CN102482240B - Novel compound, process for preparation thereof, radiation -sensitive compositions containing the novel compound, and cured films - Google Patents

Novel compound, process for preparation thereof, radiation -sensitive compositions containing the novel compound, and cured films Download PDF

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CN102482240B
CN102482240B CN201080038065.5A CN201080038065A CN102482240B CN 102482240 B CN102482240 B CN 102482240B CN 201080038065 A CN201080038065 A CN 201080038065A CN 102482240 B CN102482240 B CN 102482240B
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methyl
radiation sensitive
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CN102482240A (en
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岩泽晴生
一户大吾
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

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  • Materials For Photolithography (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

A compound has multiple groups represented by general formula (1') which are the same or different. In general formula (1'), R1 and R2 are each independently a C1-6 alkyl group, and n is an integer of 1 to 6.

Description

Compound and manufacture method thereof, the radiation sensitive composition and the cured film that contain this compound
Technical field
The present invention relates to a kind of new compound and the manufacture method thereof of Photoepolymerizationinitiater initiater, radiation sensitive composition and cured film that contains this new compound of can be used as.
Background technology
The cured film being formed by radiation sensitive composition, is widely used in liquid-crystal apparatus, semiconducter device, light solidified ink, photosensitive printing version etc.This radiation sensitive composition, for example, contain polymerizable compound, the Photoepolymerizationinitiater initiater etc. with ethene unsaturated link(age).Above-mentioned cured film can be upper by this radiation sensitive composition being coated on to glass substrate etc., forms film, then uses the exposure apparatus with mercuryvapour lamp expose and form.
Above-mentioned mercuryvapour lamp has the distinctive bright line spectrum of mercury in ultraviolet ray～visible wavelength region, in 254nm, 365nm, 405nm etc., has high-intensity bright line.For example, TOHKEMY 2001-233842 communique discloses the technology of the Photoepolymerizationinitiater initiater of the high ray susceptibility that effectively utilizes 365nm and 405nm bright line.The Photoepolymerizationinitiater initiater of this high ray susceptibility is mostly the compound in visible region with maximum absorption, and therefore in most cases, Photoepolymerizationinitiater initiater itself is with blush.By this cured film forming with erythroid Photoepolymerizationinitiater initiater present blush same with Photoepolymerizationinitiater initiater in the past, and the transparency declines, therefore must have in the cured film of high light transmittance in visible region for liquid crystal device etc., sometimes cannot be suitable for.
On the other hand, the disclosed acetophenones initiator of for example Japanese kokai publication sho 58-157805 communique, near 300nm, there is maximum absorption, and itself roughly presents white this Photoepolymerizationinitiater initiater, the cured film therefore being formed by this acetophenones initiator demonstrates high transparent in visible region.But the radiation-sensitive degree of this acetophenones initiator is low, in order to form the cured film with abundant surface hardness, need high exposure.In addition, the sublimability of this acetophenones initiator high (for example, referring to TOHKEMY 2007-86565 communique), it has the defect that causes baking furnace pollution and pollute photomask in the time exposing because of distillation.
In light of this situation, wish that a kind of sublimability of exploitation is low and demonstrate compound, the radiation sensitive composition that contains this compound of high ray susceptibility and there is high transparent and the cured film of surface hardness when as Photoepolymerizationinitiater initiater.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-233842 communique
Patent documentation 2: Japanese kokai publication sho 58-157805 communique
Patent documentation 3: TOHKEMY 2007-86565 communique
Patent documentation 4: the open 2003-225179 communique of the U.S.
Summary of the invention
The present invention is based on above-mentioned situation and complete, it is low and in compound and the manufacture method thereof when the Photoepolymerizationinitiater initiater with high ray susceptibility that its main purpose is to provide a kind of sublimability.And another object of the present invention is to provide a kind of in the time using this compound as Photoepolymerizationinitiater initiater, can form the radiation sensitive composition of the cured film with high transparent and surface hardness.
For address the above problem invention be a kind of compound, it has the represented multiple groups of identical or different following formula (1 '),
In formula (1 '), R 1and R 2the alkyl that is 1～6 for carbonatoms independently of one another.N is 1～6 integer.
Compound of the present invention, owing to thering is the represented group of plural above-mentioned formula (1 '), and there are two positions that produce above free radical, therefore when as Photoepolymerizationinitiater initiater, show high ray susceptibility, result just can obtain having pattern and the fully cured film of surface hardness accurately by less exposure.In addition, because this compound has low sublimability, therefore can effectively suppress because distillation is to equipment and the photomask produced pollution.And then, in the time using this compound as Photoepolymerizationinitiater initiater, can obtain having the cured film of high transparent.
As compound of the present invention, be preferably the represented compound of following formula (1),
In formula (1), R 1, R 2with n and above-mentioned formula (1 ') synonym.X be formula (2) (i)～(iv) any in represented divalent group.
Formula (2) (i) in, the integer that m is 1～6.Formula (2) (iii) in, R 3and R 4the alkoxyl group that is 1～6 for hydrogen atom, the carbonatoms alkyl that is 1～12 or carbonatoms independently of one another.
There is the represented ad hoc structure of above-mentioned formula (1) by this compound, when as Photoepolymerizationinitiater initiater, shown higher radiation-sensitive degree.In addition, this compound has lower sublimability.And then, while using this compound as Photoepolymerizationinitiater initiater, can obtain having the more cured film of high transparent.
Be used as the Photoepolymerizationinitiater initiater of above-claimed cpd as [A] composition, and then comprise the polymerizable compound with ethene unsaturated double-bond as [B] composition, form can form radiation sensitive composition thus.This radiation sensitive composition, owing to containing above-claimed cpd, therefore has high ray susceptibility, and demonstrates low sublimability.In addition,, by this radiation sensitive composition, can obtain having high surface hardness and transparent cured film.
This radiation sensitive composition, preferably and then contain alkali soluble resin as [C] composition.Said, contain alkali soluble resin by radiation sensitive composition, this alkali soluble resin demonstrates solubility for alkali used in developing procedure, therefore can show high developability, and forms the cured film with accurate pattern.
In addition, the manufacture method of the represented compound of above-mentioned formula (1), be included under alkali existence, at least one operation of reacting that makes the represented precursor compound of following formula (3) and select from following group, this group is made up of phosgene, triphosgene and the represented organic acid diacid chloride of following formula (4)
In formula (3), R 1, R 2with n and above-mentioned formula (1) synonym.In formula (4), R 5for formula (5) (i)～(iii) any in represented divalent group.Formula (5) (i) in, the integer that m is 1～6.Formula (5) (ii) in, R 3and R 4the alkoxyl group that is 1～6 for hydrogen atom, the carbonatoms alkyl that is 1～12 or carbonatoms independently of one another.
These methods are new manufacture method of the represented compound of above-mentioned formula (1).By this method, can be economical and effectively manufacture the represented compound of above-mentioned formula (1).
New compound of the present invention, when as Photoepolymerizationinitiater initiater, demonstrate high ray susceptibility, and then the radiation sensitive composition that contains this compound is by less exposure, just can obtain having the cured film of pattern, high surface hardness and high transparent accurately.In addition, because this compound has low sublimability, therefore can effectively suppress because distillation is to produced pollution such as equipment.
Embodiment
The compound > that < is new
Compound of the present invention is the compound with the represented multiple groups of identical or different above-mentioned formula (1 ').In above-mentioned formula (1 '), R 1and R 2represent that independently of one another carbonatoms is 1～6 alkyl.N is 1～6 integer.The alkyl that is 1～6 as carbonatoms, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc.
As the represented compound of above-mentioned formula (1 '), for example, can enumerate the represented compound in following formula (6)～(12) etc.
As compound of the present invention, be preferably the represented compound of above-mentioned formula (1).In above-mentioned formula (1), R 1, R 2with n and above-mentioned formula (1 ') synonym.X be formula (2) (i)～(iv) any in represented divalent group.
