TW201239531A - Radiation-sensitive composition, cured film and forming method thereof - Google Patents

Abstract

This invention provides a radiation-sensitive composition that is for forming a cured film, wherein properties of a protective film or interlayer insulating layer can be maintained in good balance and high level, and can be developed even in an inorganic alkali developing agent. The radiation-sensitive composition of this invention includes the following components [A1], [B] and [C]: [A1] a polysiloxane obtained by hydrolysis-condensating tetraethoxysilane or partial hydrolyte thereof, hydrolytic silane compound represented by the following formula (1) or partial hydrolyte thereof and hydrolytic silane compound represented by the following formula (2) or partial hydrolyte thereof; [B] a compound having two or more ethylene unsaturating groups (excluding component [A1]); [C] a photo radical polymerization initiator.

Description

201239531 ^1/1/pif VI. Description of the Invention: [Technical Field] The present invention relates to a radiation-sensitive composition suitable for forming a protective film or an interlayer insulating film of a display element, and the sense A cured film formed by a radioactive composition and a method of forming the same. [Prior Art] In a display element such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, or an organic electroluminescence (EL), a display element for preventing a touch panel (t〇uch panel) is provided. A cured film such as a protective film that deteriorates or damages an electronic component, or an interlayer insulating film that maintains an insulating property between wirings arranged in a layer. In order to form such a cured film, a (four)-distributing (four) composition, a coating film on which a radiation-sensitive composition is formed on a substrate, is irradiated with radiation through a mask having a pre-language ( Hereinafter, it is called "exposure"), __ shadow liquid is carried out (4) - unnecessary portions are dissolved and removed, and _ is post bake, thereby forming a cured film. " The cured film used as the protective film of the touch panel has high adhesion to the wiring of the touch panel element, excellent scratch resistance of the film itself, and no discoloration under high temperature conditions, and is transparent. Heat-resistant transparency), such as cracking (cracking property), radiation-sensitivity«, and formation of j-pattern (developability) under high-temperature conditions. On the other hand, in the cured film used as the interlayer insulating film, the contact hole for wiring is less 、, and the 旳 pattern, in addition to the required characteristics of the 201239531 4171/pif protective film described above. In addition, it is further required to form a pattern image (high resolution) or the like with high resolution with high resolution. In the past, the composition of the radiation-sensitive composition was mainly made of an acrylic resin, but in recent years, the 1st stone-rolled material which is more excellent in heat resistance and transparency than the acrylic resin has been attracting attention (Patent Document 1 to Patent) Document 3). However, the adhesion between the polyoxyalkylene-based material and the indium tin oxide (ITO) substrate is insufficient, and cracking is likely to occur, so that it is a protective film and is not practical. In addition, the material for forming an interlayer insulating film of a liquid crystal display element is being developed in the form of a negative-type radiation-sensitive composition which is advantageous in terms of cost (Patent Document 4). However, such a negative-type radiation-radiating composition is difficult to form and has practical use. A hole-controlled contact hole of the level (l_=vel) that can be used. Therefore, in order to form the interlayer insulating film of the display element, a positive-type radiation-radiating composition is widely used (Patent Document 5). In addition, the following radiation-sensitive composition has been proposed, which is a conjugated compound containing a saturated saturated acid and/or an unsaturated slow acid anhydride with other unsaturated compounds, a polyunsaturated compound and a photopolymerization initiator. The composition ^, in the form of an additive, contains a very small amount of oxiranyl oximnyl), an oxygen-transferred ((tetra)tanyl) or a secret (tetra) oxygen-burning oligomerization, and the money shouting radiation can be suitably The spacer (sp·) for forming (Patent Document 6), however, the display 70 and the B spacer are different from the use of the protective film or the interlayer insulating film, and therefore it is difficult to sufficiently satisfy all the required characteristics for the shaft or the layer. [Prior Art Document] 5 201239531 η / 1 / pif [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 2 No. Hei. [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2, No. [Patent Document 6] Japanese Patent Laid-Open Publication No. Hei. No. 2-233518 discloses that the required characteristics of the protective film and the interlayer insulating film are as described above, and in some cases, 'however, the actual situation is to use a variety of feelings according to the purpose or the step. Radiation linear composition. If a sensible composition can be used to form a cured film such as a protective film or an interlayer insulating film, and the 转印ίί film can be set to a negative type, the cost is swayed. A negative-type radiation linear composition that can be combined with both of the interlayer insulating films. In addition, the 'developing solution' is usually made of Tetramethyl Ammonium Hydroxide (ΤΜΑΗ), and it is expected to develop a radioactive linear composition that can be developed by the method of improving the temperature. Things. SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a cured film having a radiation-induced linear composition and having a desired balance with a protective film or a good balance.筮β ., ', shirt. Further, another object of the present invention is to provide the above-mentioned protective film and interlayer insulating film at a high level and with a good balance.

S 6 201239531 41717pif A cured film of the required characteristics and a method of forming the same. The tetraethoxy cerium or its partial hydrolyzate is obtained by the following formula (1) to obtain a dazzling compound or a partial hydrolyzed mirror thereof: a dimorphic electric ΙΠ Γ ,, the first invention provides a component under the 4 sense radiation H [ Al], component _ component [C]: (2) The above-mentioned L is a tetrahydrocarb, or a partial hydrolyzate thereof, a hydrolyzable sulphur compound or a partial hydrolyzate thereof of the following formula (1), and the following formula Indigo fiber sulphate-based (in which [c] photoradical polymerization initiator. [Chem. 1] (Rl〇fcs+(CH VII R2]m (1) [Chemical 2]

[In the formula (1), R1 represents a carbon number of 3, a aryl group having a carbon number of 6 to 14 or (intermolecular η of the methyl group 1 of 1 to 3, η represents 〇~". In the case of 12), R3 201239531 41717pif An alkyl group having a carbon number of 1 to 6, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3. Second, the present invention provides a radiation sensitive composition comprising the following The component [A2], the component [B], and the component [C]: [A2] a polyfluorene having a SiO 2 unit, a structural unit represented by the following formula (la), and a structural unit represented by the following formula (2a) [B] a compound having two or more ethylenically unsaturated groups (excluding the component [A2]); [C] a photoradical polymerization initiator. Η匕3] RHCH2)^; Si-〇 ( 4-m)/2 (la) [化4]

[In the formula (la), R2 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or an (indenyl) acryloxy group, wherein m represents an integer of 1 to 3, and η represents 0 to 6; Integer. In the formula (2a), R4 represents a hydrogen atom or a carbon group having 1 to 6 carbon atoms, X represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3] 201239531 41717pif Third, the present invention provides a cured film formed. ϊ ϊ , , , 明 提供 提供 提供 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 提供 种 提供 提供 种 提供 提供 提供 种 提供 提供 提供 提供 提供 种 提供 提供 提供 提供 提供 提供 提供 提供a step of at least partially irradiating the radiation; (3) a step of developing the radiation-coated coating film in the step (2) with an alkali developing solution; and () a step of heating the developed coating film in the v (3) . [Effects of the Invention] According to the present invention, it is possible to provide an effective formation at a high level and with good heat resistance, heat resistance, hardness, scratch resistance, heat cracking, engorgage, sensitivity and The feeling of the cured film of various properties such as developability = linear composition H The neon hybrid of the present invention has sufficient resolution. Therefore, fine contact holes can be formed, and development can be performed by using an inorganic developer. Therefore, the cured film formed using the radiation sensitive composition of the present invention is extremely useful as a protective film for a touch panel of a display element and an interlayer insulating film of a display element. [Embodiment] Radiation-sensitive composition The radiation-sensitive composition of the present invention contains the component [A1] or the component 201239531 41717pif [A2], the component [B], and the following description, and the components are detailed. Description, [A]. The knives [A] and the components [A2] are collectively described as the component [A] component [A1] is simply referred to as "TEOS", 虱I decane or a partial hydrolyzate thereof (hereinafter, or a partial hydrolyzate thereof) The hydrolyzable decane compound represented by the following formula is also referred to as "compound (1)"), and the following is also referred to as "compound 1 alkyl compound or a partial hydrolyzate thereof (hereinafter referred to as This component [A1 ^ 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚'The developability can be improved, and it is called "partial ΓΧ Γ Γ 、 、 、 、 、 、 、 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The number of atoms is from 2 to 100 and is from 2 to 30 or so of a nonoxyl oligomer. (R 5 ) (Rl〇feSi-HCH2tR2l (1) J m [Chem. 6] 10 201239531 4i/l/plf

In the formula (1), R1 represents an alkyl group having 1 to 6 carbon atoms, R2 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or an (indenyl) acryloxy group, and 茁 represents 〜 An integer of 3, η represents an integer of 0 to 6. In the formula (2), R3 represents an alkyl group having 1 to 6 carbon atoms, χ represents an integer of 丄~], y represents an integer of 1 to 6, and z represents an integer of 〇3. First, the definitions of the symbols in the equations (1) and (2) will be described. The alkyl group of R1 and R3 may be any of a linear chain, a branched chain, and a cyclic chain. The carbon number of the base of R1 and R3 is from 1 to 6, and the carbon number is preferably from 1 to 4, more preferably 丨 or 2, in terms of the reactivity of the hydrolysis condensation. Specific examples thereof include: ί, n-propyl: isopropyl, n-butyl, butyl, tributyl, pentyl, hexyl, hexyl, etc., wherein the methyl group is in the same-molecular memory. In many cases, the secret; phase = can also be different. The same is true for R3. A R j phase 冋 two good = ring positive twelve ~ ten: recorded, positive two hearts Heptyl, cyclooctyl and so on. The aryl group of R = 10, alkyl, and ring R is a monocyclic to tricyclic aromatic 11 201239531 4171 /pif hydrocarbon group having a carbon number of 6 to 14, and specific examples thereof include a phenyl group, a naphthyl group, and a fluorenyl group. Fickey and so on. Among them, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The alkyl group and the aryl group of R2 may have a substituent, and examples of the substituent include a halogen atom, a trans group, a nitro group, a cyano group, and an alkoxy group having a carbon number of 1-6. Further, the position and the number of the substituents are arbitrary, and in the case of having two or more substituents, the substituents may be the same or different. Examples of the halogen atom include a fluorine atom, a "smoke atom, a gas atom, and a lion". Among them, a fluorine atom is preferable. The dentate atom may be substituted with a part or all of a hydrogen atom of an alkyl group and an aryl group, and is preferably all substituted. Specific examples of the alkyl group include a trifluoroantimony, a perfluoroalkyl group such as a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, or a perfluorocyclopropyl group. Further, an alkoxy group having a carbon number of 1 to fluorene Examples of the group include a decyloxy group, a n-propoxy group, an isopropoxy group, etc. When the soil latex and the propyl)propyl group are in the case of containing an acryloxy group and a methyl group, a group or a (fluorenyl) propylene group R2, In the above, R2 is preferably an alkyloxy group having 1 to 6 carbon atoms. Further, a plurality of r2 may be the same or different in the same molecule. m is an integer of 1 to 3, preferably 1 Or 2, more preferably 1 η is an integer of 〇~6' is preferably an integer of 〇~3 ° 3 X is an integer of 1 to 3' preferably 丨 or 2, more preferably ^ί is 0 or 3. y An integer of 1 to 6 is preferably an integer of 1 to 3: , , , . . . z is an integer of 〇 〜3, preferably 〇 or 1, more preferably, and further, for the composition of the component [A1] Oxane composition [A1] contains TEOS as an essential component to illustrate. Knife 〇S is a polyfunctional decane compound having 4 12 201239531 41717 pif hydrolyzable groups. It is predicted that if the polyoxy siloxane contains structural units derived from TEOS Further, the adhesion to the substrate by the interaction with the hydroxyl group on the surface of the metal substrate such as ITO is increased, and the crosslinking density of the polyoxyalkylene can be further increased, and the obtained cured film can have a higher hardness, however In the present invention, it is found that the compound (1) and the compound (2) described later are combined in TEOS to form a polyoxane and to make it more brittle. By containing the component [B], even if the TEOS is contained at a high concentration, it is possible to unexpectedly obtain a cured film which is excellent in not only hardness and substrate adhesion but also excellent in scratch resistance and crack resistance. It is completely unpredictable. In terms of hardness, adhesion, scratch resistance, and heat crack resistance, the TEOS addition ratio is preferably 5 mol% (mole percent) with respect to the total amount of the raw material compound. Ratio of ~75 m〇l%, more preferably 1〇m〇1% to 70 mol% 'and more preferably 25^οΐ%~65 mol%. The component [A1] further contains the compound (1) as an essential component. The compound (J ) suppresses an excessive crosslinking density increase caused by TEOS, maintains a moderate crosslinking density, and contributes to an improvement in crack resistance and scratch resistance. The compound (1) may be a decane compound having m of 1. The decane compound in which m is 2 and the decane compound in which m is 3. Specific examples include the following compounds: The compound (1) may be used singly or in combination of two or more. Examples of the sinter compound include: methyl trimethoxy silane, decyl diethoxy decane, decyl tri-isopropoxy decane, decyl tributoxy fluorene 13 201239531 Hi /1 /pif, Ethyl Dimethoxy Oxime, Ethyl Triethoxy Oxide, Ethyl Tris-Isopropoxydecane, Ethyl Tributoxydecane, Butyl Trioxetane a hydrolyzable pyroxene compound having one alkyl group having 1 to 20 carbon atoms, such as mercaptotrimethoxydecane; trifluoropropyltriazine a hydrolyzable decane compound having one halogen-substituted alkyl group having 1 to 20 carbon atoms, such as trifluoropropyl trimethoxy silane; phenyl trimethoxy silane, stupid triethoxy a hydrolyzable sulphuric acid compound having one aryl group having 6 to 14 carbon atoms such as decane; 3-methacryloyloxypropyl propyl trimethoxy silane, 3-mercaptopropene醯oxypropyl triethoxy decane, 3-mercapto propylene methoxy propyl tripropoxy decane, 3-propenyl methoxy propyl trimethoxy decane, 3- propylene methoxy propyl three A hydrolyzable calcining compound having one (indenyl) acryloxy group, such as ethoxylate or 3-propoxymethoxypropyltripropoxylate. Examples of the decane compound having a m of 2 include a hydrolyzable smelting compound having two carbon atoms of 1 to 20, such as dimethyldimethoxy decane or dibutyl decyloxydecane; 'monomethoxy-burning hydrolyzable decane compound having 2 aryl groups having 6 to 14 carbon atoms; 3-methacryloxypropyl decyl dimethoxy decane, 3-propene oxime An alkoxydecane compound having a (meth) acryloxy group and an alkyl group having 1 to 20 carbon atoms, such as a propyl fluorenyl group;

