ⁴More than the Pas, compare resin molding of the present invention mobile little when melt flows with the resin molding of forming by known radiation sensitive resin composition.

On the other hand, during the melt flows of the resin molding of making by radiation sensitive resin composition of the present invention (for example patterned resin film) to the wetting state (moistening れ) of substrate surface, just, the heating and melting resin molding is to the wetting extendability (moistening れ Wide Ga り) of substrate surface, the critical surface tension evaluation that can measure according to method of record in (5) of aftermentioned embodiment (evaluation of radiation sensitive resin composition).

That is little capillary liquid can wetting expansion on solid surface, to have critical surface tension than solid (with the different liquid assay contact angle θ of surface tension, be equivalent to by complete wetting, be the surface tension of the liquid of cos θ=1 o'clock).Therefore, if the surface tension of the resin molding relatively when the critical surface tension of solid substrate and melt flows just can be estimated the wetting state of this resin molding to substrate.The critical surface tension of known substrate is about 10～40mN/m, and the surface tension of the resin molding when we can say melt flows is compared big more with the critical surface tension of substrate, and this resin molding is more little to the wetting state of substrate surface.In addition, so-called contact angle is meant that the contact portion of the drop that the liquid contact generates is with respect to the solid surface angulation on solid surface.

Because it is difficult directly measuring the surface tension of resin molding under the heating and melting state, so in the method for in above-mentioned (5), putting down in writing, further heat the resin molding that obtains by heating and melting, carry out fully crosslinked, the critical surface tension of the surface tension of the resin molding during with melt flows resin molding after crosslinked and obtaining approx as this.As the critical surface tension of the resin molding among the present invention, normally more than the 19mN/m, to compare with the resin molding of making by known radiation sensitive resin composition, the wetting state of the resin molding during melt flows among the present invention is little.

Like this, radiation sensitive resin composition of the present invention has following characteristic: the MV minium viscosity of the resin molding of being made by said composition when heating and melting is 2.5 * 10 ⁴More than the Pas, and behind the heating and melting, further the critical surface tension of the resin molding of heat cross-linking is more than the 19mN/m; Mobile and little during the melt flows of the resin molding of making by said composition to the wetting state of substrate surface.

But radiation sensitive resin composition of the present invention can be suitably uses as the eurymeric erosion resistant, but the manufacture method of the laminated body that forms according to form the patterned resin film on above-mentioned substrate, can obtain the corrosion-resisting pattern of excellent resolution.

Thus, can make laminated body of the present invention, particularly on substrate, form the patterned resin film and the laminated body that obtains, but in the present invention, after forming resin molding (comprising the patterned resin film) on the substrate, according to hope, also can carry out crosslinked again to this film.The present invention also comprises the method for following manufacturing laminated body, and this method is carried out the crosslinked operation of this film after also being included in and forming resin molding (comprising the patterned resin film) on the substrate.

Be formed on the crosslinked of resin molding on the substrate, for example, can select suitable method according to the crosslinking chemical kind of using, but be undertaken by heating usually.For example, heating means can use electric hot plate, baking oven etc. to carry out.Normally 180～250 ℃ of heating-up temperatures, suitably select according to the size of resin molding and the machine of thickness and use etc. heat time heating time, for example, and when using electric hot plate, normally 5～60 minutes, when using baking oven, 30～90 minutes scope normally.According to hope, heating also can be carried out under non-active gas atmosphere gas.As non-active gas, so long as oxygen-free and can not make the non-active gas of resin molding oxidation just passable for example, can be enumerated nitrogen, argon gas, helium, neon, xenon, krypton gas etc.Wherein preferred nitrogen and argon gas, special preferred nitrogen.The non-active gas that particularly oxygen level 0.1 volume % is following, preferred 0.01 volume % is following, special preferred nitrogen.These non-active gas can be used alone or in combination of two or more kinds respectively.

The above-mentioned laminated body of the present invention that obtains is suitable as for example electronic unit and opticses such as integrated circuit component, liquid crystal display cells, solid-state imager.These electronic units or optics can use radiation sensitive resin composition of the present invention or laminated body, according to the known method manufacturing.The optics and the electronic unit that comprise laminated body of the present invention comprise in the present invention.