In addition, in above-mentioned formula (2), R 3and R 4the alkoxyl group that is 1～6 for hydrogen atom, the carbonatoms alkyl that is 1～12 or carbonatoms independently of one another.The alkyl that is 1～12 as carbonatoms, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl etc.The alkoxyl group that is 1～6 as carbonatoms, for example, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, butoxy, pentyloxy etc.
As the represented compound of above-mentioned formula (1), for example, can enumerate following formula (13)～(21) represented compound.
This compound has demonstrated the high ray susceptibility as Photoepolymerizationinitiater initiater, and does not need more exposure, just can obtain having the cured film of high surface hardness.In addition,, because this compound has low sublimability, therefore can effectively prevent from baking furnace and photomask etc. to produce and pollute.Can think that this low sublimability results from the molecular structure of compound.And then, because the transparency of this compound itself is good, therefore can obtain having the cured film of high transparent.
For the manufacture method of the represented compound of above-mentioned formula (1), be not particularly limited, for example be included under alkali existence, make the represented precursor compound of above-mentioned formula (3), with at least one operation of reacting of selecting from following group, this group is made up of phosgene, triphosgene and the represented organic acid diacid chloride of above-mentioned formula (4).That is to say, first disclose according to the U.S. method that 2003-225179 communique (patent documentation 4) is recorded, precursor compound (for example, the R that synthesis type (3) is represented 1and R 2for methyl, the precursor compound that n is 2,1-[4-(2-hydroxyl ethylmercapto group)-phenyl]-2-methyl-2-morpholinyl-propane-1-ketone).Then, under alkali exists, drip wherein phosgene, triphosgene or organic acid diacid chloride (the represented compound of formula (4)), and for example, under specified temperature (,-50 DEG C above below 100 DEG C, and preferred-20 DEG C above 50 DEG C following), the reaction specified time (for example, 30 points below above 300 points), then separation and purification, can obtain the compound of wishing.As the preference of alkali that can be used for this reaction, can enumerate pyridine, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, tri-isopropyl amine, Tri-n-Propylamine, tri-n-butylamine, N, N-dimethylcyclohexylamine, picoline, lutidine, trimethylpyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, N-methyl piperidine, N-crassitude, 1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, 5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N, N-dimethyl aminopyridine, N, N-dimethyl-9-acridine amine, sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood etc., and in these alkali, particularly preferably pyridine and triethylamine.In addition, as the preference of solvent that can be used for this reaction, can enumerate N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1, 3-dimethyl-2-imidazolidone, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF), diox, diethyl ether, dipropyl ether, dibutyl ether, phenyl ether, methylene dichloride, 1, 2-ethylene dichloride, chloroform, tetracol phenixin, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane etc., and in these solvents, particularly preferably methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), tetracol phenixin is with diox.In the represented compound in above-mentioned formula (13)～(21) of specifically enumerating, by using phosgene or triphosgene, can obtain the compound of formula (15) and (16), by using organic acid diacid chloride, can obtain the compound of formula (13), (14) and (17)～(21).In addition, for the represented compound of above-mentioned formula (1 '), also can manufacture according to the method described above.
< radiation sensitive composition >
Radiation sensitive composition of the present invention, contains [A] and has as the above-claimed cpd of Photoepolymerizationinitiater initiater and [B] polymerizable compound of ethene unsaturated double-bond.In addition, this radiation sensitive composition can contain [C] alkali soluble resin as suitable optional member.And then, only otherwise can damage effect of the present invention, can also contain other Photoepolymerizationinitiater initiater, [E] multi-functional epoxy compound, [F] bonding agent, [G] tensio-active agent as [D] of other optional member.Below, each composition is described in detail.In addition, can, as the compound of [A] Photoepolymerizationinitiater initiater, describe hereinbefore, therefore description thereof is omitted here it.
<[B] there is the polymerizable compound > of ethene unsaturated double-bond
As the preference of the operable polymerizable compound with ethene unsaturated double-bond in this radiation sensitive composition, can enumerate simple function (methyl) acrylate, 2 officials can (methyl) acrylate or 3 officials can be above (methyl) acrylate.By use these compounds in this radiation sensitive composition, can height of formation balance the cured film of the transparency and surface hardness.
As simple function (methyl) acrylate, for example, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) ethoxy ethoxyethylacrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid 3-methoxyl group butyl ester, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester etc.As the commodity example of these simple functions (methyl) acrylate, can enumerate ア ロ ニ Star Network ス M-101, ア ロ ニ Star Network ス M-111, ア ロ ニ Star Network ス M-114 (East Asia synthetic (strain) system), KAYARAD TC-110S, KAYARADTC-120S (Japanese chemical drug (strain) system), PVC ス コ mono-ト 158, PVC ス コ mono-ト 2311 (Osaka organic chemistry industry (strain) system) etc.
As 2 officials' energy (methyl) acrylate, for example can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, 9,9-bis-[(4-hydroxy ethoxy) phenyl] fluorenes two (methyl) acrylate etc.As the commodity of these 2 officials energy (methyl) acrylate, for example, can enumerate ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-6200 (East Asia synthetic (strain) system), KAYARADHDDA, KAYARAD HX-220, KAYARAD R-604 (Japanese chemical drug (strain) system), PVC ス コ mono-ト 260, PVC ス コ mono-ト 312, PVC ス コ mono-ト 335HP (Osaka organic chemistry industry (strain) system) etc.
(methyl) acrylate that can be above as 3 officials, for example can enumerate trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, three ((methyl) acryloxy ethyl) phosphoric acid ester, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, succinic acid list-[3-(3-(methyl) acryloxy-2, 2-pair-(methyl) acryloyl-oxy ylmethyl-propoxy-)-2, 2-pair-(methyl) acryloyl-oxy ylmethyl-propyl group] ester, succinic acid modification tetramethylolmethane three (methyl) acrylate etc.The commodity of (methyl) acrylate that can be above as these 3 officials, for example can enumerate ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-7100, ア ロ ニ Star Network ス M-8030, ア ロ ニ Star Network ス M-8060, ア ロ ニ Star Network ス TO-756 (East Asia synthetic (strain) system), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (Japanese chemical drug (strain) system), PVC ス コ mono-ト 295, PVC ス コ mono-ト 300, PVC ス コ mono-ト 360, PVC ス コ mono-ト GPT, PVC ス コ mono-ト 3PA, PVC ス コ mono-ト 400 (Osaka organic chemistry industry (strain) system) etc.
Have in the polymerizable compound of ethene unsaturated double-bond at these, consider from the solidified nature viewpoint of radiation sensitive composition, preferably use (methyl) acrylate that 3 officials can be above.Wherein, particularly preferably trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, succinic acid list-[3-(3-(methyl) acryloxy-2,2-is two-(methyl) acryloyl-oxy ylmethyl-propoxy-) and-2,2-is two-(methyl) acryloyl-oxy ylmethyl-propyl group] ester, succinic acid modification tetramethylolmethane three (methyl) acrylate.These have the polymerizable compound of ethene unsaturated double-bond, can use separately, or be use mixing two or more.
In this radiation sensitive composition, [B] has the addition of the polymerizable compound of ethene unsaturated link(age), and be not particularly limited, but with respect to [A] Photoepolymerizationinitiater initiater 1 mass parts, be preferably 3～50 mass parts, and 5～30 mass parts more preferably.Be 3～50 mass parts by making the usage quantity of this polymerizable compound, can form the radiation sensitive composition of the transparency height balance of radiation-sensitive degree and gained cured film.
<[C] alkali soluble resin >
As [C] alkali soluble resin containing in this radiation sensitive composition, as long as thering is solubility with respect to alkaline developer used in the development treatment operation of the radiation sensitive composition that contains this composition, be just not particularly limited.As this alkali soluble resin, be preferably the alkali soluble resin with carboxyl, and it is (following to be particularly preferably at least a kind of selecting the group from being made up of (a1) unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, be called " compound (a1) ") and (a2) (a1) unsaturated compound is in addition (following, be called " compound (a2) ") multipolymer (following, be called multipolymer [α]).