S 14 201239531 4I717pif 3-methyl (10) fluorenyl phenyloxy Wei, 3- propylene, propyl phenyl di? Alkoxydecane compound having an aryl group and an aryl group having a carbon number of ό~14; a 3,3'-dimethyl propyloxypropyl dimethoxy group The 3,3,-dipropane oxomethoxydicarb has two (meth)acryloxy alkoxy decane compounds. Examples of the chopping compound having a m of 3 include tributyl decyl oxy-stone, trimethyl methoxy cerium, trimethyl ethoxylate, tributyl ethoxy, and the like. a hydrolyzable decane compound of a mercapto group; a hydrolyzable decane compound having three aryl groups of 6 to 14; 3,3',3"-trimethylpropene oxime A hydrolyzable decane compound of propyl methoxy decane, 3 3, 3" _ tripropylene oxy-oxomethoxy methoxy, etc. Among these compounds (1), a 7-decomposing Wei compound having a carbon number of ketone, a hydrolyzable zeolitic compound having a Wei 6 to 14 base group, and a hydrolyzable property having a (meth)propoxy group are preferable. In the case of these compounds, a compound of the above formula (1) wherein m is oxime is particularly preferred. Specific examples of a suitable compound (1) include methyl dimethoxy oxylithus, decyl triethoxy sulphur, ethyl trimethoxy sulphate, ethyl triethoxy wei, butyl trimethoxy An alkoxydecane compound having i alkyl groups having 1 to 6 carbon atoms; a phenyl group having a carbon number of 6 to 14 such as phenyltrimethoxywei; 15 201239531 *-H / 1 /pif Oxydecane compound; 3 - propylene methoxy propyl trimethoxy decane, 3 - methacryloxypropyl dimethoxy decane, 3 - propylene methoxy propyl triethoxy decane, An alkoxydecane compound having one (meth) propylene fluorenyloxy group such as mercapto acryloxypropyltriethoxy decane. From the viewpoint of improvement of heat-resistant transparency, hardness, scratch resistance, heat crack resistance, adhesion, sensitivity 'resolution and developability, the total addition ratio of the compound (1) is preferably based on the total amount of the raw material compounds. It is 1〇mol%~80 m〇i%, more preferably 1〇m〇1%~75 m〇1%, and further 15 mol0/〇~7〇m〇i%. In the present invention, in the case of further improving the scratch resistance and the heat cracking resistance, in the above-mentioned suitable compound (1), it is preferred to use an alkyl group selected from the group having a slave number of ~6. The hydrolyzable decane compound and the at least one type 7-sintering compound j of the hydrolyzable 7-sintering compound + having an aryl group of carbon number ～14 are also referred to as "Wei compound (lbl)"), and these Wei compounds (ibl) Particularly preferred is a decane compound in which m of the above formula (1) is 1. Τι yp ... the person "Wang Jin Yi Shao Shang Shang's point of view, the above compound (1) towel 'preferably uses (meth) propylene oxime: a decomposing Wei compound, especially in the above formula (1) Hydrolyzable stone having a thioloxy group as a base; (4) Hydrolyzable C having a fluorenyl group as a "complex (ic1)"), and having a catalyzed compound (The following is also referred to as "the shi yi to y-type, and it is more preferable to use the Shi Xixuan compound 201239531 41717pif (lc1) and the decane compound (Id1). In addition, the hydrolyzable decane compound having a (fluorenyl) propylene oxime group It is preferably used together with the decane compound (lb1). When the decane compound (lb1) is used as the compound (1), the raw material compound is improved from the viewpoint of further improvement in scratch resistance and heat cracking resistance. The total addition ratio of the decane compound (lbi) is preferably from 10 mol% to 80 mol%, more preferably from 15 mol% to 75 m〇1%, still more preferably from 30 mol% to 70 mol%. From the viewpoint of further improvement in sensitivity and resolution, relative to the combination of raw materials The total addition ratio of the hydrolyzable decane compound having a (fluorenyl) acryloxy group is preferably from 5 mol% to 25 mol%, more preferably from 1 mol% to 20 m〇l〇/0 〇 In the case of using a decane compound (lci) and a decane compound (ldl) j, the addition ratio (1) (four) of the two is preferably 〇〇s3 in terms of a molar ratio from the viewpoint of further improving the scratch resistance and the heat crack resistance. More preferably, it is 0.2 to 1.5, and more preferably 〇.3 to]. The θ component [Α1] further contains the compound (2) as an essential component. The ruthenium inhibits excessive crosslinking density caused by TEOS 婵=sex and resistance The improvement of the scratching property is also helpful to the two compounds (2), which may be exemplified by a decane compound, a decane compound or a decane compound having a ruthenium of 3. As a compound, (2), the compound (2) may be used alone. Further, the above-mentioned decane compound having 17 201239531 41/1 /pif x is exemplified by 2-trimethoxy silyl ethyl succinic anhydride, 3-tri曱 矽 矽 propyl propyl benzoic anhydride, 3-triethoxy decyl propyl succinic anhydride , 3-triphenoxydecylpropyl succinic anhydride, 3-trimethoxyoxydecyl propyl glutaric anhydride, 3-triethoxydecyl propyl glutaric anhydride, 3-triphenoxy fluorenyl And propyl glutaric anhydride, etc. The cerium compound of which X is 2 may, for example, be di-1-butoxy-bis[3-(dihydro-2,5-furandioni)propyl]decane (di) -l-butoxy-bis[3-(dihydro-2,5-furandionyl)propyl]silane ), bis[3-(dihydro-2,5-furandioni)propyl]dimethoxy decane, double [3-(di-1 -2H- 0 vs. 0-South-2,6(5H)-dione)propyl]dimethoxy oxalate (bis[3-(dihydro-2H-pyran-2,6() 5H)-dionyl)propyl]dimethox y silane) and the like. Examples of the ceramsite-containing compound having x of 3 include tris[3_(dihydro-2,5-α-pentan-2-yl)propyl]methoxylate and the like. Among these compounds (2), a Shi Xi Yuan compound wherein X is 1 is preferable, and specific examples of the suitable compound (2) include 3-trimethoxysulfonylpropyl succinic anhydride and 3-triethoxy group.矽alkylpropyl water succinic anhydride and the like. From the viewpoint of improvement in heat-resistant transparency, hardness, scratch resistance, heat crack resistance, adhesion, sensitivity, resolution, and developability, the total addition ratio of the compound (2) is preferably based on the total amount of the raw material compounds. It is 15 mol% or less, more preferably 13 mol% or less, further preferably 1 〇 m 〇 1% or less, further preferably 7 mol% or less. Further, the lower limit of the total addition ratio of the compound (2) is preferably 〇5 with respect to the total amount of the raw material compounds.

S 18 201239531 41717pif m〇1% 'more preferably 1 mGl%' and further preferably 2 mol%, especially 1%. The compound (2), 3 addition ratio is preferably in the range of 0.5 mol based on the total amount of the raw material compounds. /. 〜15 mol%, more preferably: ° ten mol / 〇 ~ 13 m 〇 l 〇 / 0, and more preferably 2 m 〇 1% ~ 1 〇 m 〇 1 〇 /. The second is more preferably 3 mol%~7. y, the compound (1) and the compound (7) are hydrolyzed and condensed. The method of the pulverization method is as follows: S, the compound (1) and the compound (2) which are mixed as a raw material, and the mixture is stirred and liquefied in a mixed solution. In this case, the reaction can be carried out once in the reaction system, and each of the raw material compounds and water can be reacted in a stage, and the raw material compound and water are added to the reaction system in portions. The hydrolysis condensation reaction is carried out. Further, the hydrolysis condensate contains not only the product of the hydrolysis condensation (4) of all the water-based groups but also the hydrolyzable group: a partially unhydrolyzed or condensed product. In the hydrolysis condensation reaction, the acid anhydride group of the compound (2) is ring-opened as shown in the following scheme (sdieme) to form a thiol group. Further, the 〇r4 base table in the formula does not originate from an alkoxy group formed by hydrolysis to form an alkohyl group which has an alkyl group and a carbon number of 1 to 6 which is formed in the reaction system by hydrolysis. base. [Chemistry 7]

19 201239531 41717pif wherein R4 represents a hydrogen atom or a carbon group having 1 to 6 carbon atoms, and Z has the same meaning as described above. The alkyl group of R4 may be the same as those of R1, and its specific constitution is as described in R1. The solvent to be used in the hydrolysis condensation reaction is not particularly limited, and a solvent similar to the solvent used for the preparation of the radiation sensitive composition is usually used. Such a solvent may, for example, be an ethylene glycol monoalkylether acetate, a diethylene glycol dialkyl ether, a propylene glycol monoalkyl ether, or a propylene glycol monoalkyl ether. Acetate, propionate. These solvents may be used alone or in combination of two or more. Among these solvents, diethylene glycol di-t-ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxypropionic acid are preferred. Oxime ester. The water used for the reaction and the reaction towel is preferably water which has been purified by a reverse osmosis membrane treatment, an ion 3C exchange treatment, or a steaming method. By using such purified water, the reaction can be suppressed, and the water contact reactivity is improved. Relative to the hydrolyzable soil of TE〇S, compound (1) and compound (7). . The amount of water used in the first ten moles of water is preferably ❹]mole ~ 3 moles, preferably 0.3 moles to 2 moles, and more preferably 〇 5 moles ~ work $ moer. The wrong water of 2 such $ can optimize the reaction rate of hydrolysis condensation. The character condensation reaction, even if it is not a special lion plus a catalyst, can be carried out by means of self-touching by means of _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Organic acids such as 41717pif (trifluoromethane sulfonic acid), acidic ion exchange resins, etc. From the viewpoint of promoting the hydrolysis and condensation reaction, the use amount of the catalyst is preferably 0% with respect to the compound (1) and the compound (2), and the use of the catalyst. 2 Moel below, more preferably 〇〇〇〇〇 1 Mo Er ~ 〇 "Mer. The reaction temperature and reaction time of the hydrolysis condensation reaction can be appropriately set, and for example, the following conditions can be employed. The reaction temperature is preferably 4 (rc 2 Torr (rc, more preferably 50 ° C to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 12 hours. The reaction temperature and the reaction time can be carried out most efficiently in the hydrolysis condensation reaction. After the hydrolysis condensation reaction, a dehydrating agent is added, followed by evaporation, whereby water and the produced alcohol can be removed from the reaction system. The dehydrating agent used in the process generally adsorbs or entraps excess water and the dehydration ability is completely consumed or removed by evaporation. Component [A2] Component [A2] has Si〇2 unit derived from TEOS, derived from compound (1) a structural unit represented by the following formula (la) (hereinafter also referred to as "structural unit (la)"), and a structural unit represented by the following formula (2a) derived from the compound (2) (hereinafter) Also known as "structural unit. Si〇2 unit, structural unit (la) and structural unit (2a) each structural unit can be a single 'can also contain two or more. [Chemical 8] RHCH2^Si-〇 (4. m)/2 (la) 21 201239531 41 /1/pif [Chemistry 9]

[wherein, R2, R4, m, n, x, y, and z are the same as those described above.] In the above, especially in the formula (la), m is preferably 1, in the formula (2a) Preferably, X is 1. The structural unit in the case where m is 1 in the formula (1a) and X is 1 in the formula (2a) is shown in the following formula (Ι-la) and (2-la), respectively. 1/2 Ο R2-(cH 士 Si—Ο 1/2 (1-la) 0 1/2 [化 ll]

1/2 1/2 Si—〇1/2 〇1/2 (2-la)

22 201239531 41717plf t insert, R, n, y & z are the same as described above] This gas can be obtained by subjecting TE〇s, compound (1) and compound CJ to the above hydrolysis condensation reaction The two compounds in the brain 'compound (1) and the compound (7) are obtained by a hydrolysis condensation reaction of the remaining compound. That is, the SW2 single-it, the structural unit (la), and the structural unit (5) may be contained in any form of random copolymerization or block-bonding, respectively. It is t,,,, transparency, hardness, scratch resistance, heat crack resistance, adhesion, and sensitivity. In view of the improvement of the resolution and the developability, the respective ratios of S, 〇2, 7L, structural unit (la), and structural unit (2a) in the component [VIII2] are as follows. In all the structural units of the component [A2], the si〇2 unit is preferably 5 m〇1% to 75 m〇1%, more preferably 10 mol% to 70 mol%, and still more preferably 25 mol0/〇~ 65 mol%. In all the structural units of the component [A2], the structural unit (u) is preferably 10 m〇1% to 80 mol%, more preferably 10 mol〇/〇 to 75 mol%, and still more preferably 15 mol%~ 70 mol%. In all the structural units of the yoke [A], the structural unit (2a) is preferably 15 m 〇 1% or less, more preferably 13 mol % or less, still more preferably 1 〇 mol % or less, and further preferably 7 m 〇 1 Below %, the lower limit is preferably ο", then 1% 'more preferably 1' and further preferably 2 mol%, particularly preferably 3 mol%. Regarding the range of the content ratio of the structural unit (2a), in all the structural unit tissues of the component [a2], it is preferable to be more than 15 m%, more preferably 1 mol% to 13 m〇l%, and further preferably It is 2 m〇1%~1〇m〇1%, and further 23 201239531 ^1/1/pif is preferably 3 mol% to 7 mol%. In addition, it is preferable to contain one or more structural units represented by the following formula (lb) (hereinafter also referred to as "structural unit (lb)") from the viewpoint of further improving heat-resistant cracking resistance and scratch resistance. As a structural unit (la). (R5_)^Si~0(4-m)/2 (10) In the formula (lb), R5 represents an alkyl group having 1 to 6 carbon atoms or an aryl group m having a carbon number of 6 to 14 and the above Said the same meaning. The alkyl group of R5 may be the same as the above R1, and the aryl group may be the same as the above R2. The specific configuration is as described above. Further, 'm is preferably 1. The social unit in the case where m is 1 in the formula (lb) is shown in the following formula (l_lb).化 1/2 (l-lb) R5-S|i—〇1/2 01/2

L ^ τ A, 丄·丄 and π你冯; f目问令,蒽J in all the structural units of the component [A2], the structural unit (the proportion is preferably 10 m〇1%~80 m〇1%) More preferably moP/o, and more preferably 3GmGl%~7G_%. '·., m〇/.~7 and then 'this is a fortune, the sensitivity and developability are improved _ 24 201239531 /1/pif It is difficult to contain a structure I element (hereinafter also referred to as "structural unit (le)") and a lower structural unit (hereinafter also referred to as "structural unit ((4)") which are selected from the following formula (lc:) The present invention is more preferably a structural unit (1C) and a structural unit (Id), but preferably contains a structural unit (10) and contains a structure selected from the group (lc) and the structural unit (ld). At least one of them. CH14 Ο I II , CH2=C—CO-fCH: -Si—〇(4 - m)/2 (lc) [Chem. 15]