Embodiment

Below enumerate synthesis example, embodiment, be described more specifically the present invention.In addition, when being not particularly limited, part and % in each example are weight basis.In addition, following test, evaluation are as follows.

(weight average molecular weight of polymkeric substance (Mw) and number mean molecular weight (Mn))

With tetrahydrofuran (THF) is eluant, the HLC-8020 that uses gel permeation chromatography (eastern Cao company (East ソ one society) to produce), obtain with the form of polyisoprene conversion molecular weight.

(hydrogenation ratio)

Hydrogenation ratio by ¹The H-NMR spectrogram is obtained in the mode of the ratio (percent %) of the carbon-to-carbon double bond molal quantity that the is hydrogenated carbon-to-carbon double bond molal quantity before with respect to hydrogenation (behind the hydrogenation/hydrogenation before).

(iodine number)

Measure according to JIS K 0070B.

(evaluation of radiation sensitive resin composition)

(1) formation of patterned resin film

Spin coating radiation sensitive resin composition on the silicon wafer substrate that has been coated with thermosetting resin film uses electric hot plate to descend dry 120 seconds at 100 ℃, and dried thickness film forming is 1.2 μ m.

By the pattern mask in 3.5 μ m round dots, 1.5 μ m spaces, in air this resin molding being shone the 600ms light intensity is 0.5W/cm ²The i line.Then, use 0.6～0.8% tetramethyl ammonium hydroxide solution, after carrying out 80～110 seconds development treatment under 23 ℃, carry out flushing in 30 seconds with ultrapure water and handle, form 3.5 μ m round dot patterning resin moldings of eurymeric.In addition, so-called W is equivalent to J/s.

(2) the heat-resisting shape retention of patterned resin film

With the cross sectional shape of electron microscope (SEM) observation patterned resin film,, measure wide a between the round dot pattern based on SEM picture (10000 times of multiplying powers).Then, in air whole patterned resin film being shone 30 seconds is 5mW/cm in 365nm place optical wavelength ²Ultraviolet ray, then use electric hot plate to the substrate that is formed with this pattern under the most suitable temperature between 140～170 ℃ to carry out the 1st heat treated (middle heating (ミ De Le ベィ Network) 1) in 10 minutes, make the resin molding fusion that is patterned, pattern is deformed into the hemisphere shape from examples of dot shaped.Re-use electric hot plate the substrate that has applied middle heating 1 is applied the 2nd heat treated (back heating (Port ストベィ Network) 1) under 230 ℃, 10 minutes.With above-mentioned same operation, with the pattern cross sectional shape after the SEM observation back heating 1, according to wide b between the SEM determining image round dot pattern.Between the round dot pattern between the round dot pattern after obtaining the patterned resin film and forming after wide a and the back heating 1 wide b poor (a-b), according to the heat-resisting shape retention of following metewand evaluation pattern generating resin molding.

(metewand)

Excellent: pattern is the hemisphere shape, (a-b) is below the 0.5 μ m

Well: pattern is the hemisphere shape, (a-b) greater than 0.5 μ m but below 1 μ m

Still can: pattern is the hemisphere shape, (a-b) greater than 1 μ m but below 1.5 μ m

Difference: the complete fusion of pattern, merge with adjacent patterns

Temperature limit during melt flows when (3) forming the patterned resin film

With above-mentioned same operation, with the cross sectional shape of SEM observation patterned resin film, according to wide a ' between the SEM determining image round dot pattern.Then, in air whole patterned resin film being shone 30 seconds is 5mW/cm in 365nm place optical wavelength ²Ultraviolet ray, then use electric hot plate under the temperature between 140～170 ℃, the substrate that forms this pattern to be carried out 10 minutes the 1st time heat treated (middle heating 2), make the resin molding fusion that is patterned, pattern is deformed into the hemisphere shape from examples of dot shaped.Re-use electric hot plate and under 230 ℃, 10 minutes, the substrate that has applied middle heating 2 is applied the 2nd heat treated (back heating 2).With above-mentioned same operation, observe the cross sectional shape that the pattern after 2 is heated in the back with SEM, according to the SEM image, measure wide b ' between the round dot pattern.Between the round dot pattern between the round dot pattern after obtaining the patterned resin film and forming after wide a ' and the back heating 2 wide b ' poor (a '-b '), the temperature limit during melt flows when forming the patterned resin film according to following metewand evaluation.