As the concrete example of compound (a1), can enumerate:
The monocarboxylic acids such as vinylformic acid, methacrylic acid, butenoic acid, succinic acid 2-acryloxy ethyl ester, succinic acid 2-methacryloxy ethyl ester, hexahydrophthalic acid 2-acryloxy ethyl ester, hexahydrophthalic acid 2-methacryloxy ethyl ester;
The dicarboxylic acid such as toxilic acid, fumaric acid, citraconic acid;
The acid anhydrides of above-mentioned dicarboxylic acid etc.
In these compounds (a1), from copolyreaction, gained multipolymer, the deliquescent viewpoint of alkaline developer is considered preferably vinylformic acid, methacrylic acid, succinic acid 2-acryloxy ethyl ester, succinic acid 2-methacryloxy ethyl ester, maleic anhydride.
In multipolymer [α], compound (a1) can use separately, or is use mixing two or more.In multipolymer [α], come from the containing ratio of the repeating unit of compound (a1), be preferably 5～60 quality %, and then be preferably 7～50 quality %, and be particularly preferably 8～40 quality %.Be 5～60 quality % by making the containing ratio of the repeating unit that comes from compound (a1), can obtain the radiation sensitive composition of the various characteristicses such as radiation-sensitive degree and developability with higher degree balance.
As the concrete example of compound (a2), can enumerate:
The alkyl acrylates such as methyl acrylate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate;
The alkyl methacrylates such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate;
Cyclohexyl acrylate, vinylformic acid 2-methyl cyclohexyl, vinylformic acid three encircle [5.2.1.0 2,6] last of the ten Heavenly stems-8-ester, vinylformic acid 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base oxygen base) the CALCIUM ACRYLATE ring type ester such as ethyl ester, isobornyl acrylate;
Cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexyl, methacrylic acid three encircle [5.2.1.0 2,6] last of the ten Heavenly stems-8-ester, methacrylic acid 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base oxygen base) the methacrylic acid ester ring type ester such as ethyl ester, isobornyl methacrylate;
Acrylic acid aryl ester such as phenyl acrylate, benzyl acrylate or aralkyl ester;
The hydroxyalkyl acrylate class of the methacrylic acids such as 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester;
The aryl ester of the methacrylic acid such as phenyl methacrylate, benzyl methacrylate or aralkyl ester;
The unsaturated dicarboxylic acid such as ethyl maleate, DEF dialkyl;
Vinylformic acid tetrahydrofuran (THF)-2-ester, vinylformic acid tetrahydropyrans-2-ester, vinylformic acid 2-methyl tetrahydropyrans-2-ester etc. have containing 5 yuan of heterocycles of oxygen or containing the acrylate of 6 yuan of heterocycles of oxygen;
Methacrylic acid tetrahydrofuran (THF)-2-ester, methacrylic acid tetrahydropyrans-2-ester, methacrylic acid 2-methyl tetrahydropyrans-2-ester etc. have containing 5 yuan of heterocycles of oxygen or containing the methacrylic ester of 6 yuan of heterocycles of oxygen;
Vinylbenzene, alpha-methyl styrene, to vinyl aromatic compounds such as methoxy styrenes;
1,3-butadiene, isoprene equiconjugate dienes compound;
In addition, can also enumerate vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide etc.
In these compounds (a2), to consider from the viewpoint of copolyreaction, preferable methyl n-butyl acrylate, benzyl methacrylate, methacrylic acid three encircle [5.2.1.0 2,6] last of the ten Heavenly stems-8-ester, vinylbenzene, to methoxy styrene, methacrylic acid tetrahydrofuran (THF)-2-ester, 1,3-butadiene, 2-hydroxyethyl methacrylate etc.
In multipolymer [α], compound (a2) can use separately, or is use mixing two or more.In multipolymer [α], come from the containing ratio of the repeating unit of compound (a2), be preferably 10～70 quality %, and then be preferably 20～50 quality %, and be particularly preferably 30～50 quality %.The containing ratio of the repeating unit by making compound (a2) is 10～70 quality %, can control easily the molecular weight of multipolymer, and can obtain the radiation sensitive composition with higher degree balance such as developability, radiation-sensitive degree.
For multipolymer [α], can be by suitable solvent, under the existence of radical polymerization initiator, the monomer of polymerization constituent and manufacturing.As operable solvent in this polymerization, be preferably Diethylene Glycol alkyl oxide, propylene-glycol monoalky lether acetic ester, alkoxypropan acid alkyl ester, acetic ester etc.These solvents can use separately, or are use mixing two or more.
In addition, as above-mentioned radical polymerization initiator, be not particularly limited, for example can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two-(2,4-methyl pentane nitrile), 2,2 '-azo two-(4-methoxyl group-2,4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2, the azo-compounds such as 2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile).These radical polymerization initiators can use separately, or are use mixing two or more.
Multipolymer [α] by the polystyrene conversion weight-average molecular weight (Mw) of gel permeation chromatography (GPC) gained, is preferably 2000～100000, and more preferably 5000～50000.Be 2000～100000 by making the Mw of multipolymer [α], can obtain the radiation sensitive composition with higher degree balance such as developability, radiation-sensitive degree, and the cured film of high heat resistance.
The usage quantity of [C] alkali soluble resin in this radiation sensitive composition, with respect to [A] Photoepolymerizationinitiater initiater 1 mass parts, is preferably 5～60 mass parts, and 8～40 mass parts more preferably.Be 5～60 mass parts by making the usage quantity of alkali soluble resin, can form the radiation sensitive composition that developability is good.
<[D] other Photoepolymerizationinitiater initiater >
In this radiation sensitive composition, except [A] composition, can also add other the Photoepolymerizationinitiater initiater as [D] composition.As radiation sensitive polymerization starter, thereby as long as ray is produced and responds to the composition that generates the spike that can cause the polymerizable compound polymerization with ethene unsaturated double-bond, be just not particularly limited.As this other the example of radiation sensitive polymerization starter, can enumerate O-acyl group oxime compound, acetophenone compound, united imidazole etc.
As the concrete example of above-mentioned O-acyl group oxime compound, can enumerate ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-1-octanone oxime-O-acetic ester, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-ethyl ketone oxime-O-benzoic ether, 1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-yl]-1-ethyl ketone oxime-O-benzoic ether, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxolanyl) anisoyl }-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) etc.
Wherein, as preferred O-acyl group oxime compound; can enumerate ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-DOX base) anisoyl }-9H-carbazole-3-yl]-1-(O-acetyl oxime).These O-acyl group oxime compounds can use separately, or are use mixing two or more.
As above-mentioned acetophenone compound, for example, can enumerate alpha-amino group ketone compound, alpha-hydroxyacetone compounds (still, except [A] Photoepolymerizationinitiater initiater).
As the concrete example of alpha-amino group ketone compound, can enumerate 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-1-butanone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone etc.
As the concrete example of alpha-hydroxyacetone compounds, can enumerate 1-phenyl-2-hydroxy-2-methyl-1-acetone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl-1-acetone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone etc.
In these acetophenone compounds, preferably alpha-amino group ketone compound, and particularly preferably 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholinyl-4-base-phenyl)-1-butanone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone.These acetophenone compounds can use separately, or are use mixing two or more.
As the concrete example of above-mentioned united imidazole, can enumerate 2,2 '-bis-(2-chloro-phenyl-s)-4,4 ', 5,5 '-tetra-(4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In these united imidazoles, preferably 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, and 2,2 '-bis-(2,4 dichloro benzene bases)-4 particularly preferably, 4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.These united imidazoles can use separately, or are use mixing two or more.
In radiation sensitive composition of the present invention, while being used as united imidazole as [D] radiation sensitive polymerization starter, for by its sensitizing, can add aliphatics or the aromatics (following, to be called " amino sensitizer ") with dialkyl amido.