ΟII CH2=CH-C— 〇~(- 〇 〇 (4 O Od) In the formula (lc) and (Id), m&n has the same meaning as described above, m is preferably 1, and η is preferred. 3. The structural units in the case where m is 1 in the formula (lc) and the formula (Id) are respectively shown by the following formula (Ι-lc) and the formula (Ι-ld). Knife [Chemistry 16] 〇 = c H3I C——C II π2 c

2 CT ο—si—ο /2 /2 /2 01 1C) 25 201239531 Buck 1 /1 /pif [Π] ? ?1/2 CH2=CH-C-〇-(cH2);rSj--〇1 /2 (1.ld) 〇 1/2 [wherein n is the same as described above] In terms of sensitivity and resolution improvement, all structural unit tissues of component [A2], The total content of the structural unit (le) and the structural unit ((4) is preferably 5 mol% to 25 mol%, more preferably 1 〇m〇l% to 20 mol%. In addition, the structural unit (lc) and the structure are contained. In the case of the unit, the ratio of the structural unit (le) to the structural unit (ld) (le/ld) is better than that of the unit in terms of which damage and resistance to the turtle are difficult to advance. 5 to 3, more preferably 仏?~;! 5, and more preferably 〇3 〜1 〇 In addition, the structural unit (2a) may be a structural unit derived from the above compound (2), preferably derived from A structural unit such as a tris(hydroxy) hydroxyalkyl propyl sulfonate or a 3-triethoxy decyl propyl succinic anhydride. The component [Α] may be used singly or in combination of two or more. The molecular weight of the component [Α] can be determined by using mobile phase using tetrahydrogen Gel permeation Chromatography (GPC) of furan is measured in the form of a polyphenylene oxide-based weight average molecular weight. The weight average molecular weight (Mw) of the component [A] is preferably 5 〇〇. The loooo is more preferably from 1000 to 7000. By setting the weight average molecular weight of the component [A] to 500 to 26 201239531 41717pif, the film formation property of the coating film of the radiation sensitive composition can be improved. When the average weight is 10% or less, the alkali developability of the anti-radiation composition can be lowered. Further, the ratio of the weight average molecular weight (Mw) to the molecular weight (Mn) of the amount measured by the same conditions, that is, The degree of dispersion (Mw/Mn) is preferably 1.0 to 15 Å, more preferably 〜2, and still more preferably i 5 5 〇. By setting it to such a range, it is possible to have both alkali developability and adhesion. And the heat-resistant cracking property. The component [B] is a compound having two or more ethylenically unsaturated groups, and is irradiated by the presence of the component [C] photoradical polymerization initiator described later. a polyfunctional monomer which is polymerized by radiation, wherein component [B] contains component [A] In view of the fact that the polymerizability is good and the strength of the obtained cured film is improved, such a compound can preferably use a bifunctional or trifunctional or higher (fluorenyl) propionate. The ester may be a polyfunctional (fluorenyl) propylene which is obtained by reacting a divalent aliphatic poly-based compound such as ethylene glycol, propylene glycol, polyethylene glycol or polypropylene glycol with (mercapto)acrylic acid. Acid g. Specific examples thereof include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimercapto acrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol. Alcohol dimercapto acrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimercapto acrylate, 1 , 9_decanediol 27 201239531 HI /1 /pif diacrylate, 1,9-nonanediol dimercapto acrylate, and the like. Commercial products include, for example, Aronix M-210, Aronix M-240, Aronix M-6200 (above manufactured by East Asia Synthetic Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above is Sakamoto Chemical Co., Ltd.) Manufactured; Viscoat 260, Viscoat 312, Viscoat 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate 1, 9-NDA (manufactured by Kyoeisha Chemical Co., Ltd.).

The trifunctional or higher (fluorenyl) acrylate may, for example, be a trihydric or higher aliphatic polyhydroxy compound such as glycerine, trimethylol propane, pentaerythritol or dipentaerythritol. A polyfunctional (fluorenyl) acrylate obtained by the reaction of acrylic acid. Specific examples thereof include trimethylolpropane triacrylate, trihydroxydecyl propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tridecyl acrylate, pentaerythritol tetraacrylate, pentaerythritol tetradecyl acrylate, dipentaerythritol. Pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, a mixture of dipentaerythritol hexa-butanoic acid, dipentaerythritol hexamethacrylate, ethylene oxide Modified dipentaerythritol hexaacrylate and the like. Commercially available products include, for example, Aronix M-309, Aronix M-315, Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix TO- 1450 (above manufactured by East Asia Synthetic Company); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 'KAYARAD DPCA-120 > KAYARAD

S 28 201239531 41717pif DPEA-12 (above is manufactured by Sakamoto Chemical Co., Ltd.); viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.). In addition, in addition to tris(2-acryl〇yl〇Xyethyl)ph〇sphate, tris(2-methylpropenyloxyethyl) acetoate, amber Acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and tri(acryloxyethyl)ococyanurate may also be used to have a linear chain. a compound having an alkyl group and an alicyclic structure and having two or more isocyanate groups, and reacting with a compound having more than one hydroxyl group in the molecule and having three, four or five (meth) acryloxy groups The obtained polyfunctional acryl polyamine g is a compound or the like. Commercial products containing a polyfunctional acrylic polyamine vinegar compound can be exemplified by New Frontier R-ll5(R) (manufactured by Daiichi Kogyo Co., Ltd.), 艮八丫八尺8 0卩11 8-4011 (manufactured by Nippon Kayaku Co., Ltd.) Wait. "Hei II is preferably 1,9-nonanediol dimercapto acrylic acid, three thiol propyl hydride, quaternary alcohol lysine §|, quaternary tetraol tetraacrylic acid Vinegar, dipentaerythritol, penta-propan vinegar, dipentaerythritol hexa-acrylic acid, glutaric alcohol, sulphuric acid, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate The quality season ^ four leave three -, aza miscellaneous modified dipentaerythritol pentaacrylic acid, face thiol ethyl) heterodimeric acid brewing, commercial products containing polyfunctional acrylic poly Wa 曰糸 5 substances. Among them, a trifunctional or higher functional group, a monofunctional 3-membered to 6-functional (fluorenyl) acrylic acid vinegar, particularly preferably: pentaerythritol 29 201239531 41717plf a mixture of hexaacrylic acid and dipentaerythritol pentaacrylate. The component [B] may be used singly or in combination of two or more. The content of the component [B] is preferably 5 parts by mass to 300 parts by mass, more preferably 10 parts by mass to 2 parts by mass, even more preferably 15 parts by mass to 1 GG parts by mass, based on the component [Αμοο(four) parts of the component [B]. The step-by-step is better for 2 () parts by mass ~ 8 enamel. When the content of the component [B] is within the above range, the hardness, heat resistance and sensitivity are further improved. ^ Component [C] Component [C] is a photoradical polymerization initiator. The photoradical polymerization initiator is a compound which can generate an active species which can initiate a hardening reaction of the above component [Β] by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray. The photoradical polymerization initiator used in the present invention may, for example, be an O-acyl oxime compound, an acetophenone compound, a cation phosphine oxide compound or the like. mum. Sitting compound (biimidazole compound) and the like. Specific examples of the 0-fluorenyl hydrazine compound include ethyl ketone, 1-[9-ethyl-6-(2-methylphenylindenyl)-9H-indazol-3-yl]-, 1-( 0-Ethyl group) (ethanone, 1 -[9-ethyl-6-(2-methyl benzoyl)-9H-carbazol-3-yl]-, l-(0-acetyl oxime), l-[9- Ethyl 6-benzoinyl-9.H, oxazol-3-yl]-octane-1-one oxime-indole-acetate, 1-[9-ethyl-6-(2-A Benzopyridinyl)-9.Η·-oxazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1-[9-n-butyl-6-(2-B Benzoyl)-9·Η·-carbazole-3-

30 201239531 41717pif base]-Ethylene-1-phenanthrene-O-benzoate, ethyl ketone ethyl _6_(2_曱基_4_ 四氲氲基基曱醯基)-9.H.+ Shishiji from (9) B with base month loss ^ ethyl ketone, 1-[9-ethyl-6-(2-mercapto-4-tetrahydropyranylphenyl fluorenyl) 9 H.-carbazole 3-yl]-, 1-(0-ethenyl), B, X-ethyl_6_(2_methyl_5_tetrahydrofuranylphenyl)-9.Η·-carbazole -3-yl]_,;!_(〇_乙醯基肟), ethyl ketone, 1-[9-ethyl_6-{2_methyl ice (2,2-didecyl _U_ two Oxocyclopentyl) methoxybenzoinyl}-9. 圧-carbazole _3_yl Kl_(〇_6醯 肟), acetamidine, 1-[9-ethyl-6-(2 -mercapto-4-tetrahydrofuranyl decyloxybenzhydryl)-9·Η·-η卡吐-3-yl]-,l-(〇-ethylidene 肟), 12_辛二嗣卜(四) Phenylthio)-, 2-(0-benzylidene) will, and the like. The 〇_醯 base compound may be used singly or in combination of two or more. Among these compounds, preferred 〇 醯 醯 肟 compounds are exemplified by ethyl lactate I, l-[9-ethyl-6-(2-mercaptobenzoquinone)-sister-. Carboxy-3-yl]-,l-(〇-acetamidoxime), ethyl ketone, 1-[9-ethyl-6-(2-mercapto-4·tetrahydrofuryl methoxybenzoquinone醯基)-9.Η.-α card. Sodium-3-yl]-, l-(〇-acetoxy group), ethyl ketone, i_[9_ethyl-6-{2-mercapto-4-(2,2-dimercapto-1, 3 · Dioxolyl) decyl phenyl hydrazino}-9.11.-° carbazino-3-yl]-, 1-(0-ethyl aryl), ι, 2 octyl ketone (Phenylthio)-, 2-(0-benzhydrylhydrazine)]. Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound. The acetophenone compound may be used singly or in combination of two or more. Specific examples of the α-aminoketone compound include 2-benzyl-2-didecylamino-1-(4-morpholinylphenyl)-butane ketone (2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butane-1-one), 2-dimethylamino-2-(4-methylfyl)-1-(4-morpholin-4-yl-benzene 31 201239531 41717pif Ethyl butane-1-one and 2-methyl-1-(4-sulfonylphenyl)-2-morpholinylpropane are similar. (Specific examples of the X-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-l-one, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1 - Hydroxycyclohexylphenyl group, etc. Among the acetophenone compounds, α-amino group g is the same compound, particularly preferably 2-monodecylamino-2-(4-indolyl)- 1-(4-?~lin-4-yl-phenyl)-butyrol-1-oxime, 2-mercapto-1-(4-sulfonylphenyl)-2-morphinylpropanone-1 - 嗣. Specific examples of the fluorenylphosphine oxide compound include: 2,4,6-trimethyl benzoyl-diphenyl-phosphine oxide, Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, etc. The fluorenylphosphine oxide compound may be used singly or in combination of two or more. Among the fluorenylphosphine oxide compounds, preferably Bis(2,4,6-trimercaptobenzylidene)-phenylphosphine oxide. Specific examples of the biimidazole compound include 2,2,-bis(2-chlorophenyl)-4,4', 5,5,·tetrakis(4-ethoxycarbonylphenylbiimidazole (2,2-bis(2-) Chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbony 1 phenyl)-l,2'-biimidazole), 2,2,-bis(2-phenylphenyl)-4,4',5 , 5'-tetraphenyl-1,2'-linkage rice", 2,2'-bis(2,4-diphenyl)-4,4,5,5,-tetraphenyl- 1,2,-Lianwei saliva, 2,2'-bis(2,4,6-trichlorophenyl)_4,4,5,5,·tetraphenyl-1,2,·Lian Mijun, etc. The sulfonium compound may be used singly or in combination of two or more.