(metewand)

Excellent: pattern is that hemisphere shape, (a '-b ') are that the following middle heating-up temperature amplitude of 1 μ m is more than 20 ℃

Well: pattern is that hemisphere shape, (a '-b ') are that the following middle heating-up temperature amplitude of 1 μ m is more than 10 ℃ but less than 20 ℃

Still can: pattern is that hemisphere shape, (a '-b ') are that the following middle heating-up temperature amplitude of 1 μ m is more than 5 ℃ and less than 10 ℃

Difference: pattern is that hemisphere shape, (a '-b ') are that the following middle heating-up temperature amplitude of 1 μ m is less than 5 ℃.

In addition, what is called in above-mentioned metewand " middle heating-up temperature amplitude " is meant, temperature between 140～170 ℃ was carried out centre heating at 2 o'clock with per 5 ℃ interval design temperature, (a '-b ') minimum temperature and maximum temperature poor when value reaches the value of stipulating in each metewand.

(4) MV minium viscosity of the resin molding during melt flows

In eggplant type flask, add radiation sensitive resin composition, concentrate with evaporator.With vacuum drier at one night of radiation sensitive resin composition vacuum drying that makes under the room temperature (25 ℃) after concentrating.Be heated 2 minutes with 100 ℃ baking oven again.Add the powder that obtains in the tablet former of diameter 8mm, discoid tablet is made in pressurization.

8mm parallel-plate (パラレ Le プレ one ト) with Deformation control type determination of viscoelasticity device (Li Womite makes every effort to overcome the ARES that this company (レォメトリ Network ス society) produces) is clamped tablet, be warmed up to 280 ℃ with 10 ℃/minute speed from 80 ℃ with the heating furnace under the nitrogen, simultaneously by this device in the plain viscosity of the multiple plain viscosity (Complex of 10rad/s frequency measurement) Eta*[Pas].The minimum of obtaining the multiple plain viscosity that obtains is as MV minium viscosity.

(5) critical surface tension of the resin molding of further heat cross-linking after the melt flows

In above-mentioned (1) in this (evaluation of radiation sensitive resin composition), do not carry out the patterning operations of resin molding, above-mentioned (1) and (2) according in this (evaluation of radiation sensitive resin composition) form the not resin molding of patterning.In addition, by changing the blending ratio (volume reference) of water-ethanol solution, 5 kinds of different liquid of preparation surface tension adopt sessile drop method to measure the surface tension γ of this liquid _L[mN/m].Use this 5 kinds of liquid, with contact angle meter (CA-X150 that consonance interface science society produces) measure each liquid and resin molding contact angle θ [°].Surface tension γ from liquid _LThe surface tension (critical surface tension) of the resin molding the when relation of [mN/m] and cos θ is obtained θ=0 ° by first-order approximation.

Synthesis example 1

In the glass voltage-resistant reactor that nitrogen replacement is crossed, add 62.5 parts of 8-hydroxycarbonyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10] 12 carbon-3-alkene, 37.5 parts of N-(4-phenyl)-(5-norborene-2,3-dicarboxyl acid imide), 1.3 parts of 1-hexenes, 0.05 part of dichloro 1,3-methylimidazole quinoline-2-subunit (thricyclohexyl phosphorus) benzal closes ruthenium and 400 parts of tetrahydrofurans, make it while stirring to obtain polymer solution A (solid component concentration: about 20%) 70 ℃ of reactions 2 hours.

This polymer solution of part A immigration is equipped with in the autoclave of stirring machine, under 150 ℃, make the hydrogen dissolving with 4MPa pressure, reacted again 5 hours, and obtained containing the polymer solution B (solid component concentration: about 20%) of the polymkeric substance (hydrogenation ratio 100%) that is hydrogenated.