As this amino sensitizer, for example, can enumerate 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone etc.In these amino sensitizers, particularly preferably 4,4 '-bis-(diethylamino) benzophenone.Above-mentioned amino sensitizer can use separately, or is use mixing two or more.
And then, in this radiation sensitive composition, by united imidazole and amino sensitizer used time, can add the mercaptan compound that agent is provided as hydroperoxyl radical.Although united imidazole, can make its sensitizing, division by amino sensitizer, and produce imidazole radical, in the time directly using, sometimes cannot show high polymerization initiating power.But, by the system that united imidazole and amino sensitizer coexist, add mercaptan compound, can provide hydroperoxyl radical to imidazole radical by mercaptan compound.Therefore, when imidazole radical changes neutral imidazoles into, produce the composition of the Thiyl Radical with high polymerization initiating power, can form thus the cured film that surface hardness is high.
As the concrete example of this mercaptan compound, can enumerate:
The aromatic mercaptans compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxybenzothiazole;
The aliphatics list mercaptan compounds such as 3-thiohydracrylic acid, 3-mercapto-propionate;
2 officials such as tetramethylolmethane four (mercaptoacetate), tetramethylolmethane four (3-mercaptopropionic acid ester) can be above analiphatic sulphur alkylol cpd.In these mercaptan compounds, particularly preferably 2-mercaptobenzothiazole.
By united imidazole and amino sensitizer used time, the addition of amino sensitizer, with respect to united imidazole 100 mass parts, is preferably 0.1～50 mass parts, and 1～20 mass parts more preferably.Be 0.1～50 mass parts by making the addition of amino sensitizer, can improve the solidification reactivity of radiation sensitive composition in the time of exposure, and can improve the surface hardness of gained cured film.
In addition, by united imidazole, amino sensitizer and mercaptan compound used time, as the addition of mercaptan compound, with respect to united imidazole 100 mass parts, be preferably 0.1～50 mass parts, and 1～20 mass parts more preferably.Be 0.1～50 mass parts by making the addition of mercaptan compound, can improve the surface hardness of gained cured film.
[D] radiation sensitive polymerization starter, preferably contains from being formed at least a kind that selects group by O-acyl group oxime compound and acetophenone compound.In addition, [D] radiation sensitive polymerization starter, also can contain by O-acyl group oxime compound and acetophenone compound and be formed at least a kind that in group, selects, and united imidazole.
The usage quantity of [D] radiation sensitive polymerization starter in this radiation sensitive composition, with respect to [A] Photoepolymerizationinitiater initiater 1 mass parts, is preferably 0.05～10 mass parts, and 0.1～5 mass parts more preferably.Be 0.05～10 mass parts by making [D] other usage quantity of Photoepolymerizationinitiater initiater, this radiation sensitive composition, even in the time of low exposure, also can form the cured film that demonstrates high ray susceptibility and have abundant surface hardness.
<[E] multi-functional epoxy compound >
In order to improve polymerisation reactivity, and improve the surface hardness of the cured film that formed by radiation sensitive composition, can in radiation sensitive composition, add [E] multi-functional epoxy compound.As multi-functional epoxy compound, can use the cationically polymerizable compound in 1 molecule with more than two epoxy group(ing).
As the concrete example of this cationically polymerizable compound in 1 molecule with more than two epoxy group(ing), can enumerate the poly epihydric alcohol ethers of the bis-phenols such as bisphenol A diglycidyl ether, Bisphenol F diglycidylether, bisphenol-S diglycidyl ether, Hydrogenated Bisphenol A diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, Hydrogenated Bisphenol A D diglycidylether; 1,4-butanediol diglycidyl ether, 1, the poly epihydric alcohol ethers of the polyvalent alcohols such as 6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether; Make the aliphatic poly Racemic glycidol ethers of the polyether glycol of the aliphatic polyols such as ethylene glycol, propylene glycol, glycerol and a kind or two or more oxyalkylene addition gained; In 1 molecule, have plural 3, the compound of 4-epoxy group(ing) cyclohexyl; The phenol novolak type epoxy resin such as bisphenol-A phenolic varnish type epoxy resin; Cresols phenolic resin varnish type epoxy resin; Poly-phenol-type epoxy resin; Cyclic aliphatic epoxy resin; The 2-glycidyl ester class of aliphatic long-chain diprotic acid; The glycidyl ester class of higher fatty acid; Epoxidised soybean oil, epoxidation linseed oil wet goods.In these 1 molecules, have in the cationically polymerizable compound of more than two epoxy group(ing), preferably phenol novolak type epoxy resin and poly-phenol-type epoxy resin.
As have plural 3 in 1 molecule, the concrete example of the compound of 4-epoxy group(ing) cyclohexyl, can enumerate 3, 4-epoxy group(ing) cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylicesters, 2-(3, 4-epoxy group(ing) cyclohexyl-5, 5-spiral shell-3, 4-epoxy group(ing)) hexanaphthene-Jian dioxs, two (3, 4-epoxy group(ing) cyclohexyl methyl) adipic acid ester, two (3, 4-epoxy group(ing)-6-methyl cyclohexane ylmethyl) adipic acid ester, 3, 4-epoxy group(ing)-6-methylcyclohexyl-3 ', 4 '-epoxy group(ing)-6 '-methylcyclohexanecarboxylic acid ester, methylene radical two (3, 4-epoxy-cyclohexane), Dicyclopentadiene (DCPD) diepoxide, two (3 of ethylene glycol, 4-epoxy group(ing) cyclohexyl methyl) ether, ethylene (3, 4-epoxy-cyclohexane carboxylicesters), interior ester modified 3, 4-epoxy group(ing) cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylicesters etc.
As the commercially available product in 1 molecule with more than two compound of epoxy group(ing), for example, as bisphenol A type epoxy resin, can enumerate エ ピ コ mono-ト 1001, エ ピ コ mono-ト 1002, エ ピ コ mono-ト 1003, エ ピ コ mono-ト 1004, エ ピ コ mono-ト 1007, エ ピ コ mono-ト 1009, エ ピ コ mono-ト 1010, エ ピ コ mono-ト 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system), as bisphenol f type epoxy resin, can enumerate エ ピ コ mono-ト 807 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system), as phenol novolak type epoxy resin (bisphenol-A phenolic varnish type epoxy resin etc.), can enumerate エ ピ コ mono-ト 152, エ ピ コ mono-ト 154, エ ピ コ mono-ト 157S65 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system), EPPN201, EPPN202 (Japanese chemical drug (strain) system), as cresols phenolic resin varnish type epoxy resin, can enumerate EOCN102, EOCN103S, EOCN104S, EOCN1020, EOCN1025, EOCN1027 (Japanese chemical drug (strain) system), エ ピ コ mono-ト 180S75 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system), as poly-phenol-type epoxy resin, can enumerate エ ピ コ mono-ト 1032H60, エ ピ コ mono-ト XY-4000 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system), as cyclic aliphatic epoxy resin, can enumerate CY-175, CY-177, CY-179, ア ラ Le ダ イ ト CY-182, ア ラ Le ダ イ ト CY-192, ア ラ Le ダ イ ト CY-184 (チ バ ス ペ シ ヤ Le テ イ mono-ケ ミ カ Le ズ (strain) system), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (U.C.C company system), シ ヨ mono-ダ イ Application 509 (clear and electrician's (strain) system), エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (large Japanese イ Application キ (strain) system), エ ピ コ mono-ト 871, エ ピ コ mono-ト 872 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system), ED-5661, ED-5662 (セ ラ ニ mono-ズ コ mono-テ イ Application グ society system), as aliphatic poly glycidyl ether, can enumerate エ Port ラ イ ト 100MF (common prosperity society chemistry (strain) system), エ ピ オ mono-Le TMP (Japanese grease (strain) system).
[E] multi-functional epoxy compound, can use separately or be use mixing two or more.[E] multi-functional epoxy compound's usage quantity in this radiation sensitive composition, with respect to [A] Photoepolymerizationinitiater initiater 1 mass parts, is preferably 0.05～10 mass parts, and 0.1～5 mass parts more preferably.Be 0.05～10 mass parts by making [E] multi-functional epoxy compound's usage quantity, can improve polymerisation reactivity, and the surface hardness of the cured film of formation be remained on to higher level simultaneously.