32 201239531 41/1/pif Among these biimidazole compounds, 2,2'-bis(2-phenylphenyl)-4,4|,5,5'-tetraphenyl-1,2,-linked is preferred. Imidazole, 2,2,-bis(2,4-diphenyl)-4,4,5,5,-tetraphenyl-1,2,-biimidazole, 2,2'-bis (2, 4,6-trisylphenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. Further, in the case of using a biimidazole compound, at least one selected from the group consisting of an amine sensitizer and a hydrogen donor compound may be added. Examples of the amine-based sensitizer include N-methyl diethanolamine and 4,4'-bis(dimethylamino)benzophenone. 4,4'-bis(diethylamino)benzophenone, p-didecylaminobenzoic acid ethyl ester, p-didecylaminobenzoic acid isoamyl ester, and the like. Among these amine-based sensitizers, particularly preferred is 4,4,-bis(diethylamino)benzophenone. Examples of the hydrogen donor compound include a thiol compound. The thiol compound is preferably, for example, 2-mercaptopurine benzothiazole or 2-im il. 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole. The component [C] may be used alone or in combination of two or more. In the present invention, it is preferred to contain a ruthenium-indenyl ruthenium compound as a component [q. The content of the component [f] is preferably from 10,000 parts by mass to 30 parts by mass, more preferably from 1 part by mass to 15 parts by mass, and furthermore, based on 1 part by mass of the total of the component [A] and the component [B]. Preferably, it is 1 part by mass to 10 parts by mass. By setting the content of the f component [C] within the above range, a high radiation sensitivity can be exhibited even in the case of a low exposure amount, and a cured film having sufficient hardness can be formed. Further, when the biimidazole compound is selected as the component [C] and is used in combination with at least one selected from the group consisting of the amine 33 201239531 minute 1 / wpif base sensitizer and the hydrogen donor compound, 100 parts by mass relative to the biimidazole compound. The amount of each of the amine-based sensitizer and the hydrogenated person is preferably from 0.1 part by mass to 5 parts by mass, more preferably from 1 part by mass to 20 parts by mass. By setting the amount to be used, the surface hardness of the obtained cured film can be improved. Component [D] In the present invention, 'a structural unit containing (D1) a hydroxy group (hereinafter also referred to as "structural unit (D1)") and (〇2) a structural unit having an epoxy group (hereinafter also referred to as The copolymer of "structural unit (D2)" is used as the component [D]. By containing the component [D], the sensitivity can be improved, and the solubility of the lyophobic liquid used in the development step and the inorganic developer can be improved. Therefore, the developability can be improved and the obtained cured film can be improved. Cracking. The structural unit (D1) is preferably a structural unit derived from at least one compound selected from the group consisting of (dM) unsaturated dicarboxylic acid and unsaturated carboxylic anhydride (hereinafter, these compounds are also referred to as "compound (D11)"). Examples of the compound (DM) include acrylicadd, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinic acid, 2-mercaptopropenyloxyethyl Succinic acid, 2-propenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethylhexaphthalic acid, and the like; a straight acid (maleicadd), anti a dicarboxylic acid such as fumaric acid or clstrac〇nicadd, an acid anhydride of the dicarboxylic acid or the like. Among these compounds (jy-oxime), the copolymerization reactivity and the solubility of the obtained copolymer in the developer are preferably s, preferably acrylic acid, methacrylic acid, 2-propylene propylene oxide 34. 201239531 41/1/pif-based succinic acid, 2-methylpropenyloxyethyl succinic acid, maleic anhydride. The compound (iy-i) may be used alone or in combination of two or more. In the soil, in the structural unit, the copolymerization ratio of the structural unit (Ε) 1) is preferably 1% by mass (% by mass) to 40% by mass, more preferably 2% by mass = 〜30% by volume. Good is 3% by mass to 25% by mass. By setting such a copolymerization ratio, it is possible to obtain a radiation-sensing linearity which is optimized for a higher degree of rotation, such as sensitivity, developability, and stability. The octagonal structural unit (D2) is preferably a structural unit derived from a radical polymerizable compound having an epoxy group (hereinafter also referred to as "compound (D2_2)"). Examples of the α-form (d2-2) include glycidyl acrylate diyl a: ?late, propionate 2 - fluorenyl glycidyl _, and propylene 3' 4 / oxybutyl acrylate (3) , 4_eP〇xybutyl acrylate), acrylic acid _6,7_ epoxy gypsum, acrylic acid-3,4-epoxycyclohexyl ester, acrylic acid _3,4_epoxy cyclohexyl hydrazine vinegar, etc. ; glycidyl methacrylate, methyl acetophenate glycidyl (tetra), methacrylic acid _3,4·epoxybutyl ketone, methacrylic acid _6,7-epoxyheptyl ester thioglycolic acid Epoxycyclohexyl vinegar, methacrylic acid-3:4-epoxycyclohexyl 曱g, etc. f-based acrylic acid epoxy ketone; α·ethyl propylene, glycidol g, α-n-propyl Acrylic glycidol acrylate, glycidyl butyl acrylate, α_ethyl acrylate _6,7_epoxyglycol, etc. a-alkyl acrylate epoxy §; o-vinyl ke succinyl bond (o-vmylbenzyl) Giycidyl ethe〇, m-vinylbenzyl glycidyl ether, and glycidol of the branch of the county are called 6-ene fresh glycidol scales. In addition, a polymerizable unsaturated compound containing an oxetanyl group can also be used as a compound (D2· 2) Regarding oxygen-containing transradical (tetra)-unsaturated 35 201239531 'Specific examples of 1 /pif 2', for example, 3_(mercaptopropene oxime oxybutane (3-(methacryl〇yl〇xy) ), soil = olefinic fluorenyl)-3-ethyloxazepine dumplings, 3 丨1 (mercaptopropyl) 2 - oxime oxime, butane (mercapto propylene oxime) ▲秘¥丁烧,3_(f-silyloxyethyl _(mercapto propylene methoxyethyl)·3_ethyl oxygen; clothing; heterocyclic diners, 3-(acrylic acid Base)-3-ethyl=,butyl,yl)=dimethyl, oxetane, 3_(=oxybutane: =butane, 3-(propyleneoxydiylethyl)oxyne ( Propylene oxiranyloxy) oxetane = butane, 2-ethane-2, heterodibutyl, 2-methyl" (methyl- to benzyl group, (methacrylic acid) Oxetane (methylpropyl decyloxy) oxa; ^) oxygen _ butyl, 4-methylheptyl oxetanyl)), riding, methyl acetoin male (2_ ' 2 · (..._ Oxygen / Ethyl) = Oxygen / Heterocyclic Butyryl (decyl propylene oxyethyl) _4_ 虱 虱 裱 Butane, _ oxirane, / base = heterocyclic Burning, 2 detective appearance, ~ base-2 · (acrylic Base soil; oxy-indoyl) oxetane oxo), oxetane, f-butyl, fluorenyl, butyl)), m, methacrylic acid, but methyl oxalate [曰, 2-(propionyloxyethyl)_2•methyl ((hetero: oxetanyl)) ethanediyl Hfyl oxetane 2: % butyl rot, 2 burr Isodecyl esters. (f-based) propyl-containing heterocyclic butyl groups (Ό2·2) f " high turbidity and heat crack resistance, 36 201239531 41 /l/pif propyl In the aspect of the acid "I:", it is preferable to use a methylidene group, a winter ethyl oxa propylene propylene oxybutylene or the like. "Kedding, 2_(decyl propylene oxime oxime) oxyheterocycle == yuan can be used alone or in combination with two or more types. Good for 10% by mass to 7 for two deniers. (D) The polymerization ratio is higher than that of 隹% ## „Berry is preferably 15% by mass to 70% by mass, ',, and *%% to 65% by mass. By setting such a copolymerization ratio, the molecular weight of the copolymer is particularly easy to control, and the scratch resistance, sensitivity, and developability are further improved. P may also have a structural unit (D1) and a structural unit other than the structural unit (a structural unit (hereinafter also referred to as "structural unit (Ε> 3)")) (hereinafter also referred to as " Examples of the compound (D3-3)") include (indenyl) propylene methoxy propyl trisodium oxyalkyl chopping, (meth) acrylic acid base, and (methyl) propyl fused ring. , an oxygen-containing unsaturated heteropentacyclic or six-membered ring (fluorenyl) acrylate, (mercapto) aryl acrylate, an unsaturated dicarboxylic acid diester, a maleimide compound, (曱a hydroxyalkyl acrylate, a (mercapto) acrylamide, an aromatic vinyl compound, a 1,3-butane fluorene, etc. The specificity of (mercapto) propyl methoxy propyl trialkoxy decane Examples include 3-mercaptopropenyloxypropyltrimethoxy decane, 3-propenyloxypropyltrimethoxy oxetane, 3-mercaptopropenyloxypropyltriethoxy矽37 201239531 *tl / i /pif alkane, 3-propenyloxypropyltriethoxydecane. Specific examples of the (meth)acrylic acid base are as follows: methyl propyl methacrylate A: t propylene acetonitrile, n-butyl methacrylate, methacrylic acid methacrylic acid second, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid second vinegar, acrylic acid Tributyl vinegar, etc. Specific examples of (meth) propyl ketone _ keji g can be exemplified by methacrylic acid cyclopentane, fluorenyl-acid ring (10) decyl acrylate 2 methylcyclohexanoic vinegar, methyl propyl _Sanhuan 癸 基 基 vinegar (hereinafter also referred to as the three rings [5/.1. 〇 2,6] 癸-8-based nickname ""bicyclic fluorenyl"), τ-based acrylonitrile dicyclopentyloxy Ethyl ethyl ester, isoprene methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, benzoic acid cyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.02,6] Decane_8_yl ester, 2-dicyclopentyloxyethyl acrylate, isobornyl acrylate, etc. The unsaturated heteroquinone ring or the six-membered cyclodecyl acrylate containing an oxygen atom may, for example, be tetrahydrofuran. a tetrahydrofUran) unsaturated compound of a skeleton, an unsaturated compound containing a furan skeleton, an unsaturated compound containing a tetrahydrogen, a specific skeleton, and a ratio of The unsaturated compound of the shelf, etc. Specific examples of the unsaturated compound containing a tetrahydrofuran skeleton may be exemplified by (tetrahydrofurfuryl (meth)acrylate), 2-mercaptopropenyloxy-propionic acid tetrahydrogenate. An oxime ester, 3-(meth) propylene oxime tetrahydrofuran B-an-2-one, etc. Specific examples of the unsaturated compound containing ruthenium and a south skeleton include 2-mercapto-5-(3-furan 1-methyl-5-(3-furyl)-l-pentene-3-one, (decyl) decyl acrylate, 1-furan-2-butyrate 3--3-en-2-one, 1-furan-2-butyl-3-decyloxy-3- 38 201239531 /1 /pif ene-2-one, 6-(2-furyl)-2- Mercapto-1-hexen-3-one, 6-furan-2-yl-hex-1- fine-3-S, acrylic acid-2-succin-2-yl-1-yl- Ethyl vinegar, 6-(2-α-furanyl)-6-mercapto-1-hepten-3-one, and the like. Specific examples of the unsaturated compound containing a tetrahydropyran skeleton include methacrylic acid (tetrahydropyran-2-yl) decyl phthalate and 2,6-dimercapto-8- (four mouse pyran-2) -1,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-l-ene-3-one ), 2-methylpropene The acid four mouse ratio is α-N-S, 1 _(four-mouse α-B-nan-2-oxy)-butyl-3-en-2-one, and the like. Specific examples of the unsaturated compound containing a pyran skeleton include 4-(1,4-.monooxa-5-oxo-6-heptyl)-6-fluorenyl-2-pyranyl (4). -(l,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyran)'4-(1,5-dioxa-6-oxo-7-octenyl)-6 - mercapto-2-pyrene and the like. Examples of the hydroxyalkyl ester of (mercapto)acrylic acid may be exemplified by (meth)acrylic acid-2-hydroxyethyl (meth)acrylate, (fluorenyl)acrylic acid-2- Hydroxypropyl ester, hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, and the like. Specific examples of the (fluorenyl) aryl acrylate include phenyl (meth) acrylate and benzyl (meth) acrylate. Specific examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate, and the like. Specific examples of the cis-indole-imine compound include N-phenyl maleimide and N-cyclohexylmethyleneimine: N-benzyl cis-butane Equinone imine, N_(4-hydroxyphenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-butaneimine 39 201239531 Hl / N/succinimidyl-3-maleimide benzoate, N-butyl iminoimine-4-methyleneimine butyrate , N-butyl quinone imino-6-m-butyleneimine hexanoate, N-butyl quinone imido-3-butylene imidate propionate, N_(9-吖Pyridyl) maleimide and the like. Specific examples of the (mercapto) acrylamide include acrylamide, methacrylamide, 4-hydroxyphenylpropenylamine, 4-hydroxyphenylmethacrylamide, 3-pyridyl propylene. Indoleamine, 3-hydroxyphenylmercaptopropenylamine, and the like. Examples of the aromatic vinyl compound include styrene and α-methylstyrene. Among these compounds (D3"), preferred are (fluorenyl) propylene methoxy propyl trialkoxy decane, aromatic vinyl compound, maleimide imidized s (meth) propyl Glycolic acid styrene vinegar, (meth) propyl sulfonamide, particularly preferably (meth) propylene methoxy propyl trialkyloxy decane. The chemical substances (D-3) may be used alone or in combination of two or more. In all the structural units of the component [D], the copolymerization of the structural unit (D3) is preferably from 1% by volume to 7% by weight, more preferably from 15% by mass to the amount of the acetoxy group. ,·. The mass % of the case of the structure as the structural unit (d3). Dream by ^ / 50 (four)%, more preferably 20% by mass ~ 4 kinds of copolymerization ratio, especially the copolymer's step-by-step extraction ^ additional ray, color, adhesion, etc. and compound ingredients _ such as It is produced by polymerizing a compound (dLi 201239531 ^ι/ι / pir (D2-2), if necessary, the compound (D3_3) in a solvent in the presence of a radical polymerization initiator. A solvent used in the polymerization reaction For example, an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol monoalkyl ether, a propylene glycol monoalkyl shout, a propylene glycol single-burning fine B (tetra), a propylene glycol single-recorded propionic acid vinegar芳香 芳香 知 、 鸭 鸭 鸭 鸭 鸭 鸭 鸭 嶋 嶋 嶋 嶋 嶋 嶋 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ , 2, azobisisobutyronitrile (2,2'-azobisisobmyronitrile), 2,2,-azobis-(2,4-dioxyl valeronitrile) (2,2-azobis-(2,4 -dimethyl valeronitrile)), 2,2'-azobis-(4_decyloxy-2,4-dimethylvaleronitrile), 4,4,-azobis(4-cyanovaleric acid), Methylazobis(2-mercaptopropionate) An azo compound such as 2,2ι_azobis(4_decyloxy-2,4_, methylvaleronitrile), etc. Among these radical polymerization initiators, f is preferably 2,2'-azo Double isobutyronitrile, 2,2,-azobis(2,4-dioxyl valeronitrile), etc. The radical polymerization initiator may be used singly or in combination of two or more. The amount of the radical polymerization initiator to be used is usually 0.1 part by mass to 5 parts by mass, preferably α1 by mass, to 20 parts by mass. In addition, 'in the polymerization reaction, molecular weight can be used. Specific examples of the adjusting agent to adjust the adjusting agent in the knives in the molecule include chloroform, tetra/small fossil ruthenium-halogenated nicotine, n-hexylmercaptan, n-octylmercaptan, and n-dodecane Mercaptans such as alcohol, tridecyl mercaptan, thioglycolic acid, dimethyl xanthogen sulfide, 41 201239531 1/1 /pif diisopropyl disulfide Xanthogen such as xanthate; teipinolene, α·mercaptostyrene dimer, etc., 100 parts by mass relative to the total amount of monomers The amount of the amount controlling agent to be used is usually from 50 parts by mass to 5% by mass, preferably from 2 parts by mass to 16 parts by mass, and from 0.4 parts by mass to 8 parts by mass. 'In addition, the polymerization temperature is usually 〇°C. ~15 (rc, preferably 5 〇 it ~ 120 ° C 'The polymerization time is usually 10 minutes to 20 hours, preferably 3 minutes to 6 hours. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as rMw,") of the component [D] obtained by using GPC of the mobile phase using tetrahydrofuran is 2x10?IxlO5, more preferably 5xl?3~5xl?4. By setting the Mw' of the component to 2x10 or more, a sufficient development margin of the radiation sensitive composition can be obtained and the residual film ratio of the formed coating film (the ratio of the pattern film remaining properly) is prevented from decreasing. Further, the pattern shape, heat resistance, and the like of the obtained insulating film are kept good. On the other hand, by setting the Mw' of the component [D] to 1x10 以下 5 or less, it is possible to maintain a high degree of radiation sensitivity and obtain a good pattern shape. Further, the molecular weight distribution of the component [D] (hereinafter referred to as "Mw'/Mn'") is preferably 5.0 or less, more preferably 3.0 or less. By setting Mw'/Mn of the component [D] to 5.0 or less, the pattern of the obtained insulating film can be kept good. Further, the radiation-sensitive composition containing the component [D] having the preferred range and Mw'/Mn' as described above has high developability, so that a predetermined pattern shape can be easily formed in the developing step without generation. Development residue. The component [D] may be used alone or in combination of two or more. 42 201239531 41 /1/pif The content of the component [D] per 100 parts by mass of the component [A] is preferably 1 part by mass to 45 parts by mass, more preferably 2 parts by mass to 40 parts by mass, and still more preferably 3 The mass part is preferably 35 parts by mass, more preferably 3 parts by mass to 3 parts by mass, and further preferably 3 parts by mass to 25 parts by mass. By setting the content of the component [D] within the above range, the sensitivity and developability can be further improved. In the present invention, at least one selected from the group consisting of organic particles and inorganic particles may be contained as the component [E]. By containing the component [E], scratch resistance, cracking property, and the like can be improved. As the organic particles, solid particles such as acrylic fine particles can be suitably used. Examples of the acrylic fine particles include a methyl methacrylate methyl ester polymer, a copolymer of methacrylic acid and an alkyl compound, and the like. For example, Zefiac F_32〇, Zefiac F 3〇1, F-340, Zefia (8) 25, and Zefiac F_351 (the above is manufactured by G Chemicals Co., Ltd.) 'Acrylic Micronized Rivers>>>_3〇〇 Chemical company manufacturing) and so on. Further, examples of the inorganic fine particles include particles of a composition of two (10) (dioxide, titanium oxide, zinc oxide, cerium oxide, or carbonic acid - 〇ntm〇rill〇nite). New, Oxygen, and Oxygen, as the main plate, fibrous, and fine particles, may be solid, and the shape of the inorganic fine particles may be any shape, and these may be beneficial, hollow, or porous. A...' The dioxide dioxide particles can be listed. Specific examples of such inorganic recordings 43 201239531 4Γ/1 /pif