The heatproof container that has added 1 part of active carbon powder in 100 parts of polymer solution B is put into autoclave, under 150 ℃, make hydrogen dissolving 3 hours while stirring with 4MPa pressure.Then, take out solution, with the fluororesin filtering membrane filtration of aperture 0.2 μ m, isolating active carbon obtains polymer solution.Filtration can unhinderedly be carried out.Polymer solution is injected in the ethanol, makes it to solidify, the dry fragmental products (Network ラ system) that generates obtains cycloolefin polymer.The Mw that the polyisoprene of the polymkeric substance that obtains converts is 5500, and Mn is 3200 (the Mw/Mn ratio is 1.7).In addition, iodine number is 1.

Embodiment 1

Mix 100 parts of cycloolefin polymers that in synthesis example 1, obtain, 200 parts of propylene glycol monoethyl ether acetates as solvent, 100 parts of diglycol ethyl-methyl ethers, 100 parts of N-methyl isophthalic acid-pyrrolidone, 25 parts as 1 of quinone diazido compound, 1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1, the condensation product of 2-naphthoquinones diazido-5-sulfonic acid chloride (1.9 moles), 36 parts of the multi-functional epoxy compound of containing alicyclic structure (molecular weight 2234 as crosslinking chemical, trade name " EHPE3150 ", Daicel (ダィセ Le) chemical industrial company produces), 10 parts of γ-glycidoxypropyltrime,hoxysilane, [3-(3 for 6 parts of pentaerythrites four as antioxidant, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (trade name IRGANOX (ィ Le ガッ Network ス) 1010, Ciba Specialty Chemicals (チバスペシャリティ one ケミカ Le ズ) company produces), 0.05 part polysiloxane-based surfactant (trade name kp341 as surfactant, chemical industry society of SHIN-ETSU HANTOTAI produces), after making it dissolving, Mi Liboa filtrator (Millipore filter) with aperture 0.45 μ m filters, the preparation radiation sensitive resin composition.According to the method described above, the radiation sensitive resin composition that obtains is estimated.In addition, the temperature of middle heating 1 is 160 ℃.In result shown in the table 1.

Embodiment 2

Except the addition with the γ-glycidoxypropyltrime,hoxysilane among the embodiment 1 changes to 15 parts, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 160 ℃.In result shown in the table 1.

Embodiment 3

Except the addition with the γ-glycidoxypropyltrime,hoxysilane among the embodiment 1 changes to 20 parts, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 160 ℃.In result shown in the table 1.

In addition, MV minium viscosity is 1.3 * 10 ⁴Pas, critical surface tension are 19mN/m.

Embodiment 4

Except the addition with the γ-glycidoxypropyltrime,hoxysilane among the embodiment 1 changes to 30 parts, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 150 ℃.In result shown in the table 1.

Embodiment 5

Except the addition with the γ-glycidoxypropyltrime,hoxysilane among the embodiment 1 changes to 40 parts, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 150 ℃.In result shown in the table 1.

Embodiment 6

The addition of the γ-glycidoxypropyltrime,hoxysilane in embodiment 1 changes to 60 parts, similarly prepares radiation sensitive resin composition, estimates.In addition, the temperature of middle heating 1 is 150 ℃.In result shown in the table 1.

Embodiment 7

Except the γ-glycidoxypropyltrime,hoxysilane among the embodiment 4 being changed to beyond 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 150 ℃.In result shown in the table 1.

Embodiment 8

Except the γ-glycidoxypropyltrime,hoxysilane among the embodiment 4 being changed to 3-isocyanate group propyl-triethoxysilicane, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 150 ℃.In result shown in the table 1.

In addition, MV minium viscosity is 4.6 * 10 ⁴Pas, critical surface tension are 19mN/m.

Comparative example 1

Except the addition with the γ-glycidoxypropyltrime,hoxysilane among the embodiment 1 changes to 5 parts, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 160 ℃.In result shown in the table 1.

Comparative example 2

Except the addition with the γ-glycidoxypropyltrime,hoxysilane among the embodiment 1 changes to 80 parts, similarly prepare radiation sensitive resin composition, estimate.In addition, the temperature of middle heating 1 is 150 ℃.In result shown in the table 1.