<[F] bonding agent >
In order further to improve the cured film of gained and the binding property of substrate, can use [F] bonding agent.As this bonding agent, be preferably there is carboxyl, methacryloyl, vinyl, isocyanate group, Oxyranyle isoreactivity functional group's functional silanes coupling agent.As the concrete example of bonding agent, can enumerate γ-methacryloxypropyl trimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane etc.These bonding agents, can use separately or be use mixing two or more.
The usage quantity of [F] bonding agent in this radiation sensitive composition, with respect to [A] Photoepolymerizationinitiater initiater 1 mass parts, is preferably 0.005～5 mass parts, and 0.01～3 mass parts more preferably.Be 0.005～5 mass parts by making the usage quantity of bonding agent, can improve the binding property of cured film to substrate, and pattern formation ability can be remained on to higher level.
<[G] tensio-active agent >
For so improve the film formative of radiation sensitive composition, can use [G] tensio-active agent.As this tensio-active agent, for example, can enumerate fluorine class tensio-active agent, polysiloxane-based tensio-active agent and other tensio-active agent.
As fluorine class tensio-active agent, be preferably endways, have at least arbitrary position of main chain and side chain the compound of fluoro-alkyl and/or fluoro alkylidene group.As the example of fluorine class tensio-active agent, can enumerate 1, 1, 2, 2-tetrafluoro n-octyl (1, 1, 2, 2-tetrafluoro n-propyl) ether, 1, 1, 2, 2-tetrafluoro n-octyl n-hexyl ether, six ethylene glycol (1, 1, 2, 2, 3, 3-hexafluoro n-pentyl) ether, eight ethylene glycol bisthioglycolates (1, 1, 2, 2-tetrafluoro normal-butyl) ether, six propylene glycol two (1, 1, 2, 2, 3, 3-hexafluoro n-pentyl) ether, eight propylene glycol two (1, 1, 2, 2-tetrafluoro normal-butyl) ether, perfluor n-dodecane sodium sulfonate, 1, 1, 2, 2, 3, 3-hexafluoro n-decane, 1, 1, 2, 2, 3, 3, 9, 9, 10, 10-ten fluorine n-dodecanes, fluoro-alkyl benzene sulfonic acid sodium salt, fluoro-alkyl sodium phosphate, fluoro-alkyl carboxylic acid sodium, two glycerol four (fluoro-alkyl Soxylat A 25-7), iodate fluoro-alkyl ammonium, fluoro-alkyl trimethyl-glycine, other fluoro-alkyl Soxylat A 25-7, perfluoroalkyl poly(ethylene oxide)polymers, perfluoroalkyl alcoxylates, carboxylic acid fluoroalkyl etc.
As the commercially available product of fluorine class tensio-active agent, for example, can enumerate BM-1000, BM-1100 (being that BM CHEMIE company manufactures above), メ ガ Off ア Star Network F142D, メ ガ Off ア Star Network F172, メ ガ Off ア Star Network F173, メ ガ Off ア Star Network F183, メ ガ Off ア Star Network F178, メ ガ Off ア Star Network F191, メ ガ Off ア Star Network F471, メ ガ Off ア Star Network F476 (being large Japanese イ Application キ chemical industry (strain) manufacture above), Off ロ ラ mono-De FC-170C, Off ロ ラ mono-De FC-171, Off ロ ラ mono-De FC-430, Off ロ ラ mono-De FC-431 (being that ス リ mono-エ system (strain) in Sumitomo is manufactured above), サ mono-Off ロ Application S-112, サ mono-Off ロ Application S-113, サ mono-Off ロ Application S-131, サ mono-Off ロ Application S-141, サ mono-Off ロ Application S-145, サ mono-Off ロ Application S-382, サ mono-Off ロ Application SC-101, サ mono-Off ロ Application SC-102, サ mono-Off ロ Application SC-103, サ mono-Off ロ Application SC-104, サ mono-Off ロ Application SC-105, サ mono-Off ロ Application SC-106 (being Asahi Glass (strain) manufacture above), エ Off ト Star プ EF301, エ Off ト Star プ EF303, エ Off ト Star プ EF352 (manufacturing for new autumn fields changes into (strain) above), Off タ mono-ジ エ Application ト FT-100, Off タ mono-ジ エ Application ト FT-110, Off タ mono-ジ エ Application ト FT-140A, Off タ mono-ジ エ Application ト FT-150, Off タ mono-ジ エ Application ト FT-250, Off タ mono-ジ エ Application ト FT-251, Off タ mono-ジ エ Application ト FT-300, Off タ mono-ジ エ Application ト FT-310, Off タ mono-ジ エ Application ト FT-400S, Off タ mono-ジ エ Application ト FTX-218, Off タ mono-ジ エ Application ト FTX-251 (being that (strain) ネ オ ス manufactures above) etc.
As the concrete example of polysiloxane-based tensio-active agent, with commercially available trade(brand)name, for example can enumerate ト mono-レ シ リ コ mono-Application DC3PA, ト mono-レ シ リ コ mono-Application DC7PA, ト mono-レ シ リ コ mono-Application SH11PA, ト mono-レ シ リ コ mono-Application SH21PA, ト mono-レ シ リ コ mono-Application SH28PA, ト mono-レ シ リ コ mono-Application SH29PA, ト mono-レ シ リ コ mono-Application SH30PA, ト mono-レ シ リ コ mono-Application SH-190, ト mono-レ シ リ コ mono-Application SH-193, ト mono-レ シ リ コ mono-Application SZ-6032, ト mono-レ シ リ コ mono-Application SF-8428, ト mono-レ シ リ コ mono-Application DC-57, ト mono-レ シ リ コ mono-Application DC-190 (being that (East レ ダ ウ コ mono-ニ Application グ シ リ コ mono-Application (strain) is manufactured above), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (being GE Toshiba シ リ コ mono-Application (strain) manufacture above), organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture) etc.
These [G] tensio-active agents, can use separately or be use mixing two or more.The usage quantity of [G] tensio-active agent in this radiation sensitive composition, with respect to [A] Photoepolymerizationinitiater initiater 1 mass parts, is preferably 0.001～1 mass parts, and 0.005～0.5 mass parts more preferably.Be 0.001～1 mass parts by making the usage quantity of tensio-active agent, can be reduced in coating while forming film on substrate irregular.
The modulation > of < radiation sensitive composition
Radiation sensitive composition of the present invention, can be by above-mentioned [A] Photoepolymerizationinitiater initiater and [B] being had to the polymerizable compound of ethene unsaturated double-bond, and other composition of above-mentioned optional interpolation evenly mixes and modulates.This radiation sensitive composition, preferably uses with the solution state being dissolved in appropriate solvent.For example, can be by [A] Photoepolymerizationinitiater initiater and [B] being there is to the polymerizable compound of ethene unsaturated double-bond, and optional other composition adding, mix in solvent with regulation ratio, modulate thus the radiation sensitive composition as solution state.
As can be for modulating the solvent of this radiation sensitive composition, can use can uniform dissolution [A] Photoepolymerizationinitiater initiater and [B] there is the polymerizable compound of ethene unsaturated double-bond, and each composition such as other optional member, the material that can not react with each composition simultaneously.As this solvent, the same material of solvent phase that can enumerate and exemplify as the solvent that can be used in manufacture [C] alkali soluble resin.
In this solvent, from the solvability of each composition, with each composition non-reacted, be coated with the viewpoints such as film formed easiness and consider, for example particularly preferably use diethylene glycol monoethyl ether acetic ester, diethylene glycol diethyl ether, Diethylene Glycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetic ester, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic ester, 3-methoxyl group butylacetic acid ester, adnoral acetate, benzyl alcohol, 3-methoxybutanol.These solvents, can only use separately a kind and also can be use mixing two or more.