For example: Admafine SO-E1, Admafine SO-E2, Admafine SO-E3, Admafine SO-E4, Admafine SO-E5, Admafine SE3200-SEJ (manufactured by Admatechs), SS01, SS03, SS15, SS35 (manufactured by Osaka Chemical Industry Co., Ltd.) , methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST- C, ST-N, ST-0, ST-50, ST-OL (manufactured by Gifu Chemical Industry Co., Ltd.). Further, examples of the zirconia particles include HXU-110JC, HXU-210C, NZD-3101 (manufactured by Sumitomo Osaka Cement Co., Ltd.), ID191 (manufactured by Tayca Co., Ltd.), ZRPMA15WT%-E05 (manufactured by CIKasei Co., Ltd.), and the like, and further, titanium oxide. The particles can be listed as: MT-05, MT-100W, MT-100SA, MT-100HD, MT-300HD, MT-150A, ND138, ND139, ND140, ND154, ND165, ND177, TS-063, TS-103, TS- 159 (manufactured by Tayca), etc. The inorganic fine particles may also be surface-treated by a decane coupling agent or the like. By performing such a surface treatment, compatibility with other components can be improved, and dispersibility or mechanical strength in the composition can be improved. The average particle diameter of the organic particles and the inorganic particles is preferably in the range of 〇〇〇5 μm to 0.5 μm. In the case of [Ε] ’, powder-like particles may be directly added and mixed into other components', or a solvent dispersion may be added, added to and mixed with other components, and the solvent may be distilled off. The components [Ε] may be used alone or in combination of two or more. Relative to the component [A] l 〇〇 by mass, the content of the component [Ε] is preferably i 201239531 41717pif ir parts ~ 600 parts by mass only, and live in Machuan mass parts ~ buy f you, and more preferably 50 Parts by mass to 1 part by mass. By making the content of the component [E] within the above range, the scratch resistance and heat crack resistance of the obtained protective film and interlayer insulating film can be further improved. Ingredient fFj The present invention Yin can contain a dissolving sword as a component [smart. The radiation sensitive composition is usually prepared by formulating a solvent in the form of a liquid composition. The solvent can be appropriately selected and used only if it dissolves or dissolves each component constituting the radiation sensitive composition and does not have a moderate volatility with the knife. = such a solvent 'preferably contains an alcohol = as a f-substance. Hunting uses an alcohol-based solvent to increase the radiation-sensitive linear composition _ two plates = coating properties, thereby inhibiting uneven coating, uniformity, etc., and can be used as a solvent. For example, uniformity can be cited. Long-chain silk alcohol such as 丨-hexanol d-hexanol, octyl octanol, 丨 壬 sterol, i hexane diol, octyl diol, etc.; aromatic alcohol such as benzyl alcohol; ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, alcohol monobutane and other ethylene glycol monofilament shouting; —·Zi early _, ethylene dipropylene glycol monomethyl hydrazine, propylene glycol monoethyl alcohol monobutane propylene glycol single burning fine; 4 early (four), C two shouting; Ethylene glycol monomethyl singer, diethylene glycol monoethyl sulphate, etc. diethylene glycol monoalkyl dipropylene glycol monomethyl trans, dipropylene glycol monoethyl ether, diethylene glycol mono (tetra), 45 201239531 mn /pif dipropylene glycol monobutraz Dipropylene glycol monofilament shouted. These alcohol solvents may be used singly or in combination of two or more. In the case of the improvement of the coating property, it is preferable that the propylene glycol monomethyl ether and the propylene glycol monoethyl component [F] may be used singly or in combination of two or more kinds. The content of the component [F] is preferably 篁1, 2 GG parts by mass, more preferably 1 gram by weight to 9 parts by mass, based on the mass of the component [A]. By setting the content of the component [F] to the upper ship _, the coating property of the _ substrate or the like can be improved, and the unevenness of coating (strip unevenness, unevenness of needle marks, uneven haze, etc.) can be suppressed. , can further improve the uniformity of thickness. ♦ In the present invention, other solvents such as ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatics may be contained together with the alcohol solvent. Hydrocarbons, ketones, esters, and the like. Additive The radiation sensitive composition of the present invention may contain various additives as needed. Examples of the additive include a sensitizing radioactive acid generator such as a triphenylsulfonium salt or a tetrahydrothiophenium salt; and an amine phthalic acid-2-nitro-based cycline. 2-nitrobenzylcyclohexyl carbamate), a sensitizing radioactive linear base generator such as O-carbamoyl hydroxy amide; nonionic surfactant, I-type surfactant and interfacial activity Surfactant such as surfactant; 2,2-thiobis(4-mercaptotridecyl butylbenzene) 46 201239531 /1/pif (2,2-thiobis(4-methyl-6-t-butyl phenol)) , 2,6-di-tertiary butyl phenol and other antioxidants; 2-(3-tertiary butyl_5_indolyl-2-hydroxyphenyl)_5•chlorobenzotriazole (2-(3- Ultraviolet absorption agent such as t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzobenzoazole or alkoxybenzophenone. The content of these additives can be appropriately selected within the range not impairing the object of the present invention. The radiation sensitive composition of the present invention can be produced by a suitable method, for example, by subjecting the component [A], the component [B] and the component [c] in the [F] solvent, and optionally the component [D], The component [E] or an additive or the like is mixed in a predetermined ratio to prepare a radiation-sensitive composition in a solution or dispersion state. A cured film and a method for forming the same, and a method of forming a cured film on a substrate using the radiation sensitive composition of the present invention will be described. The method comprises the following steps (1) to (4). (1) a step of applying a radiation-sensitive composition of the present invention onto a substrate to form a coating film; (2) a step of at least partially irradiating the coating film formed in the step (1); (1) using a developer solution a step of developing the irradiated film in the step (2); and a step of heating the developed coating film in the step (3) by the soil. (4) 2 (1) towel, after applying a silk dispersion liquid of the radiation sensitive composition of the present invention on a substrate, preferably by heating the coated surface (pre-47 201239531 1 / wpif baking) Remove to form a coating film. Examples of the material of the substrate which can be used include glass, quartz, rhodium, and resin. Specific examples of the resin include: polyethylene terephthalate (p〇Iyethyiene terephthalate), poly(p-phenylene terephthalate), polyether sulfone, polycarbonate, polybendimimine a ring-opening polymer of a cyclic olefin, a hydride thereof, or the like. The coating method or the dispersion method of the radiation-sensitive composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, a slit die coating method, or a bar coating method can be employed. Appropriate methods such as cloth. Among these coating methods, a spin coating method or a slit die coating method is particularly preferred. The pre-baking conditions vary depending on the type of each component, the blending ratio, etc., and are preferably set to be from 70 ° C to 120 ° C for about 1 minute to about κ minutes. Step (2) In step (2), at least a portion of the coating film formed in the step (1) is exposed. Usually, when a part of the coating film is exposed, exposure is performed through a photomask having a predetermined pattern. For the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. Among the singular radiations, radiation having a wavelength in the range of 19 〇 nm to 45 〇 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable. The exposure amount in this step is a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation by an illuminometer (〇ai mode B56, manufactured by OAI Optical a prison Ines Ine), preferably 1 〇 mj/cm 2 〜1. , 000 mJ/cm2, more preferably 2〇mJ/cm2~7〇〇(10) one. Step (3) In the step (3), the exposed coating film is subjected to a test solution using a developer solution, and is negative in the form of 201239531 41 /1 /pif. For example, the developer solution, sodium hydroxide, silk cut, sodium carbonate, stone „, 财义, scales, no ship _ 黯, silk cut methyl hydroxide tetraethyl organic test developer. Among them, the cost, From the viewpoint of the above, it is preferably an inorganic test developer which is a developer for detecting a metal hydroxide such as potassium oxyhydroxide. The radiation sensitive composition of the present invention can also be used in the case of using inorganic test development (IV). A pattern image is formed in a high-definition manner. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developer, and the development method may be, for example, a liquid-holding method or a dipping method. Appropriate methods such as (dipping meth〇d), shaking dipping method, spray method, etc. The difference between the materials is based on the composition of the radiation-sensitive composition. It is preferably about 1Q seconds to 18 seconds. After the development treatment, for example, after 3 to 90 seconds of running water cleaning, for example, air drying with compressed air or compressed nitrogen, the desired pattern can be formed. Step (4) in step (4) By using a hot plate A heating device such as an oven can heat the coating film patterned by development to obtain a cured film having a desired pattern. The heating temperature is, for example, 120 ° C to 25 (rc. The heating time is based on the type of the heating machine. Differently, for example, when the heating step is performed on a hot plate, it can be set to 5 minutes to 30 minutes, and in the case of an oven 49 201239531 41717 pif = heat: the time can be set to 3 minutes to 9 minutes. A stepwise baking method using a heating step of two or more times is used. The thickness of the cured film formed is preferably Q"_~1〇_, and the meaning is 0.1 μΓη to 6 μιη, and further preferably 〇] μιη~4哗. Good day Ϊ 经过 through the steps described above 'the cleavable base (four) adhesion good transparency, hardness, scratch resistance, heat resistance (four), sensitivity and various degrees of hardening film, and (4) The high resolution is high to form a pattern image, and the fine inorganic developer can develop the pattern 2仃. Moreover, since the obtained cured film has such characteristics, it can be suitably used as a touch of, for example, a display element. Protective film of panel, display element Inter-insulating film. A suitable aspect of the present invention is as follows. Π] - a radiation-sensitive composition containing the following components [Ah, [B] and [C]: [A1] tetraethoxy decane or a partially hydrolyzed product, a hydrolyzable decane compound represented by the above formula (丨) or a partially hydrolyzed product thereof, and a polycondensate obtained by hydrolyzing and condensing a hydrolyzable decane compound represented by the above formula (2) or a partially hydrolyzed product thereof [B] a compound having two or more ethylenically unsaturated groups (excluding the component [A1]); 〃 [C] a photoradical polymerization initiator; [2] as described in the above [1] The radiation-sensitive linear composition, wherein the ratio of the above-mentioned tetraethoxy oxime or its partial hydrolyzate is preferably from 5 mol% to 75 mol%, more preferably 1 〇m〇1, based on the total amount of the raw material compound. % 50 201239531 41 /1 /pit ~70 mol%, and more preferably 25 mol% to 65 mol%. [3] The radiation-sensitive linear composition according to the above [1] or [2], wherein the total amount of the hydrolyzable decane compound represented by the above formula (1) or a partial hydrolyzate thereof is added to the total amount of the raw material compound. The ratio is preferably i 〇 mol% to 80 mol%, more preferably 1 〇 mol% to 75 mol%, and still more preferably 15 mol% to 70 mol%. [4] The radiation sensitive linear composition according to any one of the above [1] to [3], comprising a hydrolyzable decane compound selected from the group consisting of an alkyl group having a carbon number of 丨6, and having a carbon number of 6 to 14 At least one of the sulfonated decane compounds (hereinafter also referred to as a decane compound (lbi)) is a hydrolyzable sinter compound represented by the above formula (1). [5] The radiation-sensitive composition according to the above [4], wherein the pyroxene compound (lbl) is a hydrolyzable decane compound selected from the group consisting of one alkyl group having 1 to 6 carbon atoms, and one of At least one of the hydrolyzable cyclamate compounds having an aryl group having 6 to 14 carbon atoms. [6] The radiation-sensitive composition according to the above [4] or [5], wherein the total addition ratio of the above decane compound (lbi) is preferably from 10 m〇1% to 80 rn〇 with respect to the total amount of the raw material compounds. I%, more preferably 15 m〇l% to 75 mol%' and further preferably 30 mol% to 70 mol%. [7] The radioactive linear composition as described in any one of the above [1] to [6], which contains a hydrolyzable decane compound having a (fluorenyl) acryloxy group as the hydrolysis represented by the above formula (1) A decane compound. [8] The radiation-sensitive linear composition according to the above [7], wherein the hydrolyzable decane compound having a (meth)acryloyloxy group is selected from the group consisting of methyl group 51 201239531 41/I/pif At least one of a hydrolyzable Shixia compound (hereinafter also referred to as Shi Xixuan compound (lc)) and a hydrolyzable decane compound having an acryloxy group (hereinafter also referred to as a decane compound (Id)) . [9] The radiation-sensitive composition according to the above [7] or [8], wherein the total addition ratio of the hydrolyzable decane compound having a (y-based) acryloyloxy group is preferably based on the total amount of the raw material compounds. 5 mol% to 25 mol% ' More preferably 1〇m〇1%~2〇m〇1% 〇[10] The radiation-sensitive composition as described in [8] or [9] above contains Shi Xi The calcined compound (lcl) and the Wei compound (1) 1) are hydrolyzable decane compounds having a (meth) propylene-based group, and the addition ratio (lc/ld) of the two is preferably 〇〇5 to 3 in terms of a molar ratio, more preferably Preferably, it is 2 to 丨$, and more preferably 0.3 to 1. The radiosensitive linear composition according to any one of the above (1) to (1), wherein (a) the hydrolyzable Wei compound represented by the above ruthenium (2) or a partially hydrolyzed product thereof in a total amount of a relative to the raw material compound in a The cut is 1% or less, more preferably 13 mol% or less, and even more preferably i〇m〇i% or less, and further preferably 7 mol% or less. The radiation-sensitive composition according to the above-mentioned item (1), wherein the hydrolyzable sinter compound represented by the above formula (2) or a partial hydrolyzate thereof is added to the total amount of the raw material compound. Force: the ratio is preferably 0.5 md% to 15 mol% 'better is i _%~13, then 1%, and more preferably 2 mol% to 10 mol%, further preferably 3 m〇1%~7 mol %. [13] Radiation-sensitive radiation as recorded in any of the above [1] to [12]