Table 1

	Alkoxysilane compound containing trialkylsilyl group in molecular structure content ^*(part)			Heat-resisting shape retention	Temperature limit
						I	II	III
	Embodiment 1	10	-			I	II	III	-	Well	Still can
Embodiment 2	Embodiment 1	10	-	15	-	-	Well	Well	-	Well	Still can
Embodiment 2	Embodiment 3	20	-	15	-	-	Well	Well	-	Excellent	Well
Embodiment 4	Embodiment 3	20	-	30	-	-	Excellent	Excellent	-	Excellent	Well
Embodiment 4	Embodiment 5	40	-	30	-	-	Excellent	Excellent	-	Excellent	Excellent
Embodiment 6	Embodiment 5	40	-	60	-	-	Excellent	Excellent	-	Excellent	Excellent
Embodiment 6	Embodiment 7	-	30	60	-	-	Excellent	Excellent	-	Excellent	Excellent
Embodiment 8	Embodiment 7	-	30	-	-	30	Excellent	Excellent	-	Excellent	Excellent
Embodiment 8	Comparative example 1	5	-	-	-	30	Excellent	Excellent	-	Still can	Difference
Comparative example 2	Comparative example 1	5	-	80	-	-	Difference	Difference	-	Still can	Difference

^*: the amount of relative 100 parts of cycloolefin polymers

Alkoxysilane compound containing trialkylsilyl group in molecular structure I: γ-glycidoxypropyltrime,hoxysilane

Alkoxysilane compound containing trialkylsilyl group in molecular structure II:2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane

Alkoxysilane compound containing trialkylsilyl group in molecular structure III:3-isocyanate group propyl-triethoxysilicane

As shown in Table 1, use relative 100 parts of cycloolefin polymers contain 10～60 parts of scope alkoxysilane compound containing trialkylsilyl group in molecular structure embodiment 1～8 radiation sensitive resin composition and the heat-resisting shape keeping quality excellence of the patterned resin that obtains has wide temperature limit.Especially as can be known the alkoxysilane compound containing trialkylsilyl group in molecular structure amount can be brought into play significant effect greater than the radiation sensitive resin composition below 20 parts and 60 parts.With respect to this, the amount of using alkoxysilane compound containing trialkylsilyl group in molecular structure as can be known is less than 10 parts comparative example 1 or greater than the radiation sensitive resin composition of 60 parts comparative example 2 and the heat-resisting shape keeping quality of the patterned resin film that obtains is poor, and temperature limit is also narrow.

Industrial applicibility

Radiation sensitive resin composition of the present invention can obtain the resin molding of heat-resisting shape retention excellence, and the temperature limit the during melt flows when forming the patterned resin film is broad, therefore, adopt said composition, can realize for example stablizing and produce the product that carries out patterning and obtain or improve yield rate. In addition, adopt radiation sensitive resin composition of the present invention can obtain the corrosion-resisting pattern of resolution excellence. The present invention help to make the electronic unit such as integrated circuit component, liquid crystal display cells, solid-state imager or optics the manufacturing stabilisation, improve yield rate.

Claims

1. radiation sensitive resin composition, said composition comprises:

Cycloolefin polymer,

The radiation-sensitive compound and

2. according to the described radiation sensitive resin composition of claim 1, it also contains crosslinking chemical.

3. according to claim 1 or 2 described radiation sensitive resin compositions, wherein, cycloolefin polymer contains the protic polar group.

4. according to any 1 described radiation sensitive resin composition in the claim 1～3, wherein, alkoxysilane compound containing trialkylsilyl group in molecular structure contains the functional group with the reaction of protic polar group.

5. laminated body making method, this method comprises: use any 1 described radiation sensitive resin composition in the claim 1～4, form the operation of resin molding on substrate.

6. according to the described laminated body making method of claim 5, this method also comprises:

7. according to the described laminated body making method of claim 6, this method also comprises: heating is formed on the patterned resin film on the substrate, makes the operation of pattern form distortion.

8. according to any 1 described laminated body making method in the claim 5～7, this method also comprises the crosslinked operation of resin molding that will be formed on the substrate.

9. laminated body, its resin molding of being made by any 1 described radiation sensitive resin composition in the claim 1～4 at the substrate superimposed layer forms.

10. according to the described laminated body of claim 9, wherein, resin molding is the resin molding of patterning.

11. electronic unit or optics, it comprises claim 9 or 10 described laminated body.