Using this radiation sensitive composition when solution state is modulated, solid component concentration (the composition in composition solution beyond solvent, above-mentioned [A] Photoepolymerizationinitiater initiater and [B] have the ratio of the polymerizable compound of ethene unsaturated double-bond and the total amount of other optional member), can be set as concentration (for example 5～50 quality %) arbitrarily according to application target and desirable film thickness value etc.The radiation sensitive composition solution of so modulating can be, after the millipore filter etc. of 0.2～0.5 μ m left and right filters, to provide use using aperture.
The formation method > of < cured film
Below, the method that uses radiation sensitive composition of the present invention to form cured film is described.The cured film formation method that uses this radiation sensitive composition, is characterized in that, at least comprises following operation (1)～(4) according to following order.Operation (3) can be carried out in the time must forming pattern.
That is to say, the formation method of cured film, comprises:
(1) on substrate, form the operation of radiation sensitive composition film of the present invention;
(2) operation of at least a portion useful to irradiation of rays to this film;
(3) by the operation of the painting film development after radiation exposure; And
(4) add the operation of the film after thermal development.
Below, successively described each operation is described.
(1) on substrate, form the operation of the film of radiation sensitive composition of the present invention
Can in the one side of transparency carrier, form nesa coating, and on this nesa coating, form the film of radiation sensitive composition.As operable transparency carrier herein, for example, can enumerate glass substrate, resin substrate etc.As the concrete example of these transparency carriers, can enumerate the glass substrate such as soda-lime glass, non-alkali glass; The resin substrate being formed by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide.
As the nesa coating that can be arranged in transparency carrier one side, can enumerate by stannic oxide (SnO 2) form NESA film (registered trademark of PPG company of the U.S.), by tin indium oxide (In 2o 3-SnO 2) the ITO film that forms etc.
In the time forming film by coating method, can be by being coated with on nesa coating after the solution of radiation sensitive composition, preferably heating (prebake) coated face and form film.The solid component concentration of composition solution used in coating method, is preferably 5～50 quality %, more preferably 10～40 quality %, and then be preferably 15～35 quality %.As the coating process of composition solution, be not particularly limited, for example, can adopt the proper methods such as spray method, rolling method, method of spin coating (spin-coating method), slit die coating method, excellent painting method, ink-jet application method.In these coating processes, particularly preferably spin-coating method or slit die coating method.
The condition of above-mentioned prebake, according to kind, the mixing ratio etc. of each composition and different, carries out about 1～15 minute but be preferably at 70～120 DEG C.Film thickness after curing, is preferably 0.5～10 μ m, and more preferably about 1.0～7.0 μ m.
(2) operation of at least a portion useful to irradiation of rays to film
Then, to forming at least a portion useful to irradiation of rays of film.At this moment, in the time that only the part to film is irradiated, for example, the method that can adopt the photomask by thering is predetermined pattern to irradiate.
As irradiating the ray using, can enumerate visible ray, ultraviolet ray, far ultraviolet rays yue etc.Wherein, optimal wavelength is the ray of 250～550nm scope.
Radiation exposure (exposure), is to use luxmeter (OAI model356, Optical Associates Inc. system) to measure irradiated ray in the value of the intensity gained of wavelength 365nm, and it is preferably 100～5000J/m 2, and 200～3000J/m more preferably 2.
(3) by the operation of the painting film development after radiation exposure
Then, by the film after radiation exposure is developed, remove unwanted part, form the pattern of regulation.
As the developing solution using in developing, for example, can use the aqueous solution of the alkali such as quaternary ammonium salt (basic cpd) such as the mineral alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.In these alkali aqueous solutions, the water-miscible organic solvent such as methyl alcohol, ethanol and/or the tensio-active agent that can also add appropriate amount use.Alkali concn in alkali aqueous solution, considers from the viewpoint that obtains suitable developability, more than can being preferably 0.1 quality %, below 5 quality %.As developing method, can for contain liquid method (revolve and cover immersion method), pickling process, shower method etc. any, development time is preferably and carries out at normal temperatures about 10 second～180 seconds.
(4) add the operation of the film after thermal development
After above-mentioned development treatment, can be preferably carry out the flowing water washing in 30～90 seconds to forming the film of pattern, and then carry out air-dry with pressurized air or compressed nitrogen.Then, use the suitable heating units such as hot plate, baking oven, to the pattern-like film of gained in specified temperature for example at 100～250 DEG C, heating (the curing afterwards) specified time, it on hot plate, is for example 5～30 minutes, in baking oven, be 30～180 minutes, can obtain having the cured film of high surface hardness.
This cured film being formed by radiation sensitive composition of the present invention, from embodiment described later, it has high surface hardness and the excellent transparency.
Embodiment
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not limited to these embodiment.
<[A] the synthetic > of Photoepolymerizationinitiater initiater
[embodiment 1]
Thermometer, dropping funnel are installed in the there-necked flask of 1L, and under nitrogen atmosphere, by 110g 1-[4-(2-hydroxyl ethylmercapto group)-phenyl]-2-methyl-2-morpholinyl-propyl-1-ketone (referring to patent documentation 4 (U.S. discloses 2003-225179 communique)) and 60g pyridine be dissolved in 360g methylene dichloride, and in ice-water bath, be iced to below 5 DEG C.Then,, by dropping funnel, the solution that 33.2g Adipoyl Chloride is dissolved in to gained in 100g methylene dichloride dripped through 2 hours.After dropping finishes, stir 2 hours.After reaction finishes, add 500mL water, the salt generating is dissolved in water layer, then use separating funnel to extract organic layer.To this organic layer washed twice, then use twice of 200mL distilled water wash with 200mL 10 quality %HCl water.In the organic layer of separatory, add anhydrous sodium sulphate, remove moisture, more separating anhydrous sodium sulfate, then with the concentrated organic layer of vaporizer.In the coarse crystallization of gained, add 400g diisopropyl ether, after a rising temperature for dissolving, be cooled to 10 DEG C, carry out recrystallization.After the crystallization that filtration is separated out is also dried, obtain the white solid of 98.5g.Then, reuse 400g diisopropyl ether and carry out recrystallization, and it is filtered and is dried, obtain the white powder compound (A-1) of 85～g.
This compound is carried out 1h-NMR measures, FT-IR measures and UV measures, and confirms to have obtained target compound.Analytical results is as described below.
1h-NMR measures (solvent: CDCl 3) chemical shift σ: 8.50ppm (aromatic nucleus hydrogen, 4H), 7.32ppm (aromatic nucleus hydrogen, 4H), 4.35ppm (ester group-O-CH 2, 4H), 3.68ppm (morpholine ring hydrogen-O-CH 2, 8H), 3.27ppm (S-CH 2, 4H), 2.56ppm (morpholine ring hydrogen-N-CH 2, 8H), 2.21ppm (methylene radical-CO-CH 2, 2H), 1.50ppm (methylene radical-CH 2-CH 2, 4H), 1.31ppm (dimethyl, 12H)
IR measures (KBr) 3005cm -1, 2973cm -1, 2935cm -1, 2850cm -1, 2821cm -1, 1754cm -1, 1666cm -1, 1585cm -1
UV measures (solvent: methylene dichloride) maximum absorption wavelength: 295nm
[embodiment 2]
Thermometer, dropping funnel are installed in the there-necked flask of 1L, and under nitrogen atmosphere, by 110g 1-[4-(2-hydroxyl ethylmercapto group)-phenyl]-2-methyl-2-morpholinyl-propyl-1-ketone (referring to patent documentation 4 (U.S. open 2003-225179 communique)) and 60g pyridine be dissolved in 360g methylene dichloride, and in ice-water bath, be iced to below 5 DEG C.Then,, by dropping funnel, the solution that 53.8g triphosgene is dissolved in to gained in 100g methylene dichloride dripped through 2 hours.After dropping finishes, stir 2 hours.After reaction finishes, add 500mL water, the salt generating is dissolved in water layer, then use separating funnel to extract organic layer.To this organic layer washed twice, then use twice of 200mL distilled water wash with 200mL 10 quality %HCl water.In the organic layer of separatory, add anhydrous sodium sulphate, remove moisture, more separating anhydrous sodium sulfate, then with the concentrated organic layer of vaporizer.In the coarse crystallization of gained, add 400g diisopropyl ether, after a rising temperature for dissolving, be cooled to 10 DEG C, carry out recrystallization.The crystallization that filtration is separated out obtains 100.4g yellow solid after being also dried.Then, reuse 400g diisopropyl ether and carry out recrystallization, and it is filtered and is dried, obtain the yellow powder compound (A-2) of 90.2g.