52 201239531 4I/17pxf Composition ' wherein the hydrolyzable decane compound represented by the above formula (2) is 3-trimethoxydecyl propyl succinic anhydride or 3-triethoxydecyl propyl sulphonate. [14] A radiation sensitive composition comprising the following component [A2], component [B], and component [C]: [A2] having a Si〇2 unit, a structural unit represented by the above formula (ia), and the above a polyoxyalkylene of the structural unit represented by the formula (2a); [B] a compound having two or more ethylenically unsaturated groups (excluding the component [A2]); [C] a photoradical polymerization initiator. [15] The radiation sensitive composition according to the above [14], wherein the content of the SiO 2 unit is preferably from 5 mol% to 75 mol%, more preferably in all the structural units of the component [A·2]. It is 1〇m〇i〇/. 〜7〇 m〇i%, and more preferably 25 mol% to 65 mol%. [16] The radiation sensitive composition according to [14] or [15], wherein, in all the structural units of the component [A2], the content ratio of the structural unit (la) is preferably 10 m〇l%~ 80 mol%, more preferably 10 moi% to 75 m〇l% 'and more preferably 15 mol% to 70 mol%. The radiosensitive linear composition as described in any one of the above [14] to [16] wherein, in all the structural units of the component [A2], the content of the structural unit (2a) is preferably 15 mol. % or less, more preferably 13 m〇1% or less, still more preferably 10 m〇l% or less, and further preferably 7 m〇1% or less. [18] The radiation sensitive composition according to any one of the above [14] to [16] wherein, in all structural units of the component [A2], the structural unit (2a) 53 201239531 41 /1/pif The proportion of cerium is preferably 〇5 m〇l%~15 m〇i%, more preferably i mol% 〜13 mol%, further preferably 2 m 〇 1% 〜1 〇 inol%, further preferably 3 mol% ～7 mol% 〇 [19] The radiation sensitive composition described in any one of the above [14] to [18] contains one or more structural units represented by the above formula (lb) (hereinafter also referred to as The structural unit (lb) is taken as the structural unit (la). [20] The radiation sensitive composition according to the above [19], wherein, in all the structural units of the component [A2], the content of the structural unit (lb) is preferably from 10 mol% to 80 mol%, more preferably It is 15 mol% to 75 mol%, and more preferably 30 mol% to 70 mol%. P1] The radiation sensitive composition as described in any one of the above [14] to [20] contains a structural unit selected from the above formula (lc) (hereinafter also referred to as "structural unit (1c)") At least one of the structural unit (hereinafter also referred to as "structural unit (ld)") represented by the above formula (ld) is used as the structural element (1 a ). [22] The radiation sensitive composition as described in the above [21], wherein in all the structural units of the component [A2], the total content ratio of the structural unit (ic) to the structural unit (Id) is preferably 5 m. 1% to 25 mol%, more preferably 10 mol% to 20 mol% 〇 [23] The radiation sensitive composition as described in [21] or [22] above, which contains structural unit (lc) and structural unit (id) As the structural unit (la), the content ratio (lc/ld) of the structural unit (lc) to the structural unit (id) is preferably 0.05 to 3, more preferably 0.2 to 1.5, and still more preferably 0 in terms of a molar ratio. ·3 ~1 〇

The radiation sensitive composition according to any one of the above [14] to [23] wherein the structural unit (2a) is derived from 3-trimethoxyoxyalkylalkylpropyl group. A structural unit of succinic anhydride or 3-triethoxydecylpropyl succinic anhydride. [25] The radiation sensitive composition according to any one of the above [1] to [13] wherein the carbon number of R1 of the above formula (1) and the alkyl group of R3 of the above formula (2) is preferably 1 to 4, more preferably 1 or 2. [26] The radiation sensitive composition according to any one of the above [1] to [25] wherein the alkyl group of R2 of the above formula (1) and formula (la) preferably has 1 to 10 carbon atoms. More preferably 1 to 6. [27] The radiation sensitive composition according to any one of the above [1] to [26] wherein the aryl group of R2 in the above formula (1) and formula (la) is preferably a phenyl group or a naphthyl group. More preferably, it is a phenyl group. [28] The radiation sensitive composition according to any one of the above [1] to [27] wherein the above formula (1), formula (la), formula (lb), formula (lc), and formula (Id) m is preferably 1 or 2, more preferably 1. [29] The radiation sensitive composition according to any one of the above [1] to [28] wherein the above formula (1), formula (la), formula (lb), formula (lc), and formula (Id) η is preferably an integer of 0 to 3, more preferably 0 or 3. [30] The radiation sensitive composition according to any one of the above [1] to [29] wherein X of the above formula (2) and formula (2a) is preferably 1 or 2, more preferably 1. [31] The radiation sensitive composition according to any one of the above [1] to [30], wherein y of the above formula (2) and formula (2a) is preferably 1 to 3, 2012, 2012, 31, 531, 41, 1 /pif integer, more preferably 3. [32] The radiation sensitive composition according to any one of the above [1] to [31] wherein z of the above formula (2) and formula (2a) is preferably 〇 or 1 ', more preferably 〇. [33] The radiation-sensitive linear composition of any one of the above [1] to [32] wherein the weight average molecular weight (Mw) of the component [A1] and the component [A2] is preferably 500 to 10,000, more preferably Good for 1000~7000. [34] The radiation sensitive composition according to any one of [1] to [33] wherein the dispersion degree (Mw/Mn) of the component [A1] and the component [A2] is preferably 1.0 to 15.0. More preferably 1.1 to ι〇·〇, and even more preferably 1.1 to 5.0. [35] The radiation sensitive composition according to any one of the above [1] to [34] wherein the component [Β] is preferably a bifunctional or trifunctional or higher (fluorenyl) acrylate, more preferably It is a trifunctional or higher (meth) acrylate, and more preferably a trifunctional to hexafunctional (meth) acrylate. [36] The radiosensing linearity of any one of the above [1] to [35], wherein the content of the component [Β] is 5 parts by mass relative to 100 parts by mass of the component [Α]. 〜3〇〇质量份, more preferably ι〇质量份~2〇〇质量二二等更优选为15质量份~100质量份,少更更优选为20质量直份〜80质量份. Composition] The radiographic recording described in any one of the above [1] to [3 6 ] is combined with a 0-fluorenyl hydrazine compound as the component [c]. The content of the composition is _ part, the octagonal [] and the composition [the total amount of 100 ^ knives [C] is preferably G.G5 parts by mass to 3Qf parts, |

56 201239531 41717pif is 0.1 part by mass to 15 parts by mass' and more preferably i part by mass to 1 part by mass. [39] The radiation sensitive composition according to any one of [D] to [38], further comprising (D1) a structural unit having a carboxyl group (hereinafter also referred to as structural unit Di) and (D2) having A copolymer of a structural unit of an epoxy group (hereinafter also referred to as a structural unit 〇 2) is known as a component. [40] The radiation-sensitive linear composition according to [39] above, wherein the element (7) is derived from (7)1·1) (4) and the ship and the unsaturated ferulic anhydride (hereinafter referred to as "the compound" A structural unit of at least one compound of (DM)"). 1 in the upper middle f on the 3:] or [40] recorded radioactive linear composition 'early 70 (D) is derived from the epoxy group-containing radical polymerizability also known as "compound (D2 ~ 2)" The structural unit. The sensitizing radioactivity = the product described in any one of [39] to [41], wherein in all the structural units, the amount of aggregation of the structural unit (D1) is % to 4 (% by mass), More preferably 2% by mass, Berry/〇, and more preferably 3% by mass to 25% 〇/

Ji3] The composition, wherein in all the structural units, the ratio of _ is preferably H) mass% to 75 f white copolymerization 7. % by mass, and more preferably 20 quality; ^ =. 15% by mass to 2 4丨ί to the radiation-sensitive composition of any one of the components, wherein the component [D] is more * (the structural unit of D3 5 propyltrialkoxydecane. 彳', ., Soil-gas 57 201239531 n /pif u[I5] The radiosensing linearity described in any one of [39] to [44] is 100 parts by mass of the above-mentioned polyoxoxime, and the component [D] ^ 罝 (four) is 1 part by mass to 45 parts by volume, more preferably 2 parts by mass to ~4 〇: more, parts by mass to 35 parts by mass, better in the step-by-step 〜 刀 0 ~ 0 quality reading 'and then preferably 3 parts by mass ~ 25 The mass-sensing linearity 3 described in any one of [1] to [45] has at least one selected from the group consisting of organic particles and inorganic particles as a component [E] [45] The radiation-sensitive linear composition is characterized in that the content of the component [Ε] of the mass fraction of the second and second chambers is preferably 1 mass 篁 胄, more preferably 10 parts by mass to 200 parts by mass, and further preferably The radiation sensitive composition according to any one of the above [1] to [47] further contains a solvent as the component [F]. μ ^9] as described in the above [48] Recorded radiation The linear composition contains a relatively protonic paste and a more desirable riding solvent as a component. [5〇] The radiation sensitive composition as described in [48] or [49] above, i 1 1 〇 0 parts by mass, the content of the component [F] is preferably 罝 叫 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The radiation-sensitive ί 崎 崎 赖 控 控 控 臈 臈 臈 臈 臈 臈 臈 臈 问 问 问 问 问 问 问 问 问 问 问 问 问 问 问 问 问 问 问 问 问 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ The method of forming the step-cured film includes the following steps (1) sexy radiation ray step), at least partial irradiation of the coating film formed in the step (1), and irradiation with the radiation (3) a step of developing the film of the step (2) with an alkali developer; and (4) a step of heating the developed film in the step (3). [54] The formation method according to the above [53], wherein the radiation in the step (2) contains radiation preferably having a wavelength of from 190 nm to 450 nm, more preferably ultraviolet light having a wavelength of 365 nm. [55] The formation method according to the above [53] or [54], wherein a non-computer-developed developer is used as the secret developer in the step (1). [Cross Example] The present invention will be more specifically described below by way of Synthesis Examples and Examples, but the present invention is not limited to the following examples. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyoxyalkylene obtained by each of the following synthesis examples are gel permeation chromatography (GdPermeati〇nChr〇mat〇graphy, gpc) of the following specifications. To determine. Device · GPC-101 (manufactured by Showa Denko Electric Co., Ltd.) Pipe column. Manufactured by GPC-KF-801, GPC-KF-802, GPC-KF-803 59 201239531 41 /l/pif and GPC804 (Showa Denko) Synthesis Example of Polyoxane Connecting the Mobile Phase: Tetrahydronaphthene Component [Synthesis Example 1] A single part of propylene glycol is added to a container with a scrambler, followed by addition of methyltrimethoxy ( Hereinafter, it is referred to as "MTMs = parts by mass, tetraethoxy Wei (TE〇s) 12 parts by mass, and "Hi Shixiji" propyl adenosine (hereinafter referred to as "TMs ^: oxy group (MTMS/TEOS/). TMSPS (Morby) = 8 〇 / 1 parts by mass: After the temperature of the solution reaches the temperature, add two parts of work, ion exchange water mass parts, heat to listen, negatively cool to 45 < t after 'add as dehydration When the original acid of the agent is _ t, it is stirred for 1 hour, and then the temperature of the solution is adjusted to 40. 匚, -Berry, and the surface is evaporated, thereby removing the ion-exchanged water and the methanol by the water. The solid content concentration of the calcined oxygen (4) obtained by the above operation was 30% by mass: 2); the oxygen (Mw) was 2,500, and the degree of dispersion (Mw/Mn) was 22. In addition: The term "solid component" in the book refers to the remaining component obtained by removing the volatile matter by using a 17-well hot plate to dry the sample for 1 hour. You [Synthesis Example 2] used 3-methylpropene MPTMS") in the case of 68/15/15/2, in addition to the synthesis example! The same operation was carried out to obtain a polyglycoloxypropyltrimethoxysulfonate (hereinafter referred to as MTMS/TEOS/MPTMS/TMSPS (Morbi) 201239531 41 /1/plf oxime (excluding MTMS, TEOS and TMSPS). A-2) The polysiloxane (a-2) has a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,300, and a degree of dispersion (Mw/Mn) of 2. [Synthetic Example 3] Polyoxane (A-3) was obtained by the same operation as in Synthesis Example 2 except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/TMSPS was changed to 62/15/15/8. The solid content concentration of (A-3) was 30% by mass, the weight average molecular weight (Mw) was 2,200, and the degree of dispersion (Mw/Mn) was 2.1. [Synthesis Example 4] In addition to the ratio of MTMS/TEOS/MPTMS/TMSPS ( Polyoxane (A-4) was obtained by the same operation as in Synthesis Example 2 except that the molar ratio was changed to 55/15/15/15. The solid concentration of polyoxyalkylene (A-4) was 30% by mass, a weight average molecular weight (Mw) of 2,200, and a degree of dispersion (Mw/Mn) of 2.3. [Synthesis Example 5] In addition to MTMS, TEOS and TMSS, MPTMS and phenyltrimethoxy decane (hereinafter referred to as for PTMS") was used in the ratio of MTMS/TEOS/PTMS/MPTMS/TMSPS (Morby) = 50/15/15/15/5, except that the same operation as in Synthesis Example 1 was carried out to obtain polyfluorene oxide. The alkane (A-5). The polysiloxane (A-6) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 1,900, and a degree of dispersion (Mw/Mn) of 1.9. [Synthesis Example 6 ] 61 201239531 41 /1/pif In addition to MTMS, TEOS and TMSS, 3-acryloxypropyltrimethoxydecane (hereinafter referred to as "APTMS") is used as MTMS/TEOS/APTMS/TMSPS (Morbi) A polyoxane (A-6) was obtained by the same operation as in Synthesis Example 1, except that the ratio of 65/15/15/5 was used. The solid content of polyoxane (A-6) was obtained. The concentration was 30% by mass, and the weight average molecular weight (Mw) was 2,400' dispersion (Mw/Mn) was 2 to 3. [Synthesis Example 7] In addition to changing the ratio of MTMS/TEOS/APTMS/TMSPS (Mohr ratio) to 50/ A polyoxyalkylene (A-7) was obtained by the same operation as in Synthesis Example 6 except for 30/15/5. The solid concentration of polyoxymethane (A-7) was 30% by mass, and the weight average molecular weight ( Mw) is 3,500, dispersion (Mw/Mn) 2.4. [Synthesis Example 8] In addition to MTMS, TEOS, and TMSS, MPTMS and APTMS were used in the ratio of MTMS/TEOS/MPTMS/APTMS/TMSPS (Morby)=77/7/1/10/5, among other things. Polyoxane (A-8) was obtained by the same operation as in Synthesis Example 1. The polysiloxane (A-8) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,000, and a degree of dispersion (Mw/Mn) of 2.0. [Synthesis Example 9] Polyfluorene was obtained by the same operation as in Synthesis Example 8, except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/APTMS/TMSPS was changed to 50/30/5/10/5. Alkane (A-9). Solidification of polyoxyalkylene (A-9)