This compound is carried out 1h-NMR measures, FT-IR measures and UV measures, and confirms to have obtained target compound.Analytical results is as described below.
1h-NMR (solvent: CDCl 3) chemical shift σ: 8.50ppm (aromatic nucleus hydrogen, 4H), 7.32ppm (aromatic nucleus hydrogen, 4H), 4.35ppm (ester group-O-CH 2, 4H), 3.68ppm (morpholine ring hydrogen-O-CH 2, 8H), 3.27ppm (S-CH 2, 4H), 2.56ppm (morpholine ring hydrogen-N-CH 2, 8H), 1.31ppm (dimethyl, 12H)
IR measures (KBr) 2973cm -1, 2935cm -1, 2850cm -1, 2821cm -1, 1754cm -1, 1666cm -1, 1585cm -1
UV measures (solvent: methylene dichloride) maximum absorption wavelength: 299nm
[embodiment 3]
Thermometer, dropping funnel are installed in the there-necked flask of 1L, and under nitrogen atmosphere, by 110g 1-[4-(2-hydroxyl ethylmercapto group)-phenyl]-2-methyl-2-morpholinyl-propyl-1-ketone (referring to patent documentation 4 (U.S. open 2003-225179 communique)) and 60g pyridine be dissolved in 360g methylene dichloride, and in ice-water bath, be iced to below 5 DEG C.Then, by dropping funnel, 42.3g 4-methoxyl group phthalyl chloride is dissolved in 100g methylene dichloride, the solution of gained was dripped through 2 hours.After dropping finishes, stir 2 hours.After reaction finishes, add 500mL water, the salt generating is dissolved in water layer, then use separating funnel to extract organic layer.To this organic layer washed twice, then use twice of 200mL distilled water wash with 200mL 10 quality %HCl water.In the organic layer of separatory, add anhydrous sodium sulphate, remove moisture, more separating anhydrous sodium sulfate, then with the concentrated organic layer of vaporizer.In the coarse crystallization of gained, add 400g diisopropyl ether, after a rising temperature for dissolving, be cooled to 10 DEG C, carry out recrystallization.The crystallization that filtration is separated out obtains 98.4g yellow solid after being also dried.Then, reuse 400g diisopropyl ether and carry out recrystallization, and it is filtered and is dried, obtain the yellow powder compound (A-3) of 88.2g.
This compound is carried out 1h-NMR measures, FT-IR measures and UV measures, and confirms to have obtained target compound.Analytical results is as described below.
1h-NMR (solvent: CDCl 3) chemical shift σ: 8.50ppm (aromatic nucleus hydrogen, 4H), 7.62ppm (aromatic nucleus hydrogen, 1H), 7.45ppm (aromatic nucleus hydrogen, 1H), 7.37ppm (aromatic nucleus hydrogen, 1H), 7.32ppm (aromatic nucleus hydrogen, 4H), 4.35ppm (ester group-O-CH 2, 4H), 3.74ppm (aromatic nucleus-O-CH 3, 3H), 3.68ppm (morpholine ring hydrogen-O-CH 2, 8H), 3.27ppm (S-CH 2, 4H), 2.56ppm (morpholine ring hydrogen-N-CH 2, 8H), 1.31ppm (dimethyl, 12H)
IR measures (KBr) 2973cm -1, 2935cm -1, 2850cm -1, 2821cm -1, 1754cm -1, 1666cm -1, 1585cm -1
UV measures (solvent: methylene dichloride) maximum absorption wavelength: 305nm
[embodiment 4]
Thermometer, dropping funnel are installed in the there-necked flask of 1L, and under nitrogen atmosphere, by 110g 1-[4-(2-hydroxyl ethylmercapto group)-phenyl]-2-methyl-2-morpholinyl-propyl-1-ketone (referring to patent documentation 4 (U.S. open 2003-225179 communique)) and 60g pyridine be dissolved in 360g methylene dichloride, and in ice-water bath, be iced to below 5 DEG C.Then, 37.9g Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid diacid chloride is dissolved in 100g methylene dichloride, the solution of gained was dripped with dropping funnel through 2 hours.After dropping finishes, stir 2 hours.After reaction finishes, add 500mL water, the salt generating is dissolved in water layer, then use separating funnel to extract organic layer.To this organic layer washed twice, then use twice of 200mL distilled water wash with 200mL 10 quality %HCl water.In the organic layer of separatory, add anhydrous sodium sulphate, remove moisture, more separating anhydrous sodium sulfate, then with the concentrated organic layer of vaporizer.In the coarse crystallization of gained, add 400g diisopropyl ether, after a rising temperature for dissolving, be cooled to 10 DEG C, carry out recrystallization.The crystallization that filtration is separated out obtains 88.3g white solid after being also dried.Then, reuse 400g diisopropyl ether and carry out recrystallization, and it is filtered and is dried, obtain the white powder compound (A-4) of 82.3g.
This compound is carried out 1h-NMR measures, FT-IR measures and UV measures, and confirms to have obtained target compound.Analytical results is as described below.
1h-NMR (solvent: CDCl 3) chemical shift σ: 8.50ppm (aromatic nucleus hydrogen, 4H), 7.32ppm (aromatic nucleus hydrogen, 4H), 4.35ppm (ester group-O-CH 2, 4H), 3.68ppm (morpholine ring hydrogen-O-CH 2, 8H), 3.27ppm (S-CH 2, 4H), 2.72ppm (hexanaphthene-CH 2, 8H), 2.56ppm (morpholine ring hydrogen-N-CH 2, 8H), 1.31ppm (dimethyl, 12H)
IR measures (KBr) 3005cm -1, 2973cm -1, 2935cm -1, 2850cm -1, 2821cm -1, 1754cm -1, 1666cm -1, 1585cm -1
UV measures (solvent: methylene dichloride) maximum absorption wavelength: 295nm
<[C] the synthetic > of alkali soluble resin
[synthesis example 1]
In the flask with prolong and agitator, add 5 mass parts 2,2 '-Diisopropyl azodicarboxylate and 250 mass parts propylene glycol methyl ether acetates, then add 18 mass parts methacrylic acids, 25 mass parts methacrylic acids three to encircle [5.2.1.0 2,6] last of the ten Heavenly stems-8-ester, 5 mass parts vinylbenzene, 30 mass parts 2-hydroxyethyl methacrylates and 22 mass parts benzyl methacrylates, and carry out nitrogen replacement.Then, slowly stir on one side, make solution temperature rise to 70 DEG C on one side, and at this temperature, keep within 5 hours, carrying out polymerization, obtain thus solid component concentration and be 28.8% multipolymer (C-1) solution.Use with lower device and condition, the multipolymer (C-1) to gained is measured Mw, and result is 13000.
Device: GPC-101 (clear and electrician's (strain) system)
Post: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are used in combination
Mobile phase: tetrahydrofuran (THF)
The modulation > of < radiation sensitive composition
[embodiment 5]
Mix the solution as the compound (A-1) of [A] composition that contains that is equivalent to 1 mass parts (solids component) amount, 15 mass parts have the dipentaerythritol acrylate (" KAYARADDPHA " of Japanese chemical drug (strain) system) of the polymerizable compound of ethene unsaturated double-bond as [B], 0.01 mass parts is the fluorine class tensio-active agent (" FTX-218 " of (strain) ネ オ ス system) as [G] tensio-active agent as the γ-glycidoxypropyltrimewasxysilane of [F] bonding agent and 0.01 mass parts, and they are dissolved in Diethylene Glycol ethyl-methyl ether, after making solid component concentration be 30 quality %, it is the film filter filtration of 0.2 μ m with aperture, the solution of modulation radiation sensitive composition.
[embodiment 6～14, comparative example 1～6]
Except as [A]～[G] composition, use outside the kind and amount described in table 1, and embodiment 5 similarly modulates the solution of X-ray sensitive resin composition.
In table 1, the abbreviation of [B], [D], [E], [F] and [G] composition, is expressed as follows respectively compound.
B-1: dipentaerythritol acrylate (" the KAYARAD DPHA " of Japanese chemical drug (strain) system)
B-2: succinic acid modification pentaerythritol triacrylate (" the ア ロ ニ Star Network ス TO-756 " of East Asia synthetic (strain) system)
D-1: ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (" the イ Le ガ キ ユ ア OXE02 " of チ バ ス ペ シ ヤ Le テ イ mono-ケ ミ カ Le ズ company system)
D-2:2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl) butane-1-ketone (" the イ Le ガ キ ユ ア 379 " of チ バ ス ペ シ ヤ Le テ イ mono-ケ ミ カ Le ズ company system)
D-3:2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl propane-1-ketone (trade(brand)name " イ Le ガ キ ユ ア 907 ", チ バ ス ペ シ ヤ Le テ イ mono-ケ ミ カ Le ズ company system)
E-1: phenol novolak type epoxy resin (" エ ピ コ mono-ト 152 " of ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system)
E-2: bisphenol-A phenolic varnish type epoxy resin (" the エ ピ コ mono-ト 157S65 " of ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system)
F-1: γ-glycidoxypropyltrimewasxysilane
G-1: fluorine class tensio-active agent (" FTX-218 " of (strain) ネ オ ス system)
The evaluating characteristics > of < radiation sensitive composition and cured film
Radiation sensitive composition to above-mentioned modulation as described below and the cured film implementation evaluation being formed by them.Evaluation result is shown in table 1.
[evaluation of the radiation-sensitive degree of (1) radiation sensitive composition]
Use spin coater respectively by the solution coat of radiation sensitive composition on alkali-free glass substrate, then prebake 3 minutes on the hot plate of 80 DEG C, form radiation sensitive composition film (thickness be 4.0 μ m).On the film of gained, use the photomask with multiple residual circular patterns for diameter 15 μ m to expose.At this moment, between film coated surface and photomask, be provided with the gap (exposing clearance) of regulation.Then, use high pressure mercury vapour lamp and by above-mentioned photomask, change exposure on one side, on one side film is exposed.Then, working concentration is the potassium hydroxide aqueous solution of 0.05 quality %, and develops with the development time in 20 seconds at 25 DEG C by shower method, then carries out the pure water washing of 1 minute, then cures 20 minutes after at 230 DEG C in baking oven, forms circular pattern.The height of this circular pattern after curing after using laser microscope (キ mono-エ Application ス VK-8500 processed) to measure.By by the following formula of this value substitution, obtain residual film ratio (%).
Residual film ratio (%)=(pattern height/initial stage thickness 4.0 μ m) × 100 after curing afterwards
Be that more than 90% minimum exposure amount is shown in table 1 as the radiation-sensitive degree of radiation sensitive composition using this residual film ratio.When exposure is 1000J/m 2when following, can think that radiation-sensitive degree is good.
[evaluation of (2) cured film transparency]
Except not using photomask, making exposure is 1500J/m 2in addition, and above-mentioned " evaluation of the radiation-sensitive degree of (1) radiation sensitive composition " similarly in the upper cured film that forms of glass substrate (" NA35 (NH テ Network ノ グ ラ ス (strain) society system) ").Use spectrophotometer " 150-20 type twin-beam ((strain) Hitachi system) "; and taking the glass substrate without protective membrane as with reference to side, under the wavelength of 400～800nm scope, measure the light penetration of the glass substrate with this cured film.At this moment minimum light penetration value is shown in to table 1 as the evaluation of the cured film transparency.When this value is 95% when above, can think that the transparency of cured film is good.
[mensuration of the pencil hardness (surface hardness) of (3) cured film]
For with above-mentioned " evaluation of (2) cured film transparency " the same substrate with cured film forming, by the 8.4.1 pencil scraping experiment of JIS K-5400-1990, the pencil hardness (surface hardness) of measuring cured film, the results are shown in table 1.When this value is 3H or when larger, can think that the surface hardness of cured film is good.
[evaluation of sublimate volatile quantity when (4) cured film forms]
Use spinner respectively by the solution coat of radiation sensitive composition on silicon substrate, form coating film thickness be the film of 6.0 μ m.For this film, use gas chromatographic head space analysis/mass analysis (sampler on liquid level: Japanese analytical industry (strain) system, model name " JHS-100A "; Gas-chromatography/quality analysis apparatus: NEC industry (strain) system, " JEOL JMS-AX505W type mass analyzer ") analyze.Cleaning condition is 100 DEG C/10min, obtains and comes from the peak area A that the volatile component of Photoepolymerizationinitiater initiater produces.Use octane (proportion: 0.701; Injection rate: 0.02 μ L) as reference material, and taking its peak area as benchmark, convert and obtain the sublimate volatile quantity that comes from Photoepolymerizationinitiater initiater by octane by following formula, the results are shown in table 1.
Sublimate volatile quantity (μ g)=A × (amount (μ g))/(peak area of octane) of octane
Below this sublimate volatile quantity is 1.5 μ g time, the sublimate in cured film is few, can think that the sublimability of Photoepolymerizationinitiater initiater is enough low.
Result is as shown in Table 1 known, use in the embodiment 5～14 of radiation sensitive composition of the Photoepolymerizationinitiater initiater of compound new in the present invention, the transparency and the surface hardness of its radiation-sensitive degree of excellent balance, gained cured film, simultaneously, compare with comparative example 1～6, its sublimate volatile quantity also reduces very significantly.
Industrial applicibility
New compound in the present invention, when as Photoepolymerizationinitiater initiater, demonstrate high ray susceptibility, have low sublimability simultaneously, and can form the cured film with high transparent and sufficient surface hardness, therefore its composition as radiation sensitive composition is extremely useful.

Claims (5)

1. a compound, it has the represented multiple groups of identical or different following formula (1 '),
In formula (1 '), R 1and R 2the alkyl that is 1～6 for carbonatoms independently of one another, the integer that n is 1～6,
Described compound is represented by following formula (1),
In formula (1), R 1, R 2with n and above-mentioned formula (1 ') synonym, X be formula (2) (i)～(iv) any in represented divalent group,
Formula (2) (i) in, the integer that m is 1～6, formula (2) (iii) in, R 3and R 4the alkoxyl group that is 1～6 for hydrogen atom, the carbonatoms alkyl that is 1～12 or carbonatoms independently of one another.
2. a radiation sensitive composition, it contains [A] as the compound described in the claim 1 of Photoepolymerizationinitiater initiater, and [B] has the polymerizable compound of ethene unsaturated double-bond.
3. radiation sensitive composition as described in claim 2, it further contains [C] alkali soluble resin.
4. a cured film, is formed by the radiation sensitive composition described in claim 2 or 3.
5. the manufacture method of compound as described in claim 1, it is included under alkali existence, at least one operation of reacting that makes the represented precursor compound of following formula (3) and select from following group, this group is made up of phosgene, triphosgene and the represented organic acid diacid chloride of following formula (4)
In formula (3), R 1, R 2with n and above-mentioned formula (1) synonym, in formula (4), R 5for formula (5) (i)～(iii) any in represented divalent group, formula (5) (i) in, the integer that m is 1～6, formula (5) (ii) in, R 3and R 4the alkoxyl group that is 1～6 for hydrogen atom, the carbonatoms alkyl that is 1～12 or carbonatoms independently of one another.
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