62 201239531 41717pif The body component concentration was 30% by mass, the weight average molecular weight (Mw) was 3,400, and the degree of dispersion (Mw/Mn) was 2.3. [Synthesis Example 10] Polyfluorene was obtained by the same operation as in Synthesis Example 8, except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/APTMS/TMSPS was changed to 15/62/8/10/5. Alkane (A-10). The polysiloxane (A-10) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5,400, and a degree of dispersion (Mw/Mn) of 2.6. [Synthesis Example 11] Polyfluorene was obtained by the same operation as in Synthesis Example 8, except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/APTMS/TMSPS was changed to 50/30/10/5/5. Alkane (A-11). The polysiloxane (A-11) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 3,100, and a degree of dispersion (Mw/Mn) of 2.3. [Synthesis Example 12] Polyoxane (A-) was obtained by the same operation as in Synthesis Example 2 except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/TMSPS was changed to 50/30/15/5. 12). The polysiloxane (A-12) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5,000, and a degree of dispersion (Mw/Mn) of 2.0. [Synthesis Example 13] Polyoxane (A-) was obtained by the same operation as in Synthesis Example 6, except that the ratio (mol ratio) of MTMS/TEOS/APTMS/TMSPS was changed to 50/30/15/5. 13). The solid content concentration of polyoxyalkylene (A-13) 63 201239531 41 /l/pif was 30% by mass, the weight average molecular weight (Mw) was 5,000, and the degree of dispersion (Mw/Mn) was 2.3. [Synthesis Example 14] The polyoxin (A-14) was obtained by the same operation as in Synthesis Example 1 except that the ratio (mol ratio) of MTMS/TEOS/TMSPS was changed to 60/3 (V10. The polysiloxane (A-14) had a solid content concentration of 28% by mass, a weight average molecular weight (Mw) of 5,000, and a degree of dispersion (Mw/Mn) of 2.0. [Comparative Synthesis Example 1] APTMS was used instead of TEOS, and set. Polyoxane (a-1) was obtained by the same operation as in Synthesis Example 1 except for the ratio of MTMS/APTMS/TMSPS (Morby) = 80/15/5. Polyoxane (a-) Ι) has a solid content concentration of 30% by mass, and a weight average molecular weight (Mw) of 2,000' dispersion degree (Mw/Mn) of 1.9. [Comparative Synthesis Example 2] Using MPTMS and APTMS instead of TEOS, and setting it to MTMS/MPTMS/ In addition to the ratio of APTMS/TMSPS (Morby) = 80/5/10/5, polyoxocycloalkane (a-2) was obtained by the same operation as in Synthesis Example 1. Polyoxane ( The solid content concentration of a-2) was 3% by mass, the weight average molecular weight (Mw) was 2,000, and the degree of dispersion (Mw/Mn) was 1,9. [Comparative Synthesis Example 3] APTMS was used instead of TMSS, and was set to The ratio of MTMS/TEOS/APTMS (Morby)=70/15/15, in addition to the 64 201239531 41717pif, the solid concentration of the compound by the synthesis method 聚 聚 氧 氧 氧 -3 U-3) %, molecular weight (MW) is 2, _, and the degree of dispersion (Mw/discussion) is 21. [Comparative Synthesis Example 4] TMPS was not used, and phenyltrimethoxywei (hereinafter "PTMS") was used instead of TEOS' and was set to MTMS/pTMS (proportion of Moh', = 70/30) The polysulfide (a-4) was obtained by the same operation as in Synthesis Example 6. The solid content of the polyweixuan (a-4) was 29% by mass. The weight average molecular weight (Mw) was 6, and the snoring (Mw/Mn) was obtained. 2.0. [Comparative Synthesis Example 5] In a 500 mL three-necked flask, MTMS 27 2 g and trimethoprimic acid decane (MEPTMS) 39.2 g were placed, and == alcohol methyl ether 100 g was added thereto. To dissolve it, the obtained mixed solution was heated to /〇 by stirring with a magnetic stirrer. MTMS/MEPTMS = 50/50, in which it was continuously added for 1 hour. 8 to 6 g of ion-exchanged water containing 1% by mass of oxalic acid. Then, after reacting at 6 Torr for 4 hours, the resulting reaction solution was cooled to room temperature. Then, the alcohol component as a by-product of the reaction was decompressed from the reaction solution. Steam removal. #_ The above operation gave polyoxyalkylene (a-5). The concentration of the polysiloxane (a_5) was 45 mass%. The average molecular weight (mw) is j 9 〇〇: the dispersion (Mw/Mn) is 2.3 ^ ' ' The synthesis of the copolymer of the component [D] [Synthesis Example 15] 65 201239531 Ηί / 1 /pif with a condenser tube and 5 parts by mass of 2,2,-azobis(2,4-dimercapto valeronitrile) and 220 parts by mass of diethylene glycol decyl ethyl ether were added to the flask of the stirrer. Styrene was added (hereinafter referred to as " ST") 20 parts by mass of thioglycolic acid (hereinafter referred to as rMA) 20 parts by mass, Ν_cyclohexyl-butenylene hydrazine (hereinafter referred to as "CHMI") 22 mass-damaged methacrylic acid 40 parts by mass of glycidyl ester (hereinafter referred to as "GMA"), nitrogen substitution, slow sandalwood mixing, and raising the temperature of the solution to 70 ° C. 'The temperature was maintained for 5 hours to carry out polymerization', thereby obtaining a copolymer containing A solution of (D-1). The obtained copolymer solution had a solid content concentration of 31%, and the copolymer (d-1) had a weight average molecular weight (Mw') of 12,500' dispersion (MwVMn) of 2.5. Example 16] Dicyclopentyl methacrylate (hereinafter referred to as "DCM") and p-hydroxydecyl acrylonitrile (hereinafter referred to as "HMAd") The copolymer was obtained by the same operation as in Synthesis Example 15 except that the ratio of ST/GMA/MA/DCM/HMAd (weight ratio)=20/14/5/21/40 was set instead of CHMI. D-2) The copolymer (D-2) had a solid content concentration of 32% by mass, a weight average molecular weight (Mw') of 13, and a degree of dispersion (Mw, /Mn·) of 2.0. [Synthesis Example 17] Instead of ST and CHMI, 3-mercaptopropoxypropyltrimethoxydecane (MPTMS) was used, and the ratio of MA/GMA/MPTMS (weight ratio) = 5/65/30 was set. Except that, the copolymer (D-3) was obtained by the same operation as in Synthesis Example 15. The solid content concentration of the copolymer (d-3) is

S 66 201239531 41717 pif 31.5% by mass, weight average molecular weight (Mw') was 12,000, and degree of dispersion (Mw'/Mn,) was 2.3. [Synthesis Example 18] The same operation as in Synthesis Example 15 was carried out except that MPTMS was used instead of CHMI and set to a ratio of ST/GMA/MA/MPTMS (weight ratio) = 10/55/5/30. Copolymer (D-4). The copolymer (D-4) had a solid content concentration of 31.3% by mass, a weight average molecular weight (Mw') of 11,500, and a degree of dispersion (Mw, /Mn,) of 2.3. [Synthesis Example 19] In addition to ST, CHMI, GMA, and MA, MPTMS was used, and the ratio of ST/GMA/MA/CHMI/MPTMS (weight ratio) = 10/45/5/10/30 was set. The copolymer (D-5) was obtained by the same operation as in Synthesis Example 15 except for the same procedure. The solid content of the copolymer (D_5) was 31.7% by mass. The weight average molecular weight (Mw) was 12, and the degree of dispersion (Mw, /Mn) was 2.0. [Synthesis Example 20] 2,2,-azobis monomethylvaleronitrile)4.G f parts and diethylene glycol decyl ethyl ether 245 were added to a flask equipped with a condenser and a mixer. Then, 18 parts by mass of MA, 38 parts by mass of sputum, and 1 part of ST5 are added, and after nitrogen substitution, 5 parts by mass of the following "$BD" is produced in the mouth and the resulting solution is obtained. The polymerization was carried out for 4 hours, and the solid content concentration of the copolymer (D_6) was 29.3 67 201239531 ^Tl / 1 /pif mass%, and the weight average molecular weight (Mw,) was 2〇, 〇〇〇, dispersed. The degree (Mw'/Mn') was 2.0. [Preparation of a radiation-sensitive composition and formation of a protective film and an interlayer insulating film [Example 1] A solution containing a polysiloxane (a solution of Α_υ (100 parts by mass in terms of solid content) obtained in Synthesis Example 1 a mixture of (Β-1) dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (mol/r ratio 50/50) as 20 mg parts by weight of (c_j) ethyl ketone as component [c], 3 parts by mass of 1-[9-ethyl-6-(2-methylbenzhydryl)_9Η-carbazole-3-yl], ethoxylated hydrazine), and further added propylene glycol so that the solid content concentration becomes mass% A mixed solvent of monomethyl ether and ethylene glycol monobutyl ether (mixing ratio of 80/20 w/w%) 'Preparation of a radiation sensitive composition. Then, the radiation sensitive composition was applied onto a Si〇2 impregnated glass substrate using a spinner, and then prebaked on a hot plate at 9 Torr for 2 minutes to form a coating film (IT described later) A substrate with =〇 was used for the evaluation of the adhesion. Then, the obtained coating film was exposed to ultraviolet rays at an exposure amount of 3 〇〇 mJ/cm 2 . Then, it was developed by using 238% by mass of tetradecyl ammonium hydroxide in water at 60 C for 60 seconds, then washed with pure water for 1 minute, and further heated in an oven at 230 ° C for 6 minutes to form a film thickness. It is a protective film of 2 inches. Further, the rotation speed of the rotator at the time of forming the coating film was adjusted so that the film thickness after heating was 3 〇 μίη, and light having a contact hole pattern having a size of 2 μm, 3 μm, 4 μm, and 50 μm was interposed therebetween. Cover with 15 曝光 exposure gap

An interlayer insulating film is formed in the same manner as the above-described protective film formation except that exposure is performed in the case of the above-mentioned protective film. The obtained protective film and interlayer insulating film were evaluated for the following physical properties. The results are shown together in Table 1. Physical property evaluation 1) Heat-resistant transparency of the film according to the film. The substrate having the protective film formed as described above was heated in a clean oven at 250 C for 1 hour, and a wavelength of 4 前后 before and after heating was measured using a spectrophotometer (150-20 type double beam manufactured by Sigma). The light transmittance (%) at 〇 nm was measured, and then heat-resistant transparency (%) was calculated according to the following formula. When the value is 4% or less, it is judged that the heat-resistant transparency of the protective film is good. Heat-resistant transparency (%) = light transmittance before heating (%) _ light transmittance after heating (%) 2) Pencil hardness of protective film For a substrate having a protective film formed as described above by rJIS K- The error of the protective film (surface hardness) was measured by the 8.4.1 pen stroke test of 5400-1990. When the value is 4H or more, it is judged that the surface hardness of the protective film is good. 3) The scratch resistance of the protective film The substrate having the protective film formed as described above was subjected to a load of 200 g on a steel wool pile #〇〇〇〇 using a vibration-type wear tester's and transferred back and forth 1〇69 201239531 T 丄/i / jJlf" times. The condition of the scratch was evaluated by the naked eye according to the following criteria. When the score is ◎ or 〇, it is judged to have good scratch resistance. Judgment criteria ◎: No damage at all, 〇: There are 1 to 3 scars, △. There are 4 to 10 scars, and X: There are more than 10 scars. 4) Heat-resistant cracking of the protective film The substrate having the protective film formed as described above was additionally calcined at 30°C for 30 minutes, and then placed at 2; rc for 24 hours, and the laser was used according to the following criteria. A microscope (VK-8500 manufactured by Keyence) was used to confirm whether or not cracks were formed on the surface of the protective film. When the score was ◎ or 〇, it was judged that the heat-resistant crack was good. The criterion ◎: no crack, 〇: There are 1 to 3 cracks, △: 4 to 1 crack, x: 10 or more cracks. 5) ITO adhesion of protective film. Substrate with ITO is used instead of Si〇2 In the same manner as above, a protective film was formed and a pressure cooker test (120 ° C, humidity: 1%, 4 hours) was carried out. Then, the "8.5.3 Adhesive Mesh Tape Method of JIS K-5400-1990" was carried out, and the number of meshes remaining in one cell was determined to evaluate the IT〇 adhesion of the protective film. When the number of grids remaining in one of the 201239531 Hi/1/pif grids is 80 or less, it is judged that the IT interface is poor. 6) Sensitivity of the protective film The coating film formed by the same operation as above is an exposure machine (TME-400PRJ 'Topcon) manufactured by a line and a gap having a line of 1〇μηι/3〇μηι The mask of the pattern of the space and the exposure was exposed to light, and then developed by a dipping method at 25 ° C for 60 seconds using a 4% by mass aqueous KOH solution. Then, it was washed with ultrapure water for 1 minute, and dried to form a pattern on the glass substrate. At this time, the minimum exposure amount required for the pattern of the line and the gap of 忉 μιη/30 μηη was not peeled off and measured. This minimum exposure amount was evaluated as the radiation sensitivity. When the minimum exposure amount is 1 〇〇 mj/cm2 or less, it is judged that the sensitivity is a good sentence. Further, the case where the pattern cannot be formed is evaluated as x. 7) Resolution of interlayer insulating film In the formation of the above interlayer insulating film, the size of the resolvable contact hole was measured. If the contact hole pattern of 30 μη or less can be analyzed, the analytical resolution of Li and break is good. In addition, the case where the pattern could not be formed was evaluated as χ18) K〇H developability of the protective film,” A coating film of 3 Å was formed on the substrate having the protective ruth formed as described above, and the amount of Μ4 f was used. The %K〇H aqueous solution was developed under the pit for 60 seconds by the collapse method. Then, it was washed with water, and the presence or absence of the film residue on the substrate was evaluated by the following micro-mirror. In the case of the film residue, it is judged that the K〇H developability is sub-related, and when the film is completely confirmed on the substrate, 71 201239531 Hi / i /pif is judged to have no KOH developability, which is a bad criterion. 〇: No film residue was observed Δ: A slight film residue was confirmed: Film residue was confirmed on the entire substrate [Example 2 to Example is and Comparative Example 1 to Comparative Example 4] In addition to the type and amount of each compound (quality) In the same manner as in Example 1, a radiation sensitive composition was prepared in the same manner as in Example 1. Then, using the obtained radiation sensitive linear composition, a protective film and an interlayer insulating film were formed in the same manner as in Example 1. The obtained protective film was obtained. Interlayer insulating film The same physical properties were evaluated as in Example 1. The results are shown in Table 1. [Examples 16 to 26 and Comparative Examples 5 to 7] The types and the amounts (parts by mass) of the respective components were as follows. In the same manner as in Example 1, a radiation sensitive composition was prepared in the same manner as in Example 1. Then, a protective film and an interlayer insulating film were formed in the same manner as in Example 1 using the obtained radiation sensitive composition. The obtained protective film and interlayer insulating film were obtained. The same physical property evaluation as in Example 1 was carried out. The results are shown in Table 1. Further, in Tables 1 and 2, the components [A], the components [B], the components [C], and the components [D] and The respective symbols of the component [E] indicate the following items, respectively. Component [A] Α-Ϊ : MTMS/TEOS/TMSPS=80/15/5 (mol%) A-2 : MTMS/TEOS/MPTMS/TMSPS=68/l 5/15/2 (m〇l%) A-3 : MTMS/TEOS/MPTMS/TMSPS=62/15/15/8 72 201239531 41/1/plf (mol% ) A-4 : MTMS/TEOS/MPTMS /TMSPS=55/l 5/15/15 (mol% ) A-5 : MTMS/TEOS/PTMS/MPTMS/TMSPS=50/15/15/15/5 (mol% ) A-6 : MTMS/TEOS/ APTMS/TMSPS=65/l 5/15/5( mol% ) A-7 : MTMS/TEOS/APTMS/TMSPS=50/30/15/5( mol% ) A-8 : MTMS/TEOS/MPTMS /APTMS/TMSPS=77/7/l/10/5 (mol%) » lcVld1=0.1 A-9 : MTMS/TEOS/MPTMS/APTMS/TMSPS=50/30/5/10/5 (mol%) 5 lcVld1=0.5 A-10 :

MTMS/TEOS/MPTMS/APTMS/TMSPS= 15/62/8/10/5 (mol%), lcVldLOJ A-ll : MTMS/TEOS/MPTMS/APTMS/TMSPS=50/30/10/5/5 (mol %) > lc1/ld1=2.0 A-12 : MTMS/TEOS/MPTMS/TMSPS=50/30/15/5 (mol% ) A-13 : MTMS/TEOS/APTMS/TMSPS=50/30/15/ 5 (mol% ) 73 201239531 41 /1/pif A-14 : MTMS/TEOS/TMSPS=60/30/10 (mol%) a-1 : MTMS/APTMS/TMSPS=80/15/5 (mol%) A-2 : MTMS/MPTMS/APTMS/TMSPS=80/5/10/5 (mol% ) a-3 : MTMS/TEOS/APTMS=70/15/15 (mol%) a-4 : MTMS/PTMS= 70/30 (mol%) a-5 : MTMS/MEPTMS=50/50 (mol%) Ingredient [B] Bl: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Morby ratio 50/50) (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) B-2: Pentaerythritol triacrylate vinegar (manufactured by Shin-Nakamura Chemical Co., Ltd.) B-3: succinic acid-modified dipentaerythritol pentaacrylate (trade name: Aronix M-520, B-4: Tris(propylene methoxyethyl) isocyanate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.) B-5: Polyfunctional urethane compound containing polyfunctional acrylate Available product (trade name: KAYRAD DPHA-40H, manufactured by Nippon Kayaku Corporation) Component [C]

C-1: ethyl ketone, 1-[9-ethyl-6-(2-mercaptophenyl)-9H-indazol-3-yl]-, l-(0-ethylindenyl) ( Product name: IRGACURE 0X02, manufactured by BASF Corporation 02: Bis(2,4,6-trimercaptophenyl)-phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF Corporation)

S 74 201239531 4Γ/1 /pif C_3 : l,2-octanedione, i_[4_(phenylthio)_,2_(〇_benzothymidine)] (trade name: IRGACURE OXE01, manufactured by BASF) C-4 : 2-mercapto-1-(4-methylthiophenyl)_2-morpholinopropan-1-one C-5 : 2,2'-bis(2-chlorophenyl)-4, 4,5,5,-tetraphenyl-1,2,-biimidazole C-6 : 4,4'-bis(diethylamino)benzophenone C-7. 2-phenylene塞ββ坐成分[D] D-1 : ST/GMA/MA/CHMI=18/40/20/22 (wt%) D-2 : ST/GMA/MA/DCM/HMAd=20/14/5 /21/40 (wt%) D-3 : MA/GMA/MPTMS=5/65/30 (wt%) D-4 : ST/GMA/MA/MPTMS=10/55/5/30 (wt%) D-5 : ST/GMA/MA/CHMI/MPTMS=10/45/5/10/30 (wt% ) D-6 : ST/GMA/MA/DCM/BD=5/38/l8/34/5 (wt%) Ingredient [E] El: Poly(mercapto acrylate) microparticles (trade name: MP-300, manufactured by Amika Chemical Co., Ltd.) E-2: Organic bismuth sol (trade name: IPA-ST, 曰Chemical Industry) Manufactured by the company) E-3 : Zr02 sol (trade name: ID19, manufactured by Tayca Co., Ltd.) E-4 : Ti02 sol (trade name: TS-103, manufactured by Tayca Co., Ltd.) 75 201239531 [1<] Ja Bu Ξ inch (牟¥铋) Comparative example m tr> X inch < cn O m X inch < CS 〇m 00 X CN X o ro r- (NX example o Ο 〇»〇^T) CN ffi 卜 o Ο o yn m yrt (NX v〇 ◎ ΓΟ o ο oi〇in CO ◎ CN o ο in r〇ο o fn m X inch 〇Ο om rH X ◎ On 1 loo 1 CO X VO ◎ 00 100 mm X inch oo o ο ^T) fS inch X ο v〇o ο om 寸 inch » τ» o (N CN m ffi ^T) ο inch 100 mm ◎ m 100 m cn X <n 0 CN o *—H CO ffi ο om inch X inch 〇 type < A-2 A-3 A-4 A-5 A-6 A-7 i A-8 A-9 A-10 A-ll cd <N cd cn cij ώ B-2 B-3 B-4 ό C -2 ! C-4 Heat-resistant transparency (%) Pencil hardness and scratch resistance m 2 201239531 Ja <N |25〇J Ο X o XXXX IT) 〇X ο ◎ ο § o ο ◎ ο § o 〇 ◎ ο i〇〇 ◎ ο in 〇〇ο g 〇 Ο Ο 〇 ◎ ο Τ Η 〇 ο ο 〇O 〇〇ο S o 〇〇ο 〇o 1—H 〇〇ο 〇o 〇〇ο ο 〇00 〇〇100 § o 〇〇W") Ον § v〇〇Ο Ο 〇1—^ 〇 heat resistant Cracking ιτο adhesion /^-N fN s Η Resolution (μιη) ΚΟΗ developability 201239531 T1 / 1 f \Jli [Table 2] (mass parts) Comparison of types of examples 16 17 18 19 20 21 22 23 24 25 26 5 6 7 Α-9 100 100 100 Α-12 100 100 [A] Α-13 100 100 100 Α-14 100 100 100 a-4 100 100 a-5 5 Bl 20 20 20 20 10 20 20 20 20 60 20 20 60 B-2 10 10 [B] Β·3 10 B-4 5 10 B-5 60 60 Cl .3 3 3 3 3 3 3 3 3 5 3 3 5 C-2 3 1 1 1 1 C -3 5 [C] C-4 10 C-5 5 5 C-6 5 5 C-7 2.5 2.5 Dl D-2 50 [D] D-3 50 30 10 5 5 5 5 10 D-4 5 D-5 5 D-6 5 100 El 100 [E] E-2 100 E-3 100 E-4 100 Heat-resistant transparency (%) 5 4 3 2 3 3 3 3 3 3 4 4 5 6 Pencil hardness 4H 5H 5H 6H 6H 5H 6H 6H 6H 6H 4H 4H 4H 4H Scratch resistance Δ Δ o ◎ ◎ o ◎ ◎ ◎ ◎ 0 Δ Δ Δ Heat-resistant cracking 0 〇〇 ◎ o 〇 ◎ ◎ ◎ Δ Δ Δ X ITO adhesion 90 90 100 100 100 100 100 100 100 100 100 90 90 95 Sensitivity (mJ/cm2) 80. 60 60 40 30 60 60 60 60 60 80 X 200 100 Resolution (μηι) 10 10 10 10 5 10 10 10 10 10 10 X 40 15 ΚΟΗ developability ooooo 〇o 〇o 〇〇X Δ 〇

78 201239531 41717pif [Simple diagram description] jStil 〇 》", [Main component symbol description] No 0

Claims (1)

201239531 Hi / 1 /pif VII. Patent application scope: L A radiation-sensitive linear composition containing the component [A1] of [B] and the component [C]: and the tetraethoxy decane or its [A1] a hydrolyzable decane compound represented by the following formula (1) or a partial hydrolyzate thereof, and a polyhydrazin obtained by the following formula (2); Hydrolysis condensation [B] has two or more ethylenically unsaturated groups [except for [A1]); wherein [C] photoradical polymerization initiator; [Chem. 1] (Rl °fcshf (cH seven r2L) (1) [Chemical 2] (R3〇)^Si ~ -^CH2 [In the formula (1), R1 represents an alkyl group having 1 to 6 carbon atoms, an aryl group of 14 or a (fluorenyl group) R2 represents an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 201239531 4171/pit propylene decyloxy group, and m represents An integer of 1 to 3, η represents an integer of 〇~6; in the formula (2), R3 represents a condensing group having a carbon number of 1 to 6, X represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents 〇 An integer of ~3]. 2. The radiation-sensitive composition according to claim 1, wherein the hydrolyzable second-burning compound represented by the above formula (2) or a partial hydrolyzate thereof is added in an amount of 15 or less based on the total amount of the raw material compound. M〇1% or less. 3. The hydrolyzable decane compound containing a fluoro group having an alkyl group having 1 to 6 carbon atoms or a carbon number of 6 to 4 as described in the first or second aspect of the invention, as the above formula (1) The hydrolyzable decane compound represented. 4. The radiation-sensitive linear composition of the first or second aspect of the patent application, comprising a hydrolyzed (tetra)-sintering compound having a mercaptopropenyloxy group and a hydrolyzable property having a propenyloxy group. At least one type of the Wei compound towel is a (four) hydrolyzed chemical compound as shown in the above formula (1). Eight "Top: t-sensing linear composition" contains the following components [A2], knives [B], and components [C]: and the following 1^·! has ^1〇2 units, and the following formula (la) a structural unit represented, (a) a polyoxyalkylene of the structural unit represented; 81 201239531 41 /1/pif [B] a compound having two or more ethylenically unsaturated groups (excluding the component [A2]); [C] photoradical polymerization initiator; [Chemical 3] RHCH silicon Si-〇(4-m)/2 (10) [Chemical 4] [In the formula (la), R2 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or an alkyl group of (indenyl) acrylate, m represents an integer of 1 to 3, and η represents 0 to 6 In the formula (2b), R4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3]. 6. The radiation-sensitive linear composition according to claim 5, wherein the content of the structural unit represented by the above formula (2a) is 15 mol% or less in all structural units. . 7. The radiation-sensitive linear composition according to claim 5 or 6, comprising a structural unit represented by the following formula (lb) as a structural unit represented by the above formula (la), [Chem. 5] (R+Si-O (4 - m)/2 (lb) [In the formula (lb), R5 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, m being as described above 8. The radioactive linear composition according to claim 5 or 6, comprising a structural unit selected from the following formula (lc) and represented by the following formula (Id); At least one of the structural units is a structural unit represented by the above formula (la), [Chem. 6] » 2 ct I 〇 = c H3 - C - C II H2 c [Chemical 7] CH 〇 II = CH - C - 〇—^*CH2' -Si-0 (4 - m)/2 (Id) 83 201239531 /1 /pif meaning]. [Formula (lc) and formula (ld)] as and n are as described above The radiation-sensitive linear composition described in the 1st, 2nd, 5th, and 6th paragraphs of the same claim = the scope of the patent, including the 〇 y); the object = 3 plant and (〇 2) has a ring Copolymerization of structural units of an oxy group 10. Radiation-sensitive as described in claim 9 The composition [D] further has (d3) a structural unit derived from (fluorenyl) propylene oxypropyltrialkoxy decane. 11. The radiation-sensitive linear composition according to claim 9, wherein the content of the component [D] is from 1 part by mass to 45 parts by mass based on 1 part by mass of the polysiloxane. 12. The radiation-sensitive linear composition according to any one of claims 1, 2, 5, and 6, further comprising a group selected from the group consisting of organic particles and inorganic particles. At least one as component I; E]. 13. The radiation-sensitive linear composition according to any one of the first, second, fifth, and sixth aspects of the invention, for forming a protective film of a touch panel or an interlayer insulating film of a display element . A cured film formed by using the radiation-sensitive linear composition according to any one of claims 1 to 13. A method for forming a cured film, comprising the following steps (1) to (4); (1) applying the radiation-sensitive linear composition according to any one of claims 1 to 13 a step of forming a coating film on the substrate; 84 201239531 41/1/pif (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation; (3) using an alkali developing solution for the step (2) a step of developing a coating film irradiated with radiation; and (4) a step of heating the developed coating film in the step (3). 16. The method of forming a cured film according to claim 15, wherein an inorganic developer is used as the developer. 85 201239531 41717pif IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0